cz

TWELFTH EUROPEAN CRYSTALLOGRAPHY MEETING

COLLECTED ABSTRACTS

Vol. 2

MOSCOW, USSR, AUGUST 20—29, 1989 USSR Academy of Sciences

TWELFTH EUROPEAN CRYSTALLOGRAPHIC MEETING

Moscow, USSR August 20-29, 1989

COLLECTED ABSTRACTS Vol.2

The meeting is arranged by the Soviet National Committee of Cryst.allographers and the Institute of Crystallography of the USSR Academy of Sciences on behalf of the European Crystallographic Committee under the auspices of the USSR Academy of Sciences and the International Union of Crystallography.

Moscow-198 9 Organizing Committee:

Co—chairmen: B.K. Vainshtein, A.M.Prokhorov

Conference secretary: EJH.Harutyunyan V.V.Davydov, V.P. Fatieva, P.P. Fedorov, N.P. Goltzova, A.G. Kocharov, Yu. A. Kostenko, EX. Lube, I.S. Lyubutin, Yu.M. L'vov, I.L.Minaeve, V.I. Ryabchenkov_, V.I. Simonov, E.V.Suvorov, D.I.Svergun, V.E.Volkov

International Programme Committee:

Chairman: V.I. Simonov (USSR)

H.D.Bartunic (FRG), E.F.Bertaut (France), T.L. Blundell (U.K.), S. Garcia—Blanco (Spain), A.Kalman (Hungary)^K. Lukaszevicz (Poland), L.I.Man (USSR), Yu. Z.Nozik (USSR), H.Schenk (The

Netherlands)fD.L.M.Viterbo (Italy)

Collected Abstracts have been compiled by V.V. Klechkovskaya, L .L. Aksenova, О. V. Konovalov 3. CRYSTAL CHEMISTRY

Oral presentations

1-3 - 4­ FFOH BRONZE PHASES TO BROH20IDS AND PBASOIDS ­ EXCURSION INTO SOME COMPLEX TOHGSTEH OXIDE SYSTEMS Arne MagnSli Arrhenius Laboratory, University of Stockholm, S­106 91 Stockholm, Sweden

By hie X­ray diffraction studies in 1935 of the cubic sodium tungsten Ьгопгев НЙдд was able to solve the more than 100 years old problem of the chemical character of this peculiar group of substances. What he found was not a nuaber of discrete compounds but rather one phase with an extraordinarily

wide region of composition NaxW03, with values of x ranging from about 1/3 to close to 1. The berthollide character is associated with the crystal structure where a variable proportion of sodium atoms occupy the interstices in an ЛеОз­ type skeleton of WOg­o^tahedra. An alternative way of lookiTiq at the structure is as perovskite type with a variable deficiency of sodium atoos (PTB|.

Subsequent studies on bronzes containing alkali atoms larger than sodium revealed other types of skeletons of corner­linked WOg­octahedia. In addition to PTB­type interstices the tetragonal tungsten bronze type (TTBJ contains larger ones, situated in pentagonal tunnels or tubes (PT) formed by rings of five octahedra. Even larger are the interstices in the hexagonal tungsten bronze type IHTB) which contains six­sided tunnels formed by coupling of six octahedra.

The skeletons of the bronze structures show a remarkable stability. Hot only can they accommodate a large variety of atoms to substitute *t the alkali atom positions, but substitution may also occur in the skeleton it­ self. Thus ГТВ­type phases occur in the XNbjOsF­wOj system, where Nb and F partly replace W and O, respectively. This phase, while possessing a bronze structure, lacks other characteristics of bronzes such as metallic lustre and electric conductivity and may properly be designated a bronzoid. Other types of bronze­like phases occur in systems like N^Os­WO^. Here some PTs in a TTB framework are filled with alternating metal and oxygen atoms which, to­ gether with the 0 five­rings of the tunnel, form pentagonal metal­oxygen bi­ pyramids linked by 0 apices to a spine which transforms the PT to a PC (penta­ gonal column)­ The PC is a frequently occurring structure element in transition metal oxides and fluorides. High resolution electron microscopy (HREM) and electron diffraction have been indespensible complements to X­ray diffraction techniques in studies of such materials and of those described below.

Intergrowth tungsten bronzes (ITB) forming at low contents of large alkali atoms, e.ej. Cs, have been extensively studied by Kihlborg and coworkers.

Their «ОД skeleton is formed by intergrowth of lamellae of НТВ and W03 struc­ tures. Both can vary in width, and crystallites of a particular sample almost invariably differ with respect to the thickness of the slabs. Such variations also abound within the crystallites. Thus there is no obvious correlation between gross composition and structure of the ITBs, and under practically attainable conditions the concepts of compound and phase los^ their meaning for these substances. The region of gross composition as a function of tempe­ rature of preparation seems to be fairly well defined, and the ensemble of ITBs thus behaves rather like a phase and may therefore be described as a phasoid. The conditions are similar in bronzoid ITBs with a pentavalent metal partially substituting for tungsten. ­ 5 ­ NEW MINERALS НТВ TBTBJLHEDBJLL AND MIXED RADICALS U.Yu.PushcharovBky. N.A.Yamnova, T.N.Nadezhina Moscow State University, Faculty of Geology, Moscow, USSB

The review summarizes the results of recent structural determinations of four new minerals with original tetrahedral and mixed radicals.

The structure of grumentite NafsigO.COH)]H20 contains an interrupted framework of tertiary [SiO.] tetrahedri, which ie

untypical for the tetrahedral radical [ЧгоЛ. This silicate anion is one of 11 (Si,0)­tetrahedral configurations, revealed at the Chair of Crystallography of Moscow State University during the last 40 years. The structure of olinobehoite Be(OH), is composed of 3­ layered sheets of Be­tetrahedra linked by H­bonds. The common and distinctive features of 3­layered tetrahedral sheets in

clinobehoite, zusmanite, Na,Si,07 and NaPrSigO.,. are discussed.

New carbonate mineral Ha6BaTh(CO,)g.6H20 has hexagonal sym­ metry, space group R3 with unit cell parameters a = 14,175, с = 8,605 А, Нщ^ад ­ 0,035 for 565 reflections. A new type of isolated mixed radical composed of Th­icosahedron sharing edges with six [CO,]­triangles, is revealed in this structure. The deviation of C­atoms from the plane formed by three 0­atoms is 0,05 A. The framework mixed radical formed by Mg­octahedra and S­ tetrahedra makes the basis of the structure of new sulphate mi­ neral Mg­(S0.)2(0H) The crystals have tetragonal symmetry, space group P 4­|/amd ilth lattice dimensions a = 5,254, с = 12,971, Rgj^ao • 0,035 for 238 reflections. This mineral is a structural analogue of previously investigated synthetic crystal ME1(33S04(OH)1>33[H2O]0(67. The comparative crystal­chemical analysis of studied minerals allowed us to represent the connections between chemi­ cal compositions end their structures. ­ 6 ­ AIMMM Grat: SyntSwiiit StmcUf t, md шммг яя Nn Sptcfrescflfy yjjHjr', G.A. Lager2, G. Anrthausr3, J.F. rschardson*. and T. Armbruster5 'Tcchniicht Universitat Berin, Ernst Router Platz 1, D­1000 Berlin 12. zDept. fisohjIU. Uniy. LourtY*., Lean»»», KY 40292. U.S.A.. 3mstitut fik­ Gaowissen­ schaften, UramrsHIt Salzburg, A­S020 Salzba­f. Austria. *Оар<. Chemistry, Univ. Loutsvise. sUb. (or Chemical and Mnaratofjcal frystafeo/aphy. Univ. Barn. Freiestrasse 3. СН­Э012. Barn, Switzerland.

Singio crystals of almandeur garnet (Fo3Al2Si30t2) up to ~ 1 mm in size have been synthesized at 1073 К and 1.5 GPa in a piaten­cvRnder apparatus. Larfa cryslala ef this size hove not bean synthesized previously. The crystals Mora grown hydrefhermafy from an aside and re­metal mix in iron capsules for two days duration. We report the first single crystal X­ray structure refinement, NIR spectrum and crystal fiaW stebifezation anorajt (WSE) for synthetic end menibar akmndine. The X­ray work at 2M X Luntliiiied the space group Ia3d, «nth a,= 11.521 A (1), and osygen parameters X = 0 033*5 (10), Y = 0.04912 (10), and Z = 0.65306 (Ю). Selected bond kmgths in A aro SHOO) = 1.633 (1), FelD­OU) ­= 2.218 (1). FM2>­OU) • 2.36» (1) and At­Ot» ­ 1.893 (1). These vahies are vary similar to those reported for naturaiy occurring аитшняпе­­г1сп garnets /1/, /2/. Mossbauer spoclro taken on other armandine syntheses consisting of smaler cryslala have imilnauli seetttnei of 3.S9 I 0.01 mm/sec (298 Kl and 3.65 (78 K) and leeaw shifts of 1.28 ! 0.01 mm/sec 1298 K) and 1.42 (78 Ю for the Fa1* doublet. Sight asymmetries and different Kne vrktths. In the ooualil wore observed and hence, two components could be fit to the spectra /3/. Ilowavar, the X­ray data do not Indkato the preaonce of more than one crystalegrephic dadecahodral «No and, tharsfore, a garnet symmetry tower than Ia3d И.о. 12,31 at 2»i K. The asymmetry of the Fea* doublet in the Moasbalnv spectra could bo due to relaxation effocte. FT­MR moasuramonts were made on single crystale betwaan 10,000 and 3.000 cm'1 ta locate the ваеЮеае of throe bands rotated ta dd electronic

2 transition» ef tks t2, orbHal of Fa * In the dodocahodral site of point group symmetry D2. The bands are located at 7561, S7I3. and 4348 cm"'. This gives \* 5324 cm"' and.a CFSE of 3744 cm'1, assuming that the lower energy a, transition sA­»­5B, Is ItOO cm"1 /4/. These values are lower than those calculated for natural abnandines /4/. Two Ifl bands were also observed at 3«13 cm­1 and ­ 3490 cm"1 (298 K) end 3617 cm"1 and 3595 cm"1 (78 K). They are interpreted aa OH~ stretching vibrations related to a small number

4 of (04H4) ~ groups substituting for the SK>4 tetrahedra in the hydrogarnel substitution.

/1/ Pram* W„ Zeit. KiistjU. Щ. 333 (19711. /2/ Novak 0Л. and Slabs G.V.. Am. Mneral. 56, 791 (1971). /3/ Murad E., Wagner Г.Е.. Phys. Chom. Mineral» it 264 (1987). /4/ Burin; R.G.. й RMVYJWS in Mineraloey v. 14, Macroscopic to Microscopic, Am. Mbwal. Society, Washington D.C., (1985). ­ ? ­ MODELLING OF STRUCTURAL AND ELASTIC CHANGES UNDER STRESS OF

FORSTERITE (Mg2Si04) H. Catti Dipartimento di Chimica Fisica ed Elettrochimica, University, via Golgi 19, Milano, Italy The investigation of crystalline materials at high pressure is Important both for geophysical applications and for understanding the behaviour of matter in extreme conditions. Computer simula­ tion methods are valuable in making up for lacking or poor expe­ rimental results, particularly for anisotropic pressure. The method of crystal static deformation /1/, including inner strain effects /2/, was applied to calculate the structure configuration and elastic.constants of forsterite under anisotropic and isotro­ pic pressure. A Born type interatomic potential, Eij " e4zj/rij + «"pLdi+rj­rijJ/IPi+Pj)] "Oij/rfj ­ Чц/Лу was used; г.. is the interatomic­distance and e the electron charge. SiO, tetrahedra are approximated as rigid units. Atomic charges z., repulsive radii r, and hardness parameters p^^ were fitted to room­pressure structural and'elastic experimental data, obtaining zQ—1.20 e, Zjj"1.59 e, zSi»1.62 e, r^­1.25 A, r^=

0.81 A, prt­0.135 A, frM ­0.125 A. By applying a general stress т,

1 ­1 the consequent lattice strain in,*C" £ and inner strain U«TC T; can be calculated} С and T are tKe elastic and inner strain tensors, respectively, reTated to second derivatives of the cry­ ptal energy with respect to lattice constants and atomic displa­ cements. The «trains д and u yield the new unit­cell geometry and atomic positions,""respectively, in equilibrium under stress i_. Computations were performed both within the linear approximation for stress­strain dependence and also Including non­linear effects by an iterative procedure. The three uniaxial accesses T T T and 1' 2' 3 isotropic pressure (т1»т2*т3­р) were considered. Calculations were carried out in the range 1+8 GPa, with steps of 1 GPa. By interpolation of results, interatomic distances and elastic constants are shown to depend quadratically on the magni­ tude of stress. A non­linear behaviour generally appears above 4 GPaj the importance of inner strain and non­linear effects is analyzed. Mg­0 bond lengths jnd 0­0 edges of coordination poly­ hedra respond differently t anisotropic and to isotropic stresses, according to the topological features of th& structure. Elastic and structural results for hydrostatic pressure are compared to experimental literature data /3/: a very good agreement is obtained, with average deviations between computed and measured values of 0.005 A and 0.012 A for Mg­0 and O­o distances, respe­ ctively, at p­5 GPa. The range of validity of the rigid body approximation for Si04 groups is discussed.

/1/ Catti M., Acta Cryst. A«1, 494 (1985) /2/ Catti M., Acta Cryst. A45, 20 (1989) /3/ Kudoh Y., Tak«uchi Y., 2. Kristall. 171, 291 (1985) ­ 8 ­ X­RAY POLARIZATION РНЮКЖВНА ADD CRYSTAL STRUCTURE STUDIES

Т.Е. Dnitrlenko, 7.A. Belyalcov All­Unlon Surface and Vacuum Research Centre, 117334 Moscow USSR

The X­ray polarization phenomena and their application to the Investigations In crystallography and solid state physics are discussed* In principle, the X­ray polarization measurements enable one to resolve some general and special problems of the structure analysis (determination of space groups, atomic posi­ tions, degree of crystal perfection, orientations of chemical bonds and magnetic moments, etc.). Recently, the considerable progress in this field was achieved; the progress «as connected in large part with the availability of synchrotron radiation sources. It is underlined that there are two different physical phenomena which lead to the polarisation dependence in the in­ teraction of X­ray with crystals: (a) the Bragg diffraction and (b) the anisotropy of X­ray susceptibility of atoms /1/. The polarisation effiots in diffraction such as the dif­ fraotlon­lnduoed birefringence and dlohrolsm have been mainly studied till now. In this report the depolarization of X­ray beams in arystals (especially in Imperfect samples) is also de­ scribed. The effects of the anisotropy of X­ray susceptibility (suoh aa the existence ot forbidden reflections with unusual po­ larization properties) are discussed in detail. The properties of magnetic X­ray scattering, which provides a new powerful tool to study the magnetic ordering in crystals, are considered. The different schemes of X­ray polarizers, analyzers, and quarter­ wave plates, which are needed for complete X­ray polarization measurements, are discussed and compared.

/1/ Belyakov V.A., Dmltrlenko V.E., Usp. Piz. Nauk, _1j>8, 1989. (Engl. Translation: Sov. Phys. Usp., 3^, 1989) ­ 9 ­ 0­D(H)­­­8 HYDROGEN BONDS IN CRYSTALLINE HYDRATES

A.Preieinaer* , K.tiereiter* , tf­fiikenda" • Institut fur Mineralogie, Kristallographie und Strukturchemle Techn.Univ.Vienna, Austria ** Institut Cur Organische Chemie, Univ.Vienna, Austria

A survey and correlation of vibrational spectroscopic and structural data of B5 Ow­D(H)'**S H­bonds in 16 different crystalline hydrates will be given. From all these hydrates accurate" structural data *(n«utron and/or X­ray diffraction measurements on single crystals), as well as high quality V OP stretching frequency data (low temperature Raman and/or IR measurements of isotoplcally dilute samples) were obtained. The data will be discussed with respect to the different typee of water molecules, with геврееt to the different types 01 hydrogen bonds, and with rtspect to the reliability' of assignments of frequencies to the individual 0­0(H) groups. From the correlation between VOD frequencies and Ro...• bond distances the exiaten:­ of significant and systematic differences oetween different kinds of sulfur atoms becomes evident. It will

be shown in particular that at comparable bond distances the V0B stretching frequencies of 0­D­ • ­s H'­bonds in different compounds significantly increase within the series S"*<

1 to 2530 cm­ at Ro*..B=3.3 A. The observed differences will be interpreted in terms of different mean net charges of the different kinds of sulfur acceptors, which systematically decrease within this series.

=*

2­1 ­ 10 ­ Symbolism of inorganic Structure Types E.E. Hellner, W.B. Pearson*, R. Schwarz Institute for Mineralogy, Philippe University, D­3550 Marburg, PRO * Depts. of Physics and Chemistry, University of Waterloo, Waterloo, Ont., Canada

The symbolism is based on ideas of P. Niggli (1919) and P. Laves (1930); the nomenclature of lattice complexes is proposed by C. Hermann (I960) and of coordination polyhedra as dual of the 47 face forms by J.D.H. Donnay et al. (1964). AU cubic homogeneous and heterogeneous frameworks are published in Phyeics Data 16­2 & 3, all tetragonal intermetallic compounds in 16­5, 6 & 7, all hexagonal & rhombonedral types are also on a retrieval capable database based on Pearson's Handbook (1985), die lower symmetric one will be included too. A first introduction (1986) of the resulting relation­ ships of structure types shows families, main­ & subclasses of the I­,P­,F­,Y**,Q and С (IT. 1983) invariant complexes of different orders and sucking frequencies; combinations of complexes [1+W], [Ш­Т'] etc form heterogeneous families. If coordination (CN) polyhedra replace or surround "invariant" points of the complexes, the symbol of CN polyhedra may be added in addition. 2­dimensional nets may be characterized by О (graphite 63), H (hex. closed packed net 3*), Kagome net (6363) or any «her Schlaffli­ «ymboi like N(43243) in CuAb, N(6434) m the hex. Bronze etc. Their atapd sequence may be described by orientation symmetry. CN pofyhedra sod orientation symmetry may be used to desribe also 1­dimensional networks.

(1919) "Qeonetriecte KdnUotnebta des Outnanssarai": (1930)ИЩИ ТЗ.ШВ; (I960)?' ч 142В; (1964) ~ S4B; Pbrtk .,(!«'.19в5)р«Ы.Р12<1С«ЬпЛ.И(0; Pbytv ,o*7(19»6,19«7.l9SI>r*bl.nZ4, K»*niKFRG; (1915) AaatrJocMHak. Otrdsod, ОЫо; (19a6)Z.Krk».l7J.227n\ ­ II ­ CRYSTAL CHEMISTRY OF INORGANIC COMPOUNDS WITH HEAVY CATIONS S.V. Borlsov, N.A. liznjuk Institute of Inorganic Cmsraistry, the USSR Acar'^my of Sciences, Siberian «ranch, Novosibirsk, USSR Geometry of cation arrangment is a determining factor in struc­ tures of inorganic compounds with heavy cations. A lot of them are characterized by planar cation networ'­ _ with high density of ca­ tions and a specific distance between networks, d^0.8 a^,, where a is a mean intercation distance in the first cation­cation sphere. The most regular cation matrices have cation subcells whose cocrdinate planes are three cloae=rpacked cation networks with (b^k.,1.,), (hgkplo). (h,k~l,) orientation [/lj , respectively. The similar cation matrices are known as linear ones. They are peculiar, for instance, to all high­temperature supercondactors presently available. Crystallographlc shift operations or twin­ ning allow the layers of the finite thickness from the linear matrix to form linear^block cation matrices of different types, nonrlinear matrices being also discovered (A15, ТЬ,Р^, etc. struc­ ture types). Crystal structures of double molybdates and tungs­ tates Й • and some fluorides [ЗЗ have been earlier analyzed, for different chemical classes, i.e. silicates, phosphates, sulphates, and complex oxides, there have been ­discovered the examples of matrices of rather similar geometry with different sort of cation­'j, different arrangment of cations upon nodes of the matrix, diffe­ . rent anion filling. When comparing structures and analyzins^pos­ sible mechanism of solid phase transitions a quantitativeVof simi­ larity measure has been used.

/1/ Borisov S.V. Zh. Strukt. Khim.,22, 164 (1986). /2/ Borisov S.V., Klevtsova R.F. Kristallografija, ^2, 113 (1987). /3/ Borisov S.V., Stoporeva N.A. Zh. Strukt. Khim., 26, 98 (1985).

2­2 ­ 12 ­ POLTfTYPrSM IK THE LIGHT OF THE OD THEORY S. fJurovic Ins ti tute of I nor gani с Chemi slry, Si ovaк Academy of Sciences, 84S 36 Bratislava, Czechoslovakia

The classlcal geometMcal def i ni ti on of crystals as bodies with a three­dimenslonally periodic iistribution of atoms and^or ions was a deci si ve step in the develop­ ment, of crystal 1ography because the entire geometry of crystal structures cou! d be d^ri ved from 11 and i t hel p­ ed to correlate physical proper tie. wi th their geometry С and thus also with their symmetry}. The controversy .about the notion of polytypism is mai nly due to the fact that the present official def1m­ Lion s\ у is not enough geometrical, leaving thus room for ambi guiLies. Recent generalized deflm Lions /£,3/ however, are even less geome cical and their consequent ces go too far. The troubles were caused by a deviation from the original sti pulation of Baumhauer S4/ that al1 polytypes have to be grown in the same system under С near 1yO the sam^ condilions. At present, the ter m "po­ lytype" means often also structural type with different degree of idealization and abstracti on wh.ch in turn de­ pends on the purpose of the investigation. The notion of abstract pot уtypes is indlsponsible for analytical and classification purposes. The uiclnity condition which lies at the bottom of the theory of OO structures s$/ is a sound basis for a geometrical definition of layer polytypism and envisages *lso a generalizatlon for rod­ and block polytypism. The theory deals with abstract polytypes and its application made it possible to establish a consistent geometrical crystallography of layer polytypes including their clas­ sification and symmetry. It Is also a considerftole help in interpreting diffraction patterns of Сalso non­perio­ diO polytypes. /lx v. inter A. et al. . Acta Cr /stall ogr. A40, 399 С1984). /SS Thompson J. B. . in: Structure and 0ondin$ in Crye­ tctm IZ, p. 167 ff. Academic Press. Mew York 1981. /3S Angel R. J. , Z. Krlstallogr. 176, 19Э C19863. /*> Baumhauer H. , Z. Kri stall ogr. TO. 249 C1915). •Sx Dornberger­Schiff K. . Abh. dt. Akad. tflss. *Beri m 2964. ­ 13 ­ HiAGHKWlAHITY AB A FUMBAMKHTAI MAJURB OP CRTSTAL HTRUCTUliEa

IGEM, USSR Au. Ho., 10901? Moscow, ttjSR

Ae It was demonstrated already In the clasaloal works of Bragg» Pauling and Belov at the formation of crystal etruotores the nature operates with some ready and energetically approved .fragments of simple oompounde ensuring thus the stability of more oomplloated о отроил da. At variation of the relative quanti­ ties of these fragments series of substances may arise whioh Thompeon aptly oalled polysomatlo biopyriboles being a charao­ teristlo example of them. The most Important form of fragmentary structures is defined by layers as building unite periodical In two dimensions. It lnoludes mixed­layered­1 hybride­1 polytype­ and OD­utruotures forming a auooession of Btruotural oommunltles in whioh each preoedlnp is wider and oontalnes as some port of It the subsequent one. Excel­ lent examples of fragmentary layer structures are present in the works originating from the Crystallography oholr of the Uosoow State University oonoernlng the rare­earth borates, Ca­ferrltes and tltanum­ailloate analogues of mloas. The fragmentary layer structures satisfying the homogeneity oondltlon are available for application of some general princip­ les established by Dornbergex­Sohlff for the того narrow area of CU>Btruotures. Thus, depending on the number of the layer kinds they кау be subdivided into 3 and 4 oategoriee. ue rules of layer stacking being taken in aooount possible fragmentary struc­ tures may be theoretically derived together with their symmetries and diffraotlonal distinguishing features ae means for their identification. The prlnolplee of syabolio description developed for polytypes and OD­atruoture» may be generalised and applied to fragmentary structures with the use of notation» of layers and relating them operations defining their mutual arrangement. This presents a simple end effeotlve means for dealing with oompliosr ted three^ulmensloaal oryatslloohemloel objeots. Suoh a prooadure is iiustrated for the вам of olose peaked oompounde (A,B)jS^. - 14 - POLYTYPIC AND POLYSOMATIC RELATIONSHIPS IN MINERALS OF THE AENIGMAT1TE GROUP. $. HerHno. E. flonaccorsi,И . Pasero Olpartimenta di Sclenze del la Terra, Unlverslta eM Pisa, Via S. Maria 53, 56100 Pisa, Italy

A number of natural (aenigmatite, rhonite, krlnovlte, serendibUe, welshlte, dorrite) and synthetic phases ("baikovite", SFCA) have the same structure-type of sapphirlne

(Нд,А1)д(А1,51)дО20 and present the crystal chemical formula *2B6T6°20 twhere А, В and T Indicate atoms In eightfold, octahedral end tetrahedral coordination respectively). The close structural relationships between sapphlrine on one side and aen1gmat1te-Mfce minerals on the other side неге discussed by Dornberger-Schiff an-j Merlino (1974) 1n terms of the 00 theory. Recent microstsuctural Investigations on sapphirlne (Christy and Putnis, 1988) and a sapph1rfne-I1ke phase (Barbier and Hyde, 1988) Indicated that sapphlrine may be described as a member of the polysomatic series having pyroxene and spinel as end members. The polysomatic concepts introduced by Christy end Putnis (1988) and ВагЫer and Hyde (1988) for sapphir1ne may be appHed also to aenfqwatfte-Hfce minerals. Moreover whereas in sapphlrine the "pyroxene" modules present a close-packed oxygen array, the corresponding modules in aenlgmatlte, rhonlte and krinovlte are not only topologlcally but also metrically pyroxene-Hke slabs. The polysomatic series we present and discuss, mainly on the basis of structural studies of rhonite from different sources, 1s another example of the usefulness of the modular approach for the understanding of the structural relations as well as of the crystal chemical relations among the various related phases.

BarMer J., Hyde B.G. (1988), Acta Cryst., B44, 373, Christy A.G., Putnis A. (1988), Phys. Chen. Minerals, 15, 548. Oornberger-ScMff K,, Merllno S. (1974), Acta Cryit., A30, 168. ­16 ­ SIHGLE CRYSTAL X­RAY ANALYSIS AMD CHEMICAL STRUCTURES Off POSTAGE STAMPS

Bane Preut Faohberelch Chenle, Universitat Dortmund, Postfaoh 500500, D­+600 Dortmund 50, FRG

In order to perform single crystal X­ray analyses on& needs oryetale, X­rays, nathematloal formulas, oomputers and corres­ ponding programs. Suoh analyses give us atom by atom tre oryatal structures and, 1л the case of molecular oryatals, the molecular structures. The precision of this method Is so good that the electron distribution In bonds can be made "visible". Postage stamps will be used as the basis of a review of the method, its development from Hlels Stensen to protein engenee­ rlng, and some of the most Important milestones in its history. - 16 - THREE=DIMENSIONAL MODEL FOR ELECTRON TRANSFER STUDIES

С PASCARD and J. GTJILHEM Insiitut dc Chimie des Substances Naturelles, C.N.R.S. 91198 CIF/YVETTE CEDEX FRANCE

In the course of the study of photoelectronic transfer U), compound 1 was synthetized:

Cl48Hi58NioZn2 a = 55.5 A M.W. = 2205.7 b = 26.9 A с = 25.3 A p = 100.8° V = 37115 & R = 16.9 %

The bis:porphyrine_-phenanthroline crystallizes with sufficient space for the unit cell to contain 515 atoms in the asymmetric unit. The structure was solved by Patterson technics, and showed two independent molecules (ca. 350 atoms), the rest (32 % solvent) consisting of ethanol and water molecules, a few of them only being localized. The 2 molecules of the asymmetric unit are very similar: bow shaped, with the porphyrines at the extremities perpendicular to the phenanthroline plane. Each one of the 4 zinc atoms, bonded to the pyrrole nitrogens, exhibits a fifth ligand, directed towards an atom we identified as the oxygen of a water or ethanol molecule. These ligands are directed differently in the 2 independent molecules: endo-endo (Mol.l), and endo=exo (Mol.2). The most surprising feature of the structure is the molecular packing: independent columns, parallel to the b axis, made of one type of "lokcnle, repeated either by the screw axis (Mol.l) either by a symmetry center (Mol.2), show an astonishing regular stacking. The porphyrine orientations, in one column, bears a strong resemblance to the haems disposition inside the photoreaction center <2>-

(1) S.Chardon-Noblat, J.-F.Sauvagc & P.MMhis, Angew. Chemie, in press. tfjJ.Deisenhofer, O.Epp, K.Miki. R.Huber 4 H.Michel, Nature, vol.318, 19/26 December 19S5. ­ 17

STRATEGIC DESIGN OF ORGANIC CONDUCTORS. STRUCTURAL CHARACTERIZATION OF ELECTRON­DONOR­ACCEPTOR COMPLEXES WITH PREFIXED STOICHIOMETRY.* J.Y. Becker, J. Bernstein S. Bittner, E. Harlev,, J.A.R.P. Sarma and S.S. Shaifc, Department of Chemistry, Ben­Gurion University of the Negev, Beer Sheva 84120, Israel

The archetypal molecular units (1) and (2) are potentially endowed with a number of properties D­­»­A«#­D (1) A~#~D«»­­A (2) *= spacer which are considered to be necessary conditions for electrical conduction in organic charge­transfer complexes: the sloichio*netric donoracceptor (DA) ratio is predesigned into the molecule; appropriate chemicfll variations in A and D may be employed to modify the degree of charge­transfer frcm D to A and to obtain the desired delocalized electronic state (e.g.,... о P+ DP+ ...II... A P ­ A P ­...) along mtermolecular stacks rather than the localised ones (e.g.,... D+ D° ...II... A ­ A°...). For the D—A­D motif we have prepared 2,5­ and 2,6­disubstituted derivatives of oenzoquinone Л1, dicyanoquinonediimine (DCNQI) A2, and TCNQ A3, ­CH2­and­S­ as ж and various aromatic 6 ф СХУ OCH,

A1 A2 A3 D1 D2 D3 hydrocarbons such as 01­D3. The set bued on 2,5­disubstituted TCNQ's shows a remarkable tendency for the A units to stack in the desired segregated stack mode, and systf^atic 'tuning' of A, D and a along with the mode of substitution has led to some generalizations about obtaining stacking of the O's as well. For the A—D—A motif, a number of derivatives have been prepared, and these also exhibit a strong tendency to form segregated stacks for both O's and A's. We will present results of the structural characterization and structural trends in a number гергммЧаНуе nmhnrftob «l«« nf compound». Work supported by the Erna and Victor Hasselblad Foundation (Sweden), the German­Israel Cooperative Science Program administered by the Israel Council for Research and Development and The U.S. Army Research, Development and Standarization Group (UK).

3­1 ­ :e­ РОЬТШСЬЫН TRAHSITIOH NKCAL 010­ AND PLDORO­rCARBOZILATES ­ ЖШГОЗ ОТ БТАВ1ЫТХ A.S.Batsanova. Yu.T.Strucnkov8, N.V.Gerbeleu* and G.A.Timkob aHeaaeyanov Institute of Organoelement Compounds, Moscow, Institute of Chemistry, Hoi davian' Academy of Science a, Kishinev, 0.S.3.R. Polynuolear d­metal carboxylates of the olueter type, promis­ tog as catalysts, models for enzyme centers, etc. are most stable with OgCH Uganda bearing bulky R groups, e.g. OgCCMe, (Piv). We have studied by X­ray crystallography three groups of such comp­ lexes.

1. Molecules of Je602(0H)2Piv12 (I), ItogOgPiv^ (II) and аг12°12И­тХ5 (III, crystallizing as at­methylnaphthalene, dimeth­ ylforaamide and n^propanol solvates) are stabilized by oxo=brldg­ •si i^­tstranedral in II and III, «,­trigonal planar in I an&ju,­ pyraaidal in III. Uetal atoms fora distorted planar hexagons in [, a pair of tttrabedra with a coonon edge in II, and a body­ centered pentaoapped twisted trigonal prism in III.

2. In the molaoules of (0rEPiv2J8 (IT) and (FeifPiv2)6 (V) the nearly'ooplanar metal atoms are linked pairwies by one fluorine and two 000 bridges, forming a macrocyole with oavities accomoda­ ting small guest molecules, which is vital for crystal stability. Holeoule» 17 and T have 0* symmetry) local in the isomorphous mo­ noelinio crystals of IV­2Ue200 and V­^BtgllH, and crystallographio in tetragonal lt>2CgHg and its isomorphous analogue with partial substitution of benzene for ferrooene.

5. Triangular complexes Pd,Piv6 and Pd,(02°0F,)6 are stable without additional bridges. Small distortions of the D­^ molecu­ lar symmetry are shown to result from crystal packing effects only, indicating sterlo nonsrigidity of the molecules which con­ tain no Fd­Fd covalent bonds. A review of Z^sray structural data on carboxylate complexes, their gaa?*phaee structures (from mass spectra), decomposition pathways under an electron impact, and chemical behaviour, makes possible to distinguish a number of very stable polynuolear con­ figurations, acting as individual molecule skeletons or "building bloaks" for more complicated ones. ­ 19­ THE STUDY OF S­CONTAISIHG OHOIF­ETHERS ЖВТА1, CCKFLSXES

т.т.м.Ипотекзг. Yu.A.SiaonoT, A.A.Dvorkin, L.I.Budarln, B.V.Fhesenko, S.V.Pavlova Institute of Applied Physics of the Holdarian Acad.Sol..lishlneT Institute of Fhys.Chem., Ukrainian Acad.Sci., Нет, U3SH

The X­ray study of the Au(III), Au(I), Cu(I), Pt(II) and Ag(I) complexes with ,S­contsining crown­ether* of the type

r­0~\~­^ r— 00—% /— 6 o—\ у—О b­^v >S 2 >S S( оЛ sioHe­S <*«• ^­•00 0—' ^—v­00 0—0—'' N> 00 00—­ ' N­­0 &—/

r.3

was oarried out. It ia shown, that the Main factor in the folia­ tion of the nolecular struoture of the complexes is the ^­bon­ ding of the metsl with the sulphur atoms of the eyolt. For the Ь

ligand the [PtL Cl„] and [AU2 Ь01J structures are typical. In the latter L appears as a bridge in a two nuolear moleoul». The L ligand carriea the bridge function in the polymeric structure L The £(CuCl)2 Joo­ «T'­bond formation between metal and sulphur atoms takes place in all these oases. The ether oxygen atoms don't' participate in the metal coordination. The sulphur and »ul­ phojd.de oxygen atoms manifest the coordinations! aotlvity in Ir. 3 So, in (AglOOob the crown­ether appears as a fourdantate g02­ type ligand. Besides, it oomes forward as a bridge in polymeric 3 (AgNO,)2 ohain. In HAuCl. L S­eontainlng cro­m­ether Ir comes out as a monodentate O­type ligand, joining AuCl. on an apical Au­ coordinate through one aulphoJd.de oxygen atom (Au...O 3,12 ­ 3,16 A). Ь* forme only ion­type structures, appearing in thee as a twocharged organic cation. The construction of П, and Ь

(AuCl.)2 Is being widly discussed. The conformational changes in crown­ether at the 0 ­ S exchange as a base fer endodentate con­ figuration of S atoms in S­containing crown­ethers are examined inthe work.

3­2 ­ 20 ­ THE STRUCTURAL FEATURES OF THE COMPLEX FORMATION IN SYSTEMS METAL CHLORIDE ­ CROWN­ETHER ­ SOLVENT

V.K.Belekij, :i.3.Ctreltaovat B.M.Bulychev

L.i'a.}:art'OV c'/iyeiao-Chemical Institute, Moecow, USSR

Basing on the comparative analysis of X­ray structural data the features of metal coordination are revealed and the classifi­ cation of crown­ethers (CS) metal complexes is worked out being closely related to the complex formation reactions mechanisms. Three types of such structures are suggested which differ by the mode of metal atom and CE molecule respective disposition: 1) A ­ metal atom lies in the center of CE cavity and has practi­ cally identical bonds Me­O» 2) В ­ metal atom lies outside of CE cavity being coordinated by one or two of CE oxygene atoms; 3) С ­ metal atom does not have the direct interaction with oxygen atoms of CE, the latter binds with the chloride by means of secondary bonds (e.g. H=bonds) using the solvent molecules. The main factors determining the process of complex forma­ tion and the structure of the yielding products are: ability of chloride for ion1гаtion and autocomplexingi ratio of basicities of solvent and CE) coordination potencies of metal atom; conformatio­ nal flexibility of CE. The new types of 18­crown­6 conformations are observed that has confirmed its conformational flexibility, on the other hand, the set of possible confocmers for 15­crown­5 in metal halogeni­ des complexes la more limited. The conclusions ace made on the basis of the original resul­ ts' by X­ray structure analysis of metal chlorides CE complexes (~ 30 entries) and the data of Cambridge Bank (

The long accepted formulation of rhenium poryhydrides such at {ReH^PPh^] (I) ts being complexes to Revu with seven discrete hydride Uganda, has been called Into Question recently In the literature with the 'noo­classicaV formulation involving Re1*' and co­ordinated molecular dihydrogen suggested on the basis of *H n.m.r relaxation parameters /1/. We have determined the molecular structures of a series of Transition Metal polysydride complexes by low temperature single crystal X­ray and neutron diffraction 111, and none of these show any non­classical behaviour In the solid state. The evidence from JH n.m.r data is inconclusive where the full variable temperature data exists and where there appears lo be in obvious discrepancy, ft remains possible that the solution structure could differ from that observed in the solid state. The structures will be discussed in detail, together with pertinent n.m.r results.

WD

<» ' (ID We also report tbe resuttt from reaction* carried out between the parent polyhydrlde complexes and dirferent aUyl yielding new complexes (П) and (ГЛ) by successive replacement of hydride Uganda.

co«,

(№1

i cr 1 <, K (ReH5(SlH2R)j(PR3)2J [ReHs(SlHR2)tPR3hn «­ »" ­ l * (III) - 32 - The details of these and related structures from low temperature X-ray diffraction studies /3/ will be presented.

Ш Hamilton, D.G., and Crabtree, R.H., J.Amer.Chem.Soc., Щ, 4126, (1988); Kubas, G.J., Acc.Cfaem.Res. 21,, 120 (1988), and refs therein. OJ Grepoo, D., Mason, Sax A., Howard, Judith A.K., and Spencer, John L.,

borf.Cbem. Л, 4103 0984), ibid 2£, 2930, ibid J-Chem.Soc., Chem.Comm.,; 1502, (1988), and other unpublished remits. /3/ Taylor. A.L., B.Sc. Thesis (1989), University of Bristol and Keller, P.A., unpublished results. CfSSOL ЭВНСТШВ OP UUUMCIUIXSBS

E.P. Paulue, E. Dietz, A. lurch, F. Prokschy Hoechst AG, 6230 Frankfurt/tain BO, FUG G. Lincke, EH Niederrheln, 4150 Krefeld, F№ 7 Quinacridones and derivatives of Quinacridones were investigated ty single crystal x-ray structure analysis.' Tie molecules are arranged in ­ 24­ piles and these piles are connected by hydrogen bonds, resulting in twodiroensio­ nal "macrarolecules". The polar groups are eandwichlike hidden between non polar groups. These endless sandwiches are only connected by van der Waals forces and parallel to a crystal face. There are tw> structure types: Tn one of than the molecules of all the piles are parallel, and each пгЯьгйе is hydrogen bonded to two other ones of the neighbouring piles; in the othet type the molecules of neighbouring piles are putting up rather large angles wtf.li one another, so that each molecule can be hydrogen bonded to two molecules of each of the two neigh­ bouring piles, resulting in 4 hydrogen bonded neighbours for every molecule. In the piles of the last compound of the table the molecules a­­s only parallel in pairs, putting up angles of Зв.7"Ьешееп. The et«p heights between neighbouring piles of the type 1 structures are running from 0.Э5 (/s­quinacridon) to 2.10 ft (Deaoxyquinacridon). Compensating for too many or boo less carbonyle groups, like in the two last given compounds in the table, there Is bifurcated hydrogen bon­ ding or one oxygen is accepting two hydrogen bonds. Compounds with type 1 struc­ ture are more bathochromic and those with type 2 structure тэге hypeochrcmic. Crystals were made partly by sublimation and partly by recrystallisatlon from a solvent. 3.1. INORGANIC MATERIALS AND MINERAL?

Posters

4-1 - 36 - CRYSTAL STRUCTURE OP MERCURY ARSENIC IODIDE HgAel

A. Afir, A. Renbah Institut de Chimle - USTHB - BP 32 El Alia (Bab EzzoUAR) Algiers - Algeria

The crystal structure of HgAsI has been solved and refined with R - 3% (Rw • 3.8%) for 565 unique observed reflections. The framework, lsostructural to that of CdAel, is described either as a pseudo-cuMo close packing of Hg atoms with As and I atoms In the interstices or a complete arrangement of two sorts of polyhedra surrounding Hgt sharing corners or edges. The cohesion of the structure is assumed to be due As atoms with strong bonds As-As. A discussion about Hg-I distances is proposed, involving a iono-covalent character to the correspon• ding bond. ­ 27 _ COMPOSITION AND CHEMICAL BOND IN BINARY "CffllPLETB=VALEHCE" AND "FOUR­ELECTJTON" COHPOUNDS

K.B.AleJnikova Voronezh state university, Voronezh, USSR

The composition of many binary compounds formed by the elements arranged by both sides of Zintle border is known to follow two rules: realization of complete valency and "com­ plete­electron" rule. The latter assumes such fornula compo­ sition that each atom shares four electrons. In the simplest case of (8­N) these two conditions determine the only one monoatomic conposition. Metals with totally occupied d shell form structures of sphalerite or wurtzlte while alkali ones ­ NaCI or CsCl wieh means presumably covalent or ionic bond. Compounds of the elements from any other groups are of more complex composition and structure. Analysis of constitution diagrams reveals that "complete valence" compounds are ob­ served almost In all systems and bond Ionicity is maximum for compounds of the system. The structures of these compo­ unds can be described in terms of close paoking of atoms model with a various ocoupancy of tetrahedral or octahedral

voids (ZngPg, In2Te3, Cu20 etc). Compounds following "four­ electron" rule are much more rare and are usually formed from the elements far distant as from each other as from Zintle border (e.g. II­V and III­VI compounds ZngPg, IiigTeg etc). Their structures are complex for interpretation but geometry of interatomic bonds is in a good agreement with chemical bond soheme. Formation of anion­anion or cation­ cation bonds is quite probable in these compounds. The frag­ ments of structures of "complete­valence" and "four­elect­ tron" compounds can be derived In the structures of other r'g intermediate phases. The presented approaoh proves to be и rather fruitful as for prediction of new compounds ma for 1 classification and interpretation of known compounds and structures.

4­2 ­ 28 ­

CRYSTAL­ CHQIIOAX MODEL OF AMORPHOUS STATE IK THIN FILM II­V saHCONDUCTORS

K.B.Alejnikova, M.V.Lesovoj, Yu.N.Perin Voronezh state university, Voronezh, USSR

Ae work seeks to analyze the atonic structure of thin film aiorphous II­V semiconductors by Deans of radial functions of atotic densities (RFAD). The fills were deposited by laser sputtering of II­V polycrystals and following тарэр eeadensa­ tion on various substrates: single crystal silicon, fresh­ chipped NaCl or glass. Substrate temperature was about 233 K. Laser sputtering nade it possible to obtain thin layers free of unbound phosphorus. The crystallochemistry model of amorphous state in condensed fills was designed with the use of short­ range order parameters obtained from RFAD. Experimental depen­ dences of intensity of diffracted electrons on the angle were obtained by direot registration. Fourier transform of electron scattering curves processed by standard technique permits one to obtain RFAD. In order to eliminate the influence of RFAD false oscillations on short­range order parameters extracted from these functions for amorphous condensed films the calcula­ tion of pair atom functions (PAF) was performed. This technique was developed for the case of RFAD calculations of multiatom systems from X­ray scattering curves. Its application for dif­ fraction of electrons is possible only in assumption of simila­ rity for atomic scattering factors. Using parmeters of corres­ poding crystals initial PAF were calculated. Varying short­range order parameters in calculating PAF and comparing PAF and RFAD short­range order parameters of amorphous condensed films were obtained neglecting the influence of the cut­off waves. The cry­ stal, ^chemitat model of amorphous state in thin­film II­V semi­ conductors can be represented either on the basis of short­range order for corresponding crystal or as a couple of microregions inoluding fragments of structures of polymorphfcmodifications in the sputtered orystals. ­ 29 ­ ROUE OF LOCAL ЗШЕШ OF COORDINATION POLYHEDRONS IN MICROTWNNING OF A2B^ SQIICONMJCTORS

Alejnikova H.B., Rabotkina N.S., Zavalishin E.I. Voronezh state university, Voronezh, USSR

Some specific features of micrbtwinning in crystals due to local symmetry in the structure are considered with A B& semi­ conductors as a case in point. In all the cases twinning is found to occur by rotation of a crystal around noncrystallograpnic syaaetry axis of coordina­ tion polyhedron. The random location of coordination polyhedron, the elemental cell dimensions and syaaetry yield various diffrac­ tion effects for particular compounds.

Thus, for aicrotwin of CdP4 with (201) twinning plane and P 2j/c space group the only diffraction refleriiWare superim­ posed that correspond to the twinning plane. All the rest ones form two non­overlaying systeas of reflections. Coordination polyhedron with the twinning plane along it is octahedron around Cd atom. Phosphides and arsenides of ABg type with P 2j/c space group are twinned around the axis of tetrahedron fragment. The twinning plane is (100). The geometry of eleaental cell is of such form that superposition of diffraction refledfaerwith the even indexes takes place upon twinning. As a result, the pseudo­ syaaetry of rhoabic crystal arises wich can be characterized by its own space group.

The twinning in tetragonal Zn3P2 crystal is realized through tetragonal coordination polyhedron. The twinning plane is (101). Reflexes are partially overleyed. Syaaetry of diffrac­ tion pattern correspond!to rhombic crystal. Twinning aechanisa considered for \2B5 compounds aust be coaaon for twinning of inorganic coc idination compounds of another composition. The cryetallocheaistry nature of microtwinning is the pre sence of local noncrystallographic ay»­try of coordination polyhedrons with twinning planes along .hea. 30 ­ ­BbLajF7­ : A NEW ANION­EXCESS FLUORITE­RELATED SUPERSTRUCTURE PHASE

S. Aleonard. Y. Le Fur. M.T. Roux, M. Perroux. J. Ilafl. Laboratoire de Cristallographie, associe a I'Universite J. Fourier, C.N.R.S., 166X, 25 Avenue des Martyrs. 38042 Grenoble cedex, France.

The crystaltographic characteristics of the superstructure phase have been determined by electron diffraction. It crystallises in the monocSnic space group Cm. Its parameters are related to those cf the cubic

fluoritecell'aF.bF. CF) by the relations am = 2aF + 2bp­ 2CF. bm = b? ­» ­» „­> 9 v+ 9 ­* , _ .. + CF.Cm ­ 2a F —J­bF +­g­CF(P=126°).

Single crystals have been obtained and an X­ray diffraction study has been carried out. Cations are observed on the ideal sites of the basis structure and LaeFas clusters have been detected. A structural model is proposed : it is characterised by the juxtaposition of LaeFsg clusters and LaFe cubes chains parallel to the b direction arid it would correspond to the formula Rbo.346 Laot654 Fz.31­

It is shown that difficulties observed during the refinements for distributing the cations among the various sites and placing all the F atoms with precision are explained by the existence in the monoclinic cell of ordered domains wich are all described In a triclinic cell with the characteristics : с* ­* ,г­> «т* ­». ­» OF . CF г?, т­> ­* ­*, 3aF 3bF „­>

11 a'= an . -f ­ 3 ^ . b' = bF+ CF. С = ­j • -£• + 2CF(OC» «3;.P= 112'9').7= 112°11) Identical phases are observed with Pr and Nd. ­ 31 ­ HOMOLOGOUS SERIES OP POLTTYPIC FAMILIES IN HEXAGONAL Ca­PBRRITE STRUCTURES А.У.АгаИсЬеета. O.G.Karplnsky Institute of Metallurgy, USSR Acadeay of Sciences. Moscow.USSR Crystal structures of hexagonal Ca­terrltes bare been estab­ lished by X­ray aetbods /1/. Polytypic Foraula Sp­ gr. lattice Polytypic really paraaeteres

S6B OagyeggOga R32 a=6.0 c=62.2 3<16­..T)l«..0J

o­CagPe160 R32 a=6.0 c=94.7 3(24.1T)I».0]

e a=6.0 c=31.4 (2 1T) S.B HV 16°25 P3c1 V e a=6.0 c=15.7 (1 J) T­CV )6°25 P321 4 c­CapPe^Ogj R32 a=6.0 c=47.6 3(14.T)t«.0l

Bexagonal Ca­JTerrltes compose homologous series of polytypic fa­ mllles with general formula [oa2Pe.n(Fe.Ca)304]IPe309]=SBB.«here

n Is even; Sn is a layer fragment or splnei magnetite structure containing R oxygen nets; В Is a layer of (PeOgl­Mpyralds con­ nected by basis tops. Sn Is Halted by cation nets containing both Pe and Ga atoae. Sn­8itd В layers alternate along 3­fold ax­

is, each of tbea baring two orientations (Sn it S„. В * Б) conne­ cted by 2­fold axis. SjjB­layers vben conjunctlng can bare one of 3 vectors of the Independent relative dlsplaceaent: о,+.­.Ш the variety of Ca­heiaferrlte structures Is described In general ± t as (S^ + ...). Two «embers of the homologous series, corres­ ponding to*n=4 and n=6, bare been established. The Ca4Peg017 /3/ my be attributed to » «tries with n=2. The polytypic fami­ lies of Ca­hexaferrltes are the particular case In a polysoaatlc series of bigslze cation ferrlte structures /4/. /1/ Arakcheeva A.V..Karplnsky O.G..Cry3tallograpby.3.642,0988). /?/ Arakcheeva A.V..Karplnsky O.G.,Crystallograi*y,3,766,(1988). /3/ Malaaan B. et all, aat.Res.Bull.,17.795,(1988). /4/ Arakcneeva А.У.,Кагр1пзку О.С..Crystallography,3,646,(1988). ­ 32 ­ CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF A DIMERIC

COPPER (H) TERPYRIDINE COMPLEX : [ Cu (C15H11N3) (N3) ]2 (PF4)2 .

M.I. ARRIORTUA', J. VIA1, G. BARANDIKA, J.L. MESA, L. LEZAMA, T. ROJO 1 Dpto. Mineralogfa ­ Pctrologfa у Dpio. Qufmica Inorganica. Universidad del Pais Vasco. Apdo. 644.48080 Bilbao.

To progress in the study of magneto structural correlations in Cu (II) complexes we have approached the structural analysis of [ Cu (terpy) (N3)12 (РРб>2 ­The structure has been solved using the MULTAN 11/84 system and refined by weighted anisotropic full matrix least squares with the SHELX 76 system. The final R value is 0.077 (wR = 0.077). The complex [ Cu (C15H11N3) №)h (Р?б)2 is monoclinic, space group P2[/n, a = 10.149(2),

b= 15.593(2), c=l 1.694(4) A , p = 103.57(2)*, V= 1799(9) A}, Z=4, p„p.=a.83(3), pc>,.= 1.79 M.m­3, F(000)= 964, ц<Мо­Ка) =13.76 cm'1, room temperature. The coordination polyhedron of each copper atom is a distorted square pyramid with four short (1.969(44) A] Cu­N bonds (from the tridentate tcrpyridine and one azide ligand) and other longei Cu­N [2.492(10)A] bond (from die second azide ligand). The nitrogen atoms of the N3 groups bridge two copper (П) atoms. Only half of the geometry need be specified as the dimers lie on centres of symmetry. We have quantified the distortion of the coordination polyhedron using the Muetterties and Guggenbcrger description *nd by considering the regular square pyramid (SP) and the ideal trigonal bypiramid (TBP) as the limiting geometries. The deviation (л) from TBP for this compound is д=0.97. The value obtained shows a topology of regular square pyramid (SP). Fig. 1 View of the dimeric complex. The EPR powder spectrum is axial (g||= 2.242, gj.= 2.070). The weak absorption observed at ­1650 G, corresponding to the AMs= 2 transition, indicates a magnetic coupling between two Cu(II) ions. The magnetic measurements show that there is no exchange interaction detectable in the temperature range 4.2­100 K. ­ 33­ SINGLE CRYSTAL STUDY OF AN IGNEOUS BIOTITE: COMPARISON OF DATA COLLECTION TECHNIQUES

G. Artioll', MT. Brlgattl"

' Istituto di Mtneralogia « Petrologia, Univereita di Modena, Modena, Italy "* btituto di Chimica, Univereita delta BasHicata, Potenza, Italy

Biotite ie a phyllositicate known to produce crystals which are hard to collect good diffraction data on, because of its highly flat shape and its broad anisotropic mosaiclty. Diffraction data were collected on the same crystal with conventional and rotating anode Х­глуа using different collection techniques. Conventional data were collected on a CAD4 dlffractometcr, graphite monochromated Mo radiation, 52 kV, 40 mA, using an ordinary w ­ scan, w—20 scan and anew technique with variable^ angleO. The effect of source intensity on structural information was tesiod with a data collection using a Rigaku rotating anode generator, graphite mo^ochrom&ted Mo radiation, 42 kV, ISO mA, using only an w ­ 28 scan because of short source availability.

F0b, values have been statistically compared for the tour data set and their bearing on final structural and crystal chemical par&meters is discussed.

10 Doiwnben A.J.M­, Acta Cry*. A. 30, 211­316 (1963).

8

5­1 ­ 34 ­ DO WATER CONTAINING STRUCTURES OF THE ALUNITE­JAROSITE TYPE EXIST? S.Aslanian», H.Mayer**, A.Preisinger** * Geological Institute, Bulgarian Academy of Sciences, Sofia, Bulgaria; ** Inatitut fOr Mineralogie, Kriatallographie und Struhturchemie Techn.Univ.Vienna, Austria

Alunite, KAl3(OHJ6(S04»;,, a=7.020(2), c­17.223(8)8, R3m and

jaroeite, KFe3(OHt6(S04>2, a­7.135(2), C=17.224(6)8, R3m are iso­ atructural /1/ and important representatives of a larger series of minerals. Recently several authors /2/,/3/ claimed that under hydrothermal conditions at 100°C water containing and Al, and (Al+Fe), respectively deficient variants of this aeriee are formed

+3 3 [K(Al +Fe* )2 52(OH)4 5(H20)^1>6]. Products synthesized according to /2/ and /3/ at the tempera­

F(i S0 П WRre ture of 100*C in the system K­S04­A1 _(S0A) 2~ 2 * 4* з" 2° studied by differential­thermal analysis, IR­spectroscopy and X­ ray diffraction. It was found that the reaction products synthesi­ zed exactly according to /2/ and /3/ consist not only of crystals of alunite­jaroeite type but also of a certain amount of one

additional compound, KAHS0.)2.12H20 (alum). Drying of this two­ component product at 110­120'C leaves the alunite­jarosite crystals unaltered but leads to a partial dehydration of the alum and to the formation of an X­ray amorphous product. On standing at room temperature (for few days) the amorphous part of the product recrystallizes to KA1 (SO^)2 .6H­,0. Our findings do not provide support for the existence of ­a water containing and Al, and (Al+Fe), respectively deficient alunite and aluniterjarosite series. It should be emphasized that the c­lattice constant of the aocalled "water containing alunite" is "1 \ smaller than the true alunite.

/1/ Menchetti* S., Sabelli, С N.Jb.Miner.Mh.£,406(1976). /2/ Aslanian, S., Minkova, N., Cryst.Res.Technol.^2,123(1987). /3/ H&rtig, C, Brand, P., Bohmhaimnel, K., 2.anorg.allq.Chem.508, 159(1984). ­ 36 ­

+ г+ иотшюеиааи or в> с1.ае с1г.гвго SALTS («е*» i, нь, c«) ».M­ vq, »«, со, ii)

flhrfBalara*. S.TepaTltohareTa Institute of Ooneral an& Inorganlo Chemistry, Bulgarian aoaaeay of Solanoes, 1040 Sofia, Bulgaria

The orystal.structures of the Mo Cl.Me (П^га^О salts

are bulla a; by peeking of fnes* Ги« 01 (a20)J­oetahe*ra ana •»+­lon». The dlffereaeea In the lonlo radii of •о* and in too eleotronlo configuration of Ш» cause tho «lfferen­

г,, «ea In th* fusion as«e of tho Гт'а (а..(Вг0)г]­0й*аЬваг*.

г •ban rB#t»j ra. (..g. Cs­aalts), th. [ш« *014(Вг0)г]­ ootshsdra fe«sj Infinite oonlna ebarlag two of tho vertsxea with Cl~ In tranaTpoeltloaa (orthorboaMo structure, Pooa). The remaining tvo С1~­1ово, as «oil aa tho two bUO noleeuloe aro In ols­poeltlonn. man r(j,+

(trlollmlo structure, ?7). The B20 molecules are In traae­ poeltloua la tha ootsheire. i» a reaalt af tha lateraedlate loalo nllu of ah , aoth straetare types ara poealale for tha ВЬ­sslts. laoaaaa

of tha rsqalre* distortions la tha Гаа^СД,(H,0)2]­ot.tah»ara thaaa atraotaraa ara realised ansa tha tlMloaa ara la ooasl­ aatloa «1th an^Chlgh apln stata) or fa2*, l.a.loma with aara or low eryatal flald stabilisation anargT /'/• **• Ibsaalts ooatalalng He^­loas «1th hlghar oryatal field stabilisation energy (e.g. Co ­lone) oryatalllae In aa lateraedlate, aa to eyaaetry, oryatal straoture (aoaoollnlo, CZ/o). In tela straotore the [le^Cl^B^o^j­oetshedra for» Infinite ohalna (snob aa In tha Ce­talte), hot tha HjO moltoult are la. trana­poaltlana (alallar to the (Vaults). en Й /1/ Balaraw Ohr., Z.Irlat. Щ., 35 (1987).

6­2 36 - X­RAY STRUCTURE ANALYSIS OF SYNTHETIC MnSb»S« AHD STRUCTURE REFINKHENT OF NATURAL PeSbiS4 (BERTHIBRITE) K.Bente and A.Edenharter Mineralogisch­Kristallogrephisches Institut der Universitat Gottingen, PRG

Single crystals of HnSbi S, неге hydrothermally grown at 300е С and 500 bar from powders of corresponding composition in evacuated ai­ lica tubes with outer pressure of Ar. The crystals showed maximal dimensions of lx.5x.5 пипЗ. In contrast to Fe­berthierite which can be synthesized under dry and hydrothereal conditions, the Mn­ berthierite ia not stable under dry conditions

The X­ray measurements were carried out by a stoe four circle diffTactometer using monochrometized Mo­Kalpha­radiation. The mea­ suring routines and resulting R­values were: 2theta/omega­scan = .02/.03»/step, 2Theta = 10 ­ 90", min. steps/reflexion •= €5, max. time /step ­ 2 sec, H » ­14 to +14, К =» ­17 to +17, L = 0 to +5, LP­corretion after Langhoff (reduc2> and absorption correction after SheldricK (XBMP4) basing on psi­всап data set, anisotropic refinement by ORXFLS by 24ЭВ observed unique reflexions for FeSbtS4 with R ­ 0.051 (unit weigths) and by 1498 unique refle­ xions for MnSbiSt with R« 0.038 (unit weigthe).

Crystallographic data: .

FeSbiS . •- :LI.420(3 ) Ь- :14.178(5 ) c- 3.766(1) S. G. Pnam X У ' z JS11 022 ЭЗЗ 012 Fe .3167(1) .3351(1) .25 .0021(1) . .00144(6) .0223(9) .00009(6) Sbll) .1448(1) .0631(1) .25 .0028(1) .00153(2) .0195(3) - .00011(2) Sb(2) .0386(1) .3856(11 .75 .0020(1) .00135(2) .0164(8) - .00005(2) SU) .1955(3) .2703(1) .75 .0019(1) .001(10(8) .0211(15) .00002(8) S(2) .4221(2) .1839(1) .25 .0024(1) ..00173(9 ) .0172(15) .00062(8) S(3) .2232(2) .4943(1) .25 .0018(1) .00157(8) .0204(15) .00001(8) SU) .4508(2) .4045(1) .75 .0018(1) .00132(7) .0202(14) .00004(7)

MnSbi S • a - 11.459(5) b - 14.351(8) 1 с - 3.823(2) S.c . Pna» X У. z 011 Э22 ЭЗЗ 012 Hn .3161(2) .3334(1) .25 .0031(1) .0016(1) .0291(12) .00006(8) Sb(l) .1440(1) .0591(1) .25 .0036(1) .0017(1) .0256(1) - .00016(1) Sb(2) .0414(1) •3859(1) .75 .0028(1) .0016(1) .0212(5) - .00010(4) S(l) .1906(3) .2673(3) .75 .0028(2) .0017(1) .OlfllT) .00000(1) S(2) .4221(3) .1772(3) .25 .0030(2) .0020(1) .0249(17) .00048(1) SO) .2224(3) .4943(3) .25 .0026(2) .0019(1) .0236(16) .00004(1) S(4> .4550(3) .4049(3) .75 .0026(2) .0015(1) .0259(16)- .00001(1)

MnSbiS* is a hew synthetic compound with the structure of the ber­ thierite (FeSb*S«>. The lattice parameters and interatomic distan­ ces of the measured materials increase from the Fe­ to the Mn­ compound according to the ionic radii of Fe* * and Mn* * . r;ynthotic and structural studies on Co­ and Hi­bearing berthierites are in progress;.

Literature: 1/ Buerger,M.J.. Hahn,Th.: Amer.Miner.40.(1955»,226­2*3 2/ Chang.L., Li.X., Zheng,L..* Can.Miner.25, U987), £57­672 ­ 37 ­ X­RAY STRUCTURE REFINEMENT OF JINGLE CRYSTALS OF CeB, AND Cei­^B* (x = 0.26, 0.50, 0 75) SOLID SOLUTIONS GROWN BY THE SOLUTION METHOD M­K­Blomberg**, M.J.Merisalo", M.M.Korsukov**, V.N.Gurin' ••University of Helsinki, Department of Pbyeica, Helsinki, FINLAND "A.F.Iotfe Physical­ ГссЬшЫ Institute, Academy of Sciences of USSR, Leningrad, USSR

CeBe, LaB*, and their solid solutions have a crystal structure with cubic symmetry

(Pm3mt О'ъ) characterized by a three­dimensional skeleton of boron oct&hedra B», the interstices of which are filled by the rare earth atoms. LaB« ia & typical n­onovnlent

metal, widely used as thermionic cathodes in electronic devices. CeBe is the most typical dense Kondo compound. According to band structure calculations the Be oc­ tahedron requires for its stability two extra electrons which are donated by the rare earth metal atoms. Therefore, it is possible that the hexaboridee of trivalent rare earth metals have, in principle, up to 1/3 of their metal sites vacant.

The purpose of the present work was, in particular, to determine the possible occur­ rence of vacancies and, alto, to study how different structural properties are effected by

variation of the Се/La ratio of the crystal. Single crystals of CeBe and Се^^^Вв (x ~ 0.25, 0.50,0.75) solid solutions, prepared by crystallisation from solutions in molten alu­ minium, were invcoligalcd uoing automatic 4­circle diffractometer at 296 К using MoKV radiation. Experimental data were corrected for thermal diffuse scattering, extinction and absorption effects. Structural parameters were refined and the residual electron density calculated. The results obtained for CeB« and Ceo.nLto.iiB» were compared with the previous studies. Vacancies at the boron site, rather than in the metal lattice, as predicted, were established.

Further, the possible compositional variation of different crystals of the same nominal composition was studied. The Се/La ratio for a number of individual single crystals, as well as for several crystals simultaneously, was determined by x­ray fluorescence spectrometry using a high resolution Ge detector. No significant variations in the com­ positions were observed. ­ 38 ­ СВТЭГАЬ STROCTOHE OF THE COMPOUND Nc^Rh^Se, O.I.Bodak, O.Ii.Sologub, V.K.Pecharaky, P.S.Salamaha bvov State University, I/rov, USSR­

During the interaction of neodymlum, rhodium and germanium, if the content is close to equiatomic , a compound with an unknown structure is formed. A single platy crystal measuring 0.05x xo.010x0.010 mm was obtained from a specimen NdjgRh­gOeggCat.SO. Preliminary investigation by photomethod followed by a full investigation using a CAD­4 automated diffractometerttJoKrt ­radiation, 8 ­26­method, 26^^=70° yielded the following lat­ tice parameters» a­21.021(5), b=?.941(2), c»5.652(1) A,J" = •110.08°(2).The intensities of 1120 independent (I> 26l) ref­ lections were measured. All the calculations were made on a SH­4 computer using XT1SH program system. The analysis of sys­ tematic absences (only reflections of the'common type, for whivn h­+l«2n, and of type hkO with h,k­2n are present; testi­ fied to one of the two possible space groupssB2/b or Bb.

The structure was solved by dirsot methods in spaoe group B2/b. The final atonic positions arei 8 Hd1i 8(f) X у z 2 (x­O,0665O(5), y­0,1683(1), ».©,1*79(1),B.0,2B(2) A )t 8 Hd2>

8(f) (x­0,329*2(3), 7­0,1007(1), s­Ct11.541),B­0,49(2))i 8 bolt 8(f) (x­0,22152(5), 7­0.3­151O), «­0,1509(1),B­0,52(5)); 8 Ю>2: 8(f) (x­0,56212(5), 7­0,017741), e­0,13«>(1),B­0,31(3)); 40e1: »(e) 1/2 1A z (*­0,1*93(3),B­0,*8(7»; 8 Ge2: 8(f) (x­0,17W7(7), 7­0.5582(1), «­0,1187(2), B­0,*3(5)). The final value of B«0,034 in the anysotropio approximation. The compound Nd^Bh^Qej is the first representative of a new tyne of structures of intermetallic compounds. The coordination polyhedra of neodymlum atoms are 17,16= pointed figures, while rhodium atoms form icosahedra and tri­ gonal prisms with four additional atoms. Icosahedra and tet­ ragonal antiprisms with two additional atoms are the coordi­ nation polyhedra for germanium atoms. The ь tacking of the polyhedra in tht structure of Nd4Rh40e3 is the same M in y30e5 structure.In contrast with the latte­, the structure of Rd.Rh.Oe, contains every two rows of trigon .1 prisms divided by octahedra row. ­ЗЭ­ КЕ» STHUCTURAb TIPIEB ­ GERMANITOS' Oe, Hh AMD Ft O.I.Bodak, "u.D.Seropegin, O.I.Sologub, VoK.Pecharalcy, A.V.Gribanxv Lvov State University, Lvov, USSR Moacow State University, Moaoow, USSR

Turing the investigation of Ce­U­Oe system»* where M ia Rh or Pt, oompounds having an unknown structures СвМ^.х^з+х (x­0.325) and CePtOe, were found. The oryetal structure of the indicated compound» wa» de­ termined by a single orystal raethod( Enraf­NoniuB CM*­*' auto­ matic diffraotometer, 0­2Q­ ecan mode and graphite­monoohro­ mated ВоКл. ­radiation). All the calculations were made on an SII­4 computer using XTLSH program system.

The oompound CeRh^ ж0«^|х Cx­0.325) Cap, group Pmmn. «­4,322(2), b­4,359(2), 0­17.101(7) A). The final atomio parame­ ters arei Cell 1/4 1/4 в (а­0,148в(1)),В­0,4(2) A2( Ce2i 1Л 5/* * (»­0,6367O)),B.0,7(2); (0,35Rl"O,65Ge): 1/4 1/* * («­0,9369(1)),В­0,5(2); 0e1i 1/4 1/4 с (г­О,795(2)),В­0,8(Э)­, Ge2i 1/4 ЗА * (х­О,2в4(2)),В­!,50*)­, <ЗеЗ« 1/* 1/4 а (в­О,5063(1)),В­0,4(2)1 Ge4: 1/4 5/^ * (•—O,OO"0(9)),B­O,9(2)i ВЫ! 1/4 J/4 г (в­0,4247(9)),В­0,7(2). The final value of K­0,058 in the anyaotropio approximation. Coordination numbers of Ce atoms are 19, Ю ­ for Rh atoma end 9» 12 ­ for Gr atoms. The compound CeRh­j 0e2+I (x­0,325) i» similar to CeNiSig. The structure of compound CePtGe­ (op. group Pnnm, a­8,839(2), Ъ­4,423(Г), 0­52,444(5) 1) is very complicated. The coordination polyhedra of germanium atoms are trigonal prisma and tetragonal antiprlems. _ 40 ­ 1КБ CLASSIFICATION OF THE SILICATE «ПЛИ SINGLB ТВИШШИАЬ LAIER G.B.Bokl:!. Z.V.VrublevskaJa Institute of Ore Mineralogy (IGEM), USSR Academy of Sciences, Kosoow, USSR

The main principles of silicate classification were worked out earlier on the basis of the OiSi ratio and form of tetrahed­ ral radicals /1/. There are 10 subclasses differing in the struc­ ture of tetrahedral construction; island (circular, noncircularX chain, ribbon, tube, layer (single, double, triple), framework, aeolite framework» Each of these subclasses Is divided into different orders in accordance with the composition (0:Si ratio) of tetrahedral radicals. Among them the silicates with a single tetrahedral layer are represented by 14 orders. The group of minerals (0:Si ratio«2,50) with a tetrahedral layer made up of hexagonal rings was analyzed in /2/. All the other orders of this subclass are described in this work. The motifs of the single tetrahedral ­layers are listed in the table: Order 0:Si Type of Minerals number ratio tetr.iring s 1. 2.86 a=16 Meliphanite 2 2.80 Q=12 Zeophyllite 3 2.66 n=8 synth. NagZnfeijOg] 4. _"_ a=6, 10 synth. HagCuiSioOgI syntb..K Sb fSi 0 | (OH) 5 n=6, 8, 12 8 3 6 16 2 6 2.51 П=4, 6, В Tobarmorite 7 2.50 n=6 Clay minerals 8 _"_ Q=4, 8 Apophyllte 9 _"_ n=5, 8 Okenite 10 ~ — n=4, 6, 8 Dalyita 11 _' _ 0=4, 6, 12 Hanganpyroamalite 12 2.40 n=4. 5, 8 Semenovite 13 2.33 n=5 Searlesite

14 2.25 n=4, 6 synth. K4Si8018 /1/ Bokij G.B. Notes of Onion mineral society, CUV,! 5, 528 (1985) /2/ BokXi G.B., Vmblevskeja Z.V. Abstracts of X Buropsan Crystallographio Meeting, Poland, 20­29, 270 С19В6). - 41 - QUANTITATIVE DETERMINATION OF KAOLINITE IN BALL CLAY BY X-RAY DIFFRACTION AND INFRA-RED SPECTROSCOPY

M О Boles and К Vivian, Polytechnic South West, Plymouth, United Kingdom.

The quantitative determination of kaolinite in'clay minerals by XRD is beset with problems of preferred orientation and disorder in the kaolinite. Use of an end loading technique reduces the effect of preferred orientation on the intensity of the X-ray reflections to an acceptable level.

Disorder in kaolinite has been studied by infra-red spectroscopy and a crystallinity index has been defined as the ratio of the absorption of the infra-red peaks at 3700 cm and 910 cm" (ref. 1). Further work has showr that there is a linear relationship between the crystallinity index and the area of the principal basal peak for particular clay samples (ref. 2)

The present work is directed towards the development of a simple and convenient XRD/IR method for quantitative determination of kaolinite in ball clay. The method uses boehmite as internal standard and takes account of the crystallinity index from the IR spectra. The work is ongoing and the results obtained so far are encouraging. The results of our investigations will be presented for discussion.

1) Neal, M, and Worrall, W. E. Trans. Brit. Ceramic Soc, Vol 2£- 57-61 (1977) 2) Al-Khalissi, F, and Worrall, W. E. Trans. Brit. Ceramic Soc. Vol 81, 43-46 (1982)

о CO

6-1 ­ 42 ­ KBUTRON DIFFRACTION STUDY OF THE CRYSTAL STRUCTURE OP THE RARE­ EARTH AND YTTRIUM ANHYDROUS DEUTERATED FORMATES H.L.BolotovBKy , A.F.Bulkin , O.A.Krutov , V.A.Kudrjashev , * » ** *« V.A.Trunov .V.A.Ul'janov , A.A.Loahmanov , N.O.Furmanova , O.Anteon *, H.Poyry* , A.Tiitta , P.Hiismaki * Leningrad Nuclear Physics Institute, USSR Academy of Sclenoee, Gatchlna^ •• Institute of Crystallography, USSR Aoademy of Sciences, Uoacow', U£>S&> ••• Technical fteeearch Centre of Pinland, Eepoo, Finland

The powder samples of formates with general formula He(DCOO),, where Ue ie La,Ce,Tb,Tin,Y, have been prepared. The crystal structure measurements have been accomplished by mesne of the So­ viet­Finnish high resolution neutron tlme­of­flight powder diffrac­ tometer called Hini­Sfinko /1/. The profile refinement of the structure have been carried out, using the structure model, sup­ posed in /2/. All of the formates have been shown to be isostruc­ tural and have a rhombohedral lattice. The unit cell dimensions are decrees with the decreasing of the He ionic radii. The space group is R3mi the He atome ere located on the special sites of symmetry 3m and linked in a framework structure by the formate DCOO­groups, lying in the planes m. The coordination polyhedron of He Is a 3m­Bynmetry trioapped trigonal prism. The DCOO­group symmetry is m, the deviation from the ideal symmetry mm2 being caused both by the unsymmetrical He environment of the formate groups and by the partial covalenoy of the Ue­0 bonds. There'1з also a C­D...O­type'hydrogen bond in the structure. The D...0 distance and the effective isotropic thermal factor for D are de­ crees with the decreasing of the Me ionic radii. The D atom has it's maximum amplitude of vibration in the plane whioh is perpendicular to the hydrogen bond direction.

/1/ Trunov T.A..Kudrjashev V.A..Ul'Janov V.A.,Bulkln A.P.,Hura­ tov Т.О.,Korotkova T.K.,Schebetov A.F..Hiismaki P.,Foyry H., Tlltta A.,Anteon O­.Hutka H. .Kukkonen H. .Tilli K., LNPI repoi* 1277. (1987) /2/ Furaanova B.G..Razmanova Z.P.,Soboleva L.V. .Haeljanytsyn I.A., Slgert Q.,Shlgorin T.D.,Shipulo G.P., Kristallografijs 22, (1964). ­ 43­ CRYSTAl CHEMISTRY 0» ISOMORPHISM IN EU11A.LITES B.B.Borutaky». R.K.Rastsretaeva Institute of Oeology, Mineralogy and Petrography, USSR Acad.Scl.; Institute of Crystallography, USSR Acad.Scl., Moscow, USSR

The problem of Isomorphism in eudi ilites formed under the conditions of high alkalinity of minera ^forming environment is connected with complicated chemical СОЕ osition of the mineral which, being zirkonium and calcium silicate, contains up to' 16 other elements in various amounts, & detailed X­ray diffraction­ al study of seven eudialite samples (BNAAT­HONIUS.diffractometer, AREN­88 program system, Rgjjiao" 2.5­3.5*) made it possible to establish a relatively stable framework{cagZr^i­0„l ^igOgXf124 ­ free of isomorphous replacements. Only .то samples showed some Ca deficit, compensated by Mn and Mg (1: ovftlent isomorphism with the unchanged coordination polyhedra ­ octahedral. This fact explains a remarkable stability in unit cell parameters of eudia­ lites. All the isomorphous replacements in eudialites are owing to Impurity atoms occupying the framewo 1c voids, various in size and shape. Atomic distribution obeys th Pauling rule of electro­ static valency first of all, the values of radii being of secon­ dary importance, because these atoms ca: be displaced, changing the distances to the framework anions EL Л coordinanion numbers, The central parts of large voids are populated by alkali cations, mainly Da. 7e atoms are positioned over thr void edges in two rare polyhedra ­ flat square (He ) and semioctahedxon. Kie smal­ lest impurity atoms ­ Si and AT. ­ are 1 icated in central regi­ ons of nine­membered Si­0 rings. In ace rdance with the avai­ lable microregions the elements which i oraorphously replace each other form the following groups: I ­ Ha, TH, K, Sr, Un, Mg, HjO; 2 ­ Pe2+, I­e3+,Mn, Al, Ti; 3 ­ Si Al, Zr, Hb, Ti, H. Vari­ ous in size ieo­ and heterovalent catic is alter void structure. This leads to structural individualization of eudialites within one structural type. The investigation of the real structure of eudiali.e glveB a new insight into Isomorphism and its influ­ ence on the formation of mineral struct ire. 6­2 - 44 - CRYSTAL STRUCTURE OF SILVER DIHYDflOGEN TETRAOXOARSENATE

( SDA ) AgH2AsO- THE SERIE MDX ( X = P or As). A. BOUDJADA. Haut Commissariat A La Recherche, Centre de DeVeloppement des Materiaux ALGER, ALGERIE.

The single crystals of title compound were grown from the solution. The crystal structure was determined by X-Ray diffraction. This compound crystallises in tKe monoclinic system ; space group : P2 /a. The cell parameters are : a = 12.821 (7)X , Ь * 5.604ШХ. с = 4.73<(2)X andf- 90.40(2)" The unit cell contains four formula units.'The crystal structure was solved with 132? independent reflexions and refined to a final R value : 0.059- The structure consists of tetrahedra Aso and trigonal Archimedean prisms Ago . These potyhedra link as to form a three-dimensional network, A very possible hydrogen position confirm the existence of blacidlc group :

As02 (0H>2. It is worth noticing the effect produced by the cation size in the MDX series. When the ionic radius increases, the hydrogen bonds decrease and the coordination number of cation M increases. It teems that only very short hydrogen bonds associated with the large cations are able to create a ferroelectric behaviour. ­ 45 ­ DISPIRATIONAL=«ODULB SIMULATION OF SOUHCi­S OP HELICOIDAL CRYSTAL LAIJiRS IN DlAMONDrLIKE STRUCTURES N.A.Boulienkov, L.I.,Cynpber Research Institute for the Synthesis of Minerals, Alexandrov, USSR

The claseic dislocations­based model of helicoidal source» for non­expiring layers in diamond­like (Fd3m and 16, /nunc)

crystals has been shown unacceptable for <111> f <100> and <0OO1^ directions because there are no screw dislocations with similar parameters /1/. A possible source of helicoidal growth of cubic (S) and hexagonal (W) diamond­like crystals along <111>, < 100 > and К 001У may be some form of low­energy configurational de­ fects consisting of dispirational К and H moduli /2,3/ with disclination and translation (spiral) components. Layers distorted due to the presence of these defects in S ana 4 structures (with disclination components) become regular if b- a*id 7­member cycles are introduced in the close surroun­ dings of the dispirational chain. The high selectivity of spiral growth mechanises along Oil У t OOO^in S structures and <0001>in iV structures ia necessary since dispirational transformation of moduli is . only possible in the structures of non­spherical symmetry of atoms and in the exclusive direc­ tions of helicoidal exes of thoir space group symmetry /4/. The proposed mechanism of helicoidal growth in diamond­ like crystals may manifest itself in spiral growth of diamond polytypes or whiakers and in the so cal­ led normal growth of natural and synthetic diamonde /5,6/.

/1/ Hornstra Ъ. Defecty poluprovodnikov. W.t 19&9 /2/ Boulienkov N.A. Dokl. AN USSR 284, 1392, (19ЗД /3/ Boulienkov N.A. Kristallografia 33, 424, (19B0) A/ Harris .V.N. Sci.Amer. ^'37, 130, (1977) /5/ Oriov Г.А. .Boulienkov N.A; .Martnvifcski V.y. Oo~kl.AH ПЯРЯ,

2Ъг% 703 ,O9B0) /6/ Martovitski ;/.Г. ,2adneprovski B.I.,Boulienkov t:.A.,Samoi­ lovich I.'..I. Kristsllograiia 30, 1203­ (19»5) ­ 4В ­ PECULIARITIES OP STRUCTURE AKD PROPERTIES OF POLYCRYSTALLINE LilfbO, IN THE TEMPERATURE IMTBRVAL 70 ­ 1270 К V.A.Chemiehkov, L.A.Reznlchenka, Ye.I.Bondarenko, A.H.Pavlov, Ya.E.Cherner Rostov State University, Rostov­onrDon, USSR

Results on X­ray structural (parameters of hexagonal cell а^Сд), dilatometric i^/lo), dielectric (/V. £ ) end piezoelect­ ric (с*») studies are presented in a wide (70­1270 K) temperatu­ re interval of polycrystalline LiUoO,, obtained under pressure

20­60 HPa. On the dependences a^, and" cH on temperature there is observed a number of anomalies part of whioh ooincides with the

anomalous behaviour of p, , fl^and **/ie . The peculiarity £(l)i.B the strongly pronounced maximum "f жг/t» 10 u the manifestation of the 'l,1l 130 irf effeot of positive tempera­ 11, ture coefficient of resis­ JO L 5,JZ 110 L—> "// tance (at 290 X) related *A 1a 'VJ­V; C„­1D with both the extremum of 11 nm an 5,4 19.» &//& * with the formation 10 20 10 | Л>­ f\2L^< of potential barriers on the 15» 11 5,10 1J.07 boundaries of crystallines; 10 % 1 10 Comparing the results z obtained with the literature s^J \ 5,11 11,05 90 г \\ data nucler magietic reso­ , i , i^­« i I 7 nance on Li and nuclear qua­ dripole resonance on Nb powders of LiNoO,, one may suppose the existence of a phase tran­ sition in our polycrystals at 270­290 К which is due to the chan­ ges in the arrangement of Li­ions. An abrupt growth of */£. at 500­600 К may be due to the presence of high­ohmic layers jn the boundaries of crystallites appearing at the expense of nonuniform distribution of defects. A dependence of measurement results of djj on the value is established and a sharp decrease of d' in the interval 700­800 К is related with the screening action of conductivity. ­ 47 ­ STRUCTURE, DIELECTRIC AND ELASTIC' PROPERTIES OP POLYCRYSTALLI1JE LITHIUM AND TANTALUM NIOBATES V.A.Chernlshkoy, A.V.Turik, L.A.Reznlchenko, L.A.Shilklna, G.I.Khaeabova Rostov State University, Rostov­on­Don, USSR

For the first time by hot pressing technique high­density po­ . lysrystalline specimens of lithium and tantalum niooates have been obtained. High melting temperature (1500 K), structure type (ilmenite distorted),crystal ayBtem(rhomboheonU£he correspondence of oell parameters (LiNbO,i Ящ,­ 5­494 A,e* = 55.8S°, Cosct=0.56l2,

3 3 V » 106.01 A ,/>x ­ 4.63 g/cm | LiTaO^: Л№= 5.465 A,

3 oL. 56,27°. Cosot­ 0.5553, V ­ 105.45 A? J>x ­ 7.43 g/em ) to structural characteristics of single crystals verified the forma­ tions of stolchometric compounds. Their dielectric and elastic properties have been studied. It ia shown that the low frequenoy dielectri'j permittivity of polyorystaliine LiHbO­ and LITaO, is near to the values ob­ tained by direot averaging of physical constants corresponding to single domain crystals and is £.»/£« 50 for LiHbO, and £н//^*г •*• 40 for LiTaO,, the piezoelectric oonstants depend on the pola­ rization regime, but complete polarization of polycrystalline specimens (with the realization of all possible reorientations) appears impossible. In the frequenoy dependence of dielectric permittivity in LiSbO,, two regions of dispersion were revealed ­ In the ranges IO3 ­ IO5 and 10 ­I09Hz conditioned by the migra­ tion of carriers and the inertional clamping of domaine.reepea­ tiv.l,. It is established that the elastic compliance S^ of poly­ crystals is essentially larger, and the moo/ale of elasticity C^ is eignificantly smaller than the theoretical values obtained by averaging the constants of corresponding cryatels. A hypothesis la suggested according to which an additional contribution into the elastic compliances Is related with the re­ orientation of elastic dipoles, whioh become possible on account of an incomplete arrangement of Li+ ions in the single domain crystals forming the polycrystal. ­ 48 ­

2+ CRYSTAL STRUCTURE OF gaNgAl C^? :Eu (ABE) N.G.Chernaya, V. A.Ef rernov, V.к.Trunov, V.F .Pisarenko Kuban State University, Krasnodar, USSR

Using R SAD­4SDP autodifiractometer {Mo­IC^ ­radiation the crystal structure of an ARE crystal has been studied. Space group

Рб/minc» с=22.й95б(3) , a=5,645(3), Z=2 {R^O,027, Rw=0,042). According to the structural data obtained the precise chemical forr..;;la of ABE is

+2 3

It is shown that Mg ions are statistically distributed over tetra­ hedral aluminium positions of quasispinel blocks. The luminescence data agree with X­ray data. Eu ions form three types of luminescent centres. The models of such centres are suggested.

The coordinates of(the ions in the ABE crystal unit cell are given in the table.

Ate** f Si te Populat. X Y Z B^ ,A

Ba 2d 1.819(4) 2/3 1/3 1/4 В.89(6) Eu 2d «.M7I5I 0.7839(1) И.2961(1) 1/4 И.6И<1) Alt 12k 12 0.8338(3) В.1662(3) в 1В55<1) а.б2<2> Й12 41ч 4 1/3 г/з в 024В Г1) 0.21(3) B13 "i 4 1/3 2/3 в 1743(1) В.57(3) AM lo 2 И в В В.53(4) 01 17k 12 И.134216) В. 8438(6) в В51К1) 0.78(4) 02 17> 12 B.5B4t<6> а.4939(6) в 1479(1) 0.68(4) n» «<1 4 2/3 1/3 в ВЗВЗ(2) В.69(6) П4 4» 4 в в в 1439(2) В.61 (6) ОЯ 2c 2 •­313(41 В. 684 (4) 1/4 0.93(21 ­ 49 ­ X*RAY ANALYSIS OF CUBIC BORON NT'."RIDE CRYSTALS V.V.ChgmVfl|>ev, V.L.SolozhenKO1 , G.V.Fetisov, V.B.RybakOv, I.A.Petrooaha Department of Chemistry. Moscow State University, 119899, Moscow, Institute for Superhard Materials (J5M>, the Ukrainian Academy of Sciences, Kiev, USSR

Single crystals of cubic BN obtained by synthesis in different environments were •easuxed on CAD4 X­ray diffTactometer. Two crystals' were produced in IBM and the third one was chosen fro» polishing powder "Borason­sSOO", produced by General Electric Co, Weak reflections with fractional Miller indices were observed for all the samples together with correct strong reflections belonging to unit sell of cubic BN having parameter «=3.6160(31 X. Differences between integer hk 1 and fractional indices were £1/3 and all the fractional indices had the sane Bragg angles as the correct integer indices. It was shown that the samples consisted of two or йоге single crystals disoriented with respect to each other. So, in ISM samples there exist single crystals disoriented to 190° about axis Э, and in case of "General Electric" crystal two single crystals were disoriented about axis [112], which is the reason for appearance of additional reflections. After twin resolution for all the samples the data collection for single crystals of the biggest volume was carried out. The scale factor, thermal vibration parameters of 9 and If atoms and ideal spherical mosaic block radius were varied in least square

refinement using averaged set of t Рда|. A case of anisotropic primary extinction was viewed in the frames of Popa's formalism [13. For one of the crystals strong effect of primary extinction anisotropy was observed.

[1j Popa N.. Acta Cryst. А4Э, 453, (1987). - 50 - THU COMPARATIVE CRYSTAL CHEMISTRY OF Ca-, TR-OPTO-AND DIORTHOSILICATES H.L. Chiragov, K.G.Ragimov Azerbaijan State University, Baku, USSR

The comparative crystal chemistry analysis of Ca-, TR- ortho- and diorthosilicates shows that simple silicate structures ara often the sourse of structural minals for complex crystalline

phases. Structures of П* (ScSi207) , K3(NdSi20?), Ca(MgSiC>4),

Na6(YScSl207) can be considered as derivatives of od-Ca2S104. Structural interrelations among these compounds are demonstrated

in Fio. Q 1 . 2. AY^ 3.Ca(MgS104> ^ Я^-Е^-Ч — -—О

5.M_(S10.),A1,0,(B0,), 9"_t-~** ^-w P ^_ ° Г.5

^ЩА^А^d -

A portion of large cations and SiO.-tetrahedra form a mixed layer

[A(S104)2~) in the mentioned structures, but the other portion of these cations Is arranged among layers. If lnterlayer cations are bivalent, layers are discrete but there is a mixed framework of the composition ["ASi^O^J in case of univalent cations. It is found, that binuclear polyhedra are formed around alkaline cations. The polyhedra are bound by their peaks in the case of hydroxil group presence in the compound. Such polyhedra are discrete in Ca- silicates. It is shown that spurrit and paraspurrit will inherit structural features of ­ 51 ­ POLYSOMATISM IN 0B­SILICATE3

И. I. Chlragov, K. G. Ragiraov

Aaerbai;jan State University, Baku, USSR

The structures of inorganic oompounds, especially silicate structures can be represented as condensate of polytypic scuroe mlnala /1/ or modules /2/ whose different rations form polysoma­ tlo series of crystalline phase structures. Normally, one or two oell parumetere, corresponding to mo­ dule sizes, are identical ones in the mentioned etruotures.' Polysomatio series formed by extreme members­shennolt (Г­Са­510. and waterless trabeonit Ca.Si­O,­ with the common

0e chemical composition mCCajSlO.)+п(Са.31»010)2 » ^ 2(m+2n) '

(Si,010)n(3i0,) is deteoted in Ca­silloates with heterogeneous tetrahedric anions. Two parameters of these orystalline phases are approximate­ ly ldentioal, but the third parameter о la таг led depending on the number of modules. Sinoe с »3,4 X for f ­ 0j3 and с &7,60 А

for 0a.3l,010, suitable parameter of polyaometio series oryetals is as follows С m (3,40 x m + 7,60 x n) А. Рог instanoe, for

the synthetic 0a,(Slj010),(Si0.)8 (where m»4, n»2), с­4x3,

c 40+2x7, 60­28,80 A ( exp­28,75 X). It Is established, that CagSiO.­ and Ca(OH)j­modulee are basis of polysomatlc Ca­hondrodlt series, but a variety of

COjSlQ.­, Ca(0H)2 and Ca­jSlgO­'­raodules combinations, leads to a new number of crystalline struoturas.

/1/ Chlragov M.I., Dorfnan II.D., Dokl. Akad. Hauk 8SSH 260, 2 (1981) /2/ Tamans J., Mineral. Hag. 50, 149 (1986) 8 ­ 52 ­ INTERDEPENDENCES AKONG СПУЗТЛЬЬОСИЕОТСЛЬ, STRUCTURAL AND ELECTROPfIYSr~AL PARAHETESS OF FERROELECTRIC SOLID SOLUTIONS A.Ya.Danzi^e , I^.V.Dergunova, S.I.Dudkine and O.N.Raauraovskeya

Rostov State University, Otachki 194t544104 Rostov­on­Don USSR

A study has эеа carried out on ferroelectric solid solution? of multicoraponent systems of complex oxides of the type

PbTiO? ­ PbZrO? ­£ РЬВ^а Ъ£р3 Cn ­ 2,5) (1) where B' are th­ five­ and six­valent cations, B" are the one­ and two­vulent ations, (X ­ 1/2, 1/5» 1/4 depending on the valen­ ce of Э',Б". ?:• no solid solutions serve as a'basis for inorganic materials posse.­ sing ferroelectric properties. A strict linear dependence hus been found of spontaneous de­ formatit, of th • tetragonal cell (c/a­1) on the total electrone­ gativity of the elements B',B",TitZr in the corresponding degree of oxidation. T.e calculation of electronegativity was done with the concentrati >n of above elements contained in solid solutions (1) token into jcount. For convenie. ce, in subsequent calculations the tetragonal distortion (c/a­1) has'been expressed through the deformation parameter &t=*2 '3(c/a­1). The following relationship between О and electronegr ivity has been derived

8 - 2.9­ «Г^у ­ 0.267 (2) where T is the electronegativity expressed in WJ/ g­=atora Thuu, the deformation of the tetragonal cell of the type under connideration ; : directly related to the degree of covalence of th? bond В ­ О. It is noteworthy that the relationship (2) per­ mits prediction of the value of tetragonal distortion from the composition of jolid solutions without X­ray structural studies. Moreover, quantitative relationships were eerlipr established by the authors between the electrophysical and the structural parameters. FO: example, the spontaneous polarisation 1\ in t:ho tetragonal pho can be expressed through the parameter о as

? Ps ­ (3­ ' + 0.04/£ )yff (in C/m ) (3) Combined inspection of (t) and (>) reveals dj.recL ruluLion between Y and T^t i.e., from the composition of solid solution.­? individual electrophysical parameters may be evaluated. ­ 53 ­

OK OEIGIHS OF THE VAST ISOMORPHISM OF FbZr,,_xTl 0, N.V. Dergunova, A.1a. Danteiger, E.G. Fesenko Institute of Physics, Rostov State University J4+104 Rostov­on­Don, USSR

r1­xTlx°3 practioelly all complex perovskite­type oxidee of general formu­ la PbB'_ B^'O,, wt'ereas ite end members, PbTIO, and PbZrO,, pro­ vide considerably lower (if any) solubility. To clarify the rea­ sone for this, consideration was made of the maximum tolerable differences & r^xxin in *ne ionic radii of the substituting and substituted cations, for which a continuous series of the perovs­ klte solid solutions may be formed /1/« It lias been shown, by PbW c •n example of 1/2 d1/a°3 and "PbSb2/,y>ln1/,0J"l that the ionic radii differences between Zr and В'or Ti and В "cations are greater than the specified va­ lues, while the difference be­ "O _m ( V^;» w ' " tween the ionio radius r of the averaged гг­)/2Т11/г cation and the ionio radii of B* as well аа В "cations falle within the tolerated limits.

"O —1~ Q ) *^­ о В' (The value of raye depends on relative number of Zr and TI cations in a given PZT com­ concentratlons other than Zr. ..Ti ._. Hence, Zr (in PbZrO, ­ based systems) should be substituted preferentially by the larger B*"cationB, and Ti (in PbTiO,­ based systems) by the smaller В'cations. Solid solutions on PtHZr., Ti„)0,, however, allow simultaneous substi­ tutions of both Ti and Zr by cations of the corresponding si­ zes (Fig.), which may vary over » wide rang».At high Zr or Ti concentrations, the differences between r and the ionic radii of the substituting cations ­will increase thus reducing the li­ mits of solubility of complex oxides. Explanation hae also been Riven to a better solid solubility of the complex oxides in FbTiO­_«coaipared to PbZrO,­ /1/ N.V. Dergunova, V,P. SakhnenJco, E.G. Fesenko. Izv. VUZov. Fizdka, К 5, 119 (1980). ­ 64 ­ ГНВ CRYSTALLOCHEKICAL RELATIONSHIPS BETWEEN TUB NEW MINERAL РЫА­

3E (Balel4K0e5)lfcig(Ti,VFCr,Pe,K6)8(0,OH)l6 AMD PRIDERJTB, UANNA­ RDITB, RBD1BDGE1TB l\.T»Dmltrlevat M,.I,J7ovgorodoY­i, A.I .Gorahkov Institute of Geology of Ore Deposits, Petrology, iiineralogy and Geochemistry, USSR Academy of Soienoes, Koeoow, USSR

The orystallooheraical features of natural mineral ^Bal.lftK0.05^1.19^n5.81vl.3.' "rO.38FeO.2OM6O.l6AX0.O9^7.9B (0­,c оОН­ п)-,л have been stu ed in comparison with those of other minerals of similar composition and structure. The mineral hp.3 been discovered in the mantle xenolith from voloanic pipe Tu­ vieh (Tien­Shan). Accurate oh .aioal data obtained by mioroprobe analysis showed that it is th Ba­end member of solid­asolutlon series between K2­xTi8C16 and 3al+xTi8°l6" Powder and single crystal X­ray dlffraotion studies ot the mineral showed it to belong, as well as prlderite (K,Ba). ^(Tl,

Ре)_01й (l)( to the tunnel stn ature­type, epaae group J4/m with the unlt­oell parameters: a = 0.172 + 0.007Я, о =2.971 +0.005Й. In the structure double string ; of oxigen octahedra form a frame­ work, containing tunnels parallel to the C­axie, with the large 5a' and К oatione in tunnel cavities» The X­ray analysis and ohenloal data of the new mineral pha­ se ie similar not only to those of priderlte, but also of mannar­ dite (Ba.H20)(Ti6V2)Ol6 and redlgdgeite (Ва.Н20)(П6Сг2)01б (2), although these two minerals are characterized by another space group JAj/a and unit oell parameters: a =14.35S, о ­5.94 for man­ nardite and a *> 4.320, о ­ 5.94 or redledgeite. The diffueive superlattioe inflections are revealed in the single­crystal X­ray patterns of the mineral, that confirms the te­ ndency for superlattibe ordering in the tunnel structures. The •iailar diffusive reflections are observed in the eleotron diffrao­ tlon pattern of the new alneral phase. It IM shown (3) that the exact position of the diffuse ref­ lections Is a funotlon of ooaposlt. ­

(1) Horrlah K.( Mineral (tag. Qt «96 (1951). (2) Soott J.D., Poatfield O.K., Can. Mineral. 2Д, 55 (1986). (3) Bursill L.A., Greinlo 0., Aota C^­yst. 3.6, 2902 (1980). - 55 - POLYMORPHISM OF THE 4C AND 5C PYRRHOTITES I. Dudony, M. Ptfsfai Mineralagical Chair of Eotvos Lorend University, Budapest, Hungary

Natural pyrrhotite samples from Nagyborzsdny, Hungary were investigated by electron- and X-ray diffraction and transmission electron microscopy. Pyrrhotite (Fe^S) has a metal-deficient MiAs structure: the sulphur atoms form a hexagonal sublattice, the iron atoms are in the octahedral interstices between the sulphur layers. Regular alternations of full and defective Fe-layers produce a number of stacking sequences with different symmetries and Co values. In the present work a model was constructed to derive the several polymorphs of the UC and 5C types;

e. g. the polymorphs with c0 dimensions 4 and 5 times as large as of troilite 1С (FeS). Structure factors were calculated along certain reciprocal lattice rows for the possihle polymorphs. The reciprocal lattices of the pyrrhotite modifications were determined on the basis of SAEO patterns. 4C, twinned 4C and 5C polymorphs were found in the samples. The stacking sequences were determined by the comparison of the electron diffraction patterns with the calculated intensities- HRTEH images were useful for observi g the random stacking. Chemical composition was ca. :ulated from the structure, the results were compared with the data obtained from X-ray powder diffraction and chemical analysis. Knowing the structure and composition the temperature of formation can be r' duced. ­ 56 •

A DOUBLE SALT STRUCTURE R.Duhiev'**, I.D.Browntb> ''institute of Gentrtl and Inorqenic Chemistry, Bulgarian Academy of Sciences, 1040 Sofia, Bulgaria Institute for Materialo Research, McMaettr University, Hamilton, Ontario, L8S 4M1 Canada

In contrast to other MeX .2H О salts (Me ­ Ca.tln, Fe,Co,Ni,Cut X * F,Cl,Br> which яг* all composed Of in­ finite chains of MeX^IH 0>2 octahedra sharing X­X edges, ZnBr_.2H_0 «hows a completely different structure. In a study of the MgBr ­ZnBr ­H О system /1/, ZnBr .2H„0 was found to be isostructural with a double salt Hlth compo­ sition MgBr2.2ZnBr_.АН О . Using a method /2/ based on the relative softness and size of'the ions, the structu­ re of ZnBr_.2H2D was predicted /1/ to be composed of in­ dependent Zn(H_0>, octahedra and ZnBr4 tetrahedra form­ ing Zn_Br aimers. The X­ray structure determination /3/ confirmed the IZn(H­O) 3[Zn_Br 1 structure with a = 10.435(1), Ь ­ 10.367(1), с ­ 7.961(1), Z ­ 2 and space qroup Immm . There лгл two kinds of Zn (II) ions in the structure! one, showing fiard Lewis arid behaviour, виг— rounded by six H_Q molecules in a regular octahedroni the other, showing soft character, tetrahedral1 у cooi— dinated by four Br ions and forming dimeric Zn Br, groups. Extensive network of O­Н...Вг hydrogen bonds

/1/ Duhlev R,, Balarew Chr., Rev. Chim. miner. 23, 116 <1986>. /2/ Balarew Chr., Duhlev R., J. Solid State Chem. 55, 1 (1984). /3/ Duhlev ft., Brown I.D. , Faggiani R. , Acta Cryst. C44, 1696 (1988). ­ 57­ A METHOD OF COMPARISON OF CRYSTAL STRUCTURES A.V.Dzyabcnenkc Kaypov Tuctitutv of Physical Chemistry, 'fogcou, USSR

Due to ambiguities in the choice of the crystal basis vectors and origin, the asymmetric part of space ^nd atom numbering scheme, any crystal structure may be represented by more than one |ln tact, by Е. lot of) mutually equivalent, although appa­ rently distinct, crystallographic descriptions. This is the main source of problems arising when different structures are to be compared­with each other. We developed a method of comparison of crystal structures which takes into account the problem of multiple descriptions in a systematic way. In this method, a structure is treated as a superposition of elementary sublat-tices (PS) . Each ES consists of atoms (or molecules or any other chemical units which pre­ serve their inner geometry in different crystal structures, due to stronger interatomic forces) which belong to the same crys­ tallographic orbit. When two crystal structures, A and B, are to be compared, it is the correspondences between their constitu­ ting ES that are sought for first. This procedure is to generate all the equivalent descriptions of a given ES ot structure A. Of them, the description having the closest similarity with one of ES­descriptions of structure В is selected­ The generator of equivalent descriptions is the affine normalizer of the space group {or its direct product with the molecular symmetry group). If the correspondences are found for all the ER, the second pro­ cedure is to assertain t,hat all the normalize* operations fot­ ...:ng the selected descriptions are in agreement with each other. This means that any two of them are the same or show equality through the product with any operation of the space group.

л The method was realized in a computer program, CBYCOM (CR^y­ OJ stal COMparison], addpted to the Cambridge Structural Database. Applicat ins of this program in crystallographic and crystal chemical studies WLLI be discussed.

8­1 ­ 58 ­ STRUCTURAL I'XUHUWGX OF A HQUOUOHObC SERIES Uf ЬК11К.,.1.Щ'Л; '-' i.'ACAi'iUTK Yu.K.Kgoroy­Tismenko» E.tf.Gokoiova LOHCOW Ctutu University» Moscow» USSR

Five new minerals: sobolevite, nacaphite, inelchikite, mine­ rals "T" and "л5" have been investigated by means of single­crys­ tal X­ray mythod. A large group of udneruls such us seidozerite, rinkite, ^otzenitt^rosenbushite, murmaniufc, epistolite, baferti­ site, innelite, lomoaosovite, yuonnofuto, be^alomonosovite and those investigated by the authors has been conside­ red in terms of structural homology. Structurally the minerals n.ay be regarded as consisting of two types of blocks, that ure alternately suiaozerite and nacaphite. Seidozei'ite block consists

of three layers; the central one is formed of Tiif.*jalFelWb­octa­ hedru and sorves as a matrix for two identicul layers of [Si.jCu] ­ groupB und Ti­^octaheara, situated as on a chess­board. 'Jacapriitc structure is built of ;ia,Ca­columns with [PO Л­tetrahedra between them. Nacaphlte and oeidozerite ntructurcs may be considered as final members of such ,a scries. The structural variety of the ae­ ries depends on the siae and chemical composition of interlayer block derived from nacaphite structure. Proportionality of naca­ phite and seidozerite blocks leads to identity of two unit cell ' parameters 5»5 and ?A while "the third one increases from 9 to 41A. Nacaphite block (6A thick) occurs only in four structures including nacaphite itself. In the others atomic arrangement­ in interlayer blocks corresponds precisely to atomic arrangement in natjaphite structure but they are chemicatydistinct and sometimes the thickneee of nacaphite block is degenerated to be monoetoBic. There are three main factors resulting in structural variety of the minerals in the series: a)occurence of two types of blocks in different proportions In different minerals, b)shift of r.eido­ zerite blocks and interlayer atoms in relation to each other, c) chemical composition variations of both bl. cks. i4ic r.ories shows interesting relationships connecting unit cells and space groups and may be re^ardeJ as poly;­o;aatic oim, ГоНо.Ли^ 1'hompsonC 1^7b). ­ 59 ­ QUANTITATIVE POWDER DIFFRACTION ANALYSIS OF PHASES IN SOME PETROLEUM ROCKS Kaniat El­Saved. A.M. Abd El­Rahman, El­Zahraa El­Feky Physics Department, Faculty of Scince, Ain Shams Univ., Cairo­Egypt Three core petroleum rock samples чег« subjected to X­ray quantitative analysis by using the external end internal standard methods. Core No. 1 and core No. 3 were rebated to Baker oi 1 field and core No. 2 was related to Ramadan oil field, both fields are located in Suez Gulf. The rocks were subjected to mechanical separation into, 50, 20, 10, 5 and mu as mesh sizes before analysis. The main phases identified in all the rock samples were: e­quartz, calcite and hyperthene. From a synthetic mixture. of a­quartz and calcite a calibration constant was obtained by using least square method. This calibration coifstant was then used to construct two independent calibration constant curves for c­quartz and calcite. The third phase hyperthene could not be synthesised in polycrystalline form and accordingly one of the other two phases was used as in internal standard for analysing the hyperthene phase. By combinig those two techniques it was possible to evaluate with great accuracy not only the percentage of the three polycrystalline phases but also the amorphous phases present in the rock samples. From the percentage of the phases obtained it was also possible to determine the percentage of each element present in the whole sample. The results obtained gave a comparable results with those obtained by atomic absorption ­ Table 1 shows the average weight percent of the phases in the three core samples and table 2 shows the percentage of the amorphous materials at all *esh sizes. Table 1

Saaples 1 «eight percent I

Core No. 1 6.7+0.07 74.0+0.49 22.4±1.27 Core Ho. 2 53.9+0.99 16.8+0.64 29.0+O.85 core NO. 3 9.5+0.17 62.0+0.19 26.8+0.21 Table 2 nesh sizes 1 wt .percent of aaorphous material 1 1 core No.1 1 core No.2 I core No.3 50 au 0.60 1.40 1.07 20 au 0.99 2.12 1.12 10 au 1.08 3.00 1.37 S au 1.21 2.40 1.37 2 au 1 50 2 80 1 .63

а­г ­ 60 ­ CRYSTAL CHEMISTRY OK PYR1TE ANl> MARCASI'J'E GROUP MINERALS REVISITED

M.O. Figueiredt>% , M.J. Basto

Centra de Cri sta 1 ograf ia e Mi пега 1 ogi a , 11CT, A Lame da D. Afonso Henriques, 41­4° B, 1000 Lisbon, Portugal Lab. Miner, Petrol., e CenCro de f'elrulogia e Geoquiraica. IST/IN1C, Av, Rovisco Pais, 1096 Lisboa Codex, Portugal

Tho great ma jori ty of minerals with genera 1 formulae MX,, and MXY ­where M is a transition metal like Mn , Ke ,Си.Ni,Cu,ku,Kh,Pd. Os,t r,Pt or Au, and X, Y are elements of group VI , .4 ,.S«­, Те , or group V, As,Sh,Bi­ belong to t.he basic crystal structure types of pyrite and marcasite or corresponding derivatives. Considering the group of synthetic compounds with similar binary and ternary composite ons, those two basi с structure types become even more representative, thus sett ing up the quest ion of the morphotropic limits of pyrite and marcasi te crystal structures amongst minerals. A synopsi s is presented or» the crystal chemi stry and miner a 1 systcm.it ics of thi к i mportant к roup rove ring more than fiftymineral species whose synt tic analogues often belong; to the rank of hi gh­ ­tecno 1ogy materials. Chemical bonding arguments and electron ic features allow to pi nee such minerals in the category of polian io­ nic compounds with X(Y)­X(Y) or X­Y dimeric units /1 / • O.eometr i c. and topoJogic features accounting for changes in tin* state of bonding are analysed ­ namely, the geometry of anion and cati on cooYd i nat i on polyhedra, interatomic distances and unit anionic volumes. Further evidence is found that, lollingite (Fe As_) structure­typo ­ which

has the same crystallographic description as marensite {Fe S?, Pnnm) but significantly lower axial ratios ­ contai ns metal­meta 1 in1er­ ect ion extendi ng uni dimensi ona 1 ly along с axis . l.ikewi se , jirseno­ , pyrite (r'cAsS, Pi) and safflorite CoAs.,, \2{/<: or П2( /d /2/) * structure­types contai n metal­metal d imers, with and withoittanionic orderi ng, respect ively. Therefore , these three mineral types are simultaneously polycationic and polyanionic. Beyond such major changes i n the structural category, there are other structural variants involving only distortion and/or anionic ordering, as is the case of the scries pyritc (FcS,, Pa3 )/ulImannite (Ni Sb S, P2 T. ordered ) / rohal ti te (Co Ля S, Pen 2., order i ng­plns­di stort. i on I/As­ ­ullmannite (PI, re­ordered /3/ ) , and marcasite ( I'niim) / cost ib i te (Co Sb S, Pn2.m, ordered) /alloclasite (CoAsS, r2 [ < '>'*,r,'i ng­plns­ ­distortion /4/ )•

/1/ Figueiredo, M.O. , Brinnso, J . L., Bastо, M.J., Alvarez, A. , Acta Geol. Hispanica, 2_3, 33­38 (1988). /2/ Darmon, R. . Wintenberger, M. , Bull. Sot:. franc. Miner. Crist., 89, 213­215 (1966). /3/ Hayliss, P., Caned. Miner., 24, 27­33 (1986). /4/ Scott, J.D., Nowacki, W., Can.id. Miner., 14, S61­S*'" C1976). ~" ­ 61 ­ CRYSTAL STRUCTURES AND PROPERTIES OF SIX NEW MINERALS FROM vOLCANIC SUBLIMATES, KAMCHATKA, USSR S.К. Fi latov. T.F. Setnenova. M.G.Gorskaya, T.V.Varaksina, G.L.Sta­ * rova, Г. V.Rozhdestvenskaya, V". S.Fundamnnsky, LP. Vergasova Leningrad State University, LNPO "Burevestnik", Leningrad; Insti­ tute of Volcanology, Acad. Sci., Petropavlovsk­KamchatBky, USSR

The complex study or new minerals /1,2/ 2rom sublimates oc­ curring at Tolbachik volcano was carried out. Experimental data sets were collected using P2j autodiffractometer.. Mineral name and formula Sp.gr. a,A b,% c.K P,° R,X

Fedotovite {К,Ма)2СиэО(В04)э Сс 39.037 9.479 14.231 111.04 4.2

Kamchatkite KCu3OCl(S04)2 Рпа2г 9.741 12.658 7.001 5.5

Klyuchevskite K3Cu3Fe02

Ponomarevite K4Cu.1OCl10 C2/c 14.740 14.900 8.948 104.7S 3.8

Sophiite Zn2tSe03)Clr, Fccn 10.251 15.223 7.666 4.9

Lenlngradite PbCii4i(V04)2Cl2 ГЬат 8.ЯБ8 11.084 Э.ЗвО 4.2

In fedotovite the fragments of edgersharing 0Cu4 tetrahedra

surrounded by S04 tetrahedra which link them in­to [Cu30(S04)g]2­ layera || to (100) are the main unit3. In kamchatkite the channels 11 to the с­ахДз and filled with KC1 occur; the electrostatically neutral fi­am^ [CugOfSO^o] permits existing a compound with ouch a composition. Klyuchevskite can be obtained from piypite (carati­

2 ite), K2Cu20(S04)2, by doubling the formula and changing Cu ** K*

3+ 3 —*­Fe . Endless [Cu3F302(S04)4] " chains are 11 to the b­axis and linked by К atoms. Main units of ponomarevite are polynuclear groups

CCu40Cljn]^~ having Cu atoms in tetrahedron corners. The groups are linked by К atoms. In aophiite isolated triangles (SeOg)^" are linked by their edges with distorted Zn octahedra and form layers 11 to (010) which are linked by Zn tetrahedra. Leningra­ dite consists of Cu octahedra sharing edges and cornerз nith each other.The cctahedra are also linked by V tetrahedis. Pb ca­ tions nro 3­coordinate. Specific structural role of additional ions is discussed. Experimental results on thermal phase transformations and deformations, crystal optics and properties of these minerals are rrer.ented. A structural aspect of anisotropy is discussed. /1/ V^rgasnva L.P. et al.. Dokl. AN SSSR, 299, 961, 1197 (1988) /2/ Vergasnva L.P et al.. Zap. VMO, 459 (1988); 65­75 (1989) ­ 62 ­ ИЙГ CRYSTALLINE FORMS OP DICKITJS Y.I.Fin'ko, N.D.Samotoin. N.H.Smolyaninova; Ye.A.Borisova institute for Ore Deposit Geology, Petrography, Mineralogy and Geochemistry ox the USSR Academy of Sciences,Moscow,USSR

You can seldom come across well­formed crystals of dic­ 1,6134. Dickite crystals were found in dickite­quart': varieteis of porcelain stone. Plate crystals having a "hr^^­iike or pseudohexagonal appearances are seldom prysmatic along c­ axls. Twenty transparent dickite crystals that are up to С "* 0,3­0,5 mm in size along axes t\ and b and up to 1mm along axis с were measured on Goldschmldt goniometre. The following faces were discovered with an X­ray device on crystals as well as spheric coordinates corresponding to them. •/ „о у ji у JJ 001 90°00* 6°44' 023 6°16' 47°06' 061 0°42' 84°06' 010 0°00 90°00 011 4*"11 50°19 111 61°14 73°24 110 60° 13 90°00 043 3°0B 65°09 111 ­59°09 72°22 110 ­60°13 90«00 021 2°06 72°47 223 61°42 бё'Чг 014 16»19 22°48 041 1°ЙЗ в^Ов 443 60°59 77°1B Habitue forms are (oo1), (111), (T11) add zone faces[01$, from which (014), (Oil), (043) and (061) are most freuquently met. /1/. Biers M.A.,Mineral.Hag. 9, 41 (1890). ­63 ­ THE CRYSTAL STRUCTURES OF COPPER WSBERITES

S_i__XE£Q££n, R. E. Schmidt, W. Massa, D. Babel Fachbereich Chenie, Universitat Marburg, FRG

O. V. VaXubovich, V. S. Urusov Department of Geology, Moscow State University, Moscow, USSR

P.Huffe2 Oepartamento Quimica Inocganica, Universidad, Tenerife, Spain A. Tressaud Laboratoire du Chimie du Solide du C.N.R.5., Talence, France

Sodium copper fluorides of the weberite family have been prepared and characterized by complete X­ray single crybtal structure determinations. НДг^411^?: s­G­: Pmnb, Z ­ 4, a ­ 731.8(1), Ь ­ 1060.2(2), С ­ 771.2(1) pm, V ­ 598.3 10~30 Ш3, R ­ 0.034, WR ­ 0.025, isotypic with­Na2cuCrF7 [1]. HU2S^££^7i s­G­: C2/C, Z ­ 8, a ­ 1246(1), b ­ 736.3(4), С ­ 1293(1) pm , 0 ­ 109.36(7) °, V ­ 1171.6 10~3° m3, R ­ 0.029, wR ­ 0.028 The relations between these two compounds and the possibility of twinning misleading to other epacegroupte is pointed out. The influence of the Jahn­Teller­EEfect is shown by comparison with the structure of KS2Hiilf7*. S.G.: 12^2^ 2 = 4, a * 707.4(2), b ­ 1003.8(2), с = 731.5 (1) pm, V = 519.4 10"30 m3, R = 0.026, wR « 0.027 and Na2NiFeF7 [2], S.G.: Imma. The question of the "true" space group of weberite and the structural relations to the pyrochlore and fluorite type is discussed.

[1] S. Kummer, W. Massa, D. Babel, Z. Naturforschg., B<3(6), 694 (1988)

12) Y. Lalignant, V­ Calage, G. ;ger, J. P&nneti^r, G. Ferey, J. Solid State Chem., 78, 66 (1989) - 64 - STRUCTURAL RELATIONS BETWEEN ANION-EXCESS FLUORITE- RELATED SUPERSTRUCTURES OF COMPOSITION M0.5-X Lno,5+x F2+2x (Ln=lan1hanide and yttrium, M« alkaline cation )

Y.Le Fur, S. Aleonard. E.F. Bertaut, M. Perroux. M.F. Gorius. M.T. Roux Laboratoire de Crislallographie, associe a fUniversite J. Fourier, C.N.R.S., 166 X, 25 Avenue das Martyrs. 38042 Grenoble cedex, France

Electron detraction and single crystal structural determinations by X-ray diffraction have enabled us to show that the elementary cells of monoclinic, orthorhombic and tetragonal fluorite-related phases of composition Mo,5-x Lno,5*x F2+2x are straight related to the fluorite tetragonal cell [ aF,

(bF+cF)/2, (- bF+cF)/Zl. Their structures are characterized by chains of edge-shared Ln6 F36 (or Ln6 F37 ) groups running parallel to the directipn ( bF+CF )• These chains alternate with edge-shared LnFfl cubes chains according sequences accounting for the ratio Ln / M in the phase. The juxtaposition of these chains forms layers connected by polyhedra surrounding the alkaline cations. Besides, we show that the theory of similarity operators extended by E.F. Bertaut to the study of displacive transitions imposes strong constraints on Ihe space groups possible for the fluorite- related structures. ­ 66 ­ CRYSTAL CHEMICAL STUDY OF 1M Ti­RICH VOLCAMC BIOTITES

E. Galli'.L. Poppi"

* Istituto di Mineralogia e Petrologia, Universita di Modena, Modena, Italy ** Dipartimento di Scienze Mineralogiche, University di Bologna, Bologna, Italy

Crystal structure refinements were carried out on five 1M biotite crystals from ultrapotbaeic volcanic rocks outcropping in Southeastern Spain to study the extent of structural variations induced by a different Ti content. The Ti content of the selected samples ranges between 0.10 and 1.00 atoms per formula unit, on the basis of 24(O, OH, F, CI). Data were col­ lected using a single crystal diffractometer, with graphite monochroroated Mo radiation in w­ecan mode. All i­ellnementa were carried out in the space group C2/m (R = 0.02 ­ 0.04). The weight of chemical substitution is discussed for both the traditional parameters, like angles and single and mean bond distances, and the distor­ tion parameters of each polyhedra and of the general structure, namely: ­ tetrahedral ring distortion (a)(>>; ­ octahedral flattening angle (ф) that defines the octahedral layer distortion;

­ eu/e, measuring the particular distortion of each octahedron being inserted in layers with shared edge'3'; ­ OQE octahedral quadratic elongation^3)

(l> Hutn R.M.. Burnhwn C.W., Amer. Miami. 58, 889­900 (1973). W Tor«y» H., Zeit. Krbt. 1Б7, 173­?°n (1981). (S) Robineon K., Gibb. G.V., Ribbe P.H., Science 1T2, И7~570 (1981).

9­1 - 66 - NEW STRUCTURAL SERIES OP RARE EARTH GERIMHATES w E.A.Genkina, L.N.Demyanet3, B.F.Momin*, B.A.Woximov Institute of Crystallography, USSR Acad.Sci., Lloscbw, •Mordovian State University, Saransk, USSR

The hydrothermal analysis of more than 10 compounds of dif• ferent composition in the TRgO^-GeO^-R-I^O systems (TR - rare earth element and Y, La; R - hydroxide or fluoride of an alkali• ne metal) has been carried out. Six new structural types of non- alkaline germonates of TR-elemonts which form new homologous aeries have been singled out. The special importance of these investigations follows from the absence of natural Tft-germana- tes. Hence, their atomic arrangement and crystal chemistry can be studied using synthetic compounds only. Amonc the investigated phases compound** with all Ge atoms in rare five-fold or six-fold coordinations were obtained for

VI the first time. A new type of Oe radical (Ge-jOg) = (Ge Ge 0g)

chain infinite In one dimension was found- It was established for the first time that in germanates ortho- and diorthotetra- hedra enter the framework simultaneously. Relation to the structural types of silicates and one of the widjee- in mineralogy structural type of fluorite was con• sidered. Our investigations provided twice as many structural types as previouely known for this class of compounds- ­ 67 ­ NEW STRUCTURE TIFES OF Iin'ERKSTALLICS S°12.^40.?Ge}1 **"> So^fi5Ge8 E.I.Gladyanevsky, B.lfa.Kotur. H.I.Andrusyak Лот State University, Lvov, USSR

The crystal structures of Sc­ip. 5I,i40.7Ge31 and ' •i9^i5Ge8 compounds have been determined by means of X­ray Investigation of single oryatals» The single crystals have been isolated from the crushed ingots heated up to their Belting points and slowly cooled in the furnace under vacuum. The' structures have been solved by direct methods» The. ger­ macidee are first representatives of new structure types of in­ termetallica» Scale factors, positional parameters and anisotro­ pic temperature factors were refined for two conpounds «1th the full­matrix least­squares program*

Sc12>JMi40 Ge}1, Рб/mmm, Z=2, a=1.7865.(4), c=0.8220(2) ш». K=0.04? for 418 independent reflections (Syntax P2^ diffractome­ ter, Поло, ­radiation, (0­29 scanning mode). Sc, Hi and Ge atoms occupy 4, 9 and 8 positions respectively. Two positions (1(a) and 2(e)) are partially occupied by Sc (64(6)%) and Si (67(5)*). Coordination numbers of atoms are as follows. 17­20 for Sc, 9­1* for Hi, 11­15 for Ge. The structure is related to hexagonal clo­ eepacked structures* It'e very similar to the struoture of ter­ nary silicide Li,.JU^gSi­... The only difference between these two structures is the position of R (R=Sc, Li) and Hi atoms along the threefold and sixfold axes. The structure of germanide is one of the most complicated structures of intermetallios lnvol ­ ving scandium known today. Sc^NijGeg, Immo, z=2, a=2.0426(5), b=0.9129(1), c=0.39822(6) nm. R=0.03&. for 661 independent reflections (Syntax Pi diffrac ­ tometer, MoK^ ­radiation, в­гО scanning mode). The atoms occupy 9 sites* Coordination arrangements inolude 17, 15, 12 atoms for из Sc, 12 for Hi and 9 for Ge. The structure can be treated ae­two­

JJ dimensional hybride of d­Pe, A1B£, UoJIiB­ and TiBiSi structure types fragments. Comparison and analysis of etoichlometrles and crystal structures of two germanides and 8 other ternary compounds found in the Sc­Ui­ue system are presented* 9­2 ­ 66 ­

OEKTAIN FEATURES OF TRANSFORMATION J IN CL,, " MINiBAiS E.A.Goilo. N­V.Kotov, V.A.Frank­Kp.isenetsky Dept. of Crystallography. State University, Leningrad, USSR

Certain features of the structures of clay n nerale ( icoli­ nite, montmorillonite, bertierine, mica, mixed­layer phases et al., treated in hydrothermel environments at PHpO 1 kbar, T • 200 ­ 600°0 in the presence of K, Na, Cs, Mp; ­ chlorides, sulpha­ tee and carbonates ) were studied by X­ray powder diffraction me­ thod with profile analysis. Structural imperfections in distribution of chemical compo­ nents and layers and cation disordering have been established in genetically related mineral series • knolinite minerals ­» bertierine ­ serpentines, mixed­layer phases, micas; glauconi­ tes ­•»• biojites; montraorillonitea ­*• illites. These series ere the models of natural processes of sedimentary and metamorphic rock formation. It is shown tnat the charges of polyhedre and their distri­ butions in the transformed structures of layertdsilicat&s depend on the experimental temperature and can be used for indicating the direction of topotactic reactions. At the same time a stru­ ctural motive of a single layer, its symmetry and lattice para­ meters of these Biiicatea control certain features of structu­ ral inheritance and are realised in formation of psoudomorphs and various ways of layer stacking often with distorshion of their regularities. It was established that the polytype sequ­ entiality manifested by the preservation of aaimutal layer ori­ entation is the most important feature of structural inheritance in layer silicates» Experimental data indicate that the structu­ ral inheritance occurs in replacements of magnesium ­ aluminium octahedre by heavy atome ( nickel, iron, sine et el. ) and in the course of transformationa of layer silicates causing the origin of mixed­layer phases, where the whole structural fragments сип be replaced. Cation matrices of layer silicates were used for studing the moBt ргоЬаЫ A crystallochei^ical mechanisms and the extent of such topotac.tic transformations: two­lnyer into three­lpyer stru^ ctures and dioctahedral phases into their trioctahedrRl nnalo^ues. ­ 69 ­ THE SIMILARITY OP THE CRYSTAL STRUCTURES OP THE PLUORITE­ RELATED FLUORIDES AND SOME IHTERMETALLIDES

A.M. Golubev

CNIIOMTP, OOSSTROJ of the USSR, Moscow, USSH

It la known, that the structures of some lntermetallldes relate to the structure types of the simple ionio compounds!

CeCl, CaF2, BiF,. The relationship between the complicate struc­

tures of Ст2­Л^ and Tb|­Rh,Sn18 and the fluorite­related fluoride KTb,F was found in this work. The transformation from the flu­ orite structure to fluorite­related structures (superstructures and solid solutions) is oonneoted with the conversion of M..gFg. type clusters to MgR^Pgg type clusters /1/. The new description of the intermetallic structures Cagln., and MgcOaj as fluorite­related structures is given. The trans­ formation from the fluorite Btructure in thia case ie oonnected with the conversion of M.F03 type clusters to M.Ppg type olus­ ters, which were supposed in /2/ for the Interpretation of the structures of solid solutions MPp+x* The correlation between ­ntermetelllo structures and struc­ tures of the fluorite and of the known and hypothetical fluori­ des MFO.Y Is suggested on the base of the analysis made.

/1/ Oolubev A.M., Simonov V.I., Kristallogrfija (USSR), 21. 478 (1986) /2/ Maksimov B.A., Muradjan L.A., Simonov V.I., Monostoiohio­ metrlc fluorite type phases. In book: Kristallografija 1 kriatallochimija. ­Moscow, Nauka, 1986, p. 215. - 70 - GEOMETRY OF bOCAi CBYSTALLOGBAPHIC POSITION OF IBON AI01B BY HOBS. G.N.GonCharov Leningrad State University, Leningrad, IE3SB

An approach to estimate geometric parameters of local structu• ral position iron atoms by NGBS Is presented, Method of polinomial regression was applied for computation of the approximating equa• tions between quadrupola splitting, isomer shift, average interato• mic distance and local position distortion in the two serieses of Fe a™* %Q chemical compounds and minerals, including 85 - and 15 specimens for Fe and Pe^ accordingly- If you use all four mentioned parameters at the same time, then you receive the best correlation between geometrical parameters of local position and NGBS parameters and also Jd-, 4s-, 4p- electron densities and the effective charges of iron atoms. The latter were determined by aeniempirlcal quantum^chemical method from the NGR-, ESCA-, HE- spectra parameters. Examples of application of approximating equa• tions for determination of structural Fe and Fe'* positions in minerals are showed. The llossbauer data allow» to find the variations of geometrical parameters of local polyhedron and also electron structure of iron atoms in solid substances at the high pressure. Sometimes, when the pressure is going higher, then interatomic (Fe - 1/) distances are increasing. Increasing of coordination number, reduction of effective charge and transition Fe'* to Fe2+ attend this phenomen. The peculiarities of the geometry of local »e polyhedron in minerals after heating and radiation is estab• lished also. The results of calculation indicate, that gradual variation ferric NGBS-parametere in glauconite after geological time ie conditioned by isotropic enlargement of polyhedron and by increasing of the effective charge Ie*+ in more ancient spe• cimens. Geometrical parameters of local Fe^ positions in the X-ray amorphous ferric hydroxides to Ifossbauer data is estimated. The difference of these parameters for ferric atoms in the "volu• me" and at the "surface" of the finerdlapersional particles is determined. ­ 71 ­ TBE LCW­ WTO BIGH­TEMPBRATQRB CRYSTAL STRDCTORE OP CUgGeSeg D­ Gfitz. M. Behruzi, Th. Hahn Institut f. Kristallographie, Technische Hachschule, Aachen, PRG.

Compounds Cu8{Pi/Ge)(s/Se)6 and Cu7tSl/Ge)(S/Se)5J were prepared iron» the elements in evacuated silica tubes by thermal synthesis. They exhibit the well­known argyrodite­ettucture which can be de­

rived from the cubic Laves phase MgCu2 /l»2/j they occur in two modifications, a cubic high­temperature form (F?3m,a % 10 A) and

an orthorhombic low­temperature forro (Ртоп21га»7А,Ьг7А,с­10М with transition temperatures between 313­333K. For the iodine­contain­ ing compounds only the cubic form exists down to 160 K, Syntheses with Sn and/or Те yielded different eolid­state products. A. surprising exception is CugGeSeg which exhibits a hexagonal high­temperature as well as a hexagonal low­temperature form with a reversible displacive phase transition at 324 К [melting point 1083 K). The structures of both modifications were determined by •Ingle­crystal x­ray methods (CAD­4,AgK a jjsee Table). The struc­ ture type cannot be derived from the hexagonal Laves phaeee Hglnj or MgNi2 but rather from the hexagonal Nbl4s2 /3/. The high­tem­ perature structure consists of distorted CuSej tetrahedra.edge­ connected to form Infinite chains along £00l]. Three chains are linked into one column* the columns are linked again via common Se «tons resulting in a hexagonal columnar network of composition Cu56e5* Ite channels «re filled with Ge and additional Cu and Se atoms forming Isolated GeSe^ tetrahedra and СиБез planar triang­ les. In the low­temperature phase small shifts from the high­tem­ perature atomic positions take place.

T space lattice ­ °calc , И, . n n T group parameter * g/cm3 (refl.) K "w

298K P63cm c­l­lflj^ 6 6.467 237 0.082 0.060

2 6а4Э0 182 067 0<05S Э73К P63mc c­lli?ll* * °'

37ЭК d(Ge­Se)­2.346­2.348 A d(Cu­Se)­2.296­3.124 A

/1/ Geller S., Z. Xrlstall. 1A2., 31 U979>. /2/ Kuhs W.F.,Nitsche R., Pit. Rea. Bull. U, 241 (I960). /3/ Jellinek F.,Brauer G.,Htiller H., Nature ifiu, 376 (I960). ­ 72 J BASED OH CRYSTAL CHEMISTRY A.G.Gukalova. V.P.Glyokin Fhisical and Technical Institute, Tadjic SSR Academy of Sciences, Dushanbe, USSR

The results of structure investigation and crystal chemis­ try analysis of Indium and praseodimlum antlmonites /1,2/,be­ longing to the class of ferroelastoelectrlcs of R^Sb^O^ compo­ sition (Rcln,Sc,Y,La­Lu), yield a structural formula of & pro­ totype phaee of this family of crystals H^SbgttTbO.) „ |к21 д (ер. gr. Im3ni, 2=4,the coordination number (CM) of the first cation T­f 3+ R­^ la 8, the second one 3b equals to 6,the CN of th« third is 4 (pyramid), while for the anion and lone pairs (K) of elec­ trons being 4 (tetrahedron)). Such a detailed record of this formula allows to take into account the coordination of atoms and Erpaira,as pseudoatoms, to discern R^SbcO­Q structures from those of the garnet and may be useful in the search for other compounds with this structural type. For other transition elements containing an unbonding pairs the formation of similar coordination is,in principle,un­ prohibited. Thua,among complex oxides with non full­valent ca­ tions in lower oxidational state there,probably,can exist stru­ ctures of the investigated type. In fack,valency and coordina­ tional restriction allow a regular composition change which,ge­ nerally can be written as A^t^O^) E]4 .where Л refers to heavy elements with 1=2,3,4, for example : Ьа2'1 ,Yb3"* ,Н£** , (8)Pb4+ eta., В ­ Ae3+, Se4"1, Sb3+, Те*"1, ГЬ2* and M3+, m=0, ns4,3t2. The most stable region for the existence of these structures,probably,corresponds to l»m=ns3. The succesBful synthenjn of bismuthifcee with Yb^Bir012 composition /3/ of

l.n JUgtlJiO, К |к21 л structural type presents the first st;n^e in the v. on fi mint ion of crystal cheinistry prediction.

/1/ Guknlova A.G., Glyaxln V.P.t Tseitlin M.N. et al. Koordin. Khim., 12, 918 (1987). /2/ Glyokin V.P., Borisov S.V., Tseitlin M.N. Zh. Neor£. Khim. 22, 303 (1960). /3/ Guknluva A.G., Tseitlin M.N., Yaahlav3ky K.S„ Dokl. AN TndJJc SSR, 31, 1, 26 (190Q). ­73­ THE TWO­WAVELENGTH METHOD OF ABSORPTION CORRECTION IN QUANTITATIVE PHASE ANALYSIS

К. Hermann und M. Ermrich

Zentralinstitut fUr Festkijrperphysik und Werkstofforschung der AdH der Wisseneohaften der DI5R, Helmholtzstr. 20, DDR­8027

The X­ray Intensity scattered by a given component of a multi­phaee specimen does not depend only on the volume fraction of the component but also on absorption, texture etc. In the present note, the bulk contribution to the effect of absorption in irregularly packed multi­phase powders is analyzed. The starting point is a structural model for randomly packed powders that has been developed using methods of stochastic geometry /1,2/. The correlation function of par­ ticles of a certain phase i depends on the mean chord length 1, and the volume fraction c. of the particles. It is used to calculate the mean path length of a ray reflected from phase i. Then, the effective absorption coefficient _лд' felt by a beam reflected from phase i is determined for /i.l, << 1. It dependes on the difference (absorption contrast) between the coefficient JU, of the compact phase i and the mean value yu = 2 ck/Jjr ­ an" on the mean chord length of i­type particles. The analytical expression for/ij can be used to correct experimental scattering data for Sti.orption effects. If the scattering intensities are measured using only one wavelength of radiation, the mean chord lengths of the con­ stituents of the sample with unknown composition are re­ quired. They must be determined by means of additional ex­ perimental techniques such as stereological analysis of elec­ tron­microscopic images of transverse sections of the sample. Recording the scattering Intensities for two or more wave­ lengths of radiation, the mean chord lengths of the phases may be eliminated and the absorption correction can be car­ ried out without the need of additional experimental techni­ ques for the determination of the particle sizes /3/. The proposed two­wavelength method is proved to work correctly by means of experimental data.

/1/ Stoyan, D., Kendall, D. S., and Hecke, J., Stochastic geometry and its applications, Chichester, Wiley, 1ЭВ7 eg /2/ Hermann, H. and Ermrich, M. , Acta Cryst. A A2., 401 (19B7) со /3/ Hermann, H. and Ermrich, M., Powder Diffraction, submit­ "* ted

10­1 ­ 74 ­ И­И PAIRING IH Tilj­TVPE STRUCTURES

B.BilleDrecht. В.».«otter ud O.Thiele Institute of Inorganic and Analytical Cheaistry University of Freiburg, D­7800 Freiburg F.R.G.

Soae trihalides of transition aetals with dl (Ti,Zr,Hf) ,d3 (Ho) and d5 (Ru,Os) electron configuration crystallize in a Tilj­type structure with linear chains of face shared HX^­octahedra. Conventional X­ray structure determinations lead to a hexagonal subcell, spcgr Рб^/вса and equidistant

aetal­aetal atoas (c0/2). analysis of the weak superstructure reflections on RuBrj III and ItoBrj /"./ revealed that the hexagonal symmetry «as caused by tripling. The true cell is found by syaaetry reduction as follows P&j/acn

>Ccan—>Pnaa without any change in the hexagonal aetric (b0= /3aD). Reinvestigations on the structures of RuBrj and К0ВГ3 regarding tripling and the true symmetry lead to significant aetal­aetal pairing within the octabedra chaines. Besides, the structures of Hoi} and Oalj were deterained froa single crystals. These results are supported by magnetic aeasuraents .Raaao spectra and X­ray structure analysis of AjltjXg­coBpounds.faxtu.Ho).

Coapound Cell Diaensions (A] Jf­J* Distances [A] in between M2 pair pairs

HoBr, a=6.591(2) b=ll.416(4) c­6.075(5) 2.779(5) 3.295(5) II0I1 a=7.113(2) b=12.320(3) e=6.412(3) 2.857(4) 3.555(4) 3.153(31 RuBr3 1=6.466(1) Ml. 200(21 c=5.853(2) 2.700(3) a=7.012(9) b­12.12(21 c=6.277(7) 2.90(1) 3.3M1I

III Brodersen K., Breitbach B.R., Thiele G., Z. anorg.allg.Chaa. 357, 162 (1968). /2/ Babel в., J.Solid State Chen. 4, 410 (1972). ­ 75­ *BV COHPOaHJS I* THB ВIBART Ln­ВвНЭ SYSTEMS РОИ Ln=DT, Ho, Br, Tm, Tb B. Hodorowicz, S. A. HodornwiM. H. A. Bickt Faculty of Chemistry, Jaglellonlan University, Krakow, Poland •Department of Chenletry, Michigan State University, H.Lnnslng, USA

The report of &0K superconductivity In the Y­Ba­Cu­0 system /1/ hae produced an Intensive research effort directed and characterizing this and related to ternary oxide systems. Complete characterization requires the number and composition of all compounds In binary Ln­Ba­O (Ln = La­Lu) systems to be established. In the present paper phase relationships were determined in the ter­^erature 1 nterva 1 000­1000 'C 1 n the Lna.­0»­BaCO» eye ten far Ln=Dy, Ho, Br, Tm, Yb and for Initial mixturee of the molar ratios Ln: Ba=l­' 1, 1:2 and 1.33: 1. The compounds LnaBisOa, 1­П:*Ва*СЪ< and Ln*Ba»0* have been prepared and characterized by X­ray powder diffraction. Diffraction patterns ars in good qualitative agreement with those reported for the yttrium analogues /2,3/. The LnaBa^O* phase* are found to be stable only below 050'C; above this temperature they transform to LnxBa^Cb­. These LnaiBa^Cb phases are stable between 050 and 1000 "Cj above 1000*С Ln«Ba»Q* is stable. All of the compounds obtained ar=» metastable at room temperature.

/1/ Vu U.K., Aebburn J.R. Torng C.J., Hor P.H., Keng R.L., Geo L., Huang 2.G., Vang T.Q., Chu С V., Phys. Rev. Lett. 0Д. 006 <1©67>. /2/ Kweatroo V., van Hal H.A.K. , Langersls С , Hat. See. Bull.ft, lo31 (1074). /3/ Lopeto L.H. , Ceramurgla Int., £, 19 (1970).

10­2 ­ 76 ~ CRYSTAL STRUCTURE OF A TETRAMERIC SILVER COMPOUND,

[(CftH»NNNCJI4NNNCdHi)(HaNCaH,NUa)Aga],

M. Horner, A. G. I'edruso Universtdade Federal de Santa Maria, Departamento de Quimica, 97.1 U Santa Maria­RS, Brazil and M. Kretachmar and W. Miller Inetitut fur Anorgantsche Chemie tier Vniverahii Tubingen, FRG

Triazenido ligands in metal complexes are monodentate, (N1, N3)­chelating and bridging.

Б. g. in |(CeHkNNNCeH4NNN(H)CeH6)M]4 (M = Cu, Ag) tetrameric units are formed and each metal atom of the distorted M« rhombus is bound to two oriho N atoms and to one N atom of the bridging Nl, N3­functk>n of the ligands /1/. The title compound crystallizes monoclinic in the space group P2i/c with the lattice parameters a = 1064.9(2), b = 2041.8(2), с = 1008.5(2) pm, 0 =* 101­37(2)*, and Z = 2. In contrast to the above mentioned complexes, the telrameric unit is built up by a zigzag Age­chain with an angle (Agl­Ag2­Ag2') of 117V Each silver atom is coordinated to three N atoms. Remarkable are the Ag­Ag distances of 260 and 293 pm, respectively.

/I/ Horner, M.,Tenner, H., Hiller, W., Beck, J., Acta Cryst. C, in press. ­ 77 ­ NEW RGMBOHEDRAL MODIFICATON Ca.SlOg AND MECHANISM OF ATOMIC TRANSFORMATION DURING THE PHASE TRANSITION A.M.llinets, M.Ja.Bikbau CNIIOMTP, GOSSTROJ of the USSR, Moscow, USSR

New rombohedral phase Ca3SiO_ (a­14.142, c­25.085 A, hexagon, setting) was found in the course of the investigation

of the crystallisation in the system caO­Sio ­caCl? with SrO as dopant. Parameter a is doubled compared with the classical model of Jeffery /V­ X­ray analysis (эр. gr . R3», Zx36, R­ 0.068) brings to light on the reasons of that doubling fll. Pe­ culiarity of the structure of this new Modification C..S is various orientations of SiO.­groups wich for* vertical triples. Three of the six independent tetrahedra, are strin­ ged on the axis Э and other three­ on the pseudo­axis Э but with the alternate opposite orientations. The difference in orientation SlO.­tetrahedra leads to the doubling of parameter a. The comparison of the high tem­ perature rombohedral polymorph (a­7.056, c=24.974 A) with the triclinic polymorph (a^11.67, bd4.24, c=13.73 A,

/1/ Jeffery J.W., Acta Cryst. , 5., 28 (1952) /2/ Ilinets A.M., Bikbau M.Ja.. Itristallografija (USSR), in press /3/ Ilinets A.M., Simonov V.I., ibid, Д2,1175(1987) ­ 78­ PHASE TRANSITIONS IN DICAbCIUM SILICATE A.H.Ilineta. H.Ja.Bihbau Department of the Building Material lesearch of the State Building Committee of the USSR, Иозсои, USSR

X­ray data on the high temperature polymorphs «', af^ , a and well known structures of Q, Ц phases of C£S allowed us to observe successive changes in tiie crystal structure during phase transitions in this important cement mineral ­ Lattice parameters of the ff phase 4 tetrahedra arranged around two Ca­polyhedra displaced by 1/2 translation a .long "a". One of this Ca­polyhedra is an octahedron with sis connected and equally oriented Sio ­tetrahedra. In the second the CN increases up to nine and* two of the six connec­ ted SiO. groups have the opposite orientation. Displacement of Ca­atoms along г (CN 9) and reorientation of two Sio ­te­ trahedra take place during я­~я' phase transition . CN of Ca becomes equal to 8,6,10 and the symmetry of the crystal lattice chancres from hexagonal to orthorhombiC: a=5.555, t>=S.80l, c­ 9.317 %, sp. gr. Pmnb. Coordination of all Ca­atoms is na>n­ transition. However the bonds of cchange in layers parallel to (0 One of SiO,­tetrahedra changes the apical contact with the Ca­polyhedron to the edge one, the other has the opposite change. This leads to tripling of the unit cell a' ­C­S: a*20,696=6.955x3, b«=9.50O c­5.600 %., ар. gr. Pna? Major displacements of Sio tetrahedra result in the change in CN for one Ca­polyhedron, while the other Ca­polyhedron remains unchanged during the ffi­Й transition, our structural studies show that SiOjj­tetrahedra are more labile elements in phase transitions of. C.S­ This may be due to more covalent Si­O bond* as compared to more ionic Ca­O, the latter being more capable of the thermal energy accumulation, amplitudes of thermal vibrations for Ca and о arm more enhanced than Si­o ones with temperature increasing. C*~o si bridging oxygen accumulate tensions which vanish in the reorientation of SiO ­ tetrahedre ее е rigid body. ­ 79 ­ 10 THE PHOB1EM OF THE SECONDARY BONDING UNITS IN THE ST8UCTUK­ 0? THE PHAMEWOBK SILICATES AND THEIR ANALODS G.D.Iljuehin,

Institute of Crystallography, USSR Acad­ Sclencee, Moscow, USSR

In the frame of general theory of systems, the formal characterisation of crystalline structures of the framework silicates p.nd taeir analogs A_MT 0 iA= Ll.Na.K; ЬЫ|(2+)­ЭД6+); T=Si,Ge,P,S| p­0­3( q=1­6 waa given. The primary building unitsiM­.octahedra MO^ and T­tetrahedra TO* and secondary building units: mono­ merle pair K=*T=t4­0­T ani dlmerio complex D=K+K with the connection coefficient c­1 and 2 were distingui­ shed. The peculiarities of such MT­framework aret a) the absence of the local ruptures between polyhedra (the basic topological feature), b) the symmetrical conne­.tion of the Ц­octahedra at the construction of the MT­chains si ( the basic symmetric feature' ). The combinatorial ar.d topological analysis of д possible interaction between the monomeric complexes was given. On the base of the group theory the sys­ tematic deduction of 67 dimerlc species D(g)"KgK(where gi­tiie point operator of symmetry and g,­operator of symmetry with the translation component: 1f г^.т , г14 and t, a±,2^,&H was carried out. The distribition of the dlmeric species between 9 topologically different types( A and В with c=2 and Cj, D, Ej with c­1) could be_written_aa following:______„______„

Type А В С Cg D By E2 E3 4 3 ­ 8 В 8i 4­ HB244­ ­ 80 ­ CRYSTAL STRUCTURE OP KOaD, A.V.Irodova, 0.I.Lyakhorltakaya, fu.Z.Hozlk. V.A.Somenkov Kurchatov Institute of Atonic Energy Institute of Crystallography, USSR Acad.Sc]., Moscow, USSR

The crystal structure of potsesium tetradeiterogallate KGaD, (sp.gr.DJ6^ a»8.9870(16), b­5.6130(9), c­7.2620(13) A) was studied with the help of neutronrdlffraction data obtained on a powder sample. Neutron­dlffraction patterns were taken at T*293 and 80 К on the dlffractometer DISC 1 /1/. (The reaotor IR­8 used belongs to the Institute of Atomic Energy, X ­1.E04 A, d/d.0.8%).The neu­ tron­diffraction patterns were processed by the Rietveld method with the help of DBW 3,2 /2/ program adapted to the ES­1045 compu­ ter at the Institute of Crystallography, USSR Academy of Sciences.

The quality of the refinement is evidenoed by Яу­2.0« and RQ­9.2& KGaD. is isostruotural to BaSO. and contains isolated QaB.­tetra­ 4 * о * hedra (of.the distanoe Ba­D 1.51 A) and K­dodeoahodra (cf.the distanoe K­D 2.4S A). with the temperature fall the distances Qa­D grow, whereas the K­D ones shorten. Atomlo Coordinates and Isotropio Temperature Parasjetera(T­293 K)

Atoms x/a у/ь Z/c B, Az К 0,1822(11) 1/4 0,1590(16) 0,11(30) da 0,5684(7) 1/4 0,8099(8) 0,17(13)

D 1/4 0,8899(10) 1 0,4124(9) 4,08(24) D2 0.6793(12) 1/4 0,9648(12) 4.27(33) D 0.4230(5) 0,9755(8) 0,3142(6) 2,65(16) 3

/1/ Qlaikov V.F., Hautior I.V., Soaenkov V.A. et al. Nucl.Instr. Meth.Phys.Res., 1988, A26», 367­72. /2/ files D.B., Young R.A. J.Appl.Cryat., 1981, 14, 0.149. ­ 81 ­ CRYSTAL CHEMISTRY OF RARE EARTHS 6ULPHATES AND Si&ENATBS L.D.LskhaKova, V.K.Trunov Research Production Association "ШВА", Moscow, USSH

The data on crystal structure of normal, acidic, banio and double sulphates and oelenatea o£ trivalent rare earths (RE) ae well as Ce(IV) and Се(Ш)­Се(Ш salts are generali­ sed. The structural types distribution of compounds, the wide­ spreading °f апУ о* them and morphotropy laws are analysed with taking into account the influence of composition, ions size ratio, stereochemiotry of HS and coordination types of TO^ tetrahedra. 0?j8tallocheBl­3tsj features of classes above mentioned and other compounds with fcetrahedral anions are compared» The double sulphates are characterized by the structural typea, based on ordered substitution airi­». И* t­ Ln at position of initial structure 1H0„. In the structures of double selenates the substitution }йв­, K+ t 2хП type axe also rtoalized. Tb<" layered structure of double salts with triangular oation net­ works differ from their structural analogies with other cati­ ons and anions because of specific coordination of sulphate gronpe with RE oatioae. The most profound analogies are re­ vealed for compounds with octahadrally coordinated SE atoms

(frameworks Ln2(T0a>» and related structures, compounds with columns LnCTO,,), etc.). The ргевепсе in compound composition of mixed valence ca­ tions resulted is distortion of initial centrosymmetrie struc­ tural motives with the loss of the Bymmetry centre. The maximum number of independent structural types, spe­ cific only for KS sulphates as well as selenatee, are reali­ zed among the cr^stallohyoratee. Coordination polyhedra of KB atoafi ­ 1 characterized. The distortion of TO^ tetrahedra and distribution function of their geometrlo parameters and bond valence, in dependence with their coordination types and chemical nature of ealta are statistically analysed. .га results of orystallochemical analyses are used in "iscusaion of the compound properties and their existence region in water­salts and condenoed systems. II­I ­ tz ­ THE REGULARITIES OF CHANGING EFFECTIVE CHARGES OF ATOMS IN MINERALS ACCORDING TO THE AES AND ESCA DATA A.S.Ivanov, £..A.Zuc^erman CNIIOMTP, GOSSTROY USSR There exist various .­nethodt ot determining effect ive charge (ECt in atom» which are different •from one another and owing to this they give cii fterent value* of EC even ­for the compounds of the same type. However, the relative change o­f EC determined by these various methods is practically the same. We offer here a new method of determining EC with the help of variations of Vagner'э Auger.=­parameters of compounds and the standard method that is compared HIth others that are used for the determination of EC, in particular, with ESCA. When considering the authenticity of this method the follow­ ing points were taken into accounti 1> EC reflects the degree of ionici ty of th« chemical bond) 2> in complex compounds the direct ions of EC changes in atoms banded into compounds are op­ positef ~3) the direction of EC changes determined by means of this method should coincide with the direction of EC changes determined by other methods. Our method ;«as appl ied to tt>e stu­ dy of silicate minerals and showed the following! 1. In all kinds of silicates {from isle to carcass) EC of Si is lower than in quartz.On the one hand this confirms the fact that cations лге more positively charged than Si. Saturating the by­ atomic «sphere О wtt+i elections they deer­ease the ability of the latter to Ionize Si.On the other hand, EC of Si atoms is de­ creased by the depolimerisafcion process of SiO tetrahedra. 2. When moving from carcass to isle silicates the number of po­ sitively charged cations gets decreased and EC of Si decrease in vh.» same direction. The same happens to EC of Al. In the framework of each chemical subclass of silicates sets of mine­ rals can be constructed according to the direction of changing EC of atoms. This tendency, however, is violated wi thin wmry chemical subclass. 3. Maximum values of EC of SI a.rc inherent in beryl, pirophi­ 11 Ite» microc 1 me, i.e. in miner • ' s containing bridge and non­ bridge o.'.­узег» in SiD tetrahedra. 4. EC of cations determined on minerals agree with literature data and they change in the way following the above menticinpd cond it ions. ­ вз ­ IDBiJTIHCAMOrf OF VA^ftrJEii AHA) OAliJITK AT 'I!HJi OO­islAIdTBiWE USING fiMIROU rtlOKOJUOPY O.Ivanov­a»' A.PamiatniKh, K.DJuneva Faculty of Chemistry, University of Sofia, 1, A.lvimov Av.„ Sofia 1126, Bulgaria

The calcium carbonate at ordinary temperatures (10­40°c) .crystallizes in water solutions with simultaneous formation of vaterite and calcite. To obtain data for the rate of crystal nucleation and growth it ia necessarj to know the size distribution function. This information may be recieved from electron micrographs. Usually vaterite forme spheric and calcite ­ rombic cryetals.lt is established that at definite conditions the crystals of both modifications are spherical. The­identification is made on the mlcrorelief of crystal surface. The data are compared with the results of quantitative x­ray analisls.

П­2 ­ 84 ­ STABILIZATION OF SILICATES STRUCTURE V.G.Izotov, V.P.Kal'chev, I.Yu.Chronov Kazan State University, Kazan, USSR

The silicates of deep levels of earth's crust (SIL) have many peculiarities that caus­1 the stability of their crystal structure formed under extraordinary conditions (super.­—high pres­ sures and temperature). The phase transition occurs in silicates if some threshold is exceeded. However, the crystal structure of silicates may be stabilized by some conditions therefore, some individual modifications can preserve their structure even if critical conditions are exceeded. Such stabilization may l>e T­.A­ lized both on micro= and macroscopic levels. 1. The main structural elements of silicates are silicon­ oxygen tetrahedra. Kbssbauer and X­ray structural studies of sili­ cates 'pyroxenes of metamornhic complexes, divines of deep­ seated rocs, garnets of kimberlite formations) testify to the presence of a great number of Fe ions in tetrahedral coordinat­ ions. This is confirmed by the deficit of silicon and aluminium 3 + in many cases. The Fe. entry stabilizes the о xygen tetrahedra and prevents thein from transitions into oct.ihedra. 2. The example of olivines illustrates that SIL have nearly isotropic tensor of coefficients of relative temperature extension. Thus, the deformations of separate local positions are mutually compensated without"the changing of local symmetry of positions. This Is made for stabilization of the SIL at hioh temperature and pressure, 3. Important factors contributing to stabilization of^crystal structure of the STL are macroscopic peculiarities of these minerals. In ordinary conditions the iron­ m^ancsium silicates are perfect solid solutions, x­ray structural and Mitesbauer ii.vestina­ tions have shown that the silicates of deep levels of earth's crust are heterogeneous complex crystals that is associated with the breaks of isomornhous mixing of extreme minals. This leads to the decreasing of entropy for every phase and the increasing of their stability. •85 ­

S.P.Jatsenko, Y.II.Grin. O.K. Sichevich, N.A. Sebirslyanow, A.A. Fedorchyuk Lvov State University, Lvov, USSR Institute of Chemistry, Ural branch USSR Acad.Sci..SverdlovBk,USSR

The existence of compound with composition Ce^Gao was found during the Ce­Ga eyetem phase diagram study. Crystal structure investigation WBB carried out on a specimen, prepared bv slow cooling of a liquid and showed that the earlier information on the crystal structure (Zr^Al„ type) ie wrong. The results of structure solving enow: apace group P4/ncc, Z­4, a*6,066(3), c­H,495(3) A, R­0,035 for 389 reflexions. Ato­ mic parametera and eitee occupations are listed in the table.

At°» poa°i?io„ «».* » У

Cet 16(g) 100 0,9124(1) 0,4307(1) 0.0993(1) Ce2 4(c) 50 1/4 1/4 0,2234(2) Gal 6(f)' 100 0,8670(2) 0,1330(2) 1/4 Ga2 4(c) 100 1/4 1/4 0,4986(3)

Gallium atoms occupy trigonal prism and archemedean anti­ prlam with additional atome (CH*9). Cerium atoms have 13 or 14 nearest ligande. The ehorteBt interatomic distances in Ge^Gaj are: Ce­Ce ­ 3,321, Ce­Ga ­ 3,135, Ga­Ga ­ 2,670 A.

The structure of Ce,Ga2 may be described as a defect deriva­ tive of Ba^Si­ structure type. While comparing Ce­jGa* with

Zr­,A12 and Gd­,Al2 one can see pentagonal nets and packing of tetragonal and trigonal prisms. The disposition of polyhedra layers in structure Ce»Ga2 perpendicular to the 2 axis is similar to thoae in Gd^Gag. ­ 86 ­

CRISTAL STRUCTURE OF THE COMPOUND bu6Co26­xIn f*­8»41) Ya.MJtaljcbak, V.I.Zaremba, E.I.Gladyahevsky Lvov State University, rfvov, USSR

The compound of LuCo,In2 approximate composition was synthe­ sized from the compact metale(purity no leee than 99,9 percent) by arc melting in argon atmosphere. Crystals nearly of cubic shape with linear dimensions 0,086»0,085"0,080 mm were obtained from alloys annealed at 870 K. The experimental date was obtained using preliminary photo technique and measuring on automatic difractometer("Nicolet R32*,

НоКА­radiation, flat grafite monochromator,u/­scan mode, 28^ . 70*). The structure (a­8,652(3)A>«« solved by direct methods in Pm3 spate group and it was refined by full­matrix least squares (program CSD, <461 independent reflections with 1>

In compounds composition «orresponde to the formula LugCo17 eq iiL or bu6Co26_xIn11­ ('c"^^',•',)• Coordination numbers of Lu atoms are 15 and 15,12 for In atoms. The smallest Co atoms are characteri­ sed by coordination numbers 12(Co1, Co2), 14(Co3) and Ю(СсА,Со5) which refer to suoh' coordination polyhedral icosahedron, tetrshsxahedron and defective cubooctahedron, reapectlvely.

The compound discussed is the first representative of th< new intermetallic conpound structure type. ­ 87 ­ QUANTITATIVE ANALYSIS OF FERHMIS OXALATE IN SYNTHKT1C GOETHITE SAMPLES BY X­RAY POWDFR DIFFRACTION

T. A. Karoniangya. Cent. Inst, of Сотр. Technics and Terhnul. , Sofia, Bulgaria E.P.Evdokiraov, NIPKITOK9, pernik, Bulgaria

A net hod for quantitative pha.se anal ysi я of powder eiirapl >•» with external standard waa appl i od t.o ferrous oxaUti' deterni nation in aynthet ic goelh i t.e . Standard mixturoB (>f di fferent Oxa J ate conopntrat ions were uand . S i I i '­on WHH employed ae external standard. The measurement и we г** performf d on a goniometer equipped with variable «lit, graphite d i ffгасted­beam monochromator, and CuK a..J radiation. The measurement of each mixture was repeated 10 times and t he results were calculated by IBM PC. Regreяя i on analysi и и«я applied for plotting the dependence of norma) i ?ed intensity on oxalate concent rati on . The pol ynoroe coef f i с i i>nt и wi­rf introduced i n the d1ffractoeeter сотput cr where 1 be experimental data were processed automatically. The Ktandard deviation!* in the presented method do not exceed 2%. ­ 88 ­ THE МАШ TETRAHEDRAL MOTIVES IN SILICATE STRUCTURES A.A.Kashaev Teachers' Training Institute* Irkutsk, USSR

The rings consisting of 4­ or 4 tetrahedra are the charac­ teristic fragments of condensed tetrahedral radicals, A wide re­ presentation of these rings is explained by their ability to form simple and compact structures as well as to satisfy the maximum number of different symmetrical positions. An important peculiarity of 4­ and 6­membered rings is on easy realization of S Э­Si ­144­148° and Al­O­Si ­ 136­139° angles within them, that is the most characteristic feature of silicatea.The tenden­ cy of T­O­T angles to attain these valueB is especially obvious in amphibole and mica structures wher' the angles are 5­10° smaller. This leads to an increase n length of octahedral ed­ ges closing T­O­T angles up to 0.Э A in amphibols, and in a and b parameters in dloctahedral micas. A decreased value of the T­CMP angle In chrysotile accounts for experimentally ob­ served minimum bending radius of its monolayers.

In silicate structures the most widely represented are lenticular radicals consisting of 4­ or 6­membered rings or plane motives, made up of them, of the mica­, pyrosmalito­ and apophyllitolike types. A micalike motive with a minimum number of construction parameters is observed in the structures of minerals the number of which slightly exceeds half of all the layer and framework minerals. Pyroemailto­ and apophyllitolike motives with a larger number of parameters describe approxima­ tely equally one­third of all the structures. Less economical arrastrongito­ and melilitolike motives are represented more poorly. Other types of radicals can be found as single instan­ ces. ­ 89 з CARBURIZATION AND REGENERATION. L. Kepinskl, M. Votcyrz. J. M. JabJtonskl,. Institute for Low Temperature and Structure Research, Polish Academy of Sciences, PI. Katedralny 1, 50­pSO Wroclaw, Poland.

Pd supported on ЛЦО is an Important catalyst of partial hy­ dr­ogenatlon ' of hydrocarbons. Therefore, the insight into the metal ^support and metal*carbon interactions fs of great significance.

Samples of fresh 104 Pd / АЦ°Э catalyst were heated In H_ at Э temperatures and then carburlxc d in C­H • The qualitative , X­ray phase analysis was performed for each sample and the lattice pai­a­ 'meter of Pd was determined. The table below contains the results:

REDUCTION

Ump. 0A1 temp. tfa С ШЛ) 1 770 ­0.04 1 SSO +2.7в ,3 970 ­0.22 6 350 •1 .37 в 1 1O70 ­0.30 10 SSO +1 .43 э" 1 +О.ОЭ о ! where. 6 •оах'а , relative chance of Pd lattice parameter; С .СС >, concentration of AJt

be interpreted as a result of the partial reduction of Ai_03~ support in the vicinity of particles, Al diffusion into Pd

lattice and formation of 1^ u. uAl_« _ substitutional solid solution (X ­ 0.01­0.10>. It is a new effect, because up to now there was no conclusive evidence for strong, chemical Interaction between Pd and Al below 1000 K. A covaleni radius of С Js bigger than the effective radius of an octahedral void in Pd lattice. Thus, the decrease of the latter Cdue to Pd­Al alloying} hinders С penetra­ tion Into Pd lattice. Therefore, the deactivation takes placo. It was checked that oiddatlon of the deactivated catalyst followed by its reduction restore the initial ability of Pd to absorb carbon. It is connected with extraction of the dissolved Al from P*d grains which are almost completely converted into PdO during the oxidation. I8­I ­ 90 ­ CRYSTAL STRUCTURE OF ORDERED INTERSTITIAL PHASES, FORMED ON BASE OF B.C.С. ТУРЕ LATTICE OF METAL ATOMS B.V.Khaenko, N.T. Bugalchuk Institute for Problems of Materials Science, Ukr.SSR Acad. Sci., Kiev, USSR

The results of X­ray study of interstitial phases, formed by nitrogen or oxygen atoms ordering in the initial b.c.c. type lattice of vanadium or niobium atoms are presented. It is shown that in the primary solid solutions of the named type under annealing, cooling or quenching conditions the orde­ ring transformations take place. As a result of such transfer ­ mations the initial b.c.c. type lattice is being preserved (V­b Nb­H) or tetragonally (ortharhombically) distorted(V­N, V­0) Tetragonal (orthorhombical) elementary cells are characterized by

the axial ratio c0/a0(bQ)< 1, while the metal atoms in the sur­ roundings of the occupied octahedral site shift in such a way that the octahedral site essentially elongates in the direction of its shortest axis and somewhat shortens in other directions. The specific case of the ordering on the base of the initial b.c.c. type structure present the equilibrium tetragonal (mono­ clinic) phases with c0/a0(bQ) 7 1 in V­0 system (V^O ­ V20 com­ position) . In these phases 1 is caused by energy minimization effects of anisotropic elastic distortions in the lattice. ­ 91 ­ MOSSBAUER AND ELECTRON DIFFRACTION STUDY OF MICAS FRO» THE CRYSTALLINE BASIS OF THE TATAR ARCH Yu.E.Khalabuda, C.S.Pucalov Kazan University, Kazan, USSR Samples of mica were selected from the core' of the crystalli­ ne basis from the depth intervals 1800­2200 m.Electron diffraction patternsof "inclined" textures were obtained (angle of inclination of the samples was 60°). Trioctahedrical micas of biotite type («=5,32 A, b= 9,22 A, c=T0,02 A, i>=T00O4'), phiogopite (a=5,33 A, b=9,235 А, с=1о,4 А, A­99°5") of uolytype modification IM and .. о о о

dioctahearical mic»s of musco^ite type (a=5rl9 A, b=9 A, c= 20,1 A jb»95°11') of polytype modification 2M_, presented as impurity, have been identified. All samples exhibit sufficient ordering of three­fold silicate sheets. Disturbance in ordering can be noticed only in the order of alternation of sheets. All investigated phlo­ gopites are of highly­ordered crystalline structure. Biotite exhibits the decrease of the perfection of the crystalline struc­ ture which ia pointed to by the rotation through angles multiple 60 or in a shifting on 1/Э of a cell unit in the layers position along the axis b. There is no resolution of the first ellipse on the electron diffraction pattern of the samples from the depth intervals 1916­1939 m which points to their overage low symmetry. Variations in b,c and Д parameters of a unit cell as a function of the deposition depth apparently testify to signlfica.it isomor­ phic substitutions in the structure. In some case the Increase of о the b parameter up to 9,25­9,26 A is a result of high iron concen­ tration, which is confirmed by bauer data. Insignificant variations of the parameter с more sensitive to the pressure car. be observed with the increase in depth. The presence o.' quadiupole doublet!1,33 mm/s) in Mossbauer spectra of some phlogopites points to a great deviation of the coordination position of Fe ion from the ideal octahedral position. This deviation is due to the pre ~ sence of vacancy in the adjacent octahedral position. One can г isume that in the structure of phiogopite Fe ions tend to form clusters. Clusters appear potential centers of the dioctahedral formation and vacancies probably form at Fe /Fe > 0,33. 12­2 ­ 92 ­ CRYSTAL STRUCTURE OF MONOCLINIC ERICSSONIT IN TERMS OF THEORY' A­D. Khalilov Institute of Geology, Acad. Sci. of Azerbaijan S$R, Baku, USSR

We offer here a model of ericssonit crystal structure derived from the crystallochemical analysis of general principles of the crystal structure of Ti, Nb layered silicates £l^ . The parameters of the elementary aell are: a = 5 34; b = 7,03: г =

о 0 = 20,46 Aj /£­ 95 30'. The space group Is C2/m All Si atoms and 4 oxygen atoms are in the position of the usual state, the others are in particular positions. From the chemical analysis and the structure model offered for ericssonit the following crystallocheinical formulae may be written:

3+ (В0,РЫ2 ЛП4 Fe Si207 02{QHrF)2 2 = 2

'­® i-® J­O V­® 5­# Б­» l­o

Fig.: Projection of crystal structure of monoclinic ericssonit on the plane (Oyz)

3 1­0H, 2­Ba, 3~0,4­*tnf 5­Fe ,'6­Si, 7­7

Г0­ Khalilov A.D. About crystal structure of innelit and ioshumurait. Scientific notes of Azerbaijan State Univer­ sity; series geologo­geographical, 1967, N 4,82 ­ 93 ­ AN APPLICATION OP ELECTRON DENSITY MAPS FOR ANALYSIS OP Y ZEOLITE STATE IN ADSORPTION PROCESSES

S.D. Kirik» S.A. Dubkova, A.A. Dubkov, T.A. Vereahchagina, O.M. Sfaaronova, A.I. Kruglik, A.G. Anshits

Institute of Chemistry and Chemical Technology, Kirenaky Institute of Physios, USSR Academy of Sciences, 6&ООЭ6 Krasnoyarsk, USSR

To organize adsorption processes using zeolites one should conduct a wide research on a choice of optimal properties of ad­ sorbent апй conditions of process. These investigations' require direct structural information about the location of adsorbed and secondary species in zeolite cavltes. However, the obtaining of structural information is complicated by polycrystal form of zeolite samples. Rietveld's method does not appear to give sa­ tisfactory results in description of non­framework species due to their intensive thermal movement. In the present paper au­ thors communicate results on application of electron density maps, calculated on the basis of X­ray powder diffraction data, for searching a zeolite state. The X­ray powder diffraction da­ ta are processed with the aid of a system based on program /1/. In the first series of experiments we studied the process of dealumlnatlon of NaY zeolite by different reagents. The elec­ tron density maps gave the evidence of decrease of sodium con­ tent, the appearehce of non­framework species located at the center of sodalite cages. In 12­rings and in large cavities. Af­ ter washing with water and further calcination the zeolite loses seconder? particles from 12­rings and large cavities. In the se­ oond series the evolution of Y zeolite in multicycle adsorption of HC1 and SiHCl* was studied. In the third and fourth series the location of adsorbed SOg and HC1 molecules was determined. The data on location are in agreement with thermodeeorption da­ ta. Obtained rer *• /is prove that the use of electron density maps based on X­ray powder diffraction data is a reliable and conve­ nient technique for studies of zeolite state.

/1/ Kirik S.D., Borisov S.V., Pedorov V.E., J. Struct. Chem. 22, 130 (1981) ­ 94­ STRUCTURE AND PHASE TRANSITIONS IN COMPOUND 5Bi O­•3CdO. S.D.Kerek, V.A.Kutvitskly,_ L.S.Tsurgan, T.I.Koryagina Moscow Institute of Fine Chemical Engineering, Moscow USSR Institute of Chemistry and Chemical Technology,Siberian Branch of the USSR Academy of Sciences, Krasnoyarsk, USSR

The Bi.O,­based compounds rtraw more and more attention for reasons of their valuable physical properties. The r.'iipound 5Bi.Q_­3CdO is of interest primarily ав material which offers a substantial ionic conduction. The studies accomplished with the use of the high­temperature radiography method revealed that the high­temperature phase I of this compound is formed when it is produced from a melt and it is stable within the tempeiature range 973­923 K. It 1B easily hardened and it is rather stable {in metastable state) under normal conditions. This phase is character— о ized by a cubic body­centered cell, its parameter being 4.266A. The structure has two equivalent positions for iietal atoms filled statistically by Cd and Bi. Approximately three oxygen atoms fill statistically a 24­fold position on the cell faces. When slowly heated the phase I undergoes a transition resulting in its decomposition to initial components. In the ргосеьв of the transition some intermediate phases are formft. .\t the beginning a tyoical for the oh^re II rhombohedral "ill v. h par=uneters a=4,204 A, O6*9Q,44° is formed from phase l_ sequence of a cubic cell distortion along the 3»fold axis, ompanled by a reduction in the oxygen position multi­ i­ i .d the cell volume. This transition is reversible and the phase nay be again produce Troir­ tT,e phase II by means of a .­.*:oi.^dd annealing at temperature above 923 K. A subseguent dis­ tortion of the initial cubic cell causes a shift of the metal atom position from the centre along the 3­fold 'and a differentia­ tion of the positions (0,0,0) and (X,X,X) to be filled by Cd and Bi atoms. As a result, a new phase III is formed with its rhombo­ ° о hedral cell having parameters a=4,132 A. and o6393,63 . The phase TTI IR formed from the ph ise II at 913 К and on subsequent cooling it undergoes a transition resulting in the formation of sillenite chase. This is confirmed by the results of nmgnetochemical investi­ gations. ^95­ ARTIFICIAL SINGLE CRYSTALS AND THEIR IMPORTANCE FOR SCIENTIFIC AND TECHNICAL PROGRESS

E. Kirkova Institute of H4.gh Purity Substances, Faculty of Chemistry» University of Sofia, 1, A. Ivanov Ave., Sofia 1126, Bulgaria

All modern technological applications require man­made single crystals, most of "*vich are not to be found in the natu­ ral state. The paper contain с data on the preparation, properties and importance of: artificial single crystals for semiconductor industry, quantum electronics, optoelectronics, aeouatoolectro­ niC3 and emission electronics; optiaal single crystals and scin­ tillators; plezo­, ferro­ and pyroelectric single crystals; so­ lid electrolytes and shaped hijjh­temperature crystals. Single crystals and ceramic materials for eleotronics and for applica­ tion as high­temperature superconductors are also considered. ­ 96 ­ SYKTHESIS AKD X­RAY STUDY OP DOUBLE SODIUM MOLYBDATES OF POTASSIUM, RUBIDIUM AND CAESIUM P.V. KlevtBOY, A.P. Perepelitea*, V.H. Iehohenko* L.A. Glinskaja, Я.Р. Klevtaova Inst. Inorganic Chera. USSR Acad.Sci.Siberian Branch,Novoe 'rsk, * Kiev Pood Industry Technology Institute, Kiev, USSR

+ + M Ka3(I.IoO .)2­9H20 (M­K,Rb) and M MaMo04­2Н20{М.НЪ,Св) , ngle crystals have been grown at 20°C by water solution volatilization. The dehydratstion mechanism of the compounds and chemical reacti­ ons on heating up to 500°C were etudied by high temperature powder diffraction method. Crystal structures of the RbHaj(Mo04>2.9H, '(I) and CsHaMoO..2H20{II) double molybdates have been solved. Both the I end II structures are constructed by Mo­tetrahedra and Ne­oct..­ hedra forming the discrete [jfajOgdijO^]1" groups In I and the _.­ finite fBaO,l'~ columns in II. The letters combined with Rb(Os)­ polyhedra form three­dimensional framework. The H­bond system is analysed in detail. Rubidium compounds decompose on heating as:

RbNa3(Mo04)2­9K20 ­»­RbKaMo04.2H20 + HagMoO^HgO + 5H2ot,

Rb»aMo04.2H20 ­»P.b1+xM»1_][Mo04(III) + 0.5*­HajHo04 + 2H2oT(x^O), forming mixtures of phase III of the glaserite type structure and HaJiloO. of the spinel structure. On heating anhydrous decomposi­ tion producte enter into chemical interaction, and at temperature

+ + ^400°C Blngle phases are foiroed: M Na3(Mo04)2 and M HaMo04 as solid solutions of the glaserite structure (for M « K, Rb>, and

СвНвЛо04 crystallizing in the arkanite <£­ KgSO.) type structure. On cooling the solid solutions are slowly decomposed. The main crystal data are given in the Table.

Z d Compound Sp.gr. аД ь.Х сД x

KNa3(Mo04)2.9H20 P6,/m 9.52 12.10 2 1.89 RbNa (Mo0 ) ­9H 0 3 4 2 2 ­"­ 9.648 12.157 2 1.97

RbNaMo04­2H20 P222 6.304 8.507 13.31 4 2.82 CsNaMo0 ­2H 0 M 4 2 —— 6.379 8.625 13.671 4 3.12

KMa3(«o04)2 P3m1 5.9 7.2 1 2.99 RbHnJ.Io0 4 ­"­ 6.05 7.67 2 3.35 CnNaH'oU Pmcn 6.31 11.13 8.16 4 3.67 ­ 97 ­ SYNTHESIS AND CRYSTAL STRUCTURES OF DOUBLE MOLYBDATES

2+ K4M (Uo04)3> И ­ Со, Mg, Mn, fld

P.V. Klevtsov, S.P. Solodovnikov. L.A. Glinskaja, R.P. Klevtsova Institute of Inorganic Chemistry, USSR Academy of Sciences, Siberian Branch, Novosibirsk, USSR

The double molybdatee were synthesized from 2KgMoO.+M MoO^ by solid state reactions, complex character of chemical interac­ tions in theee systems WBS found. The single crystals were ob­ tained by spontaneous flux crystallization on slow cooling (2­3 pxad/h) with К^Мо^О­т as a solvent. Products of the syntheelB were Investigated by X­ray and DTA methods. The crystal structure of K.MnCMoO^), (I) (R ­ 0.033) was found to be analogous to the structure of triclinic ^­K.ZnCHO^K /1/, but distinguished by both the coordination of Mn (CK ­ 5+1i a distorted octahedron) versus Zn (CI? « 4+1; a distorted trigonal bipyramid) and polyhedral sharing: in ^­K.Zn("0.K ZnOc­polyhed­ ra are isolated, but in 1 MnOg­octahedra are linked by common edges in pairs. The double molybdates with M • Co, Mg, Cd crystallize in the same structural type. In addition, K.Co(MoO,), at ~ 500°C trans­ forms into the phase with structure of K.ZnCHoO^K type /21, The compound with Mg at 530°C is decomposed to give KgMgtHoO, )2 and KgHoO.. The cryetallographic characteristics of К.И (MoO.), are presented in the Table.

M Phase Sp.gr. Cell parameters • Z a,A b,A c,A Kfi, Г «•> Co o~ PT 9.912 9.963 7.67T 106.5; 106.0; 92.8 2 (5 5.966 10.35 22.63 ­ 2 «e A. PT 9.929 9.972 7.679 106.4; 106.2; 93.2 2 Mn * PT 9.955 10.156 7.613 106.7; 105.6; 92.3 2

/1/ Qevtaora R.P., Ivmnnikovm X.V., Klevtsov F.T. Iriatalloeraphija, 2±, 957 (1979). /2/ Glcquel­Hsyer C., Mayer M., Per» O. Rev. onlm. Klner., ^7. •45 (1980).

I3­I ­ 98 ­ SYNTHESIS AND X­RAY STUDY OP DOUBLE MOLYBDATBS 2+ Hb2M (Mo04)2„ M . !ii, Co, Mg

R.F. Klavtaova. L.A. Olinskaja, S.F. Solodovnikov, P.V.Klevtaov Institute of Inorganic Chemistry, the USSR Academy of Sciences, Siberian Branch, Novosibirsk, USSR

The double molybdates RbjM^MoO. )2 (M . Hi, Co, Mg) were + synthesized from Rb2Mo0.+M MoO. by sintering at 450­550°C. Ac­ cording to X­ray data those are crystallised in structure type of KgNlCMoO,),, /1/. x­he compounds melt incongruently. It Has 6 0 С found that Rb2Ni(Mo04)2 ? ° н. Hb2Mog07 (liq.) + N10 (Sol.). Single orystals of the rubidium nickel molybdate were obtai­

ned from solution In melted Rb2Mo20,_ by spontaneous crystalliza­ tion on cooling (2­3 grad/h) from бго­бЗС'С to 400°C. As solutes both single phase powders of the double molybdates and mixtures of the component oxides were used.

X­ray structure analysis of Rb2Nl(MoO.)2 crystal (."Syntex K,", MolU ­radiation, 1373 P(hkl), R­0.061) was carried out. The characteristic details of the structure, as in the K­analo­ gue, are pairs of edge­charing Ni­ootahedra forming through com­ mon vertices with Mo­tetrahedra the layers parallel to (010). Linkage of the layers are realized by two sorts of Pb­polyhedra (distorted octahedra and edge­centered octahedra). Th­» layer character of the structure explains plate habitus of the crys­ tals and presence of cleavage plane. Cryatallographic characte­ ristics of the coumpouns studied are presented In the Table.

M Sp.gr. Cell parameters. д г м р >0(; „/2ДЗ a, A b,A c,A

(fl Сиоа 8.568 19­552 10.884 8 650 228 Co " 8.65 19.58 10.94 8 550 232 Mg » 8.65 19­60 11.07 8 690 234

Polymorphism of the oompounde wae not found.

/1/ Klevtsova R.P., itlevtsov P.V. Kristallografija, 23, 261 (1978) ­ 99 ­ THE INFLUENCE OF MECHANICAL­ AND THERMAL TREATMENT ON THE STRUCTURE OF GIBBSITE POWDER U,Kretaachmari, U. Stelnikei ,E. Schierhornj , U .Bol lmarmz 1 Zentralinetitut f Phyeikalische Chemie der Akademie der Wiaeenschaften der DDR,1199 Berlin.DDR 2 Technische Hochschule "Carl Schorlemmer'Leuna Merse­ burg,4200 Merseburg.DDR

Gibbeite AL(OH)* was mechanically treated in э vibration mill and in a tube­vibration­raJ11. After mechanical treatment a thermal decomposition was carried out in a very short time (0.26/500 O.The thermal treatment produced low temperature А120э modifications. The products are nearly X­ray amorphous,Therefore we estimated the short order range of mechanically distorted and heated substances by means of X­ray wide angle diffraction and the external habit of powder by electron microscopy­The results are compared with AI2O3 modifi­ cations produced by heating of «ibbeite for 6hrs in an excess of liquid water at 250CC in an autoclave by heating of boehmlte for 5hrs at 500DC and во on. The interpretation of evaluated differential radial distri­ bution functions allowed ue to conclude that a strongly disordered А1?0з modification is achieved by means of intensive mechanical and thermal treatment(fig). The external habit of the powder results from the conditions of manufacture and is not changed by thermal treatment 1<­> 2<.> DW'Ur) [lOeJVnm]

0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8

Differential radial distribution function 1 ­ Qlbbelta/ehr autoclave 250oC 2 ­ Qlbb(ita/0.5hr vibration аЧШО.га 500°С

13­2 100 ­

1. Inst­ of Low Temp, and Structure Research PASci Wroclaw, POLAND 2. Inst, of Physics, JsDielIonian Univ. Cracow. POLAND 3. Dept, of Physics Univ. af Waterloo, Ontario, CANAOP *t. "J.Stefan" Inst, and Dept. of Metallurgy, Ljubljana University, YUGOSLAVIA

N в were r X­ray data (20365 intensities) for the Та. 72 bc уЛ^ Ц ecorded at Я.Т. using PW 1100 diffTactometer and MoKc radiation. After averaging (2.5c limit), 153*+ reflections were taken. MSRLSQ program, version C, have been used. Absorp­ tion and extinction corrections were applied. The basic structure has been refined to R­0.065 or 0.063 wit a = 6.512(3)8, с = 6.8l8(5)8 and pit/mcc or P

(1) Btthm, H.. vrn Schnering, H.G., 2. Krlstallogr. 4 71. 41­64 (1985) (2) Bronsema, 0., van Smaalen, S., de Boer, J.L., Wlegers, G.A., Jet IInek, F. and Mahy, j.,.Acta Cryst. W*, 305­313 (1987) (3) Budkowskl, A., Prodan, A., Kucharczyk, 0., Uszynski, l., Marinkovic, V., Boswell, F.U., submitted to Acta Cryst. В (1989)­ ­ 101 ­

CHARACTERIZATION OF CONTINUOUS SERIES OF SUPERSTRUCTURES IN M2.xX3

AND (M,Ge)2+uX3 (M = Bi.Sb ; X = Se.Te) ­ S.Kuvpers. N.Frangis*. J. Van Landuyi and S.Amelinckx University of Ancwcrp (RUCA), Groenenborgerlaan 17 1, B­2020 Antwcrpen . BELGIUM. University of Thessaloniki. GR­54006 Thessalonilci, GREECE .

Electron diffraction and high resolution imaging T*chniqucs were used to characterize continuous series of superstructures built from two types of lamellae with different thicknesses. The electror. diffraction patterns were analysed with (he fractional shift method /1/ and e method PJclosely related to the "cut and projection" method introduced by Kacz and Ouneau /3/. The application of [hi:

modified "cut and projection" method to mixed layer poiyiypes :n ihe high­Tc superconduc:or Tl2Ba2Ca,iCun+i02n+6 can be found in /4/. The isostructural compounds В1г5ез , Bi:.Te3 and ЭЬгТез consist of 5­layer lamellfte M2X3 perpendicular to the hexagonal c­axis and separated by Van der Waals gaps. The presence of excess meial atoms is known to lead to the formation of superstructures (see for example ftf). The exact nature of these superstructures was still uncertain, however. We carried out an extensive study of compounds of the tide systems. In «11 the systems similar electron diffraction patterns were observed . In the [hk .0] zone patterns, apart from basic spots, superstructure spots were present. These spots divide the distance between two intense basic spots (g­0.5 A­1 ) «Jong 0001 in 5n+7m intervals (n,m integers). Application of the fractional shift method to the commensurate spci sequences, with the M2X3 spot pattern as the basic pattern . suggests the existence of 7­layer lamellae , presumably with composition MgX* or M^GeX* depending on the system under consideration . The superstructures are therefore assumed to be built from 5­ and 7­layer lamellae. This assumpiiin is supported by {high resolution) structure imiges.Given the q­value of the experimental diffraction pattern . the stacking sequence of these lamellae for a particular superstructure can be derived with the modified "cut and projection" method For die quasi­commensurate patterns the q­value (i.e. the distance between a superstructure spot and the basic spot from which it is derived) has to be approximated by a rational value and thus (he deduced sequence of 5­ and 7­layer lamellae will only be approximate. However . the theoretical diffraction patterns due to the deduced sacking sequences are in quite good agreement with 'he experimental diffraction patterns.

/1/ Van Landuyt J.,De Ridder R.,Gevers R. and Amelinckx S., Mat.Res.Bu!l. £353 (1970). Щ Frangis N.,Kuypers S.,Manolikas C.VanTjnduyt J. and Amelinckx S.. Sol.State Comm. fi9_.8 (1989). /3/ Katz A. and Duneiu M.. J.Physique 4J.181 (1986). /4/ Verwerfi M.Van Tendeloo G. and Amelindcx S., Physic* С Л&607 (1988) /5/ Brebrick R.F., The Chemistry of Extended Defects in Non­Metallic Solids, Eds. Eyring and O'Keeffe,! 83, North Holland Publishing Company (1970). ­ 108 ­

NEW STRUCTURE TYPES Ho0Ni1bBb, Ho2Nl15Bg AND Md^Ni­yP,,. Yu.B.Kuz'ma. S.V.Orisnohin, T.Glcvyak, I.B.Oubich, N.F.Cbaban, S.I.Chikhrij I.Pranko State University, Lvov, USSR

The crystal structure*of new compounds have been determined from single crystal X­ray data. The compound Ho^Ni­jcB^ is monoclinic with space group P2j/c and a . 14,223(7), » . 10,672(5), с ­ 9,582(4) А, В . 94,23(5)°, Z . 6. It is refined to an R value of 0,047 for 1575 reflections. Ho atome have the coordination number (CN) 16 and 20, Ni atoms ­

14s 13, 12 and 11, В atoms ­ 10 and 9, The coordination polyhedra for В atoms is tetragonal prism, some В atoms ( B8 and B9 ) are connected to each other and form Bo pairs. The new compound*: Inj­NiicBc (1л ­ X, Dy) have the HOgNi­jcB­^­type structure. The structure of HOgNi­icBq is orthorombic with space group Cmca and a . 16,001(4), b . 11,656(3), с . 11,323(3) A and z . 8. It is refined to R ­ 0,041 for 783 reflections. The ONs for Ho atoms are 18 and 20, for Hi atoms ­ 16, 14 and 13.The environment of B5 atomB is dietored archemedian cube with additional Ho and Hi atoms (CM 10), other В atoms have a trigonalsprismatic coordi­ nation. B1 atoms are isolated, all other в atoms form Bo pairs. The new compounds In^Ni^cBq (In ­ Y, Tb, Dy, Er, Tm, Yb, Lu) with HOoNi.cBg­type structure are obtained* The compound NdjRi^Pc crystallizes in hexagonal Pgj/m space group with the oell constants­ 8­16,679(8), 0.3,891(1) л, Z.6. It mm refined to R * 0,061 for 205 reflections.The structure belongs to the i'r.iily of flat tworlayers structures, which are formed by

compoeiit n blooks with general formula Нш^^ш­И^д»2)тд^ш+1 ) (R ­ the largest atoma, H ­ tnbdium atoms, X ­ the smallest atons, • ­ integer positive number). Tbs environment of the p atoms is a trigonal prism of metal aton»« The nsw compounds 1л­.Н1­,Рс (ui ­ la, Pr, SB, 04, Tb) with Rd^nifP­j­t­rp* structure «re obtained. The special features of these structureв „nd their relations with other structure types are dlaouesed. ­ J03 ­ SEARCH FOR A FRAGMENT WITH KNOWN GEOMETRY IN POWDER DIFFRACTION

W. Laaooha, Л. Lasocha Faculty of ChemiBtry, Jagiellonlan University, 30­060 Cr&cow, Poland

Many authors have recently tried to solve crystal struc­ tures,, using X­ray powder diffraction data. Typical procedure is as follows: phase problem is solved by Patterson or direct me­ thod, then a trial structure is refined by the Rietvelu proce­ dure or by programs typical of single crystal methods using in­ tegrated intensities. Due to email number of unique indexed re­ flections the interpretation of Patterson map as well as direat method attempts very often fail. For any substance, however, some chemical information le available,, and such Information could be useful for structure determination by the localisation of known fragment in an elementary cell. Such approaoh ia not still commonly used in powder diffraction /1/, The possibility of using PATSEE program (Program for Fragment Search by Integra­ ted Patterson and Direot btethod /2/) with powder X­ray data was tested by ue. We thought that the search for a "known fragment" could be very useful for the following problemsi ­ partial or complete structure solution, distinction between possible "known fragments"; ­ solution ot the structures being a result of phase transi­ tion, where only rearrangement of coordination polyhedra takes place. Results of our teats for some inorganic hydrates applied for above problems, with a discussion of peraiited intensity er­ rors in powder data, will be presented.

/1/ Rius J.t Miravitllee C., J­ Appl, Cryst. 2J,S 224 (19BB) /2/ Egert E., Sheldrlok G.M.,­Aota Cryst., A4J., 262 (19B5) - 104 - MODULATED CRYSTALS OF NH,Br.4 (TRlOVRBAl (R= -3 pr -Cfa)

D.C.Levendis and EFerg Structural Chemistry Unit, Department of Chemistry, University of the Witwatersrand, Johannesburg, South Africa.

Ionic crystals of thiourea (tu) frequently occur as MX 4(tu) where M = monovalent cation, X = halide in the tetragonal space group P4/mnc (Boeyens, Acta Cryst (1970)B26, 12S1) Crystals of NHjRBr 4(tu) undergo an interesting modulation when grown from the melt The diffraction pattern is characterised by six strong satellites around each Bragg reflection- The a'^erage tetragonal structure (R=H) has a = 2fl.5lA, с я 8.33А\ The modulated structure can be approximated by a tetragonal super cell; a' = 5 x (a + 2b) = 230A and с' = с The modulations appear to involve only shifts of the Br" ions in three independent directJDO^indicated below .

(001) projection oflhe average NB(Br.4(tu) structure showing the direction of Br' shifts. 106 ­ THE PACKING ANALOGUE OF APATITE J. Lima­de­Faria Centro de Cristalografia e Mineralogia, Instituto de Investigacao. Cientifica Tropical, Alameda D. Afonso Henriques, 4l~49 E, 1000 Lisboa, Portugal

The structural formula /1/ of apatite may be written Ca^ P. [о., (OH, F) , where p means trigonal prismatic coordination, t tetrahedral coordination, and л/Ts a puckered simple hexagonal packing. The ideal packing analogue, corres­ Ts ponds to the structural formula­ Ca? P^ [oi2 (OH, F)~\ , where Ts means simple hexagonal packing. The topologies of the

packing analogue and of the real structure are not the same: and therefore the ideal structure is an improper packing analogue /2 / . A simple mechanism can be imagined, based on the phos­ phorus requirement of tetrahedral coordination and on stabi­ lity principles /2/ , which transforms the packing analogue into the real structure (see e.g. /j/ and /4/) with higher symmetry /5/ and denser packing than the packing analogue. The corresponding condensed model /6/ of the packing analogue is built of the layers 1) and 2) stacked alternately.

/1/ Lisia­de­Faria, J. and Figueiredo, M.O. , J. Solid State Chenistry, ^6, 7­20 (197^'. /2/ Lima­de­Faria, J,, Garcia de Orta ­ Serie de Geologia (in publication). /3/ Wyckoff, W.G., Crystal structures, Vol. 3, John Willey, New York, 228­231 (1965). /4/ Povarennykh, A.S., Crystal Chemical Classification of Minerals, Vol. 2, Plenum Press, New York, 54^­542 (1972;. /S/ Lima­de­Faria, J., Zeit. Krist., 18^, 28f, (19Ш /6/ Lima­de­Faria, J., Zeit. Krist., _12^, 346­358 < I965) •

I4­I ­ 106 ­ ШЕ XTRAY ANALYSIS OF ISOMORPHISM IN Щ АВЧ : M­CKYSTALS V.A. Liopq, V.V. Voyna Grodno State University, Grodno, USSR

The natural and artificial ABX,­crystals have in most cases the structure of the perovskite type with cubic, pseudocubic, tetragonal and rhombohedral lattices. The active laser media, optically active crystals, :d the high temperature superconduc­ tors may be obtained hy doping some atoms in these АЯХ,­crystals. The determination of the doping atoms and their localisation in the matrix: of the basic structure is necessary both for the optimiza­ tion of the growth crystal technology and for understanding the physical processes in these media. The method of determination of the doping atom localisations is elaborated. This method consists in X­ray powder analysis of the crystals witli different concentra­ tions of the doping atoms. The method was used to investigate KZnF,:Cr­crystals. It is determined that the chromium atoms substitute the zinc atoms. The formed structure is characterised by statistical dis­ tribution of the chromium atoms, and the zinc atoms, and the vacancies. When the chromium concentration is more than 0,05 ics valence changes from +3 to t­2. The quantity of Cr is у rowing with the increase of the concentration of dopina chromium ar.oms. The crystal as a whole has neutral electrical charge. The results of X­ray investigations correlate with the measured relations of intensity of X­ray reflexes with different evenness of their crystallographic indexes, and with dispersion of the parameter distribution, and with the experimental, picnometrical density of these crystals. The chromium concentrations varying from 0,03 to 10,Ot [l].The investigations show that this method ma^ be used for the determination of the doping atom localizations in the structu­ re of other cubic crystals too [2].

/1/ Liopo V.A., Voyna V.V. et al. Dep.VINITI N T942­V83. Tomsk. USSR (1988) . /2/ Chabarov E.N., Leonov Е.1., Liopo V.A. Coll. Abstr.X­th Europ. Crystallogr. Meet. Poland 3D­06 П9Э6). ^ 107 ­ VARIATIONS IN THE REAL STRUCTURAL FEATURES OP PALYGORSKITES

T.Z. Lygina, A.P. Zhukhlistov* Ail­Union Geological Institute of Industrial Minerals,Kazan •Institute of Ore Deposit Geology, Petrography, Mineralogy and Geochemistry, USSR Academy of Sciences, Moscow, USSR

The use of oblique­texture electron diffraction patterns permitted to reveal a number of new detailed characteristics for different samples of palygorskite» Two polytypes, 33.33 and 33.66 /1/ characterized by normal

v z v projectiona a & n» n °^ ^ a­azr'i on the bc­plane: 0, ­2/3 t 0, 1/3 ), symmetry C2/m (or I2/m), and C,0 , symmetry Pbmn, have been identified under study of nearly 400 palygorakites of different origin. The monoclinic 33­33 polytype is more wide­ spread being found as a single phase or in mlxtura with the or­ thogonal 33­66 polytype. The latter lias been mei only once аз а single phase. It should be noted that the fl angle usually ex­ ceeds the ideal 8id=105.6° defined by the relation ­acosfl/c =

­zn=*2/3; the maximal values of в and ­zn С 108.2° and 0.780 ) being characteristic for the pure polytype and less ones ( 107.3° and 0.745) ­ in the case of polytype mixture. Due to substitution of Al3+ (sometimes Pe^+) for some Mg octahedral vacancies are appeared. The comparison of experimen­ 2 tal am calculated F ­values has revealed differences in the distribution of octahedral cations for both polytypes. In the structure 33.33 the cations occupy mainly the cis­octahedra. In the structure 33.66 the occupancies of cis­ and trans­octahedra are 3/4 anc1 1 respectively. The nearly uniform distribution of octahedral cations in 33­66 polytypes and displacements of the 2:1­rods along the c­axis resulting in an Increase of the В angle in 33­33 polytype, apparently decrease the repulsion of cations overlapping in the normal projection on the bc­plane stabilizing thus the respective structures­

/i/ Zvyagin B.B. and Lygina T, Z. Abstr. 14th IMA Gen. Meeting, Stanford, Cali., USA, 284 (1986)

14­2 ­ юв ­ PHASE IDHKTIFICATIO* OP EIDXBT 5T0IBS AID THBIB SOLUBILITY II UGIBTICAI.LT TKBATBD VATBB

•T, ^.. ^u­tngi^ycirfi­Rpgqy, A.Olchawska, S. A. Hodorowlcz Faculty of Chenlstry, Jagiellonian University Krakow, Poland

Studies described here were performed in two following steps. At first the phase determination and characteristic of investigated stones were carried nut using the infrared spectroscopy and X­ray powder diffraction as conplemantary Methods /1/. The substances identified are: calclun aKalata aonohydrate, calcius. oxalate dl hydrate, uric acid sonahydrate, uric acid dlhydrate, hydroxyapatlte and carbonataapatlte. Then redistilled, Magnetically treated water was taken as a solvent for the powdered kidney stones and, Independently, for their pure conponents. Various intensities of aagnetlc field within the rang* of 0.1 to 5.0 kOe were applied for «agnatic treatsent of water. The changes in solubility were Mrvured by CDnductoeetry. The results obtained will be presented and discussed.

/1/ Schneider H.J., ­Urolithiasis ­ Etiology. Diagnosis.", Berlin, Springer ­ Verlag (1065). ­ 109­ STRUOTTJKB AND THERMAL DEHYDRATION OP LITHIUM­SOIIUM MOLYBDATE DEHYDRATE ЫНаМоО^гНдО

D.D.UakitovB. V.V.Tkachev, L.O.Atovmyan, R.S.Hiraoev, Z.G.Karov Kabardino­Balkar State University, Nal'chik, USSR; Institute of Chemical Physics., USSR Aoad.Sci. ,Chernogolovka,USSR

Compound LiHaMoO,­2HgO (I) obtained in the system Li„MoO. ­ HagKoO ­ HjO at 25°C has been investigated by methods of X­ray structural and thermal analysis. Crystals (I) belong to orthorhombic crystal system with the following lattice parameters: а в 6.219(1), Ь = 10.372(2), с = 13.277(3) A, Sbca, Z=8, d=2.64 g/cm3. The basis of the crystal structure of island type is formed by MoO. anions with a mean Mo­0 bond length of 1.768 A as well * о as Li and Ha cations. Mean values of Ы­0 and Ha­0 are 2.10 A о and 2,41 A, respectively. Two crystallographically independent water moleculeR form hydrogen bonds with oxo­anions whose values are within the range of 2.74­2.86 A. We have found that compound (I) is i30structural to Na.,MoO. hydrate. The two. structures have been compared. In (1) Li atom occupies the position of a sodium atom in (2), whose coordination polyhedron is a trigonal bipjrramid. It should be noted that despite the essential differences between the ionic radii of Ka and Li atoms, such replacement keeps the coordi­ nation of trigteial bipyramid for the latter one. The influence of this replacement on geometric parameters of the hydrogen bonds has been considered. LiHaMoO.­2HgO dehydratee at Ho­IBCC during one stage, with the formation of Li„Mo0. and Ha„HoO.. ­ по ­

SYNTHESIS AND CRYSTAL STRUCTURE OF Pt>2 (VO,) (ReO,) J. Насiсек. Т. Todorov Institute of Applied Mineralogy, Bulgarian Academy of Sciences Sofia, Bulgaria

Crystals of the title compound неге obtained from a

Po3(V04)2 ­ Po(Re04>2 quasibinary system and investigated on a CAD4SBP44 diffractometer.

Crystal data: Hr » 779.52, space group P2(/c, a ­ 9.205(1), b ­ 7.492U), С ­ 11.074(1)*, В • 90.96(1)°, V ­ 763.6(2>Д3, i Z ­ 4, 0x ­ B.77Bg.cm"' , p(Mo> = В1.45тт"'; R = 0.03S for 2004 reflections Hith 1 > 2a(l>. The structure is built up from discrete VO and RsO tetrahedra linked together Hith two types of crystallographi­ cally different Pb atoms. The V and Re atoms are arranged in alternating ­v­Re­V­ layers parallel to (100). The V­O/Re­D bond lengths are within !.712(13)­!.739(12)71.727(13)­!.749(17)*. Pb2/Pb2 have eleven/ten oxygen neighbours in a sphere of 4A radius. РЫ is coordinated by seven close 12.33­2.903 (predomi­ nantly one­3lded) and three more distant C3.2B­3.43A] 0 atoms. The eleventh D atom CPb2...0 3.76(1)1 lies farther than the central atom of the relevant V04­group [Pb...V 3.629(2)*] and thus ие exclude it from the coordination surrounding of Pb2. The coordination polyhedron of Pb2 is more regular Hith eight 0 neighbours Hithin 2.42­3.00 and tHO others at 3.51 and 3.70*. ­ ш ­ CRYSTAL CHEMISTRY Of RARE EARTH HITRATES WITH MOHOVALEHT CATIONS Yu.A.llalinovaky. A.G.Vigdorchik Institute of Crystallography, USSR Acad.Sci., Moscow, USSR The analysis of crystal­chemical structural characteristics of alkali rare earth nitrates haa been carried out on the basis of our experimental data and the data reported in the literature. The study dealt with individual peculiarities of Ln­complexes of alkali nitrates and the influence of the nature of alkali metals on the structure of In­containing complex anion. Coordination polyhedra of rare earth elements which account for the main pro­ perties of the appropriate compounds were considered. The follow­ ing compounds:Rb2[la(NO,)5(H20)2]­ Cs2[La(BOj)5(HgO)2] ,

NagLFrOKy^.HjO, KgCudtNOOjtHjO)^, Ha2[Nd(NOj)^HjO , K^HdgOKUg], RbjNdjtNOj^J­HgO, Rb^Nd^lftyg], CsLNdOro^CHgO),] .Ca^IdOJOjJjCHjOjjJ, KjOdOJO^O^O)^

K[Tb(NO3)4(H2O)2];0s[Dy(NO3)4CH2O)2i­H2O,Rb[Tm(HO3).(H2O)2>H20 were investigated by X­ray structure analysis. Ыг+ ions play the key part in the construction of coordination arrangement. Co­ ordination numbers of In atoms in all the cases are 10 and 12. Only four typos of coordination polyhedra were found for all the studied compounds. An atom of rare earth element tends to form symmetric coordination arrangement even in case when bn^+ions occupy acentric positions. Alkali cations are less responsible for the structure formation although the structures of Ln­comp­ lexes with a similar stoichiometry are different, depending on the individual peculiarities of a monovalent cation. Three types of the coordination of Ln atoms by nitrate groups were found! unldentate (found for the first time), symmetric bidentate and symmetric bridge bidentate( met in compounds without water mole­ cules in the coordination sphere of a complex­forming ion). Ac­ cording to condensation degree of la­complexes the compounds can be divided Into mononuclear, binuclear, chain and framework. In all the investigated structures water plays an important role in saturating coordinatlonally Ln ions and forming additional con­ tacts by means of hydrogen bonds. ­ П2­ CRYST ALCHEMICAL PROPERTIES OF PERITECTIC COMPOUNDS Kh.S. Mamedov , I,B. Bakhtiyarov Institute of Inorganic and Physical Chemistry Academy of Sciences of the Azerbaijan, Baku, USSR

The problems of the structural verification peritectic reac­ tions are discussed. The crystaLachemical properties of a j^umber of such reactions \j\~\ were analysed and it was established that peritectic compounds are characterized by the structure of a derived type, i.e., the structure of a peritactic compound and solid product of its destruction are related by ordinary alterna­ tive reconstruction schemes. The reverse appears to be wrong, i.e., the existence ofAderived structure is necessary but not sufficient for being a peritectic compound. Another very important criterion is the action of a cooperative mechanism that facilitates the transition between peritectic compounds and the products of their decomposition. Since the relation to a peritectic reaction indi­ cates the structural analogy of a peritectic compound and the product of solid decomposition, the structure known for one of them can be used for the prediction other structure. Solid solutions are decomposed according to the peritectic reaction, i.e., they form a solid solution of a simpler composi­ tion and a liquid, reversibly. Thus, every point of the solidus is a peritectic one. This stipulates some resemblance between solid solutions and peritectic compounds. Teritectic reactions ate vOi.y ^Oiuising frcn ths stand (.Joint of synthesizing compounds with a given structure.

[f]. Mamedov Th.S., Bakhtiyarov I.B. Preprint N2, IPhAN, 19S8, 57 p. ­ 113 ­ THE STRUCTURE AHAUSIS OF INOTROPIC CUBIC PHftSES

P.Hariani , V.Luzzati » H.Delacroix Istitutc di Flsica Medica, Un1vars1ta di Ancona ­ Italy Centre de Genetique Moleculaire, CNRS, Gif­sur­Yvette ­ France

He report the structure determination of all the six cubic phases, so far observed, as obtained by using a novel "pattern recognition approach" which leads directly from the X­ray scatte­ ring experiments to the electron density distribution maps. This approach consists of generating all ihe sets of phase angles compa tible with the observed reflections and of screenning them in a search for the "best" one: the two criteria used for screening be described and its validity verified by considering numerous examples. We use here tSe notation adopted in the Luzzati's group based upon the letter Q and a superscript specifyng the namber of the cor­ responding space group of the International Tables of Crystallogra­ 230 22й ^2S pny; the structure of Q , Q and Q cubic phases can be de­ scribed in terms of two three­dimensional networks of connected rods, joined respectively three by three» four by four and six by 212 six mutually intertwined and unconnected. The structure cf Q 227 230 and Q cubic phase are related to those of respectively 0 3nd 224 Q : one of the tvto network of rods is preserved, the other is re­ 223 placed by a lattice of closed micelles. The structure of 0 consists of a cage­like continuous three­dimensional network of co£ nectcc1 reds (or globules), coplanarly joined three by three at one end and four by four at the other, enclosing a three­dimensional lattice of closed micelles.

I5­I - 114 > HIGH*TEHPBRATURE X-RAY STUDY 0? DIPPEREHT METAMICTISATION DEGREE NATURAL ZIRCOHS A.V.maslanikov. V.B.Trofimov Institute of Preoambrian Geology and Geoohronology USSR Aoademy o- SolenoeS; Leningrad State University, Leningrad, USSR

The natural zircon samples with various metamiotieation are used by high-temperature X-ray powder diffraction method in the range 20o-1000°0 by step of 200°C. The heating velosity Is 15°/mln, the samples annealing time inoluding the X-ray experiment time is 1,5 hrs at every step. The obtained experimental data sho* that the struoture vari• ation pattern by heating essentially depends on the ideality de• gree of an initial sample» The ualt oell parameters lnorease by heating of the crystalline samples due to thermal expansion Is ob• served. The unit.oell temperature dependence for semlmetamiot samples is sore aomplioatedo The observed variations are oonneoted on the one hand with the thermal expansion (henoe with the unlt- oell parameters lnoreaee), and on the other» nlth struoture resto• ration by heating (unit oell parameters deorease). The beginning recryatalliiatios temperature la in the range 400°-600°C. In some oases this prooeas begins aimultanloualy «1th heating» It may be connected with the stability degree of alroon metaaiet phase, that is dependent, for example, on Its nature. ­ ПБ ­ STRUCTURE REFINEMENT OP MICROTUIN CRYSTAXS Of Na­BpSiO, AT 295 AHD 573 К B.A.Maximov­. M.I.Sirota Institute of Oryatallography, USSR Acad.Sci., UOBCOW. USSR

The structure of orthorhombic Ha.­.BeSiO. crystals has been determined, sp.gr. D'г­=РЪ2.а, and refined up to R=0.049, R,,, ­ «0.053 at 295 X and R = 0.046 , R,^ * 0.034 at 573 K. Silicon and berillium atoms occupy oxygen tetrahedra forming the frame­ work of the cristobalite type. The voids of the tetrahedral fra­ mework are occupied by sodium atoms. The studied crystals are pseudomerohedral twins. There are aix twinning partners. Relative twin volumes are approximately equal. Differently oriented unit cells are related by both pseu­ dotetragonal and pBeudohexagonal laws. The unit cells of pseudo­ hexagonal twine are rotated by 120" about (210] direction with respect to one another. The unit cells of peeudotetragonal twins are rotated hy go" about loioj direction with respect to one ­ another. At room temperature (295 X) unit cell parameters of a twin domain arei a . 9.861(2), b ­ 13.873(2), с ­ 4.911(2) X.

Twin lattice parameters aret atwln ­ 13.898(3), btwin •

­ 13.900(3), ctwln­ 13.886D) A, JL • p ­ % - 90». The character of twinning and relative twin volumes are not changed in the temperature range 295 ­ 573 K. At high temperatu­ res a considerable increase in thermal motion amplitudes for some sodium atoms is observed. Structural parameters were refined in anisotropic approxi­ mation using mCRYS program.

15­8 116 DEPENDENCE OP SITE DISTRIBUTIOSTRIBUT; N OP Fe2+" AND Mg IN NATURAL

OLIVINES ОИ Рл AMD T

S.3. Heahalkin, N.B. Khlslna. V.S. Uruaov Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences, Moscow, USSR

Our X­ray single crystal diffraction results and the avai­ lable literature data on Fe and Mg distribution over Ml and M2 sitea in natural olivines (Mg,Fe)2SiO. shows only a slight devi­ ation from the statist leal distribution. However, K~ values

(KD « Fe(M1) Kg(M2)/Fe(M2) Me(M1)) may be greater as «all as lese than 1. In natural olivines KD vary from 0.8C tp 1.30 /1/. The effect of Рл and T on the K~ values has been studied for two natural olivine samples: ol­RS (of hydrothermal origin) and ol­Shil (from ultramafic deep nodule). The chemical composition of both samples is close to Fa..­. The initial samples were hea­ ted to 800­1200°C at P 10"S ­ 10"1^. The crystal structures of the initial and heat­treated olivines have been refined by X­ray single crystal diffraction method (МоК„ь, SYNTEX PT, refinement programme RPINE­IV 121). Different refinement models were used, including models with restricted chemical composition. The K« values obtained for tho initial samples ol­RS and ol­Shll are 0.91 and 1.09 respectively; heating under the conditions descri­ bed above the KD become the same for both samples, 1.13(3). The Kf. for ol­Shil does not change after heating, while the initial and final К~ values in ol­RS differ. Ife assume that the observed alteration of KD in ol­RS after heating us due to the homogene­ oue "re­raduotion" reaction /3/, and not to the well known reao­ tion of ion­changing equilibrium. The experimental results show that the Ге­Hg distribution coefficient Kj, does not depend on T or F­ at T?800°C inside the olivine stability region, limited on the T ­ P. diagram by the lines of QFM and qPI buff era. These data differ from results obtained under 750°C /4/. /1/ Khieina N.R. et al., Geokhimiya (in Russian), N 2,153(1985) П/ Finger L.W., Prince B.A., Inat. for Hat.Res. NBS WAH (1975) /3/ Putnls A., KoConnell J.D.C. Principles of Mineral Behaviour. Blackwell Sol. Publ. (1980) /4/ Will 0., «over G. Phya. Ohem. Ulnar. 4., 199 (1979) ­ 117 ­ CRYSTAL STRUCTURES OF A^U^GeO° 5 '. A= Na. Ll: M» Чь. Та

Mill' B.V., Belokoneva E.L . , „Bytaahln^V Moscow State Univereity, Institute of Crystallography, USSR Acad. Sol., Moscow, USSR Theae new compounds are prepared by solid state reaction and e>coept LlMbGeO. melt incongruent ly or decompose in subaolidus

= ranee. Studying the phase equilibria in systems A,,0­Nb,,0­­Ce0o ( A

Na, Li) at 950 C, we found the only ternary compound AMGeOc. Sin­ gle crystals for structure analysis (autodi ffTactometer * wore ob­ tained by Czochralaki method ILiNbGeO. t /1/ or by slow.cooling of nonstoichlometric melts. Synthesla conditions and X­ray data of compounds are presented in table. 'Compound Tsynth'°C Sp.sr. а, Я D, * c. ii f. °

NaNbCe05 1000­1050 P2j/o 6.79814 ) 8.913(31 7.523(21 1 15.4214 I NaTaCeO. 1200­1250 C2/o 6.84314 1 8.916141 7.417(7) 1 14.7712) NaSbCeO,, 1050­1200 C2/c 6.722(6 1 8.892(71 7.22017) 114.7618) LITeGeOj 1100­1200 C2/c 7.589151 8.130C4 ) 7.50916! 119.55(51 UTaSlOg 1350 P2,/c 7.51211 1 7.927(1 J 7.44112 1 120.701 1 1

LtNbCeOs 1000­1050 Ponm 7.5221? 1 7.750(2) 6.713121 The oryetal etruoture of LiNbGeOp. la almllar to s llllmanlto

A12S105 with octahedral coordination of Ll and No /I/. All other compounds crystallize In highr (C2/c) or low^temperature \P2./6> sphene CaTlSiO. atructure /2/, DeOreaae in the NaNbGeQ. (LlT&SlO. ,TBtnetry la Oairaed by the Nb(Ta> displacement from octa­ hedron center by the valise 0.19 St I Ho­D, 1 .79* and 2.177 л>. Na po­ lyhedron (6 oxygen atomft at distances 2.Я38­2.550 я,.the 7th О at 3.065 A I ie а оno­capped trigonal prlan a tared by adgee with other

NaCL, ootahedra NbOg and tetrahedra Ga04. In LiTaGeOg structure Li la located In Isolated highly distorted trigonal bipyra&ldes LiOg (Li­0­1.B15­2.390 a, the next Ll~0»3.32 я Jahared by edges with oata­

hedra TaO­ and tatrahedra Ge04. In report the crystal ohealstry of sphena compounds is discussed^ 1. Belокоnova E.L.. Mill'B­V., Buteshin A.V. Crystallographla, 2. 290 (1985). 2. Speer J.A., Globe G.V. Aeer­Mineral., 2. 236 (1976). ­ 116­ CRYSTALLOCHEMICAL CHARACTERISATION OP LANTHANUM SILICATES AS CONSTITUENTS OP NEW MATERIALS

N. Mlnkova, S. Aslanian*. D. Todorovr' i . Donkova Sofia University, Department of Che... ._/; «Geological Institute, Bulgarian Асааъ.пу of Scienoea

Lanthanum silicates are used In radloelectronic and optical industry ae constituents of new materials. Synthetic products should be of suitable crystal structure and, as a rule» of high purity In order to take full advantage of their specific physi­ cal and chemical properties. X­Ray diffractometry are used to characterize the solid phases produoed on the basis of applied methods for synthesis and purification of lanthanum dlorthosilloate and lanthanum oxyorthosllicate /1/. X­Ray studies hare shown that the silicates always contain some oxide­admixtures due to the chemical and crystallization processes involved. Diffraction patterns are used to control the

effioienay of methods for purifying the produote of S102 and

The Interpretation of X­ray studies are accomplished by using the DIFFRAC­11 programme paokage. The cell parameters of the lanthanum dlorthosilioate and lanthanum oxyorthosilloate are specified. The crystallographlc characteristics of the fi­ nal purified products are reported.

/1/ Minkova N.. Todorovski D., Donkova B. (In press) ­ 119 ­ ORTSTALLOCHEMICAL ASPECTS OF THE METAL­OLEFIK INTERACTION IN COPPER(I) HALIDES ЗГ­COMPLEXSS

M.O.Mva'kiv Lviv State University, Lviv,, USSR

Synthesis and single crystal X­ray structure investigation of 4­2 copper(I) chloride and bromidn ST,6"­complexes with vinyl

fcH2­CH_COOHt CH2­OH­CONH2t cis­HOOC­CH­Crf­COOH, NC­CH­CH­OK ­

trans), divinyl (р­СНд­ОН­С^­СН.СНд, CH2­CH­CH,CH­COOH ,

trane­CH2­CH­CH­CH­CN and its dimer, CH2­CH­C(CH,)­CH­CN>, al~

lyl (C^­CH­CHg­OH, 0H2­0H­0Ha­0N\ diallyl ( (ChV­OH­CH,,^,

, ок2­сн_он?­сн<он)­сн­сн2, (сн2­сн­сн2)2о1 (CH2­CH­CH2 I2NH,

o­0H2­CiUCH2­0f.H^­0­CH2­CH­nH2, CCH2­0H­CH2)2NCN'> derivatives

and some alkynes (OH,­C*0­OgH­, HO­CHp­C=0­CH2­OH) and alke­

nynes (0H2­0H^C"0­0H­0H2t GH2­CH­CH2­G»C­C6H5^ allowed to re­ veal the regularities of their formation. The character of Inoretanio fragments (OuX^ (n­2,3,^,5*6» oo^ is in the consist connection with the form of Cu(l) coordinjtion polyhedron which varies in the complexes from tetrahedron «'characteristic for 6- coordinated Сц(1) atom) to triangle, ...Jing over a trigonal py­ ramid. Usi.g the geometry of copper(I> coordination sphere one may estimate the relative strength of Cu(I) ­ multiple carbon bond interaction which seens to be inessential if any aubsti­ tuent occurs at 0­C bond in a li«and molecule. The comparative analysis of ff­complexes with the unsubatitu­ ted olefins, alkynes and alkenynes shows that C­C bond repla­ cement by C«C leads to the formation of more .able compounds. The distinctive feature of CuX (X­01,Br) ^­complexes with the allyl and diallyl derivatives is polymorphism» caused by the ligand molecular conformation lability which promotes in­ creasing of the compoundrts stability due to reduced internal tensions. In view of the polymorphous transformation it­ is clear why such compounds crystallise mostly as polysynthetic twins. ­120­ тнк STRUCTURES OF SOME VERNIER PHASES IN THE Y+O+F SYSTEM AND ANION ORDERING THEREIN. J_._Mohyla and D . J . H . Bevnn . School of Physical S; .ences, Flinders University, Bedford Park, South Australia 504' B.F.Hoskins and Robyn J.SLeen, Department of inorganic Chemi stry, Melbourne University, Parkvi)ie, Victoria 3100, Australia.

Mann «nd He van /1 / found an apparent, ly infinite series' of fluorite­related superstruetures in the range YX2.12 to YX2.22 ( X = О + F). An X­ray structure onalysis of one "compound",

YTOS Fs /2. ..^ . IK • ' .; described by Hyde, Bnsjshaw, Anders son and О' K^effe /3/ as the vernier principle . Mann ond Be van /1 / have d

Yn On ­ Fn . 2 (ИпКгп.1 ). We now report the structures of the homologuea YnQs F* and _Ys 0< F? , and also of___tbe phase with nominal composition .V"I?0MF2.I [correspond Xns^toJX^Q*!'' +._2_ _Yeps FB J /4,5/. Subsequent 1 у, and wi th knowledge of some of these resuIts, Mackov i rk> and Hyde /6/ described these vernier phases quite di f fer^nl 1 > ir. t.erms of nor.­commensurate, two­layer structures. Th_e_ xepeal distances along th,e , b­ax.jis for__each layer type are noD_­commensurate, although we have necessarily approximated these to a s ingl e i­ommensurate value in defining conventional uni t cells for thp structure analyses. Volence bond sums have been calculated for all four known structures, nna it is very clear that anion ordering occurs — F atoms into one layer and 0 atoms into the other. However .complete ordering of this kind leads to Wi'ong compositions. One consequence of this reBult may he that the true symmetry of these crystale ie not orthorhombic but monoelinic. Also, because these "compounds" have non­commensurate structures, the v nventional structure determinations cannot be truly correct, although they represent a close approximation.

/1/ Mann A.V., Bevan D.J.H., J. Solid Stat.» 'hem. £, 410, (1S72).

/2/ Bevan D.J.N., Mann A.W.t Acta Cryat. Hal. 1406, (1975). /3/ Hyde B.Q., Bagahmw A.N., Anderaaon S­. u'Keeffe M., Ann. Rev. Materials Science ±, 43, (19<­ll. /i/ tfonyla J, PhD Theaia, Flindars Unlveraity (1979). /5/ Steen R.J., PhD Thesia, Helbourne University (1984).

•"6/ Hakovlcky R, , Hyde B.O.t Struct, and Bonding 4_£, 101, I19B1). ­ ш­ X­RAi DETECTSBILITY 0? SINGLE PHASE IN HEAT TREATED OCTG STEEL

VJ. Novosel­Radovlo', It. Mallna, K.B. Hensger» Steel work "Zeljesara Sleek" Siaak, Yugoslavia •Bargaakademie Freiberg, DDR

On differently heat treatment OCTG ateel /1/, the observed dlfferenoe In ldentlflaetlon phases was examined. The samples were differently heat treated, grinded, deepetched and/or ele~ otrolytloally Isolated. The prepared samples were measured on the dlffraotometrio system, type Philips and HZ03 conventional slow step­scan and continuous averaging scan technique and eleotron mioroseope. The obtained results show that using the same time grin­ ding techniques and difference scanning techniques essentially does not Influences on lnoreaslng X­ray dsteotability. On X­ray dlffraotometer ohart only reflections of etFe phase (110, 200, 211, 200) and PejO (112, 121, 122) reoorded but very weak inten­ sity. With increasing of successfully heat treating (quenching, normalising, stress relieving) and deepeaching, inorease X­ray detectable one by one phase. On X­ray dlffraotometer ohart re­ corded and other reflections of phases type: MjjCg, M^C and NbN and KojO, also determined by electron microscope. Prom these results we are able to conalude that when some­ body wants to determine the phase composition OCTG­heat treated steel, it is not necsssaxy to use the preparation samples with electrolytically Isolation always.

/1/ Uallna H., Movosel­Radovio Vj., Nenadio N. Collected Abstr. Xnternat. Conf. Adv. Method in X­Ray and Noutron Structure Anal, of Hat., Karlovy Vary, Czechoslovakia, 28 (1987)

j>

I6­I ­ 132 ­ M0HPHOIO0Y ЛИ) CROWTH MBCHABISM OP InOaAeP USER HETEROSTRUCTURE3 J. Novotny Institute of Radio Engineering end Electronics, Czeeh.Acsd.Sci., Praha, Czechoslovakia

Three version of (In,Oa)(As,P)/InP laser heterOBtructures (^­1.3 and 1.55^UB) were designed end realised On the basis of an analysis of the waveguiding properties /1/. Theoretical dependence of the thickness of the quaternary 0aO.eeInO.74AeO.6FO.4 1аУег uPon the growth time was oomputed as­ suming a supercooling LPE regime and the controlling role of the phosphorus diffusion in the growth process /2/. The results for T»630°C (sero lattice mismatch) are shown in the Figure.

A oomparieon of the experinental results with theoretloal data suggest the feasibility of growing ultrathin (d^20 ran) layers. On the ground of these findings, a three­elot sliding boat was devised whioh allows growth of Oa^In. As P. ( .Л "

1.3 /шУ/а*%1пи1кв^?^_г (Л­ 1.1 /U») superlattioes. Spiral dls­ looation growth •eohanisei was observed at low value of the super­ saturation (two­phase LPE technique). Under the one­phase LPE conditions (ДТ­> 5°CJ, rapid growth corresponding to surfaoe nuoleation aeohanlsa was observed..

/1/ Idansky C.i Htl Reeearoh Report Z­1721/A, Prague (1988). /2/ Da Crsaoux B.t OaAs and Relate Compounds, Oonf.Ser., ££, 52 (1978). ­ вз­ NEU UNARY ERBIUM, DYSPROSIUM, TERBIUM AND GADOLINIUM SERrWNIBeB Olsksyn O.Y»., Shpyrk» Z.M., Psch.rsky V.K., Bod.fc 0.1. , nolir» l.R. I ' _v 8t»t. Umv.r.lty, Lvov, USSR

Crystal structure* of the compounds ErMQ*4«­H , к­0.23 *nd DyQsa­n i ­:*0.13, .га Invastlgatad by m*.na of H­ray single crystal «•thod (autodlffractoaatar N1 col at R3). The first on. (Er„S»„­.l balongsto the apace group P4/nmm, «"14.373. c»10.22вА.7пв a£0inlc pey­ «Mtsri (final rasidual is 0.036) лгт as follows] Erl X­ 1/4 y­ 3/4 I­0.2769 Er2 и­0.0621 у­ 1/4 1­0.6242 Er3 H­0,.068 6 y­ 1/4' i­0.04Вв Er4 и­0.1097 у­ 1/2­и г­0.3376 ErS x­0..133 2 y­ 1/2*и z­ 1/2 Er6 х­0.0763 у­0.6203 z­0.1793 3*1 K­ 1/4 V­ 1/4 1­0.206 e.2 к­ .1/4 у­ 1/4 г­0.467 Q.3 X­ 1/4 V" 1/4 I­0.868 ••4 К­0.3317 у­ 1/4 z­0.3169 e

The second опо DyGe2_x is crystallized In the space group Cutoff wltft •Н­Ю2'/ b*29.705 с­3,9Я6 %. All the atoms occupy position t'n) О у z, with the following atomic parameters (final reBidual 0.032)t

Dyl y­0.0603 z­0.73 Dy2 y­0.1723 I­o:230 Qsl y­0.3331 z­0.240 . 3*2 y­0.4074 1­0.733 а«з y­0.2314 1­0.743 ­ 0«4 У­0.3О96 1­0.336 lath the compounds «г* characterized by soa* deviation* from stoichiometric composition*, that­ la caused by partial occupation of cneofthe atCMic position») fe^O. 77 «or Ba3 in Ег^ве*»—, and Q­0.70 for B*4 in DyGe .,_„>. Both of the* represent the new type* of crystal structures. The Majority of germanium atoee have (trigonal prises with additional atoms as coordination polyhedra. Borne of the smalle­ st «germanium) atoms also have cubooctahedron and Arche**dean antyp­ rlsmatlc coordination.

There are no closely related with Era#,Qea»­„ binary geraanides,

but one can see her* so** common features with Hot»Ge.o • Crystal structure of DyG»..^ is closely related; with Zr9i, i tr­ igonal prismatic ма11* and germanium atomic chains mrm interchanged equally. The only difference lies in the number of trigon­ al prleff layer*, forming the Mallet one layer for Zr61 * *"<) three

ones for DyG*a • Terbium and gadolinium form isotypical with DyQe.­. germanidea. 16­2 ­ 324 ­

2+ 2+ 3+ CaQ 59SrQ 41P2:Mn AMD CaQ 59SrQ 41P2:Un ,Hd CRYSTALS GROWTH, ItfVBSTIGATIOHS OP THEIR PHYSICAL PROPERTIES Ь.А.Olkhovayo. O.A.Karpenko, V.S.Sidorov, J.J.Ikraral, V.A.Sandulenko Institute of Chemistry, Tajik Academy of Sciences, Dushanbe, USSR

In the Mn(II) compounds doped with rare earth ions the exci­ ted states of RE ions may be optically pumped with higt epeotral efficiency. This effect oonflrms the possibility of applying these materials to solid­state rare­earth lasers.

HnP ­CaQ 5q3r0 ,1Pg binary section of the ternary system CaFg ­

3rF­ ­ MnP2 have been investigated as a basis for the growth from melts. There is a wide region of fluorite­=.type solid solution on

Accor n the base of CaQ jqSrg 41*2" *i 8 to the thermal and X­ray

powder diffraction data the solubility of MnP2 in CaQ 5gSrQ ^?2 le 70 mol./S. Lattice constant of solid solutioi* deoreases from

5,60+0,01 X for Ca0 59Sr0 41P2 to 5,34+0,01 X for

0aO,177SrO,l23,'taO,7^' 3ingle orystals of soli solution have been grown in induc­ tion furnaoe by the modified Bridgman­Stookbarger method in gra­ phite oruoibles under fluorinating atmosphere (teflon pyrolysis

products + helium). Св^ 5qSr0 я­^г, MnPg nnd H4P. melted in the fluorinating atmosphere were used as initial materials. Optically transparent single orystals (41am. 10 mm, length 50­60 mm) colorless or light yellow with Increasing con­ centration of MnF, have been obtained. The single crystals were optically isotropic. Precipitation of anisotropic second phase was observed for crystals with MnFg oontent 70 mol.%. Single crys­

P ,Nd nave al been rown tals Ca. eycSrg 40*tao,o25 2 "° « *

The'distributlon'Mni'j in CaQ 5qSrQ 41P2 and refractive Index have been obtained. The infrared absorption and luminescence speotra of the ory»­ tala obtained have. Ъееп т .asured. Luroinescenco spectra of Kn + and Hd3* are characterised I , wide band bo» for 300 К and 77 K. «a­ xloura of lin longrwave luminescence band shifts from 515 to 522 nm as UnP, ooncentratlon increrэев from 2,5 to 10 mol.sS. 2 1 1 The CaQ cqS**0 ti*? ** crystals can be regarded to the phos­ phors with intensive green omlnaecence. ­ 125­ INTERCALATION OF HYDRATED K*­IONS IN 2H­NBS, INVESTIGATED BY •IN SITU' SINGLE CRYSTAL X­RAY DIFFRACTION

W. Paulus. H. Kauke and R. SchOllhorn Institute of Inorganic Chemistry, Technical University Berlin, West­Germany

Tha Improvements of poaltlon sensitive detector systems la of great Importance for studying faat aolld atate reactlona by x­ray dlffractometry In accessible ahort time, I. e. within a fiw minutes or even aeconda. We observed the inter­ calation of K+­lone Into the layer compound 2H­NbS. from aqueous K_SO. elactrolyta by x­ray 'In mltu ' dlffractometry . Oriented single crystals of about S x 5 x 0.2 mm5 In alee were mounted In a special electrochemical cell aligned on a powder dlffractometer. Tha topotactlc Intercalation reaction :

x xK* • xe" • у HxO * NbSf • K*

maximum poaalbledegree of reduction at *тлк • 0.5. The fully reduced phaaa ahowa an additional layar separation of around 300 pm aa compared to tha binary boat lattice related to tha colntercalated solvent molecules forming water monolayera. At x • 0.08 and 0.12. however, two Intermediate phases were obaerved, ahowlng an Incommensurate Modulation perpendicular to the Uyara, with a modulation wavt vector q • 0.357 c* and 0.457 c" respectively. Under non­equlllbrlum conditions, I. a. uncontrolled chemical reduction, thee* Intermediate phases ware |uat obnarved aa precursors at the reaction' front leading to a different reaction mechanism.

Thermal treatment of ,K* tNbSs1*~ Investigated by x­ray diffraction and DTA/DTO axperlmenta Indicate for all phases a ona step dehydration mechanism leading to a different layer separation correspon­ ding to th» six* of the Intercalated cation. ­ B6­

CRKSTAL STRUCTURES 0» OOHPOUNDS Ы , jHl 4Q313, AJSD TmLl^Oe^x­O.J)

V.V. Pavlyuk, O.I. Bodak, V.K. Pscbareky, E.I. Oladyhavnky Lvov Stat* University, Lvov, USSR

Crystal structures of two net ternary eoapounda were aolved by mean» of X­ray single eryatal nethod. The flrat one,

Ll13a4.0Sl31, la oryetalllted In apaoe group Рб/вша, а • 17.092, c­7.848 A. Atoalo parameters (R­0.041, 361 independent refleotiona) are Hated belowi 12Ы11 in 12(g) X i 1/2 x­0.3157 y­0.0859 12Я12 in 12(o) X 2» a x­0.0938 1.­0.2663 6H13 in 6(1) x 2x 0 x­0.1424 6N14 in 6(a) x 2x 1/2 »­0.5424 6111? In 6(J) x О О x­0.4204

12N16 in 12(o) x 2x t 1 x­0.2650 a­0.1628 24N17 in ­24(r) X у a x­0.4440 y­0.1014 1­0.2746 2H18 in 4(b) 1/3 2/3 a 2.0.436 6511 In 6(k) x, 0 1/2 x­0.3831 6512 in 6(k) x 0 1/2 x­0.1613 12313 in 12(p) x у 0 x­0.4189 y­0.1335 6S14 In 6(J) ,x 0 0 x­0.1480 2315 In 4(b) 1/3 2/3 a c­0.041 6316 in 6(1) 1/2 0 a z­0.234 12317 in 12(o) x 2x « x­0.6045 1.0.326 12318 in 12(o) x 2x a x­0.1791 1.0.2622 6111 In 6(1) x 2x 0 x­0.574 12112 in 12(n) x 0 a x­0.280 1­0.186 21ЛЗ In 2(a) 0 0a a­0.23 6L14 In 6(a) x 2x 1/2 x­0.234 The aeoond on*, TaLl. 0s_ (x­0.5), la aonoclinlc: apace group P2,/a, a­4.008, b­8.123, С­Э.В75 A, ^­104.24°. Atonic parameters (all atoaa occupy 2(e) poaltlon x у 1/4, R­0.035 for 241 hkl) are: 2Ta x­0.396­', y­0.29271 20e1 x­0.7531, y­0.0057 20*2 x­0.0526. y­0.6059) Ш x­0.24, y­0.88. Both Investigated ooapounda repreaenta the new typea of orys­ tal etructurea. The flrat one la related to oloae packed structu­ re*, and the aaoond, TaXi^^Qej, la aonoolinlcally distorted and

partially defective derivative of the CeN1312 type. The latter (•raanld* «an be described aa the CaSb, structure type with parti­ ally filled Archaaedean antypriaaatlo holeB. ­ 127­ CRYSTAL STRUCTURES OF Ег^Щ^Сд AND Tm^Hl. Cg COMPOUNDS

A.O.Pecharskava. O.I.Bodak, E.P.Marualn M.M.Hallll Lvov state University Lvov, USSR

Crystal structure of new ternary carbldea Er4Nl13C. (1) and Tm11N160C6 *2*# are Bolved ЬУ means of X­ray single crystal method (diffractometer Syntex P2j, Mos^c ­radiation). Both of them repre­ sent the new types of crystal structures. All calculations were performed using SM­4 computer and program package CSD. Atomic parameters were reflnad up to R • 0,066 (1) and 0,050 U> for both in isotropic mods of thermal motion. Structure type Er«Nl,.C« . Bp.g'r. Сшит, 1­2, a " 1.1973(4), b­ » 1.16*4(3), с ­ 0.3836(1) nm..4Erll 4(h) к О 1/2, к ­ 0.1839(3)) 4Er2l 4(J> О у 1/2, У • 0.3486(3)1 4N11I 4(«» 1/4 1/4 1/2| 2N12I 2(a) 0 0 0| 8N13I в(р) к у О, н ­ 0.1771(6), у ­ 0.3929(6)1 SN14I »(р> х • 0.1087(6), у • 0.1836(6)1 4N13I 4(J) у ­ 0.1244(12)1 4С1|

4(g) к О 0t и ­ 0.330(7)| 4C2l 4(a) 1/4 1/4 О. Structure type T*,,MI»eC« . 8p.gr. ImSm, Z­2, a ­ l.Z4S3(7)ne. 4T«ll 6(b) О 1/2 1/2) 16T*2l. 16(«> и к к, к ­ 0.1676(2)| 12N11I 12(a) и О О, к ­ 0.1443(12)) 12M12l 12(d) 1/4 О 1/2) 48NI3I 4в(к) , и к 1, и ­ 0.1741(4), 1 ­ 0.392в(3)| 48N14I 4в(Я О у I, у у ­ 0.3176(6), I ­ 0.1461(6>| 12CI 12(a) к ­ 0.284(11). The structure type Er^NjjC. can be built from the three structural fragments) deforn*ed CaTlO. (ErNl.C), CaCu* (ErNi^J and AlBj (ErCj). Relative quantltet of named fragments in the unit cell are 2 i 1 i 1. Carbon pairs' and isolated carbon atoms can be Been here. The structure type Tm.­Nig­C­ contains only isolated carbon atoms and has not any relations with known ternary carbides structure types. ­ 128 ­ STRUCTURAL FEATURES 0? LOW­TEMPERATURB SOLID­STATE TRANSFORMATION OF MINERALS . I.I.PLiUSNINA Moscow State University t/SS%

At low temperatures minerale are often formed from gels. They are difficult to study with I­ray difraction and other met­ hods and the data are scarce. The study of low­Lumperature silica has shown a spontaneous solid­state transformation (LST) during its aging. The diminishing: of free energy in low temperature si­ lica system at different stages of its LST occurs by increasing the degreu of 310.­tetrahedrons condensation, changing tho volu­ me of ct ­crlstobalite and о*­quartz, decrease of border spa­ ces* during crlstobalite growth ( ot­quartz) and dehydratation. Diffusion on hydrated ellica grain borders allows a LST on a sca­ le from 20 40 200*10 years. Studying by different methods the natural sequence amorphous silica—* opal­—•chalcedony —v­quartfi we have found a martenoite­type phase transformation. This hetero­ genous process is due to defects of 0^­crlstobalite matrix (KT­opal), formation of metaetabla phases under gliding deforma­ tion of close­packed.layers, polytropio and polytlpic phenomena, superstructure, eutectoid desintegration, a fine­grained orien­ ted intergrowth of (jt­eristoballte and ^­quarts. The marten­ site type transformation is favoured by long aging and presence of close­packed layers and displacement defects found for many low­temperature minerals. L3TS are very likely for low­tempera­ ture processes demanding on considerable additional energy and suet have an universal character. At higher temperature and pres­ sure tliey go faster and may occure in hydrooxldes, carbonates, sulfides and other minerals formed from gele. The. LST seems to be a new approach to mineral formation in open systems. ­ 129­ СМвТАШМЙАНПГ AMD CRYSTAL СНИП13ТЯУ OP SINGLE CRYSTALS WITH SILLENIT STHUCTURE E.A.PobedimsIcaJa, A.N.Judln, A.A.Harjin, I.V.Pstrova, 'L.N.Kaplunnilc, A.B.DubovsklJ, L.E.Terentjeva All Union Research Inetltut tor the Synthesis of Minerals, Moscow 8tate University, Moscow, 117234, USSR

Single crystals and epitaxial films with slllsnlt structure were grown on a seed in the alcaline solution by hydrothsraal method. Considering morphologloal pecularities three types of •illenlt were distinguished! 1) rombododecahedronal

Bl^pSlOgQ, Bi12Ge020| 2) trigon­three­tetrahedronal

Bila(Zn,Bl)Oao, fli12(na,Bi)020i 3) cubic Bl12(Bi,V)020,

В1т,8 01,Р)0,п. The relative crystal growfli rates are determined. Two types of twins 2* ', 3 and m 3 are detected. Uicromorphology of singular faoee 1в studied. Powder diffraction method of estimation of epitaxial slllenit films structure perfection is worked out. Structures of P­V­Oa ­ slllenlts are refined as well as structures of some solid solutions on the basiV of .slllenits. It is determined that slllenits can be derided into three groups in accordance «I'ththelx Isomorphism i Ge,Ti­ sillenits are olose to Si­eillenit| tetrahedra( positions in structures of Fe­ and Zn­sillenits are occupied Btatistcally by atoms of two chemical elements| structures of P­ and V­slllenita are similar to Bi­ slllenit structure because Bi­ions are in tetrahedm£ position. Qa­alllealt is particular for his lower symmetry (rombic) and the presence of 0H~ ­ group. It is found out that 01i~ ­groups are part of the orystal structure of eille­ nlta and are located in cation terahedral position. Spectral characteristics of complex compound sillenits «re calculated on the basi? of X­ray data.

17­1 ­ 130­ P03SIBIS CETSTAL STEUCTUEBS 07 OLATHRATB НТШЛТВЗ WITH ТНЫЯ­FOLD SDtHBTRI T.M.Folyanskaya Institute of Inorganic Chemistry, USSR Academy of Sciences, Siberian Branch, Novosibirsk, USSR

A problem of prediction of compounds with new compositions and of their properties is always actual. This work represents results of the prediction of new clathrate hydrates, their com­ position, symmetry, and structure. The structures considered have the three­fold symmetry and are constructed from the layers similar to those which were occured in the structure idealized to gashydrate framework of hexagonal I type (P6/mmm) and gashy­ drate structure of cubic II type (Pd3m).. The structures contain polyhedra of 4 kindsi Hd hexakaidecahedra (5126*)| Pd pentakal­ decahedra (51263)| Td tetrakaldeoahedra (5 62) and Dd pentago­ nal dodeoahedra (5^2).An alternation of layers enables to obtain a large number of structures, Including polytype structures. On condition that a number of layers with the only Dd pentagonal dodeoahedra is «6, we have obtained the following structuresi

Distribution of guests formulae for Composition X and I Ln polyhedra Spao* filling up X I group onl^ of large Hd Pd Td Dd polyhedra X^Tg.eeHjO 4 0 0 8 P6,/mmc ХИТи^О IgT­ITloeV 4 . 2 2 11 P3m1 Х.1Э,511,0 Po^/mmc xei16.i>eyir 8 0 0 16 X.17HgO 1 6 2 2 15 X.14,2H 0 Vu' «V ­ 2 X12T1V148H20 4 4 4 14 ­ X.12,33H20

X T 1 H 0 PS»I 10 20­ 7° 2 ' 10 0„ 0 20 I.17H20 ^^„итбНгО 8 2 2 19 ­ X.14,67H20 Il4Tie­1KH2° 6 4 4 18 ­ X.IJHgO X^.ieBHgO 4 6 6 17 ­ X.11.75H20 Х Т .74Н р 2 R3m в 7 г г г 7 хиг.ззНдО The relation between aetrio and struoture characteristlce is oonsidered. ­ 131 ­ ЛИ X­HAY STUDY О? LANTHANIDg NITRATE COMPLEXES WITH 15­CROWN­5 Т.К. Polyenalcaya, О.О. Fotapova, T.N, Martynova, L.D. Nikulina Institute of lnorganio Chemistry, USSR Academy of Sciences, Siberian Branch, Novosibirsk, USSR

Interest in the lanthanlde complex compounds with crown tthers ia ouaaed by their unique propertlea. W» have obtained complexes of lanthunide nitrate aalte with 15­orown­5 In an acetone medium purified by reoryetallization In •0 6ton» and subsequent vacuum evaporation at 10" mm Hg and T tOO'C, The «ubetenoe» were identified by elementary (for C,H,N, Ln) and X­ray powder diffraction analysis. The water oontent in * was eetlmated by the Fischer method. X­ray diffraction analysis of the complexes was performed both on single oryatale and pow­ der*. The composition of the final products depends on the else of the lanthanlde Ion, For the light lanthanides (La­Eu) the ratio la HI independent of the loading order of the starting reagents. For Eu­Vb the composition of the oomplexes la deter­ mined both by the ratio of the starting reagents and the order of their loading and ln this ease they may contain 3­4 moles of water. (I) LntNO.) • (t5­o­5) (Ln­La­Eu). For Pr oompoundi a­B.892(3),

3 3 o.20.352(6)A , Z­3, V­1393.6A , ep.gr. P32, dx­1.956g/om .

(II)Ln(N03)3 *(15­0­5)2'3H20 (Ln­Eu­Vb). ?or Yb oompoundi a­ ­11.034(4), b«14.245(4), 0­18.028(4)A , J> ­ 91.69(2)°, Z­4, V­2B32.4 A3, sp. gr. Р2,/с , d^­1.987 g/cm3.

­ (Ill) Ln(N03)3 (15­o­5)­'4HzO (Ln­Er­Yb). For Er compoundi a­17.051(10), b­17.115(10), 016.251(10) к , Z­8, V­

3 3 ­ 4742.5 A , dx­ 1.808 g/cm , P­eell. Structural featurea of (I) end (II) aompounde are dlaoussed. The coordination number of Ln is 11 in (I) and 9 ln (II). Oxygen atoms of 15­C­5 are included in the Ln coordination only in (I). As indicated by the OTA ( complex thermal analysis), ther­ mal destruction of the complexes depends on their.hydrate con­ tent. AnVydrouo comploxos are thermally stable and in an Inert atmosphere they decompose at T 5 300°C while the crystsllo­ hydratee start to decompose at 85­100°C.

17­2 ­ 132 ­ HASS­TRANSPER DURING IHB GROWTH OP DOPED SINOLK 0RY3TAL3 FROM HWH­TBMPBRATURB SOLUTIONS V.I.roDQlltov. R.Ch.Biohurin, A.A.Telegenov Institute of Crystallography, USSR Aoad.Soi., Mosoow, USSR The present paper reports the effeot of various factore on the mass­transfer kinetics during the growth process on the seed of ^­TeO„ piesoelectric single oryatals doped with selenium dioxide from homogeneous and boiling solutions. The experimental facilities and the oaloulatlon technique ueed to determine the liquid medium oonveotlon rate were analogous to those in the pa­ per /1/. The main experimental and oalculatlon results obtained oan toe reduced to the followingi 1» It was found that the mass­transfer of the initial material to the sone of seed crystal growth within the homogeneous region obeys the equation dM • K'Rn (К 1в the proportionality aoeffl­ oient, R is Reynolds criterion, n is the power index), all other parameter» being oonstant. 2. It was shown that the mass­transfer to the seeds at the move­ ment rates of gaseous bubbles from 14 to 26 om/seo within tha two­phase region "gas­liquid" Increases Insignificantly,the other parameters, being constant, but soon the conditions are formed under which mass­transfer becomes oonstant. 3. The dependence of the mass­transfer rates on the temperature drop, other parameters being constant, in a homogeneous region obeys the function Л'М » K­ AT0, and in the region "gas­liquid'' Д> • К' AT (n is the index, К is the oonstant of mass­transf sr, ДТ is the temperature drop).

In the process of the experiments we obtained (TeQ .„(Se^.Oj single orystals up to 30 gr in weight out into a tet­ ragonal prism flW\, two tetragonal dlpyramlds [lOl] and {102J.

/1/ Popolitor V.I., LitTin В.». Orowth of single orystala In hydrothermal conditions. mosoow, KAUKA, pp.56­72 (1986). ­ 133 ­

A1 ЯШ STRUCTURE О* 1ПСН0АД0 00ATIW0S Of fl ­ z°3 O.O.Fotapova, H.K.Mlronova Institute of Inorganio Chemistry of USSR Academy of Sciences, Siberian Branch, Hovoeibirak, USSR

The phase composition and characteristics of anodic microaro

ooatings obtained on Al and D ­ 16 alio; In ooncentreted H2S0. by powder I ­ ray diffraction metLod were investigated. The coating •ti­ueture features are due to their formation by the microarc oxidation method. In this case the coating growth occurs under the temperature gradients ~ 40 ­ 180 degrees/м m and repeating banting and cooling /1/. The ooatings consist of low = temperature n ­ A1?°3 baving the eubio unit cell with a ­ 0,7905(2) rm, t « в, space group MJa, Ып» broadening on the diffraotion patterns is caused by the alorostrssses in the sample. The lattice nlorodeformatlon{i|) reaches its msxlaum ­ 0,26 % ­ In the ooatings obtained under low terminal voltages and current dansltles(for example, V ­ 200 7, i » 3 A/dm ). For the ooatings, formed under more severe oondltl ­ ons(U . 300 and 400 V, J « 6( 12| 13,6 A/dm2) ^ Is constant and •coounta for ~0,22 %. The ooatlng dislocation density lies within the range of 10 ­2 1­10 cm , which allows ooneidsrlng them as hardened material. The schema of polymorphous transformations of microarc coatinfu is desoribod as follows:

The calculation of theoretical diffraction pattern and de ­ termination of structure reeponsi7* reflexes showed a good agra ­ ement between resulting •)_ ­ Alo°3 and *ne model ^.S^t.OZ LB4,31B9.02] °32­ m" •odel le «le0 b"""1 for l" A12°3 foisM by plasma spraying /2/. It means that the oonnitlona of co­ ating formation In this two methods are similar,' i.e. the synthe ­ sis of metastasis phases occurs under non ­ equilibrium regime with high temperature gradients.

/1/ Markov GA.,Mlronova U.K., Potapova 0.0., Tatarchuk Т.Т., Isv.AB SSSB, Beorg. Mater. J2, » 7, 11:0(1983). /2/ Shlrasuka K., Janagida H., Yamaguchi 0., J.Ceram.Soo.Japan. ЙД, N 1­, 610(1976*. ­ 134 ЛЯ X­RAY DIFFRACTION STUDY 0? THE CRYSTALS OF A LOW­WMFEHATURB' MODIFICATION OF ti.­Kba(MoO.)j

O.Q.Fotapova, V.I.Protasova, L.Yu.Kharchenko, I.Uacichak Institute If Inorganic Chemistry, Siberian Bransh of the USSR Academy of Soleneee, Novosibirsk, USSR

Crystal» 01' the binary K­La molybdate have been obtained by hydrothermaa method In $­60 вел* St solutions of E^lloO^ at 500­650*0. Under these condition» they synthesize In two poly­ morphic modificationsi 1) a high­temperature,/в , having a soheelite structure with a disordered arrangement of I* and La'*, end 2) a low­temperature* ,ti, aeftgned to a distorted aoheelite struotur*.

The X­ray powder pattern of J. ­К1*(ио0^)2 obtained on a ШСН­2 dlffraotometer (CuH, ­radiation, N1 filter) in the 26 region of angles 20­160* oontalna a large number of weakly split or broadened double lines. Thus tiie 620,536,624 lines of the tetragonal aohaelito o«ll In the region of large angles are split Into quadruples of lines having the 602,602,206,

206i 56},56}t365tJ65 and 642,642,246,,:A lndloesjthat, aooordlng to the homology theory, corresponds to a monoollnlo unit oell. A least squares refioment performed for all resolved lines with the analysis of the standard deviation* of the experimental and oaloulated 26 value* resulted la a body­ centered unit suboell having the following parameter*i

•>5.457(1)A, в«12.205(2)А, 0­5.417(1)1, A .90.05*, 1­2,

} Л^вЧ.56 e/o* ( d^­4.59 g/om'. This unit a­iboell is In good agreement with the experimental X­ray powder pattern of •< ­

XLa(Uo04)2 ezaept for a number of unlsdexed auperlattioe •truotur* line* /1/.

The unit oell of / ­Кл(Но0ч)2 ( «• 15.833(2) A, g. 12.208(1)1, 6*2?,.205(2)1,jg=98.95*) obtained from single sryatal data mad* it possible to index all cupperlattioe structure line* not indexed In the unit *uboell/1/. 1. Potapova O.Q.,Frot*eova T.I.,Eharohenko L.Yu. Zh. neorg. khia. 52 (12), 2935, (1987). ­ 135­ PACKING ANALYSIS ON THE CRYSTALОГ THE COMPOUND RbOHHgO

H. Preul

Anor^anlsche Chemle, Unlversftlit Dortmund, Poslfach BOOSOO, D­4600 Dortmund DO, FRG.

The crystal ilructure of the compound RbOH.H„0 el room temperature has been determined /1/ vl»X­ray diffraction and coordinates are given for all atoms except the H atom of the disordered OH group. In order to get Information about possible positions for this H atom and the height of the energy barrier between the tiro positions for the disordered OH group, lattice energy calculations have been carried out using the programs PCK83 /2/ and OPEC /3/. Details of the calculations will be presented. The programs SCHAKAL /4/ and DISSPLA /6/ were used for the graphic presentation of the structure and the results of the energy calculations.

/I/ Jacobs K., Schardey A, Z. Anorg. Allg. Chem. Mb. 34 (1088).

/2/ Williams D.E.. РСК8Э: A Crystal Moleeular Packing Analysis Program. QCPE Program No. 481, Indiana University, USA, 1983.

/3/ CavesBottl A.. (1983) OPEC: Organic. Packing Energy Calculations. Ullano, Italy.

/4/ Keller I. (1987). SCHAKAL A Fortran Program for the Graphic Representation of Molecular and Crystallographlc Models, University oJ Freiburg.

/6/ DISSPLA: Integrated Software Systems Corporation, 10505 Sorrento Valley Road. San Diego, California 92121. USA. ­ 136 ­

THE STRUCTURE OF NbTeu LT1 AND LT2 PHASES

J.Stefan Institute and ­^Department of Metallurgy, University of Ljubljana, Slovenia, Yugoslavia

The inconmenaurately modulated structure of RT NoTe. was recently a natter of Intense studies /1/. There are however additional diffraction effects in NbTe^ bellow ВТ and prior to the lock­in temperature at about 50K /2,3,4/ for which no accurate X­ray analysis la possible. Badly formed reflections, which develop on slow cooling from diffuse streaks, can be separated into two sets (LJ1 and LT2) of alternating spots /5/. Although the streaks seem to be cent­ ered at commensurate 2/3 c* positions, both sets of reflections are in fact incommensurate (the closest LT1 dnd LT2 reflections are shifted by J and $12 in oposite direction from the commensurate position with J * 0.022 с J. It le those weak diffraction effects which are the subject of the present work. There are a few possible ways of describing incommensurate structures, including super­space group description /6/ and dualistlc notation 111. In this work, a computer simulation of electron diffraction was carried out to describe both, LT1 and LT2 phases as long­period commensurate superstructures. It is shown that instead of long­period diecommensurations, suggested previo­ usly /8/ a slight shift in oposite direction of next­near neighbouring columns (LTD and a twisting around the c­axis (LT2) of the same RT modulation are res­ ponsible for the formation of these two phases. Slr.oe in the RT phase 11 dls­ plaelve modulation periods fit 16с , with a phase shift ofM between neigh­ bouring columns, the same periodicity is present in LT1, while the one of LT2 is doubled . The two modulation mechanisms resemble the ones found for the Goooensurate TaTe^ RT superatructure /9/. Finally, the Influence of higher harmonics in the modulation wave is discussed.

/1/ Smaalen S.von, Bronsema K,D,, Many J., Acta Cryst.W2,43(1986) /2/ Boswell F,W., prodan A., Brandon J.K., J.Phys.C, J57T9670983) (V Eaglesha­n O.J., Bird D., Withers R.W., Steed J.W., J.Phys.C 18,1(1985) /4/ Many J., Landuyt J.van, Amellnckx S., Bronsema K.D., Smaalen~S.van, J.Phys.C, 19,5019(1986) /5/ Boswell F.W7, Prodan A., Phys.Rev.B34,2979(1986) /6/ Wolff P.M.de, JansaenT., .tanner A., TcEa Cryst, A37,625(1981) /7/ Wolff P.M.de, Acta Crst., A40.3MW) /8/ Prodan A., Boswell F.W., AcSa Cryst. B^3,165(1987) /9/ Bronsema K.D., Smaalen S.van, Boer jXTde, Wiegers G.A., Jellinek F., Mahy J;, Acta Cryst. B4?,305(1987) ­ Г37 ­

6.7.Radaev, L.y.Malakhova. l.A.Uuradyan, V.I.Slmonov Institute of Crystallography, USSR Acad.Scl., Moscow, USSR

Remarkable anlsotropy of mechanical properties of lithium tetraborate required the allowance for thermal diffusion scatter­ ing (TDS). Therefore, we developed a program Intended for takirs isotroplo and anisotroplo TDS Into acoount In the experiments carried out with a reotangular or ciroular detection window, for Ы­, в /2в ­ and intermediate scan. We used a RED­4 diffraotometer, MoK. ­radiation, graphite nonoohromator. A total of 7036 non­zero reflections with •Inв Л«1.2 A" were measured In the reolprocal lcttioe sphere. The refined lattice conetants of a tetragonal unit cell are ae folle*»i a » 9.479(Э> А, о • 10.290(4) Ai space group le one of the enantienorphous oneei 14. cd or I4­)Od.' The struotural model was refined In anisotropic approxima­ tion of thermal atonlo notion using the data array oorreoted for TDS, up to R,­ 1.63* and R » 1.33%. The analysis of eleotron den­ sity re­dlstrlbution was made using deformation eleotron density вара obtained by the X­Z method. Boron atom is positioned in co­ ordination polyhedra of two typea ­ triangle (B(1)) and tetrahed­ ron (B(2)).B­0 bonds in these polyhedra are unambiguously oovalent. Deformation electron density тара show peaks of residual eleotron density in all Б­0 bonds In B­triangle. These peaks are displaced towards oxygen atoms. Such peaks were also found In all B­0 bonds in B­tetrahedra, the peaks were elighly displaced from the bonds. The electron state of oxygen atoms was considered. Three oxygen atoms out of 4 independent ones are In 2 ]hybridisation state olosa to sp .The 4­th orystallographioally independent 0 atoa is in op­5 hybridization state. The posi­ tions of two Its lone electron pair* were located.

Deforutlon electron density in the plane of [B(1)0J triangle. Arrows denote the directions towards B(2) stoma•

I8­I ­ 138­ STRUCTURA1 INVESTIGATIONS AMD CRYSTAL CHEMISTRY 0? SILLBN1TES

Bi12no20±i S.r.Radaev. L.A.Muradyan, Yu.?.Kargin| V.A.Sarinf V.I.Simonov Institute of Crystallogiap]'.;­, U3SR Acad.Sol., Moeoowt Institute of General and Ii organic Chemistry, USSR Acad.Sol., 2 Moscow; Karpov Physli al Chemistry Institute,Obninsk,U33R

Peculiarities of slllei lte type structures with different li cations were found from n< utron diffraction studies of single

crystals of Bi120e020,Bir2T о.доО^.ао.В!^^ P05gp006)020,

B112(Bi0.5O0a0.5O)019.5O' B 12°20.27. An X­ray structural analyeii of blthmuth germanate was also made. In contrast with the accepted view­point the effective valency of oxygen atoms can be under or over 20 but not only 20. Heavy bithmuth atoms r quired the use of neutron diffrao­ tion for sillenlte accurate structural studies. Atomic mechanisms of the adaptation of alllenite cubic structure (sp.gr.123) to U oations substantially differing in size and valency were es­ tablished from the analysis of the obtained structural data. In Bii2^*eQ.35P0.59D 0.06*°2( the "tatistioal alternation of Те. and P'+ ions having to ally different radii leads to the for­ mation of H­tetrahedra of t/ a appropriate size, this Is due to the disordering of oxygen s on forming [llOJ tetrahedra. In

Bi12(Bl0 c0QaQ,50)0^0.50 *"• Isomorphism of blthmuth and. galli­ um cations is realized due о statistical replacement of a half of [OaOJ tetrahedra by [Ш0 J umbrella­like atomic arran­ gements accompanied by­losses oi some 0 ~ anions. Unusual is the fact that the valency of blthmuth occupying some of M eltes

>0 1.3*. It was found the: in Bi12(Bi0>0;JY0#a9D 0.oe 20.27 almost all N sites are populated by V'*. It has been proved that stable alllenite type struc ;ures with H cation having the affec­ tive valency over 4 can exi t. This is ensured by additional oxygen atom» which occupy ( 0 1/2 0) sites In some of the unit oells.

A neutron diffraction «tidy of Bi12(Bi,Pe)020 , also will be reported. ­ 139 ­ CHYSTAb­CHbMICAL SJTSTEMATIZATION OF DIE SULFATES R.K.Rastuvctaovo. D.Yu.Puehcharovoky Institute of Crystallography, USSR Aoad.Sci., Department of •Qeology, lloeoow State University, Moscow, USSR

The class of sulfates comprises over 300 natural and 400 synthetic representatives which have a common structural peculi­ arity ­ the presence of isolated Ц0, tetrahedra. Consideration of the available classifications of the sulfates suggested by Soviet and foreign scientists revealed their '•bottlenecks1' as well as Inconsistency In the choice of cations which, being the partners of sulfur, participate In the construction of в common «tructurul motif. The suggested here classification of the sul­ fates Is based on the ooncept of nixed radicals developed by M.V.Belov and his students. This approach, made it possible to •Ingle out four basic subclasses (Insular, chain, sheet and fra­ mework) and an additional fifth subclass comprising structures with radicals of different geometry. All the outclasses are di­ vided Into groups depending on the predominant atruotutal frag­ ment which can be represented either by a mixed radloal or la built only of H­polyhedra and isolated S­tetrahedra. In the lat­ ter case the polyhedra surround di­ or higher­valent cations. An Intermediate arrangement is realised in structures with branch­ ing motifs in which S­tetrahedra are just connected with the ba­ sis built of Jl­polyhedra but do not take part In its formation. A further subdivision ia_ made with an account of composition (Ml3) and the manner in which polyhedra are connected In the structural fragment, this classification makes it possible to sum up the structural data obtained for all the sulfate mine­ rals (about 220) and synthetic compounds (over 400) Investigated by X­ray methods. Besides, their structural­genetic relation­ ships can be established proceeding from common architectural features, and a comparative crystal­chemical analysis of the sulfates with regard to compounds belonging to other classes can be made.

со

18­2 ­ 140­ СЯУЗГЛЬ srauoruRB OP CADMIUM PHOSPHORUS CHLORIDE cajPcij

A. Rebbah et el. Inatitut de Chiralo­U.3.T.H.B­Bp 32 Bab­ezeouar, Algiers, Algeria

Cd,P01,, II • +74.53 crystallize In space group Pnma with four formula unite per oell of dimensions! a • 12.972(1), b •

7.925(2), о . 6.956{2)A, V ­ 713.92A, Z­4, \­*.HO), 40«4.*1

The Cd^FCl­3 etruoture was refined by anisotropic least squares calculations based on 1203 independent reflections re­ corded with en automatic four­circle diffraotometer. The final R is 0.041 (^«0.547). The chlorine atoms form two layers about the levels a­1/4 and e­O/4* The projection of the оhiorine atoms on these planes builds a kagome lattice but with rhombio symmet­ ry. In this rectangular lattice, the center of the hexagons whioh are vacant, correspond to the KM. tetrahedra and the stacking of the оhiorine layers is distorted hexagonal*. ­ ш ­ LOCALIZATION OP НПЖООЕН 1Я ТНВ 1Л1Ш OXIDE

Н. Hebbah, J. Fannetler* and В. Baveau*» Inetltut de Chimie­U.S.T.H.B­Bp 32 Bab­емоиаг, Alglera, Algeria •Imtltut Laua­Langarln, Grenoble, Franoe **Unlrerslta da* Solenoeo, I3MRA, Caen, Prance

The structure ofЛТ1НЬ0е has been lnreatlgated by neutron powder dlffraotioni the TiNbO­ framework and the ootabedral die­ toralon previously found for the alkalitltanoniobataa by X­ray diffraction are oonflrmed. The position of hydrogen haa been determined. The similarity of thla compound with aolda 1» shown explaining their Ion exohange properties. The abaenoa of protonlo oonduotlvity can be explained from •truotural arguments. The open oharaater of this «truoture, whloh oan play apart in Intercalation and dealnteroaletlon reao­ tlon le aleo dleoufifled. ­ ш ­ PECULIARITIES OP UORPHOTROPIC PHASE TRANSITION IH (I­x)NaNbO., ­ xPbTlO­j SYSTEM L.A.Resnlchenko, A.ya.Dantsiger, O.N.Razumovskaya, L.S.Ivanova, L.A.Shllklna, Y.F.Sakhnenko Rostov State University, Rostov­on­Don, USSR

Ferroelectric (FE) solid solutions of (I­xJNaNbO.j­xFbTiO.j system with different symmetry of crystal oell componentsiortho­ rhombic (R) and tetragonal(T) are dlsoussed. . The struotural difference results,at x » O.I9 ­ 0.23,ln the appearance of a morphotroplc region (MR), in which these phases coexist. In the vicinity of MR the dielectric permittivity ant! plezoelectrlo pa­ rameters both form two sharply pronounced maxima. This may be related with the behaviour of the structural characteristics; cell parameters, uniform deformation parameters ( (c/a ­ I), ф «fll'l ­ CaepJS. ­ I). This behaviour indicates the complicated structure of URi it is broken up Into ШЦ and MR, divided by a "clear" tetragonal phase (Т.). The peculiarity 'of the system discussed is also characte­ rized by the presence of a superstructure due to the effect of "bearing strain". By calculation the deformation of "bearing strain" was distinguished that enabled u* to establish more pre­ olaelythe dependencei­ oompositlon ­ struoture ­ properties. It is shorn that in lot­ there occurs a transition with • phase shift described by the same multlcomponent order parame­ ter with veotor К lying on the boundary of Brillouln zone, I.e. here only the character of "bearing strain" is changed. In the MRj (region) with the growth of X there occurs a transition to the tetragonal (T) Inherent 7Я phase that corresponds to the ohange of the character of unstable crystal lattice. At X>0.22 there begins the softening of R mode that is characteristic of pure PbTlOj, whereas the soft phonons in HoHbO­ with К + О becone rigid and oease making a contribution into the conden­ sate. In aocordanoe with the general thermodynamiо considerati­ ons both such transitions should be accompanied by a loss of the crystal lattice stability by sons components of order para­ meters that e/XHnmte for the observed anomalies of electrophysi­ cal parameters. ­ 143 ­ ISODIHORPHISH О? НГОЧ­Т 30 AS ТИК RBABON OF ANOMALOUS PROPERIIBS о Eugene 0. Romanoff Lebedev Physios Institute, USSR Academy of Solenoes,Moscow,USSR A representation of a hlgh­T superconductor (30) struoture as • fragmentary on» eluoldatea the regular dependence of its proper­ ties on the struotural features and the variation of compositions. The orystallographio­chemloal analyeia of the substitutions made It possible to reveal, these dependences. Some properties of hlgh­T 30 are typloal of lsomorphoue so­ lid solutions. But this is nit in accordanoe.for example,with the dlsorepanoies in the dependenoe of the lattloe oonstants on the impurity oonoentrat ions (a and h lnorease, and e decreases). It la shown that as for the properties .a hlgh­T SC oorrespo­ ads to a nor* oommon repreaentatlon about an leodlmorphoua solu­

tion. By an exampla of La« xSrxCuO,(regarding oonflguration of atoms OuO as complex R) we introduoe a binary approximation, A. B_R for the solution of component BR»La. _Sr OuO, 1­.. AR ­ I­IB ID c—X X q La,OuO. (m­0«1). Then the doping la aotually described by a rep­ lacement of not a single atoa, but a whole fragment of etruoture. By aeleotlng a single­substitution atom­perturbed area,one may take the corresponding oompound (b*2­_i"rCuO ) , as the compo­ nent BR. Here n»1»2 If only tlw nearest oxygen atom is taken Into aocsunt. But if R­lon is Involved aa a whole.then n«4»6. The lat­ ter ease oorrespondi to small oonoentratlona Z'OeO.2,and in par­ ticular , at x«0.1 (m«1/2) the cJiaraotsvlstlo anomaly la observed In the behaviour of the lattioe oonstants (as,for example, for (SaSr)TiO.). For large x when, at average, a leaser volume for 8r atoa Is alioted, n • 2. The exlstanoe of two type* of fragaente in the struoturee per­ mits ua to extend the analogous approaoh to hlgh­T0 30 without su­

•sTVutions. It la the feature of hlgh­T0 30 as eoaplex iaodlaer­ pheus solutions that two different binary approximations are si­ multaneously valid in the concentration region corresponding to high­T0 superconductivity (x»0.1*0.2 for ba^. SrOuO.), By refle­ otlng the perturbation In the structures, suoh a description in­ dicates a certain instability and the revealing of propsrtlea that are typical of nonhomogeneous ooapounds. The consideration of these features leads to new mechanisms of hlgh­T superconductrdfe ­ 144 ­ THB IFFBOT OF ТНГ Оа=* На JOT Fes (ОН) B0B3TITUTI0K IH THE STRUCTUFE8 OF HARE А10Л1ЛЕ 04ICI0 SILICATES I.V.Rozhdastvenakaya, Ь.У.МЫвпоуа ЮТО "BureTaitelk", Leningrad, Institute of Geology, Talcut Branch, Siberian Dapartaent, USSR Academy of Science*, Yakutsk, UBSB

The 31­0 bond lengths and the 0­31­0, 31­0­31 valenoe anglee baaed on deteinlnatlona and refinement* of the ory»­ tal atruoturea of rare mineral» with oomplex allloate anion* are considered, Struotural formulae after Llbau / 1 /, and R­faetor* (anleo.) are a* followai

0 uB 4 :3e 0 oanaallM *yf»a+x «6­«{ > "H l.,2 3o] (0,F,OH)4 0.033

1 3 nlsartta lOOaj {uB,* .} [ Bl6015](BlaO?)F(OH) 0.062/2/

tokkolta Ia0a4 {пВ<,2^,} [hijD^ (OH)] (F,OH) 0.032 anakalta KgEaCagW {ьВ.г^ l^i^a (OH)] 0 0.036 Although to* average 61­0 bond length* and 0­в1­0 angle* «re clew to 1.62(a) and 109.4°,Individual Taluaa In the** mine­ ral* are! Bl­0(li)i 1.52­1.67! 1.59­1.67, 1.57­1.65, 1.56­1.65 « 0­61­0 I 100.0­116.9? 102.2­119.3° 101.2­116.3? 1o2.4­117.3? Bl­O­eii 130.5­151.9? 131.О­149.6? 1Э1.*­151.в? 125.6­148.7? raspactlsaly. Bay are beyond thosa adopted for «llloate* , indicating uncoepenaated tensions la tn» structure* despite the presence of "soft" (K,Ia,Ca) cation* and additional Uganda. The Intaratonlo dl»tance» and angle» are analysed In t»ra»of chsaistry variations related to the aubatltntlona Ca2|*«a* and I si (OH) In thai* alneral*.

/1/ Libra P., Btructural Obemistry of SiHoate», Berlin, Bprlnger­Verlag (1985) /2/Boott J.D., Oan.MlJu.ral. 14, 515 (1976) ~ 145 ­ CRYSTAL STRUCTURE VARIATIONS IN THE TETRAHEDRITE:=KR£IBERGITE SERIES I .V. Rozhdestvi­nskaya , N.V.Zayakina, V.P.Samusikov LNPO "burevestnik"^Leningrad. Institute of Geology,Yrikut Branch, Siberian,Dept., USSR Academy of Science, Yakutsk, USSR

X­r;iy single; crystal stjdy was carried out on 4 samples from tetrahedrite­freibergite aeries. Tho chemical compositions and unit cell parameters (sp.gr. 1­liiri) are the following: Crystal chemical formula Unit cell parameter

Ffi I g4­\

II Cu Zn Fu Cu * 3.97 l ,24 0.84> l 3 . 2fl^g2 . 02 ) Sbj . p7Aa0 , 12^12.в5 Ю­529 О)

sb Лв s III|Cu,|i05 2n1,34Kn0t0g» (L.'U2I jf;A 3 . 92 0 . 0 7 ! 2. g330.576

EL IV(Cu4,13Zno,605K«l.j») K­''0.13'W5.U7) 3, 92­12. 00 10.492(8) It 1* known that at about 22.5 wt.V. oi Ag the u?trahedrt­ te^lrJeberei te series undergo»* a itructurel tranb format Ion , \. e. the unit cell parameter decreases from about 10.33 A /1/. Our lnvttit 19*t ion» «how that Ag­atoms *ubetltuti? Cu­atom» In Cu­site and occupy it entirely in sample IV $ the content Q­* Cul­eite is not changed. For all sampleu ­ Cul­Sl­2.34, 6b­Sl» 2.43 Й. The higher the contant of Ag in CuZ­ette n. the lon­ g»r >• the distance Cu2­Bl observed.The variations of Cu2­Cu2 distances were not analyzed earller. They increase nlmultaneous­ ly with the Ag content increase up to about 22.5 wt.V, *od in •ample 1_V the value af the Ag­Ag distance equals that in metal­ lic Ag. At the same time the number of 8­atone in B2­elte Is reduced and the Cu2­S2 distance is decreased. I II III IV Cu2­Sl 2.273(3* 2.391(41 2.416(6» 2.540(31 Cu2­Cu2 3.175(4) 3.20 8(5) 3.273(7) 2.B4 7(1) C'u2­:;2 2.245(4) 2.268(5) 2.289(7) 2.013(1) i>i(i;2) 1.0 0.97(7) 0.45(6) 0.09(3) BIS2) 1.6(2) 8.8(7) 3.3(7» 3.8(4) Thus it is supposed that odtahedral Aq­cluster is formed ar­ ound S2­site in freibergite structures with high Ag content. References: /1/ Rostov I , ,Mince\M­Stef anova J.. Sulfide minerals .Sofia, Publishing House of the Bulgarian Academy of Science.1981. I9­I ­ 146 ­

CRYSTAL STRUCTURAL REFINEMENT OF SOME SPESSARTINES (Мп3А12(Ы04)3, GARNETS).

H. Sacerdotl

Istltuto di Mineralogia, Unlverslta di Ferrara, Ferrara, Italy

Sacerdoti and Passaglia /I/ have hypothesized chat the substitution

SI ­> 4H in natural garnets is connected with the dimension of catio.i eight coordinated by oxygens. The structure of garnets тлу be described aa a packing of oxygen atoms, all symmetry related, with sites of 4

(tetrihedraj, 6 (octahedra) and 8 coordination (triangular dodecahedra).

Following Che nomenclature of oxygen atoms given by Novak and Gibbs /2/, the condition of greater stability in these compounds seems to be that were the lenght of octahedral edge 01­04 shared with the triangular do­ decahedron is shorter than the edge 01­05 of the same octahedron, but not shared. In the calcium compounds 01­04 is greater than 01­05; the substi­ tution SI ­> 4H expand the tetrahedron centered by Si, lenghthening the tetrahetral edge 01­02 shared with the triangular dodecahedron and, as a consequence» shorthening 01­04.

In natural and in synthetic spessartines a very low hydratatlon is known only for these garnets where Mn is substitute by Ca. We suppose that in the pure Mn garnet the edge 01­04 is equal to 01­05 and, as a consequence, no Si ­> 4H substitution must be possible. To verify this hypotheses, we refined some natural spes^artines. unluckily these crys­ tals contain some Fe and/or Ca substituting Mn. The results arc discussed.

/1/ Sacerdoti H. , Passaglia E. , Bull. Mineral. Ш. 1 (1985).

/2,' Novak G.A., GiKis G.V. , Amer. Mineral. 56, 791 (1971). ­ 147­

EbECTRON DBHSITY OP FOMIAIE ION IH IiHCOO­HjO CRYSTAL

A.A.Safonov, H.I.Soroklna. I.A.Verin

Institute of Jrystallogrsphy, USSH Acad.Sci., Moscow, USSR

An arraj of precisional data was obtained by X­ray diffrac­

tion from a TiHCOO.HgO single crystal. The structural and elect­

ron paramete з were refined using JOP program with the aid of

the Stuart multipole model. Deformation electron density distri­

bution for H 00" ion was determined and the parameters of the

io, multipole model were refined. The quantum chemical calcu­

lation of the formate Ion was carried out. Electron density dis­

tributions о ­allied by different methods were compared with

сов another af well as with the dat» reported in the literature.

On the whole the theoretical deformation density of the forma­

te ion is in igreement with the deformation density obtained

by the Pourie­ summation. It is especially close to the multipole

density which is also a form representing experimentally obtain­

ed donsity. С le peaks on the bonds both in theoretical and

multipole densities are virtually the same. Apparently, In cer­

tain cases the multipole analysis works as a filter extract­

ing a considt r­able part of the true electron density from the

experimental data.

3

19­2 ­ 148 ­ LKV1SLS OF KIHISRAL UNANMOMORPHISM MANIFESTATION N.D.Samotoin, L.O.Magazine, P.I.Pin'ко Institute for Ore Deposit Geology, Petrography, Mineralogy and Geochemistry of the USSR Academy of Sciences,Moscow,USSR

You come асговв the phenomenon of mineral enantiomorphlem in nature oftener than it was known. Electrons microscope inves­ tigations of layered silicates with a vacuum decoration techni­ que made it possible to enlarge our knowledge about this pheno­ menon. We offered a method of discovering enantiomorphio orys­ tala that are of microne size and have a layered struoture /1/. Enantiomorphous forms of kaollnite IT were discovered* The formation process of right and left crystals in a mineral can take place with an equal chance, but sometimes you oome across the zones where one or another form prevails. The both forms of crystal grow according to the spiral mechanism on screw dislocations with a single or enlarged Burgers vsotors. The enantiomorphism sign of kaollnite mioroorystala doesn't de­ pend on the sign of dislocation determining their spiral growth and gelikoidal structure. Usually enantiomorphism crystal signa coinside w: th eigne of spirals of growth. An unusual enantiomorphlem manifestation was dlaouverad while studying dickite 2M,, naorite 2M2< halloyaite 21!.. They are minerals with Cs*=Oc symmetry, that doesn't let either right or left crystals be formed. Enantloraorphlom of these mi­ nerals is manifested In regular alternation of left and right о " A structure layers within one and the same crystal. This fact proves their polytypics^ originality. froa the point of enantioraorphlem you are also likely to regard the polytypism of many other minerals if taeir struo­ tur* elements (layers, bands, chains) do not have th* oentr* and plans* of avowtry. So «nantiomorphlsm Is possible not only in primitive and axial classes of symmetry but in classes with a slipping reflec­ tion plan*. It oan be observed on th* level of macro­ and *dorooryst*ls, blooks, domens, layers, bands, chains and single >>oljh*uron*. Л''Ш^ШГ*^^®^УШ DlBCOVerle"'Ь»«"°п.• B"ll• ­ 149 ­ ТИС riF.HYURATION OF Ca^u^]. 4H П МОПГИГЛТГОП Г ДНО II

АПП Пв(Ч РП^ . H?0 TO Tl­Г POLYPHOSPHATE D­ (Ca„ CPOjl 4) H, 5chnMdpr, К. Н. Jnst ZentralInstllut ffir Anornanische Chemle der AdW der DDR, OUR­119? Bnrl1n­Ad)ershnf. Rudnwor Chansseo 5

The dehydration of the cy lotetrsphospnate Ca_tP.0,?]. 4H?()

modification I to the pol nhosphate G­(Ca?LP0.1.) proceeds over several steps crystal loorsphically or Inn ted. One of th» in termerfl­ ate phases la X­ray amorpf ;)us and tt Is of special Interest, that this amorphous phase does nnt interrupt the orientation relations.

The cnmpar I son of the it r ^turea of ПЙ?£Р.0|?]. 4H„0 modi Г1 cation I

end 0­(С8?СР0­Т1 i) allows to suppose, that extended building units of cation pnlyhedro preserve their orientation as it was observed in the case of thn clehyttrn • Inn of РЬЛРдО^}. 4Н2° to ^Pb2^PD3­U*x

The dehydration of ПаСН­РО^ !­ . H­O prcoeds over СвСН^РОдЬ also to en amorphous phase and f irther vie X­pnlyphnsphate to О­ССяЛРО,} . ) . In contrast to the first mentioned reaction path here exist no orientation relatione between thn respective phases. In the last time a modifies'ion II of СвДРдО.Л. *H„0 was syn­ thesized /2/, The invest1QB+ions have shown, that its dehydration behaviour Is different from hat of modification I. The ri:iults were obtained by means of oscillation and Welssenberg photographs, high temperature Gulnler technique, thermngravimetry and chemical ana lysis.

/1/ Wnrzala, H.; Thesis B, !98*, Academy of Sciences of GDR" III SchUlke, U­, not published ­ 150 ­ METASIHERONATRITE I I : AN ORDERED STRUCTURE FROM DEHYDRATION OF 0П­ S1DER0NATRITE. F.Scordar i, F . Stasi Dipartimento Geomiпега Iogiсо, University di Bar i , Campus, 70124 Bari, ITALY

Met as i deronatri te is a hydrated suIphate of sod i um and ferr i с i ron quoted in Ittcratufe w i th doubtf u f chera icaI formu t a. The uncerta i nty concern i ng its water content, is re ГIected in the

formula Na2Fe(SC4)2(0H}­nH20 with |<пч<2. Metasideronatrite II can be obtained by partially dehydration from s i deronatr i te , Na^ Fe( SO* )o (OH ) • 3H ,0, a rare m i пега I form i ng OD­structures . Th i s mi nera 1 is not stab I c> and rap i d lу rehydrates to si deronatr i te. The samp Ie was pr i vented from deter i orat i on as it was carefullу introduced into a Li ndemann gl ass conta i ning Mg­ perchI orate. Therefore the structure I study of the compound cou I d be made. Metasideronatrite II is orthorombic, s.g. Pbnm with a=7,132(7), b = 15.987(11), C=7.36H8)A\ Z=4. The crysta I structure was so I ved f ', tt i ng the s i deronatr i te atomiс coordindtes to metas ideronatrite unit cell. Out of the 1547 very 1engthen measured reflections a total of 75$ independent i m rns i t i es were obta i ned by averag i ng all the equ i valent ones . In the final st«ps of refinement 217 reflections with I ^ 2.5 S* ( I ) Ied to an i sot гор i с R vaIue 0.064•

The structure is based on the Na2 Fe( SO4 )2 ( OH ) • H20 structure I unit­s, closely linked to form e three dimensional network. The сhem i сa I compos i t i on of metas ideronatr i te II accord i ng to the structural results seems to be Na2Fe(50д)2(OH)­H20, ­ 151 ­ STRUCTURAL INVESTIGATIOH OP HP SPUTTERED BbN(C,0)­Si FI1MS Shalaeva E.V. ,Surov E. V. .Kuznetsov M.V..Ryabov E.F..Mitrofanov В.У. Inat. of Chemistry of the Ural Department Acad. Sci. USSR , 620219 Sverdlovsk , USSR The films of the HbN(C,0)­Si were prepared UBing HP ion plas­ ma sputtering ND and Si in the Ar+Np atmosphere on the NaCl sub­ strate at T «50° С The structure of the films was studied by transmission electron microscopy (including high­resolution one), x­ray electron spectroscopy and electron­probe microanalysis methods. Two phasee are observed : ultra­fine 5­NbN(C,0) phase, which has NaCl­type structure and 3C stacking ; SiC phase in form of large crystals (Fig.1). The possibility is found for SiC phase to have hexagonal 6H modification at low temperature technology conditions (Pig.2). To our knowledge, this phenomena has an impur­ ity nature.Inasmuch as the lattice parameters of the 6H­SiC phase observed experimentally and 6H phase based on 5­NbN ob­ tained theoretically are near equal and their structures are mutually complementary it is possible for atoms Kb to occupy the octahedral interstitial sites. SiK *,P

N8K,* NBLn

5

U 10 75 E, «eV Pig.1 X­ray spectra: Fig. 2 {001} plane image from a ­ 6H crystall; >>n crystall ( [100] zone axis) b ­ д­ЫЫ!(С,0) cubic phase. 30 stacking interlayers ere absent, л 1 300 000. ­ кг ­ CRYSTAL STRUCTURES О? К, RB, CS ­ EXCHANGED X ZEOLITES IK HYD­ RATES (25*0) AMD DEHYDRATED (400*0) STATES Yu.?. Shapelev, I.K. Butikova, Yu.I. Smolin Institute of Sllioave Chemistry, USSR Academy of Soience, Leningrad, USSR

ТЧгее catlonlo forma of synthetic X zeolite were prepared by ion exohange of the HaX crystals (Si/Al n 1.1) with water so­ lutions of K, Kb, Cs chlorides) the ion exchange degree wao about 50$ for all samples* X­ray data were collected on an automated three?oirolo diffractometer with MOKJ.­ radiation. The cublo spa­ ce group Fd3 was used for all compounds studied heret KNaX ­ a » 25.07 A, 233 P(hkl), R • 0.03W RbNaX ­ a . 25.12 A, 360 F(hkl), R . 0.046) CsltaX ­ a . 25.11*,656 J(hkl), R • 0.053. " Only К ions ale found to penetrate from supercages of X zeo­ lite Into В ­ cage and hexagonal prisms through eix­membered rings at room temperature. In the supercage K, Rb and Св lone are located in site II, on the threefold axis at the eix­membered ring between the p ­ unit and the superoago. In RbNaX and CeNaX this site is partially oooupied by unexchanged Ma iona too. Ra­ ther great concentration of Rb and Os ionenobeerved in site III, near the four­membered rings in the supercage. X­ray crystal etruoture study of the dehydrated forms of К1ШС (a • 24.86 X, 227 Khkl), R . 0.061) and CsNaX (a ­ 24.96 I, 376 P(hkl>, R m 0.058) was carried out at 400 С Upon the dehyd­ ration. Cs ions penetrate through the elx­membered rings into the p ­ cage (sites I' and II') and In a negligible amount lntr the hexagonal prism. In the dehydrated CsNaX zaolite Na lone oocupy completely site lit In the dehydrated KMaX site II le mixed) Ha and К lona are situated here. The dehydration of RbNaX crystal at 400 С results in a complete loss of orystallinlty. It might ori­ ginate from the migration of Rb ions into the hexagonal prisms at high temperature. One oan suppose that the preaenoe of exchan­ geable catlru of a ladge sice in those prisms causes strong di­ stortions In the baslo bonding features of the aluminosillcate leollte franwork. thus, at a great occupancy of the hexagonal pi tine by КЪ Ions the crystal is destroyed. ­ 153 ­ ТИК CONDITIONS OF THE SYNTHESIS AND THE PECULIARITIES OF THE STRUCTURE OF THE NICKEL HEXABORATES. E.3,SiJiuu, V.K.Beluky, V . V . Zavodnl k , O.V.Ozollp». Imtltutf of Inorganic Chemistry Latvian Academy of Science*,Rig», USSR.

The clarification of the interconnections: condition» of the synthesis ­ composition ­ crystalline structure of borates is a constant problca in the chemlntry of boron. Ve have 1nvest1 gated the influence of temperature and of the lower alcohols on the crystal1lzation of the aqueous hexaborate of nickel. Thr 'oilowing borates were obtained In the form of •onix.r.VHluli and investigated by. the method of X­ray diffraction JinalyKla: Hexaborate tl> Solvent I NMHiOW I Ц4О1 I0HU | HaOUrlrlinic mod.) room HzO II (NKHiOli HNllHeO? (OHIHOCHi МЫ room HJO*CHJOH III Ni(H20)f IB» О? I OHU ) HaO(*ono)(тОСНэ )j )» ­ which was detected for the f irut time, The octahedral surrounding of the nickel atone 1Л forced 03 MUf molecules and OH­groupa of B­tetrahedra in the ratio 4HlO + 2»OH In the compounds (I) and (III), 6T0CH> and 6H2 О in (II), ЗНа О • 3'OH in 4 IV) and (V) . Dependinq on the manner of combination of cation with the hexaborate ion, the basic structural units are formed: 1) asymmetrical molecular complexes

NiUI.'Oi I BtOi (OH). I in (IV) and (V) und Ni ( Из О )« ( Bt От <0H )i ] > stabilized by the ikil ronoLecul ar H­hond with the length of 2,66 A in I I ) and 2.910.X in Jill); 2) negatively charged centrosymmetrical complex (N i [ ВвОт ( Oil) J (ОСНэ )) li J1 •' in (II). The crystal 1 iite structure» are stabilized by K­bond«» The juxtaposition reveals the similarity of the structure <> Г 1 he he Mi bo rut он oi' n nke 1 find ritaijnes ium .

30­1 ­ 154 ­ uTHUCTURAX FKATUiliiS OF ТШШОГ BTANIttHEb OP HAJlU=LAia'ri AND TRANSITION METALS iUV.Skolozdra, L.r.Komorovska, Yu.V.Gtmlnik, 0.E.Koretske, '/UeK.Gorolenko Lvov State University, Lvov, U68H

On the basis of crystal structure analysis of the compounds of R­Me­Sn systems (R­rnre eorth raotale, Me­Fo ,Co,i;i ,Cu) It hna been shown that they represent structures inculcated upon atoms of the third component in. 'the known structures of binnry compo­ unds, belong to superstructures or consist of fragments of other structural types. In most superstructures Me and Sn atome are ordered ones, whereas Rand £h atano йте crdtred aweonly in two Duperotructnrnl types

C­dPt0Sn and МсЛ^Ла» structural types Sm^Cu^Snc» CeNiJJi.j,

1л,Со?ВПг,, Lu­,:.'iSn, form monomeric homological sorios based on ­he corresponding frngnmnto. It hoa been ohown that in compounds having email contents of Sn nni R tin reveals in crystallo­=ohemioal aspect the properti­ es of Me end is characterized by high coordinate! numbers.The inorea­ se of tin concentration in compounds brings to nppeernnce of structure types in which tin atoms have different coordination numbers. It has been stated thnt the increase of tin contents reve­ als two tendencies ­ the decrease of coordination numbers (like Me atmsjend conservation of high, coordination numhers. Taking into ac­ count coordination numbers end statistical distribution of Me and

Sn atoms (compounds R(Cu,6n)15, HCo,6n, R,­(Ni,Sn),, HCuSn) or R

К Нп !,п the and Sn (stonnidoa HqHio^kh^q» ^^Ч.х 4 б ­1я) conclusion has been drawn that the change of effective atom radius of Qn de­ pendc on compound composition and atone position in the structure. The compounds of Me*­Me"­Sn systems (Me' and Me" ­ traneition metals) are crystallized into structural types,that are derivatives of compact packings of the =ost freguent struc­ tural types MnCupAl end MgAgAe. Conditions of phase formation of MgAgAe type have bean examined. ­ 155 ­ THtObtTlCAL AND ЛРШЫ) ЛЫРЫЖ Of HICA POLYTTPIE 3,v«3oboleva Etiatltuae of Ore Deposit Goology, Petrography, Mineralogy and Oeoohemlstry, Aoademy of solenoes, Mouoow, UfcitfR

Tne appearenoe of mloaa In nature and among the syn­ thesis products in the form of different polytypea has mad* it possible the utilisation the mloa polytypea aa a sensi­ tive lndloatore of the natural envlromente and prooeuees. The features of the refined oryatal structures permit to reveal the structural faotora (euoh as the ordered oation distribution, OH veotor orientation, distortion of oota­ herda and tetrahedra eto.) oontrolllng the abundanoe of dlfferont polytypea in nature and to oonneot these featu­ re» with the definite condition of the oryetalllsatlon. Th' mloa» * rausoorite oomposltlon usually belong to 211 polytype. The polytypea 1Ы, ЭТ, 2Ыр are alao known, the former being widespread in the sedloiental гоокв. Muscovites 1M sooured in ore deposits (gold veins, oupreous pyrite and tln­=tungsten mineralisation) possess the more ptrfeot etruo­­ ture and шоге deviation of the monoollnio angle from the ideal values then the musoovlteB 1M of the sediment rook». The mobt oommon polytype for the trlootahedral mioaa of the blotite­phlogoplte series is 1M with the ordered layer sequence. In diamond­bearing klaberlltea it we* found the magmatogenlo pjnlogoplt* with the Bemlrrandom atruoture and statlstio rotation on the adjaoent layers on 120°. The appearance of euoh aemirran&om polytypea are due to the rapid and noil­equilibrium oryatalliaatlon prooeea during the melt nigratlon In the upper horltonta.

The rare complex polytypea (3To., 4M2, 6Hg) usuall­ ly represent the ordered thin lntergrowth of Blmple poly­ types (mainly ­in, 2Ц.) or their twins. They oan also be oonneoted with the staoklng faults In the uniform layer eequenoea with layer rotation on 0 and 120 . ­ И6­ 3TRUCTURAL FEATURES OF SHJTHESIZED SKRPKHTIHB MINERALS B.P.Solotchlna. V.V.Vellneky, I.Yu.Loekutov Institute of Geology and Qeophyslcs, Siberian Branch of the USSR Aoademy of Solenoes, Hovoslbirsk, USSR

Structural varieties of serpentine minerals, obtained by hydro thermal synthesis at F­T conditions close to natural спав In the regions of the present middle­ooeanio ridges have been studi­ ed. The synthesis was carried out in the systemsi kaolin • sea water and montmorillonlte + sea water» Synthesis produots were analysed by X­ray and eleotron mloroscopy» Serpentine minerals synthesized at the oost of kaolin mat­ rix are mainly represented by ohrysotlle with llaardlte impurity* Лл approximate ratio of oylindrloal and planar varieties is 511 ­ Cylindrical particles are mainly oomposed of two­layered and sometimes one­layered olinoohrysotlle with parametersi a0 ­ 5.32 A, bQ « 9.2 A, cQ ­ 14 I and a0 ­ 502 I, b0 ­ 9.2 A o0 с 7 A, respectively. Planar particles are represented by 11­ Eardite. Energy­dispersion analysis has shown the presenoe of oa­ tloa group elements of Hg and Si In oylindrloal partloles and Al m planar ones» Serpentine minerals synthesized at the oost of montmorlllo­ nit» matrix^ are also represented by ohrysotile with lieardite impurity» However, the oontent of liaardite oomponent has increa­ sed» Horeoverg aone­llke oyllnders are seen on electron­microsoo­ plo patterns. An approximate ratio between cylindrical particles, isometrlo and oone­like cylinders is 4I2I1. As in the case with kaolin, ohrysotile is mainly oomposed of two­layered clinochryso­ tile with the same parameters and oontent and isometric plates are oomposed of lieardite. The Investigations oarrled out allow to suggest a new point of view of origin of alpine­type aerpentin::. ­ И7­ А ТЕМ STUDY Of "DRTHOPYRPXENE" FROM A LHERZOUTE NODULE M. Sous, I, Dfidony Mtnerelogical Chair of Etttvtis Lorind University, Budapest, Hungary

Л pyroxene ("enstatite") occurring In an ultraba­ slc xenolith (locality: Szentbekkdlla, Hungary) was Investigated by transmission electron microscopy, The studied grains consist of monocllnlc nJ ortha­ rhombic (Pbca) phases with the common (100) plane. The different contrasts In the [010] projected electron micrographs show a large number of randomly distributed bands of monocllnlc and orthorhombic pyroxenes. The width of these binds varies between the unit cell size of the monocllnlc pyroxene (9A) and a few tens of this value. The high resolution micrographs clearly show the (100) lattice planes of bath phases­ Based on the high resolution micro­ graphs and selected area electron diffraction patterns the monocllnlc parts of the. "enstetlte* proved to have pigeon He symmetry (sgi P2^/c). All the monadlnlc lamellae have the same crystr*lo­ graphlc orientation. The observed microstructure and the chemical oata indicate that the calcium content of the monocllnlc bands might be relatively tilgher than that of the orthorombic ones. Our sample It considered to be the result of a sluggish marteneitlc transformation /1/: th« ortho­ enstatlte formed from Initial plgeonite atructure during cooling. /1/ Schrttpfer, l,, Neuea Jahrb. Miner, Abh., 1SB. 2. 1B3. (1988). ­ 168 ­ TUii, MUNCIPA^ 0? PRrJ>A«ING AN [NORGANIC QlAb,:Kl.J, V.A.6osnovfiky,A.B.Ystru. Kishinev politechnicul Insettute.U^Hft It was desoripted a comparison of oryutallorfrauhlc utruc­ ture having axea 2­^ and 6 order of uymmetry and ноше anorganic structures having ахов of syminutj­y 5 order (molecular «truoturt­ neving regular iaosahedron form) /1/. It was attracted a conception a coordination number notion for clearing the causes of formation in one gвашей tho aiyiitalLu­ цгарЫа etructurea in other oaueeu the btructureo having ajtea 5 order of symmetry. It. waa known a large majority of «tome of Mondtileev porlodi.c uycte^ with, even coordination numbers were characterised (4,d(12). Odd coordination number waa characterised for Htruaturea having the axes of 5 order symmetry.analogous relations have been chara­ cterised in one aide for molecular crystals (coordination number 6) and in other aid* for sherio viruses having structure of regu­ lar ioosahedron (ooordiriation number of the protein aubunit b). Consequently there exist intramolecular (a oompoeitloa of the odd coordination atoms IIIb.tb.YIIb кroup of perlodlo ay..tern) and external factors (a charaoter of one­to­one pacing in the apace answerable for forming atruotur» with axes 5 order of syuuntory. It follows from analysis of phase transition from LOlution in crystalline state and with the sharp ooollng In a pacing nonorys­ tallographlc type At last ie more an energetlo advantage (local minimum of the termodynamioal potential ) because a reverae tran­ sition of protein noleoul* lead up to lose a biological activity. к concrete example of preparing dense anorganic glasses Is treatment of melt Mo glass on temperature 950­1000° G with a liquid nitrogen on oooling epeod 1200°C/s. The specimens loaded on the bath and leaved In it till a full oooling.There determined a densi­ ty Increase of glasses on 15,2V

/V Uaokay A.L.Crystallography.?6.^nC. (19а1 > ­ 159 ­ R­1ETVI­XD R'l­JFINEMICNT OP KROKUK KAOU HI П f. :"tnr i*.rij_ . D. Gyep^'iovi And M. Chmiel ovJ Institute of Inorganic Ch^mi гД г у CCHf?, Ы ov..V Л<~л^»>ту of Sel rncci, 942 3o BraLlsLava, Czechoil c.v^l t л. 2Co.il Research Institute, 716 07 OilravaJ?af1vini'fi, Czecho­ slovak I a.

The anal ysl s of the l nteratoml с dl stances b.^sed on t fib­ res ul Is of two ref 1 noments of hi ghl у or dot od Kio) InlL»? from Keokuk, IOWA/1 ,йк has1 shown, that tholr pirdsion is significantly higher than their accuracy. Tho oi О dl stances i n the above г el" 1 nemo­nts var у f г mn 1 . Л>* to 1 . 87Л, the most extreme va) ue among the Al ­ О ijisi jrn t*% Is 1 . ftoX. We have carried out constrained I'ffini.­mr­nU wsl ng the ednte data set as /1 / but i n contr as' t m the above menti onod p^per s the spare gr oup CI wa^ nit*t1 to descr 1 be the post tl ons of 1 Э non­hydrogen д *. OHI'J . ЛI together 47 soft geomotr1 с constralnts С 33 on various inter atomi с dl stances and 1 2 &ri O­SH ­0 >tngl es> wo г (• put on to facllltato the convergence. With the род к ran<;«.' of 1 OFVtlM the number of steps used was 1104 and thi> numbor of unique Bragg diffractions 18в. The refinement converged after the final cycle with the agreement

factors Rv *0.23. Rr­0.09, S*l . 43 And Durbin­Watson rf­1.444. The most frequent e.m.

/'l/Sultch, P. R. . Young, R. А. С1903> CJays&Clay ffinerale 31. 357. /S.­'Young, R. A. , Hewat, A. W. C1BQ85 Clays&Clay tUneralm 3d. 225. •O­TJrit», V. A. . Kashaev, А. А. 00603 XriaiaUografiya B. 224. ­ 160 ­ ON THB CRYSTAL 8TBUCTUKH OP STAUROLITK

Kenny BTAHLI inorganic Chemistry 2, university of Lund, P.O.в. 124, s­22100 LUND, Sweden. Jean­Pierre LBOROSi Laboratolre de chlmle de Coordination, CURS 20b Route de Marbonne, F­31077 TOULOUSi CBDBX, Prance.

The Mingle crystal X­ray structures and chemical compositions of staurollte froa Heas, The Pyrenees (Ц) and Зсаег, Bretegne

fro» the difference between the observed and expected (ordered re site) 8laQ and model calculations.

The refinement nodeIs and site occupancies will be discussed and related to the donaln nodel described in /1/.

«3— 8 ) 0 ъЛ| Bs^ ' J X^W tf® <§. °o о • W °o • ^O * o„ • oG o, 0> L<,.r> «— ,f . e) b) Ha. 1. ylnal difference rourlar вара of ataurolUa, y­0.0, 0.0<ж<О.Ъ and ­0.1<2<0.4, levels at 0.3 a/A * a) Conventional raflneaent, Model I, b) Threa­foldly ­Jilt Pa poeltlon. aodel III.

IU atahl. «.. Kvlck, A. a Salth Л.У. J. Solid State Chem. 73. Jo2 (19 ­161 ­ CRYSTAL BTHUCTUBE 0Г Hg ОРЬ (NO )

£, BHihanrtaKe. c. Sveneaon inorganic chemictry 2, chemical Canter univornity of 6und, P.O.Box 124, 6­221 00 Lund, Sweden

Crystals оГ Hg ОРЬ (ыо ) can be obtained by mixing a morcury(I) nit rata solution, eelfled by nitric «eld, with a lead nitrate solution, The crystala art cubic, apace group N3m, with a­15.412 A and z­B. Tha heavy atom* wara located by direct Mthoda (HULTAM 60) and tha structure refined to R­0.034 for 668 obaerved reflection*. The atructure cone lata of an open framework of formula (Hg.O ) formed from ­O­Hq­Hq 0­ hexegona with tha 0 atoms, tetrahedrelly coordinated to Hg, tn the cornera. The pb lone are located in large cavities in the atructure (Pig. I). Я1х nitrate group», statlatlcally distributed over to different ров It lone, act as bldentata Uganda to each Pb ion with Pb­0 distance* In the renge 2.77­2.69 A. The Ng­0 and Hg­Hg distances are 2.106 and 2.45в А reapecttvely. The laomorphous barium compound, Hg OB* (MO ) with S­15.64B A, can be prepared in the snme way.

2+ 2+

Fig. 1. The (Hg о >n network and the Pb ions in Hg^OPbjtvOj) .

21­1 ­ 162 ­ THE INFLUENCE OF MECHANICAL TREATMENT ON QIFBSITE POWDBR U.Steinike.H.­P.Hennlg.K.Jancke,J.Jedamzik, U.Kretaachmar Zentralinstitut f. phyelkalieche Chemle der Akademie der Wiesenschaften der DDR.1199 Berlin,DDR

In recent years several groups have been concerned with the mechanical activation of glbbeits (A1(0H)», Bonoolinic layer lattice) In connection with a ehort tine heat treatment procedure 1­4].The aim of this work ie the investigation of the influence of a mechanlaal activation on structure and reactivity of glbbslte in dependence on etreae mechanism (pressure etreea and shearing etress in vibration­mi 1 In,shock stress in disintegrators). Bach of the mechanical aotlvation results In crushing or smashing of the initial agglomerates.A very high treatment results Also in a crushing of single grains. With increasing mechanical treatments time or Intensity) the upealfic surfaae is increased,the degree of order (do) and the grain size are decreased. The Influence of shock stress ie smaller than the Influence of pressure stress and shearing etreea,

Table 1: Influence of different stress mechanism on gibbalte •till spec, surface degree of order/do •u/g(S6%) rel.unitd 0.1) untreated 0.1 1 vibration и111 З.в­46 0.7­0.1 disintegrator 0.Э­ 3.1 0.6­0.7

Under the conditions of shock stress there are re­. It displacements of the layers parallel to (0l;i). By It a favoured orientation results parallel to the cleavage face. There are formed plate shaped particles. Under the conditions of pressure stress *nd shearing stress an additional destruction vertical to the layers results and the particles are rounded.

Tha Mechanical activated gibbeite has an increased reactivity (e.g. the solubility).The activation •ntorgy of the dissolution is decreased. ­ 163 ­ Table 2 Activation energy of the diaeolutio proceae of mechanically treated glbbaite treatment degree of order actlvatlo i energy do.rel.unit(tO.l) kJ/mol(t6%) untreated 1 111 [5, vibration alii 0.7 60 vlbratjon Bill 0.Б 16

The thermal dehydration of gibbaite la dependent on the mechanical treatment,that meana on the degree of order and aleo on the primer/ particle alee.The gibbaite with du=0.& and do<0.b la tranaformed under oondltiona of eh^rt­time­heatlngt1.8 10*K /nln)[6} and of a long­timvi­heating<7 .6 Ю­»К/ю1п) In thia way: do = 0.f> : glbbelte ­> boehslt ­> Al­oxldee(tf»nd other) ­>i Al oxldee(X.. amorphoua ox Idee ) <­>a£AliOi The mechanically Induced degree of order haa ftlao In­ fluence on the temperature of tranafornatlon.

Referencea: (UZolotoveklj B.P..Schharin A.V.«Krivoruohko O.P. , Krlger T.A.,BuJanov R.A. Iev.S1b.Otd.Akad.Nauk 88SR,ееr.Chla. Nauk 17(392)36(1964) f2]Paramzln 8.N.,Krlvoruohko O.P.,ZoltovaklJ B.P. sae [1] 17(382)39(1964) (3JZolotovaky B. P. , Paramain S . N. .Krivoruohko O.P.. Bujanov R.A. яви (1 ) 17(446)80(1984) [4]Bollmann U.,Becker K.,Berger H.­J.,Blrk* P., Engele 8.,Gruhn 0., Janoke K.,Kraak P., Langft R.,Stetnika U. Cryet ifee.Technol . 23', 130Э( 1В86) (&)Rinn 0..Petting P. Chen.­lng.Techn. 53,971(1961) f6JNeleeendorfer F.,Stel«ike U.,To)ochko B.ti., Shftromov И.А. Liucl. lnstrum. and Methoda in Phya.Rea. A 261,219(1987)

21­2 - 164 - STUDY OF DISTRIBUTION OF POINT-DEFECT CLUSTERS IN POTASSIUM BICHROMATE CRYSTALS BY CHEMICAL ETCHING H. Szurgot Institute of Physics, Technical University of Lodi, b5d±. Poland

Point defects determine many physico-chemical nroperties of crystals. They are usually associated with impurities and dopantB accidentally or intentionally introduced into the crystal during its growth. Therefore, formation and distribution of point defects in crystals are related ,to methods and conditions of crystal growth and post-growth treatments. Point defects usually occur individually or form clusters. Clusters can be easily revealed by chemical etching of crystals because they are instantaneous centres of preferred dissolution. The aim of thiB paper is to study the distribution of point.-def eel clusters in potassium bichromate (KBC) crystals grown from aqueous solution. For revealing theee defects. HCOOH and other dislocation etchanta were used. It waB established that flat-bottomed etch Pits localizing point-defect с Lusters are non-uniformly diatri Imted in КПО crystals. They occur in each sector of the crystal but then density in some sectore is particularly high. The f ollowing sectors: (010). (010), (100). (001), (ООП; (101). (011). (012) and (111) exhibit a large number of the point-defect clusters It means that the impurities present in growth environment are adsorbed and captured by particular crystal face.n. These impurities change growth velocities of the faces and. consequently,- influence the morphology of KBC cryatn1я. The anisotropic distribution of point defects. d i з locations and inclueons in KBC is a source of differences in lattice constants of various sectors. It leads to a good visibility of growth sector boundaries in these crystals. Apart from the point-defect clusters formed during crystal growth those created by /--rays from Co source were also revealed and analysed. It means that etching is a valuable tool for localization of these defects independently of the method of their formation. This work was carried out under Research Project ("PPP 01 20.3-2.4. ­166­ STRUCIUJUL D131W 0» 0RY3TAL3 POSSESSING ЛШОН^АЬ PHVSICO. cabuiOAL isuemcisa V.H.Talanov polytechnic el Institute, Bovooherkaaelc, U33H

A method of constructing diagrams for possible crystal sta­ tea /LitOJ/ on the basis of tba phenomenologioal theory of phase traoiitli.na of the second kind and similar transitions of the firat kind (the ao­cajled. quasi­continuous transformation) is proposed. These diagrams graphically shoe disposition of all pha­ ses poaaible ih a thsmiodyaamlo system, the unity and diversity of the structural types of oryatala /I/. DPCS make it possible to predlot matarlala having monomial properties sinoe the bounda­ ries bet«e«n some phasee correspond to a oritioal state. JL>.u.:i>li~ fiod by ni­ihcln, atructural o.e chad lams for low­syi.Ji;elry jhaen for­ ration fro.M various regions of №03 are presented, information on stratification of the equivalent points of group Pd3m le given, patterna of alilfta and redistributions of atoms are shown. A general law for mechanisms of phaeo tranaforMntionn le revealed. It Is a structural m.n3ot;ue of the well­loiown principle of Le Chatelier ­ Browm If by changing ;xternal parameters of the medium a oontinuous or quasi­continuous phase transition ao­ oompanied by changes in crystal symmetry occurs, then a microeco­ plo ir.oohanlsm of this transition /shifts arid rearrangements of fitoma / "counteracts" the aotion produoed "tending11 to maintain the symmetry and the structural type of the Initial phaae. In faot, In phase transitions in spinals aoeompanled by symmetry change W3m­I4./amd a struotural compensating effeot Is connec­ ted with a reverse oharaoter of distortions of to tetrahedron and ortahedroni in phase transition Fd3m­ F43m with a reverse oharao­ ter of the turn of tetrahedra of ootahedral oatlona and anionsj in phaae tranaltion Fd3m­J42d ­ with compression and expansion of tetr«hedra and so on. The established law determines the dlraotion of the change In the atruotura Qf the initial phase during phase transformationa.

/1/ Talanov V,M. Phys.3tat.3ol.(a), 106,к 129 (1988) ­ 166 ­ CRKSTAU/OCHKMICAL УЕАТШШЗ О? THE HYDHATION PROPERTIES ОТ SOME IHORQANIO COMBINATIONS O.S.Teimurov The Institute of Qeology,Academy of Sciences of Itorb.sSR , Baku,

One of the basic directions of e modern chemical science is the Intercommunication between the property and structural features of combinstion.The hydration properties of eome com­ pounds have definitely theoretioal and practical significances among the different chemical features.for example.hydration Is one of stages In the building stones formstion.lt Is known that In ancient times some of Inorganic compounds (CaO.CaSO,­O.^HpO) were widely applied in the building practice.Some of anhydrous e*lclum silloatss (Ce­SiOc, f ­Ca2S10,,) and eliminates (OajAl2 Og.CaAlgO.) are used in the modern astringent material compo­ sitions. All these compounds have the high hydration ability. The structural faotors,which have an influence on the hyd­ ration ability of compounds are generalized in the article,and Is ahowsn that the ion and structural unit activity Is Impor­ tant . Ths study results of orystallochsmlcal features and hyd­ ration a' lllty of sons germanates,ferrites,ohromatee,manganates, eliminates and other alkallnerearth element compounds show that the hydration ability of some combinations is conditioned by the Ion activity and the structural unit.Tor example,in the Sr QeO, structure,ths coordination strontium number is heterogeneoue (6,8) and there Is a visible alternation in the interatomic dis­ tance in ths oxygen strontium aolyhsdras (Sr­0 .2.43 ­ 2.43 ­ 2.82 A ).There are central Ion polyhedra distortion in the oth­ er structural compounds by ths stability coordination cation nueber.Tor example,in the SrPbO, (3r ­0­2.39 ­ '2.98 A ),Ca2

Sn04 (Q»­0 ­2.34 ­ 2.77 i) Ca­jAljO^ (Ca­0 ­2.55 ­ 3.075A),Ca2

»»205 (Oa­0 .2.33 I 3.00 l).Sr2Fe205

3rOa,3e4(Sr­3e­2.999 ­ 3.443 A),3r30a205Cl2 (Sr­0 ­2.336 ­ 3.

834 I , Sr ­ 01 ­3.006 ­ 3.538 A), Ba Ru60,2(Ba ­ 0 .2.66 ­ 3.41 1 ) structures and others. ­ 16? ­ KOSSBAUEROGRAFHIC INVESTIGATION OP CRYSTAL WITH 3YHMETRY Pnme AND R}o

I.O. Tolpekln. V.O. Labuohkin, Е.Я. Ovohlnnlkova, E.V. Smirniv All­Unlon Research Institute of Physical­Technical and RadJotechnlcal Measurements, Moscow, USSR

Сrye tali of the epaoe groups Pnma and R?o «ere investigated both experimentally and theoretically by using dlffraotion of Moasbauer /­radiation. The atruoture of the hyperfine fields In a fe,BO, crystal (spaoe group Рпша) пав examined for th» tempe­ rature range from 293 to 5?0 K. The magnetlo structure of a 'e,BOg orystal using a qualitative Tie» of the energy epeotra of dlffraoted radiation was determined. Th* effeot of oomblnsd hyparfln* lnteraotlon in the crystal ой th* energy speotra of diffracted radiation «as Investigated. Th* resonnnt peaks osused by combi­ ned hyperfln» lnteraotlon w«r* observed'/1/. The pu­ rely nuolear quadrupol* maxima In the.scattering of Hossbauar f­radiation were observed in the experi­ ments performed for 520 K, The Investigation of a FeBO­ orystal (spaos gro­ up R3o) was oarrled out. Ths effsot of a domain stru­ cture of th* sample on the form of th* energy spectra was examined. Th* experiments performed for twordoma­ in sample demonstrate th* possibility of th* domain struotur* investigation using dlffraotlon of Hossba­ u*r g ­radiation. /V Tolpekln I.a., Kovalenko P.P., Lsbushkln V.O., Ovcblnnikova E.H., Sarklssov S.R., Smlrnov K.V. Sov.Phys.JETP jjl» 404 (1988). ­ 168­ ВГ­PHASE GLOBULAR 2:1 LAYER SILICATES S.X.Tslpursky*, Bella B.Smollar*. N,V.Trubkln*', B.A.Salcharov", Tatjana A.Ivanovekaya' •Geological Institute of the USSR Academy of Science*; ••Institute of Or* Geology and Mineralogy, USSK Academy of 3c lances

1. X­ray and electron diffraction data show that globular dloctahedral 2:1 layer silicate samples of ancient depoelte are often represented by two micaceous mlnerala differing In Fe­contents. 2. Combination of electron microscopy, electron diffraction and energyr

tf TV IW b d« ­ (1 ~ Cr.* )<1.616 • 0,16 (C*t. /(l ­ Cr, )] "l •

v + i.eec»­M*

IV tv (CM and Cw« are Al­ and *a»+­contente In tetrahedra),

а d._. ­ 2.06CM» +1.98

+ 1.93C*i + 1.94CT1

(СЖ11в the content of the cation Rl In octahedra}. This allowed simulating the structures of 2:1 layers for each phase. 4. Diffraction criteria have been found for identification of the presence of two phases in globular dloctahedral 2:1 layer silicates. Using simulation of XRD patterns a good agraament has been obtained between the experimental profiles in the region of 060 reflections and those calculated for the blcphase samples under study. ­ 1в9­ X­RAY INVESTIGATION OF TIN COATINGS

V.Valvoda, R.fierny, R.KuSel Jr., L.Dobia5ova Faculty of Mathematica and Physics, Charles University, Prague, C?.echos) ovakia

TIN coatings are Industrially utilized for their high hardness and wear reel stance. X­ray diffraction method was used to find a possible existence of gradients of structural parameters through the TIN coatings deposited by magnetron on stainless steel substrates. Chemical composition of the coatings was determined by Electro^ Probe Microanalysis. X­ray data obtained from the stoichiometric and subatoichio­ metrlc TIN coatings before and after grinding off approximately one half of the original coating thickness were compared. In the substolchlometrlc coating there was observed a small amount of flr­phase near the coating­substrate interface. The observed differences In the lattice parameters before and after grinding have indicated the possible occurence of composition or stress gradlc­.ts (in contrast to the stoichiometric samples). Several pairs of adherent TIN coatings and their powders obtained by dissolving of the steel substrates were examined to ascertain the Influence of stress relaxation on strue tor*1 parameters. It was found that the line breadths remained unchan­ ged due to the structure defect present in grains whereas the lattice parameters and their aniaotropy decreased by the­ stress relaxatIon.

22­1 ­ 170 ­ SOME STRUCTURAL FEATURES OF PYR0VANADATE3 MM'VjO, (M ­ Ba, Pb, Sri M'« Cn, Ci, Zn, Cu, Mg) yu.A.Vellkodny, E.V.MuraBhova Research Production Association "IHEA", Moscow, USSR

Till now almost all of the above mentioned compounds have been, prepared by solid state method. They have been Investiga­ ted by single crystal X­ray. When investigating large Bo, Pb, Sr and email Ca, Cd, Zn, Cu, Mg cations varied and changes ta­ king place in crystal structures have been considered. These structure» are heterodesmio and form four families. Им first of them includes BoJl'VgO^ (M1 ­ Ca, Cd, Zn) with Infinite oolumns [M'VjCwJ^, • The nature of M' cations In­

fluences the Ы 0 and V,07 connectivity In oolumns. The Dl'v.Oj.J 4­ framework oontalnlng LV^O^V " groups characterizes the second family, which includes SrUgV^Oy and

РЬН'У2О7 (*' • zn, us). In case of small differences in the values of r(M) and r(n') (for instanoe Sr, Ca and Sr, Cd pairs) solid solutions art formed Instead of 111 compounds. PyrovancHstee Srll'VjOy ( м' ­ Zn, Cu) have unique structu­ ral types. Thus, the decrease In H radius In Ва­РЪ­Sr sequence re­ sults In structural ohangts from oolumns to frameworks. ­ m ­ CHlfBTAL CHEMISTRY 0? SOKE 5J­MHTAL COORDINATION OOMPOUNIB WITH 8ВШШЛ1 AND TELLURIUM TETRACHLORIDES Б.У. Volkov. L.A. Aalanov, Z.A. Foklna, V.B. Rybakov, .N.I. Tlmoahchenko, V.L. Kolesnlohenko InBtltute of General and Inorganic Chemistry, Klevi Lomonoaov State University of Moeoow, Moscow, UQSH

Coordination compounds of 5d­metal (rhenium IV, platinum I?, gold III) hal1.dea with eelonlum and tellurium tetrahalldea have been synthesized. The synthesis of these compounds was performed in nonaqueous chlorlne^contalning media by the equation!

iccn • ш, . ianO£Vx.

Complexes of the following general compositionst ReSe201l2

(1), ЯеТег0112 (2), PtBe20l12 (3), PtTe2Cl,,2 (4), AuSe01? (5),

AuTeOI., (6), AuSaBr? (7), AuSeOl­Br^ (8) have been obtained. exchange reaotlone Involving replacement of the llgand ­ chalcogen hallde ­ are typical of these oomplexes. Гот gold aoap­ lexes, resotiona oarrled out in thlonyl chloride by the equation!

AUIUCB'X^) t s"x4 , AuX3(s"x4) * S*X4 allowed us to establish «he

bound ligand stability serieei (aCl^ j­<­ Те01ц ^ SeOl^. Investiga­ tions of these compounds oarrled out by spectroscopic methods (IR, Raman, NQR> electronlo absorption epeotrosoopy) allowed us to obtain information on their struoture and coordination peculi­ arities, but they oould not explain some of their ohenloal pro­ perties, eapeoially the exchange reaction aequenoe. An X­ray diffraction analysis baa bean performed. The ooaaon feature of the structures of these complexes la the presenoe of the IClg fragment, «hers the ohaloogen atoa Ilea at the vertex of the regular trigonal pyraaid KXt supplemented by three exteu­ ded contaota with the halogen atoms belonging to «ha coordination sphere of the «etal, An Interesting peculiarity was observed for rhenium and gold complexes «1th tellurium tetrachloride. In whloh four nonvaleat contacts ware found whloh form the quadrangular baae of the seven­vertex polyhedron of the tellurium atom. In the atruoturaa 5­8 the gold «torn is surrounded by four halogen atoms at the vertloea of a square i In the structures 1­4 the metal atom lias at the oentre of symmetry and is aurrounded by six chlorine atom» at tha vertices of the regular octehedron

MC16 . Thus the oomplexes have the atruoturai П­ их i whloh •rpslns well their involvement In exchange reactions of tha above type. гг-2 ­ 172 ­ CRTBTAbLOGRAPHY (Я НЕГЕМЖГОЬЕАЯ Oe, Ir, Pt GOMPLEDS AHD CHibcoGBie B. V. Tolkov. V. I.Pekhnyo, V. B. Kybakov, A. A. Aslanov Institute of General and Inorganic Chemistry, Ei«v| Lomonoaov State University of Moscow, Moeoow, UBBH

The structures of oaloroohaloogenlde complexes of the compo­ г sitional 0э8гС11г (1), 0s6e2Cl,,2 ( ). 0вТе2С1,,2 О). Pt8201g

(<0, PtSe201g (5), PtTe2Cl12 (6), 1гв3С1ц(7) have been investi­ gated by X­ray diffraction analysis (Patterson method). In the complexes (1­6) the metal atom la In the particular positional (1) at the oentre of symmetry on the 3­fold axla, (S) at the centre of symmetry on the 2­roJ.d axis, (3­6) a* the centre of symmetry. In the case of the compounds (1­3, 6) it Is surrounded by 01 atoaa at the vertioea of the regular ootahed­ ron KOlg , tbe obaloogsn atoms lie at the vertices of the tri­ gonal pyramids SOI, . At the seme time, the ohaloogen atoms «re observed to be bonded to tbe 01 atoms of the metal polyhedron) a* a consequence, one of the faoea of the Os polyhedron is the supplementary triangular base of the S polyhedron in tbe oom­ pound (1). In the structure (2), the supplementary base of the S« polyhedron consists of the CI atoms of as many as t»o On po­ lyhedrons and in the complexes (3, 6) of three metal polyhed­ rons. Taking this into acoount, the coordination number of chal­ cogens increases to six, and the polyhedron itself assumes the shape of • distorted ootahedron. In the oompleios­(4, 5) the Pt atom is surrounded by four 01 atoms and two ohaloogen atoms of the BClg (E » S, Se) mole­ nui.es, oooupylng « trans­position at the vertices of a regular ootahedu Tbe ohaloogen atoms lie at the vertices of the Pyra­ mid» formed by the Pt atom and the two CI atoms of the chaloogen surroundings, oontaots with the 01 atoms of the Pt polyhedron being possible and the coordination number increasing to *, 5. In the oowplex (7), where В coordination has been first es­ tablished in different Uganda! SC12 and SC14, the Ir atom is surrounded by four CI atoms and two S atoms of SClp moleoules in * oi«­position at the vertices of a distorted octahedron. The S atom lies at' the vertex of tbe pyramid SCI, . Contacts of this atom with the CI atom of the Ir polyhedron have been found. ­ 173 ­ LOCAL STRUCTURE DEFECTS IN ZIRCON, XENOTIME,HAFNON AS AN INDICATOR OF CHYSTALHSATION CONDITIONS S.L Votyokrw, A­A.Kr^snoh^eV Institute of qeology and qeochenietry, Ural Department USSR Academy of Sciences, Sverdlovsk, USSR

Various local defects in Isostructural synthetic zircons, xe­ notlmee and hafnons obtained from solutions in different melts under hydrothermal conditions and by solid­phase reactions method at temperatures about 400­125r°C md pressures 1,250­600 bar were analyzed by the EPR and luminescence spectroscopy method, each of the Investigated minerals ia characterized by its own wide band luminescence in the region of 250 500 nm, irrespective of the type of iynthesis. 'ihis luminescence denends on oaramaqnetic defects in the structure! matrix cat.­tons in an unstable valent state and uncontrolled ions imnurity ­ Zr + (local symmetry ­ C, ), Ti

,f |DM« Ln zircon, lr (02il), S10,3­ (Cs> ,n XGnotlmc., Hf3+ ln hafnon. At the same time concentrations of these centree, their behaviour under irradiations and heat treatments depend on the temperature reqime of crystallisation and the melt composition. Such defects ав Но +, АШ ~ агз specific for zircons, obtained from melts, but Sio* for hydrothermal zircons» the centre 0 /Mo la characteristic for xenotimes obtained from melts. Oxyqen vacancies and paramaanetlc centres associated with them (SiO. ­ 2­ PLO5 ~* in zircon, PO, ­ in xenotime) appear after neutron ir­ radiation of crystals. Iaomorphic impurities of ion­activators of d­ and f­element» cause the appearance of thermostable colour (the green one for zirennn with Cr ­* Si and the yellow one ­

vated minerals within a wide temperature range allows to consider them as perspective luminonhore. The resulta obtained are of interest for. materials science and extend petrogenetic information of natural minerale of Ню zircon structure. ­ 174­ PH4LLDSIUCATE PuLYTVPES: THEIR CLASSIFICATION AHD X ­ RAf IDENTIFICATION

Z, Will» and 5. Durovlc

*Coal Research Institute, 716 07 Oetravj ­ Radvenlce.Czechoslovakia Inst. of Inorganic Chemistry, Slovak Academy of Sciencea, B42 36 Bratislava, Czechoslovakia.

Using the order­disorder theory the following number of maximum degree of order (MDO) polytypes for various phylloallicate famili­ es were derived; 6 MOO polytypea for homooctahedral micas ( Jentl­ cal occupancy of octahedral el tea), 14 MOO polytypea for me Jocta­ hedral micas (Identical occupancy of two octahedral altssl 12 H00 polytypas for hotjoactahtsdral serpentines, 36 И00 polytype for me­ BOODtahedral kaollnltea, 10 MDO polytypes for talc, 22 MI J polyty­ pea for pyrophylllte and 20 MDO polytypes for homooctahe iral chlo­ ritBB. Diffractions with к • 3n (orthogonal Indexing) corr .pond to a 3­fold hypothetical superposition structure. This If a structure which is common to a given subgroup of polytypes, the so called lubftmlly. Subfamilies are denoted А, В, С ... etc. iffractlons 201 end/or 131 are the most suitable for X­ray lder .flcatlon Df aubferalliee. According to the distribution of the ­iter.alty of the above diffractions the MDO polytypee may he divided Into two subfa­ milies А, В for tele, pyrophyllite and micas end into four subfami­ lies A, B, C, D for serpentines, kaollnltes and chlorites. Among directions with к / 3n which are characteristic for indi­ vidual polytypea, there are also diffractions " 1. These are charac­ teristic for YZ projection of the particular ­tructure. All MOO po­ lytypo» of the same family of phyllosiHcatet which have the aame YZ projection, have the same type of intensity distribution of Di­ ffractions Okl. According to the Y2 project'on of the structure, MDO polytypes «ay bo divided into NDO­ВГОи'J in the framework of • given family. Oiffrictiona 021 are suitc­Ле for X­ray identifica­ tion of HDD groups. They are denoted I, Ti ... etc. Thanks to this, • "cross" classifies! on table may be compiled for each family of phyllosillcates end ^dividual N00 polytypc may be identified if the subfamily and M00 group are determined. ­ Г75­

ON THE ftm.: OF A CLID£ PROCESS III THE FORMATION OF РЬМПОд FROM

Pb(H2P04) AMD THE ZVlSTENCt OF ANALOGOUS ARSENATE PHOSPHATES H. «.oriels, K. H. 3est ind P. A. Howl.j* Zentreling* itut f'Jr annr^an 1 sche Chemie der Akademie der Wiesenschaften der DDR, Berlin, DDR, •University uf Aberdeen, Department of Chemistry, Aberdeen, United Kingdom

н ри The reaction рь(Н2Р0д)^—* РЬНРОд + з $ proceeds crystallo­ graphlcally oriented /1/, The product Is an Intergrowtn of crystal­

line PbHPQ. and amorphous H,PQftt fcom which the latter can eaally be extncted by shaking with e. g. ethanol. The aim of cur paper le to answer the question, whether the oriented course of this re­ action rests on topotexy end ­ If eo ­ whether we сап draw воте conclusions on the structural mechanism of this reaction. A first idea of the structural mechanism was drawn by meef­.s of a comparison*" of the two cryatal structures In their orientation relation. It is to suppose that Infinite рЬ0 pDlyhedra chains arranged In layers remain almost unchanged in their structure and orientation during the reaction. These chains reach their posi­ tions In the product structure after a glide process. More de­ tailed conclusions were derived by determination of the As/P distribution between the two product phases when mixed crystals

РьГн2(Ав,Р)0Л­ were used as the. starting compound. »n the educt phase the mean Аэ/P­rstlo was determined by chemical analysis and the occupation of the two independent crystallographicslly posi­ tions, by X­ray structure analysis.

/1/ Woriala, H., Oost, X. H., (19B2), Z, anorg. allg. Chem, 4B_6, Ш ­ 176. ­ 176­ NEW MEMBERS IM Т1Ш FAMILY 0? COMPOIKDS WITH A MIXED ANIONIC TETRAHEDRAL FRAMEWORKS BASED ON ^­TRIDYMITB O.V.yaJmbovleh. O.K.Hel'nlkov, V.I.Tarasov Moscow State Unlvereityi Institute of Cryatallography, USSR Acad.Sci., Moscow; Institute of Silicate Chemistry, USSR Acad. Sci., Leningrad, USSR

Many crystals with mixed anionic tetrahedral frameworks have ferro­and pyroeleotrlo properties. An X­ray investigation, "1' three new oorapuur.de CsJMnPoX (Ha.KUZnPOA and NaSА131?с^.­ i.'i V.„( showed that their crystal structures are derivatives ь< я anionic framework of 6­tridymlte.

compound unit cell parameters, X (p.gr. z fcluTiuT * a к о gr/cmJ

CsknP04 9.575(2) 9.128(3) 5,595(1) Я>п21 4 3.84 4.32

Ola.MZnKty 17.609(5) 8.112(2) P63 24 3.41 5.21

ЯаАШ206. И,IHgO 5.225(11 8.221(2) 7.521(3) r2^m 2 2.30 3.10 W« oasis of these structures Is formed by tetrahedral Mn, Г­, Zn.,.?­ and Al,31rfrenewjrks of superimposed nets of slx­membered rings as inl­tridyrtlts, Mn.JP­framework of the ietrahedra has been found for th» first time In CaMnPO.. Na+,K+,Cs+ cations and HgO molecules arc positioned in the channels of tetrehedral framework (A­positlon). An example of the morphotropic series Ва|2пРоЛ ­(Ka,K))ZnPo2­ KJZnPO^ illustrates how the change of cation 16 the A­poeltiofi affeots the symmetry of the whole struc­ ture and the topology of the tetrahedral framework. In OsUnfO. three of four position of oxygen atoms are split and ocoupied statistically. The ordering of oxygen a' ..is will be prrbably accompanied by л phase transition(with temperature lowering) to a more energe vUy favourable state and by a reduction of the symmetry as in the case of the structures of RhAlSlO, group. The voids in the tetragonal framework of the formular analogue of analoime HalAlSigO^­1,1H„0 are о mpied by the "seolitic" water molecules which can be easily removed without a chniu:e of alumosllicate framework. The minimum dlamoti­r or th» wid.­.­!4. channel window of the framework is 5.7 A. ­ 177 ­ PECULIARITIES OF CRYSTALLINE STRUCTURES OF V­Ав SULFIDES WITH SPHALERITE­LIKE SUBCELL L.A.Vanulova, 0.V.Frank­Kamenetskaya, I.V.Rozhdestvenskaya, V.A.Frank­Kamenetsky Institute of Geology of the Komi Science Centre, Ural Division of the USSR Academy of Sciences, Syktyvkar) Chair of Crystallography of the Leningrad University, NPO "Bure­ vestnlk", Leningrad, USSR

By meane of X­ray diffraction {single­crystal diffractometer, refinement by the least­=square method in isotropic approximation) arsenooulvanite and V­As germanite structures have been determined

Cu 3 and Aa As Ge Cu D to be As2(As,Cu, о J . (V,Cu, D )fiCu.2 g 3 2 2 f « ' Ig

Cu S я (V,Cu, о )­Cu­2 g 32' " 7,4а space group P43n, 8=10,527 and 10,588 A, respectively. The basis'of the structure is a sphalerite­ like aubcell F which rtveuls itself in the moet intensive reflec­ tions h+k, k+lr l+h­4n. In contrast to sph?lerlte, tetrahedra of reverse orientation are found to be populated. A eup­er­^atructure with a doubled parameter arises due to ordered As, V, Ce, Cu distribution over tetrahedral voids oe the cubic close packing. In both structures the arsenic tetrahedron of reverse orientation le surrounded by 6 copper tetrahedra of direct orientation sharing edneB with the former. It results in reduction of arsenic­copper о distance down to 2.70Э­2.722 A in arsenosulvanite and V­As germa­ nite. In 3, position eulfbur has c.n."S and is displaced towards 1 о the M. apex. S^ —M­. distance is 2.290 A in arsenoeulvanlte and 2.220 A in V­As germanite. In M. "position arsenic reacts noc only with sulphur but also with surrounding metal atoms. The process leads to [ AeCiigj clusters formation­ the clusters having the shape of Laves polyhedra. The cluster centres coincide with the cubic !•­ lattice nodes and are similar to those in qrey ores and talnakhite. In contrast to the latter the structures show Imperfect population of non­=copper tetrahedra. Disappearance of symmetry centre «id symmetry lowerinq result from ordering in cation and vacancy distribution. Crystallomorphologlc, cheml з1 and X­ray diffraction data suggest that colusite, nekrasovite, germanite are minerals iso­ structural with those investigated before. This enables us to solect them as a separate group with the general formula,­ Cu, BS_., x .o,25, n­As,V,f>n,Sb;Ge,Fe and call it a colusite group according to tho minora 1 species ucrmitting most vide isomorphous replacements. 23­1 ­ X7S ­

A STUDY OP THE SOLID SOLUTION SYSTEM FbKtj1 /«Nb^.O, ­ ГЪТЧО,

S.M. Zaitsev, A.N. Vaekio» S.M. Ycmelyanov and V.A. 7,np;oruiko Rostov State University, Stschki 194, ^44104 Rostov­on­Don, ПЛЯН.

Lead magnoniobate PbMg^*,Nb2/*0. and its solid solutions are widely utilized in solid­rstate electronics. However, structural properties of the solid solutions have so far beon ntudiod or. \ю- lycryBtalline samples only because of the difficulties nnnocintnd with the obtaining of single crystals. In the present work, single crystals of tho во}id solutions

(1­х)РЬМ^1 /x^bp/xO* - xTbTi07, where 0 ^ X ^ 0.4, woro ,­rown from melt solution by the spontaneous crystallisation mothod. The X­ ray phase analysis has shown that a uniform phase composition is formed possessing a porovskite­typ© structure. The investigation was conducted on the dlffractorwtnrn TWON­ 2.0 and n:;0N­3.0 using the radiation of CuK, .md lruKj villi tho fc­filtors. Precision in the determination of cell paromatorn was ensured by 0.05°­otep scanning with subsequent proconsiny of tho diffraction lines on a computer by means cf a specially co/nposed program that allowed one to single the components of K# out of the diffraction profile and to separate the diffraction linos in case they overlap. To expedite the data processing, tho initial version was selected in the regime of direct dialog with tho com­ puter and then refined In accordance with the optimum agreement between the calculated and the observed diffraction profiles. The data obtained revealed that with а 20 mole !< content of FbTiO» there*appear, in addition to the cubic perovekite phase, diffractional reflections corresponding to a perovskite pbase of a different Symmetry of the cell, which arc refrained until the content of Fb­TiO» in solid solution goes as far as 40 mole ;<« A processing of the experimental data showed ..*ia phnse to be rhombohedral with avery small angle of rhombohedricity. Dependences were obtained of the elementary cell parameters on the concentration of PbTiC. for all phases observed and s quantitative analysis was performed of the dependence of the content of various phaeea on the composition of the solid solu­ tion ­ 179 ­ THE IITERGONHECTIOI OF THB STRUCTURE OF THUS fSRUBY 1ВОИ AlUMO­ SiLICIDBS IITH THB STRUCTURE ОГ TUB ВI SAM COUOUIDS OF THB TBAISITIOH MBTALS O.S.Zarecanjulc. «.V.Herman, T.I.Yeneon Ьтот state Unlweralty, Ьтот, USSR

The analyaia of the oryetal atruoturea Of Iron aluaoeilioi­

dea (Feilj 5_2 7Jlj 5_2 3, Fej 7A14S1, FeAljSi) formed at 770 К haa ahown their Interconnection «1th the eiruoturns of the binary ooapounde of the transition aetale. The first tao aaa­ pounde are oryetallised In the atructure typea oloeelj ?elcitv to the structure» of oopper, cobalt and manganese aiuainidefc» A­ the

atructuxe FeAl, R , ,3iT K „ , (the atruotura type FdOa.) one can ae* atomic neta of the earn» type CuAlg but «1th another order of their arrangeaent.

The atructure of POj 7A1431 (РЭ­j «Bioolett», HoKrf, R­0,024) il»ttrained by direot aetnode

cobalt atoaa. The atruoture of FeAl2Sl (a­7,955(2), b­I5,l62(6), o­I5|22I(6) A, ap. gr. Gaaa) la oloeelj related to the binary alualnide Fe.Al.,­,. In thla atruotnra the «Idea foraed of the fil­ led trigonal prlaaa (FeXg) are oonneoted by the ooaaon edgea la twoe and the raoant oubaa oriented by one of the double axea along X axle are parallelly diapoaed to the plana XT (i­O). For­ med of «he pentagonal prlaaa (HJ­Q) the ooluana Join the trigonal prlaaa, nine edgea (Fel„) join­the cubes. The aldea of tte filled trigonal prlaaa Ьата the соашоп rectangular sides with the penta­ gonal prlaaa and a Taoant halfoctahedron in the etructure on *» 1/2. The other apace la filled «1th the recant tetrahedra of dif­ ferent tinde. 23­2 ­ 180 ­ THE CRISTA! STRUCTURES 0? MEV АЬКАЫЛЕгЕЛНТН ALUMNIDiB O.S.Zarechnyuk, T.I.Yanson. N.B.Manyakp Lvov State University, Lvov, USSR

Ae a result of investigation of interaction between calcium, copper and aluminium the existence of two new intermetellic com­ pounds which are superstructures to the known structure typesi CaCuAlj,» CaCu­Al­ was discovered*

The structure of CaJ3uAl4 (a­5,684(1), 0­13,919(5) A, sp. gr. R3m) determined by the direct methods (P2., "Syntax", HoKa, 8­ 0,066) is a new distorted euperstruoture to the type MgCUg and closely related to the cubic MgSnCu^ phase (sp. gr. ?4}m). Unli­ ke the latter where the atoms of bigger size oocupy one atomic position there are two positions for calcium etoms each of which is half filled in OaCuAl„. As the distance between these atoms is short (6­1,19(2) A) it is not possible to piece calcium atoms si­ de by side simultaneously. Becce the Ja1 and Ce2 atoms are in position 3(a) alternatively. This special feature in the arrange­ ment of calcium atoms leads to the reduction of symmetry from p5}m to R3m. The compound CaOUjAl, (a­5,3797(3), e­4,1099(2) A, sp. gr. P6/mmm) is a superstructure to the type CaCu,­ (BZ0­4A, HolCot, R­ 0,091) in whioh the sites of copper atoms are occupied by alumi­ nium and copper atoms (as in the structure CeNi^Al,). Comparing the structures of CaCuAl», CaCupAl, with other co­ mpounds of the system Oa­Cu­Al (Ca(Cu,Al)2 ­ MgRig­type, Oa(Cu,x

Al), 1 ­ OWU dtruoture type, 0a,Cu2Al„ ­ superstructure to PuNl,­ type, CoCUgAlp ­ HaZn^j­type, OaOu^Alg ­ ThMn^g­type) one can see that the special feature of this group of compounds is ioosahed­ r«l coordination of small «torn». It was tetanias*: that the formation of superstructure is peculiar only for ternary «luainide» of oalcium and oopper. Sub­ stitution of Oa"­»8r­»Ba and Си­*Д1­»Со­»Ре does not lead to the appearance of eompounda whioh axe •uperstructures to the known etruoture types. Only «aCujAlj (a­5,3887(6), c­4,396(1) A) was found to be similar to CaCUgAli in the eystem Eu­Cu­Al. We have not disooverecyeuperatruoture to the type ThHn12 (the structure type Oelto^Alg) which was reported in some papers. ­ 181 ­ STACKING FAULTS IN FELDSPARS L.S /evin The Institutes for Applied Research »nd Materials Engineering Department, Ben­ Curlon University of the Negev, P.O. Box 1025, Beer­.Sheva, Israel

Strontium, anorthite and celslan (barium feldspar) are major crystalline phases in certain glass ceramics /1 /. At early stages of crystallization these phases exhibit diffract­ ion effects unknown In feldspars: broadening and near disappearance of reflections with odd "1" indices (Indexing Is based on the basic C~7.lA cell). These reflections sharpen with temperature of crystallization to the point where the observed pattern corresponds well with the calculated one. We explain the appearance of the observed phenomena in the light of the unconventional view of feldspar structure expressed by Bclov /2/. In this approach, feldspar Is regarded as built of silicon tetrahedra chains along the C­axis (Fig. la). The stacking of chains might be faulted due to the shift of one chain (thin lines in Fig. I) by C/2, which explains the observed diffraction effects nicely. Such faulting can be accommodated by the feldspar structure, though half of the tetrahedta In the adjacent chain will then be Inverted (Fig. lb). The probability, м estimated from peak broadening of faults occurring in the feldspars we studied, does not exceed 10%. It would be interesting to look for such distortion In natural feldspars. Faulted crystals, In particular, may be expected to lose their Intrinsic cleavage. /1/ Bogdanova, G.S., Orlova, E.M. and Zevln, L.S., Inorganic Materials L ,B16, (1965). IV Belov N.V., Proc. L'vov Mineral. Sodety N7,3, (1953).

Fig. 1. Schematic presentation of feldspar structure, a) unfaulted, b) faulted. ­ 182 ­

STRUCTURES OF Sc^feS^ AND Sc^Sl, INTERPRETED AS AN

INTSHQflOWTH Of SIMPLE PARENT TYPES JTZhaoandE Panha LaboratoVe de CrWailographJe au* Rayon» X. Untver»ite da Geneva,

24, Qua! Erne»)­Лпеалле*. CH­1211 Geneva 4. Switzerland

Among the 15 reported ternary Sc ­ N1 ­ 8J compounds /1/, the two stfll

unknown structure» located In tha 3c ­ ScNIjSI^ ­ SI triangle of the phaw dtaQram

were determined. BCJN^SIJ /2/, reported a* 'ScjNJS^', cryitallUea wtih the

2 H)3NI2Slj type, orthortxxnblc, oS32. Crncm ­ ^c . a ­ 3 9812(7), b ­ 9 688(2). с ­

13.111(2) A. Sc3NljSI« /3/, reported aa "Sc^feSt»". has a new type, onhorhombic.

оРЗв, Prima • c8, a • 11.67В(Э). b ­ 3.076(1). с ­ 11.840(3) A.

Tha 8cjNI2Sl3 structure la a member of the atructure aerie* with the general

formula Ra+nV^j'n ^ *№" ,n* atiucturea can be Interpreted aa an intergrowth of

•Jab» cut Irom tha CiB, ThOzSI31." W typaa /4/.

Tha Sc^NijSI^ atructure can ш Herpreted aa an Intergrowth of column» cut

from tha Crfi , TfNlSl and CaBe^ea type», tha taat being a aubsirtLition variant of

tha ThCr2SI3 type The projection of tftle structure type l« »hown below where ihe

different klnda of column» are Indicated by different kind» of «hading

8lnc* the CrB and tlNISI ttructum themselves can be considered a» Inter­

growth structurea, a* ternary atructuraa in (he Sc ­ ScNIjSlj . Si triangle can be

Interpreted a» an krtterqrowth ci segments cut from only four parent type» . W,

ThCrjSfe. PoejmfAJjB».

Sc,r*2b4

(РЗб.РгУпв­с' а>н67в. 6­594,eHl»40i

*«9»M se W 4. !­ О О о

/V Bodak O.I.. Kotur BYa. & QtaOylhsnMI El. DoM.Akad.Nauk UkiSSH.SbfA

65M59 (1976).

IV Zhao JT. & PvM E.. Acu CryaL h prin (1089).

IV Zhao IT & Panh* E., J. Laa*Common Мм In prim (1№9).

1*1 GladyabavaWI E.I. 4 Kotu S.Ya.. Sov.PhysOytialtoo/. a. 533S35 (1978). ­ IW­

THE INHOMOQENEOUS 3M? POLmPE OP MUSCOVITE AND LEPIDOLITE REVE­ ALED BY MEANS OP OBLIQUE­TEXTURE ELECTRON DIFFRACTIOH PATTERNS A. P. Zhukhllstov Institute of Ore Deposit Geology, Petrography, Mineralogy and Geochemistry, USSR Aoademy of Solencee, Moscow, USSR

Up to now mica polytypea with ал inhomogeneous layer alterna­ tion were found mainly among synthetic and natural trloctahe ^al ерег'оь or synthetic dioctahedral onea. The иве of oblique­ .axture electron diffraction patterns 3M, and 3TC, /1/ nay sa­ tisfy the indicated ideal fi*л­ Their symbollo notations expressed through absolute layer orientations or relative rotatlona of oon­ eeoutlve layer» are 336 or [033J, 561 ov Си?] and 431 or £123] respectively. Since the real intralayer dlsplaoementa (in projec­ tion on the ab­plane) have abaoluta values lese than the ideal a/3 (mainly in result of shortening of the shared octahedral edgj» caualng the dltrigonal rltatlon of the ootahedral basal faoea) the valuea of ­x and real p ahould be greater than 1/3 and fi^ for the polytypea 3M. and 3TC,. On the contrary the polytype 3M, for which the real ­x< 1/3 gives a aatlefaotory agreement between the observed and calculated reflection intensities and is thua unam­ biguously identified. The same polytype ha* been identified by means of OTBDP's as an admixture to the dominating i.oaogeneoua 1M polytypn (3 or [Oj ) in a natural lepidollte sample its cell being a­5.22, b­9.04, c­29.90 A, _£­92.6° (­XJJ­ 0.260. yn­OJ.

/1/ Rose M., Takeda H. and Wonee D.R. Science, j£l. 191 (1966). ­ 184­ тнж CRYSTAL srRocTosia or ишоьт­иидтю MXACYAVO­ MAXOAMATgedll), А,ВИЛ (СИ),

В. Ziealer. D. Babel Fachbereich chemie der Phillppe­Universltat, Hans­Heervein­StraBe, D­3550 Marburg

The hexacyanomanganates(lll) Hated In Table 1 have been prepared and three of them characterized by complete x­ray single crystal structure determinations. (NMe^jKHnfCNJg, the first potassium

compound isolated in the (NHe4)2BH(CH)6 seriee, ie a tetragonal "elpasoliteV exhibiting 8° rotated octahedra with respect to [110] and rotation axis [001]. The two monoclinlc cesium compounds

3 are "cryolites", in which the octahedra [Mn(CN)6) ~ reap. (NaN6)

(15,.6°) and (KH6) (20.1°) are more strongly rotated. The reasons for these different deformations compared to the cubic

elpasolites like Cs2l,iMn(CN/g [1] sre rationalized using geometrl~ cal arguments of ralativ ionic slzss. Applying the GoldBchmidt to­ lerance factor'concept, defining t ­ /2 (rA+rw)/(a'H­c+dc­N+rB+rN)' it can be shown, that cubic elpasolites only exist in the range 0.87 sts 1.00, as veil established in the fluorides series, for the cyano­cryolites Cs2BH(CN)6 (3,3) a linear relation exists

between t a*>d rotation of [BNeJ octahedra. These and further results will *>e discussed in detail.

Table j; a(pm) b(pm) c(pm) 8(°) z S.G. Hn­C(pi CSjNaDnfCN), 759.7 780.6 1095.0 90.07 2 P2j/n 198. 8

Cs2KMn(CH)6 769.8 820.4 1120.7 90.25 2 P2x/n 199.6 (НМе ) КНП(С.Ч) 884.8 tetr. 1222.2 2 201.8 4 2 б ­ H/m

(NHe4)2RbMn(CN) 889.4 hex. 2153.4 powder 3 R3 ? ?

(Nne4)2CsMH(CH) 900.5 hex. 21S3.6 only 3. R5 7 200

(1) Svanson, B.I.; Ryan, R.R.; Inorg. Cham. 12, 283 (1973) (2) Fletcher, S.R.I Gibb, Т.е.: J. Chem. Soc. Dalton Trans. 309 (1977) [3] Figgis, B.N.; Kucharski, E.; Reynolds, P.А.г white. A.H.: Acta Crystallogr. C12, 1587 (1983) ­ M5­ CwtpnitUnal Befirmtitn Тепмг Analtjsis

of Cn2,H03 ­ O^DDjNO, Stlii Salatlins

N. Zotov', K. Petrov2

i Institute of Applied Mineralogy, Bulgarian teadeiy of Sciences, Bakcvska Street 92, 1000 Sofia, Bulgaria 2 Institute of General and Inorganic Chetistry, Bulgarian ftcadeey of Sciences,

Acad. G. Bonchev Street 1, 1113 Sofia, Bulgaria

Polycrystalline samples of copper­cobalt hydroxide nitrates, Cu^COj ^(QrOjNDj have been prepared Kith x • 0.00, 0.20, 0.35, 0.47,"o.5e, 0.БЭ, 0.ЭЗ, 1.20, 1.17, 1.73. 2.00. The mixeJ crystals are monoclinic. For x < 1.0 they exhibit pseudo=hexagonal symmetry. The lattice parameters vary non­ linearly with composition /1/. The interpretation of lattice distortions using only these curves Is often difficult even phenomenologically. Recently, в пен tool for the analysis of solid solutions ­ the compositional deformation tensor %, has been proposed /2/, which has been applied in the present study. The deformablllty of the lattice of the investigated solid solutions is minimal along the twofold axla and the

principal coefficient Кг varies linearly Kith x. The deforma­ b'ility in the «• plane is much higher, the principal coeffi­

cients <( and К vary nonlinearly with composition, Kj remaining approximately equal to ­ К .

/1/ Zotov N.S., Petrov K.P., Z. Kristallog. <19B9>/submited/ /2/ Chanh N.B., Clastre J., Baultler J., Ilaget У.,Негеззе А., LajzeroHlcz J., Filhol A., Thomas M., J. Appl. Tryst., 21 (1988), 10­14

У

24­1 ­ 186 ­ THE PECULIAR STRUCTURE OF THE PRODUCTS OF HYDROTHF.RMAl. SYNTHESIS; 1:1m BORATES OF THE ALKALINE METALS I.I.Zviedre Institute оГ Inorganic Chemlatry, Latvlnn Arnrirnty of Scirnrr­R Rig», USSR

Crystallization of borates in an вциеоия яо.1 nt inn <1г­ргпНч on pH, on the concentration of the solution and я number of о HIP г factors. In a limited range of triple* «yRtrroa McjO­Hi n­i ­НгО, compounds with a con* t Ant ratio Me*0: pa Оэ ЛУГ form*1.!, wit l г h possess a def inlt* architecture and tiie same number of boron stops in the initial boraoxyg"?nous pniona, it br­ ing determ incd by the regularities of th° spatial configiirntion of en! ions. Borates 1:1: n. crystallise In the HII­ОПЦ «I kul in** rrg i on 'if the triple Bystens. The initial anion | R(OH)« |­ i ч л nmni.bo r­iri~ anion. There exists a high density of ral 1опн, «Я Uirrf* яге мп»' cation per each tetrahedron of BO*, l.'niier hydrolhermal condilionq, 1:1:8/3 borates of potaasiun and rubidium were c.­yHt л 1 1 i zrt\ out of strongly alkaline highly concentrated «olut ions, Crystalline

Btructurea Кэ I ВэО< (OH )t ) • 2HaO (1) and Rb) l Н)ПЧ toil hi • 2HtO 121 nrc extraordinarily dense. The ban l с role In lh^ atrutlurpH Is plnyrd by the threerdlfienaional frame of cation poiyhedrft. Tbe borooxygenoua anion (BjO« (OH }t J1 ­ wi iih «n unhydrat.od top ftOj of the triangle la a product of triple interan ionic polycondnnsat. ton of «onoboronsanlon with the subsequent additional inf runnt'nilr condensation. In the crystalline­ a t гиг t и го Nni ( Pi Пз ( ОН ) j ] ( Л t < hydrotherwal ­••Heeiel, a lose of one more ntolrrule of wntri leads to the *anio . BJOS (OH) i !л" fro» one BO< nnd two BOi with un­ hydrated tops. Dehydration is completed by anhydrous borates |;1 with the ring anions ЗД. The borates with partlnlly hydraii.l borooxygenous'anions are difficult to synthes izr, ThMr rryai* I • line structures, aa well as the bulk process of intrajsnSonic con­ densation of cowpletely hydrated anions a;e little 1nvpulignted. [1) Zviedre I.I., Ozola J.K.. levins A.F., Latv.pSR Zinat. Akad. Vestis, Ki«.Ser.No4, 387 (1974», [21 Zviedre I.I., levin» A.F., Latv.pSR Zihat, Akad. Vestis, Kla.Ser­ No4, 395 (1Э74). (31 Corazza E. , Menchetti S., Sabelll v., Acta Cryst. B31, 19»:i (1975). ­ 187­ ELBCTHON ш?галстюн РЛМИЫЮ ОВШШ> At сонтшам ROTAXIOH Of dlNOLE CHTSIAbS B.BtZvyagiri* i A.P.Znukhlletov*, A.IUFomlhenkoV* and H.O.KeaumoV**' *I0cU, UbSR Ao. ио.,103017 Попова, ••ЫРС Ceaa. Btud., Baku, UB8R

B««uii of the Mall eleotron way» length and oryatal teaae­ latlon eyatemetlo reflation aete may ba obtain»* for aura avan at arbitrary fixed orientation» of aingle oryatala under hlghr. energy eleotroc dlffraotlon oondltlona, MaTarthalaaa pat tarn» of oontlmioua oryatal rotation during the expoaure nay be of a apaolal Intaraat having aoaa unlqua faaturaa and advantagaa. By мал» of high­voltage alaotron dlffraotlon (aooalaratlona 350 keV) pattern» aero obtain»* of lamellar oryatala rotatad around axeo both lying In tha baaal plana and lntaraaotlng It, Ihe former ara In a oharaotarlatlo dapandanoa on tha oholoa of tb» rotation axle (hk]< All klnde of pattarna ara affaotlTa In tha determination of tha lattloa gaomatry and raal eynmetry. lhay anabla to dlatlnguiah polytypea giving ldantloal polyoryatal and taztura pattarna • Pattern» obtained for oryatala tUtad to the poaitlon normal to the lnoldent beaa under rotation around the normal» to them ara of apaolal lnt»r»at. Ihay oontaln thrae­ dlmenalonal »»t» of reflation» distributed over elllpaea like In oblique­texture pat tarn» but differ In higher quality and are mora informative* They reveal weaker reflexlona whloh In parti­ cular ara expreaelng atruotural aoduletlona and euperparlod». By variation of tha eteitlng dlreotlona of the tilting ax»» and of the rotation lntarvala one may mora definite and detailed aolve problem» of identlfloalon, polytyplam and atruoture analyele» The eleatron dlffraotlon rotation method baa bean auooeeafully applied in the etudy of alngle oryatala of CdlnOeS^, OaBe and layer minerals h'otlte and graphite. Pattern» being more abundant in raflaxlona permitted to eetabllah atruotural varlatlona of different oryatal» belon­lng to on» aaaple, refine their polytyp» oonpoaltlon avoiding any ohangaa of It o&ueed o.g* by grinding at sample preparation In other diffraction etudleo, reveal ' euperpariodB both in the beeal plana and la the layer eequenoe ' dlreotion oa «ell au «one dieorder effeota.

24­2 3.2. ORGANIC CRYSTALS, ORGANOMETALLIC AND COORDINATION COMPOUNDS.

Posters Л W . 190 ­ МГХЕО PROPIONATES OF UNTHAMIDESdlU WITH URANIUhlVH H. Adaras, A, J. Smith Department оГ Chemistry, University of Sheffield, SHEFFIELD S3 IHV, i­.K.

A aeries of mixed carboxylates LnU0iXs.nHjO, (Ln • La, Nd] X = гнj uo, CjhVOOi л = 2, 31 was reported by AHkhanova and EUert /\/. We have Investigated the crystal structures of the Usostructural) La and Nd propionate trlhydrates. The corresponding acetates dlO not yield suitable crystals. The crystals are monocUnic, Pc, wHh а в 6.i?0, b • ."Ч.О'Л, г = K.H'JY A, P = 91.9?° (La compound) and 6.019, ?0.fl89, 14.6V, 95.«в (Nd compound). Diffraction data for both compounds were collected on • Hlrolet H( ''­< In le dlffractoraeten the structures were solved by normal heavy*atom methods and refined to Я values currently about 0.06. There are two formula units p*r equivalent position) the uranium atoms form cations [UO/fCiHbCOOJj]" and the lanthanlde netsla fore a tarboxylat.e­bridged

polymeric cation [Ln(CrHjC0O)j}n*.l The propionate groups are each both chelating and'bridglngi both oxygens are coordinated to one metal atom while one bridges to « neighbouring metal atom also Infinite chalna are rormed parallel to 1100]. The lanthanlde l«na each carry three water molecules. Thus, although these compounds do contain bridging carboxylate groups, these groups do not link the lanthanlde with the uranliue a toe aa waa expected by Allkimnova and EUert.

The coordination of the uranium Is, as expected, a hexagonal blpyramld. i; "tr­a.­ide ro­tsl (a 9­coordinatei because of cr.e bridging and the short cV Eh­.­ carboxylate group, (he geoeetry la somewhat Irregular. Full details ? structures will be given and discussed.

Figure. The fat Ionic ^haln

'' AlUh^nova I. ri,, Ellert G. V., Zhur. Neorg. Krnm. \b, l.'j­iHTU. ­ MI ­ STRUCTURAL ASPECTS OF CYANOCARBENE DURON DERIVATIVES! THE UN4SUAL

II COMPLEX Fe (S05CFj)4[(CO)2(Cp)2P«2(M­C05[)j­C(8He?)(CN)]|2,CH2Cl2 V.O. Albano*, S. Bordonib, D. Braga*, L. Bue»ttob, V. Zanottib *Dipartlaento di Chlmlce '0. Clamlolan', Dipartimento di Chimiaa Flalo» • Inorganiea, Dniveraita dl Bologna, Italy

л ** hive reoently found that the oyanooerbene oatlen of iron

[Pt2(C0)2(Cp)2(fi­C0)(r­0(8Me2)(CN)]* (1) li .n excellent starting material for obtaining • variety of neutral д­oyanocarbene deriva­

tives of th* type [F«2CC0)2(Cp)20»­C0)0»­C(CN)xj (X • NR2, ОН, БЯ, H, CR,, CN). Here we report the Btruoture of (1) which has been trapped through N­ooordinetion In the title complex (2). It oonel­ eta of an lron(II) oation to vhloh four trifluoromethaneeulfonat* anion* and two oationa (1) are octahedrally coordinated. The moat unuaual feature of thla unexpected complex la the coordination of the cation (1) to th* ferroua cation in a aort of twltterlon In which four equatorial triflete unlta are the counterions. Very unatable diamagnetic dark­red crystal* have the following oel° conettmtat a * 13.558(1), b ­ 18.795(2), о ­ 12.588(5) К, a. 92.*5 («), ^» 93.52(2), /. 81.69(2) deg, apace group PI, Z • 2. U210 observed refleotlone, actual R » 0.09". Molecular aymmetry C^. Relevant bond distances averaged over ohemically equivalent bond* In two independent moieties! Fe(1)­N(1) 2.10 (1), Pe(1)­0(<*,7) 2.08(1), S(2,5)­C(18,19) 1.73(2), C­F 1.32(5), Б­0 1.»2(2), Fe(2)­Fe(5) 2.557(3), Fe(2,5)­C(1) 1.98(1), C(1)­0(2) 1Л2 (2), C(?)­N(1) 1.15(?>, c(D­sO) 1.77(D, s(D ­C(16,'i?) 1.78(2). The etructure of the precu­

reor[Fe2(CO)2(Cp)?(f»­CO)(M­C(C'ON(Me)C(0)SMe)] ,

end of two derivativea [Fe2(CO)2(Cp)?0»­CO)( ji­C(CN)x] (X ­ CN, SMe) will aleo b» deacribed.

1L. Buaetto, S. Bordonii V. Zanotti, V.G. Alb­ ano, D. Braga, Ргое. НАТО WorKahop Tranaition Metal Carbene Complexea, p. 03, wildbad Kr'euth w. Germany, Sept. 1988 ­ 192 STRUCTURAL INVESTIGATIONS ON SECKEL­ANTIMONY CARBONYL CLUSTERS

Y.G. Aluano­ , F. Pemartin , G. Longoni 'Dipartirafinto Chimico "G. Ciamician", via F. Selmi 2, 40126 BOLOGNA; ^­Jstituto di Chimica Strutturistica Inorganiea, via G. Venezian 21, 20133 MILAN'O; ^ Dipartimento di Chimica Fisica e Inorganica, viale del Risorgimento 4, &Л 136 BOLOftNA, Italy.

As a part of an investigation on nickel carbonyl clusters containing post­transition elements the diamagnetic [Nii3Sb2(CO)zi]2" and the paramagnetic £Nii3Sbz(CO)z4J3" anions have been characterized by sir?le­crystal X­ray structural analysis. [(PPh3)2N]z[Nu3Sb2(C0hi] (D is triclinic, sp.gr­ Pf with a=13.134(3), bsU. 546(2), c=15.416(2) A, 0=109.54(1), (3=01.47(2), /­=101.68(2)° and Z=1. The dianion lies on a crystallographic inversion center while the (РРпз)гИ"* cation is in general position. [(CH3)3(CHzCGH5)N]4[Nii3Sb2(C0)zi]Cl (2) is monoclinic, sp.gr. C2/c with a=2G.615(4), b=15.508(3), c=25.80b(1°) A, 0=99.21(4)° and Z=4. The anion is again located on an inversion center, two cations are in general position an the chloride ion lies on a crystallographic two­fold axis. Both structures were solved by Patterson and Fourier methods and refined by full­«atrix least­squares to R=0.036, Rv=0.050 for (1) and R=0.039, Rv=0.048 for (2). The molecular structure of the two carbonylic anions, which is essentially the same with only small differences in bond distances and angles, is shown in the figure. ­ 193­ CRYSTAL AND MOLECULAR STRUCTURE OF 2r(prDlMETHKLAMIN0rHEN¥L)­ ••lNDAN010Nfc1,3 AMD ITS DIMER 2.G. Alltv, L.O. Atovmyan, A.N. Chekhlov and L.H, Piearenko institute of Chemioal Physica of the USSR Academy of Sciences 'Chernogolovka, 142432, Moscow Region, USSR

2­(p?I>imeth}laminophenyl)rlr.dandloneH,3 (1) crystallizes In three oolour modifications ­ yellow, red and black ­ depending on pH of the medium. Th» crystal oolourlng la evidently oonneot«d with th» realization of one of the three tautomeric forma

0 U" Он @ty<&* <§§&« @фф~

Compound» 1 while oxidized by different agents form dimara (II)* Cryetals 11 have meuhanoohromlo properties. When ground In the mortar, lights el low oryetal» II turn green. We have used an Xr­ray analysis to etudy the atruoture of red crystals \ and dimer 1J. It has bean eatabllahed that the red modification corres­ ponds to bipolar struoture (b). In the orystal, the moleaules are linked by hydrogen bonds M...g in infinite chains. We have predicted and performed eleotroohemloally an lateraoleoular proton transfer in a aolld phase with a corresponding oolour change. The dinar molecule 1_J has a gauche conformation. The length of the central 0­C bond Is 1.569 a anion Is only 0.03 A longer than the bond in ethane» Sterle strains in the molecule are uniformly distributed over the whole ethane part of the Molecule.

I

25­1 194 ­ STRUCTURE OF B!S<3­CYANC­2,4­PENTANEDI0NAT0)r.0BALT(lI)

0. Angel ova Department of Chemistry, Unlverelty of Sofia, A. Ivanov I, 112B Sofia, Bulgaria

Complexes of 3­cyano­2,4­pentanedlone Hlth several divalent d­Ыоск metals have been prepared and structurally characterized. X­гву poHder diffraction analysis shoned that Co and N1 complexes неге lsostructural and differed from the Cu end Zn species. Single crystal structure determination revealed the Intrinsic nature of coordination.

The title compound, Со<СвН9НОг)г, crystallizes In space group

Р4гЛ1 (88) Hlth' a • 14.45(7) and с ­ B.B2(20)A. The centro­ symmetrlc chelate molecule» are associated in an Infinite 30­netHork by participation of both cyano groups In Inter­ molecular bonding.

Coordination polyhedron of the metal atom la a tetragonally distorted octahedron Hlth Co­0 end Co­N dlstancea of 2.044(3) and 2.127(4)* reap, and Inner O­Co­0 angle of BB.4*. The Co atom la displaced from the llgand plane by 0.51* and the angle o' folding alone the 0...О line Is 160.2(3)'. The llgand in this structure la trldentate: 0,0­chalatlng and 0,N­brldge bonding in contrast to thoae in the Cu and Zn complexes Hhere the Drldglng Is only partially presented. ­ 196 STRUCTURAL CONSEQUENCE OP STBRIO INTERACTIONS И O.O'­DISUBSTITU­ TED DER1VATIVB3 OP BIPHENYI.. DEPIHITIO» 0? DEPOBMATIOH PARAHETSRS

R. Anuiewlot. Т.Н. KrygowBkl Department of Chemistry, University of Warsaw, Warsaw, Poland

Solution of the crystal and moleoular structure of 2­metoxy­ 2'­carboxy­blphenyl a* well as literature data «how that overcrow­ ding od substituents In the region 0,0'­ of the title oompounds Is a reason of substantial deformation» of respective endo­ and exo­ oycllo angles. In order to study this problem in an objeotiv» way, we hava defined Repulsion Deformation Parameter /1/.

RDP( f) m \f. fg (1)

where u? Is a Beasured value of ал angle In question whereas \fQ Is an expeoted one calculated by use of the Domenloano­Murray­Rust /2/ angllar substltuest parameter. If RDr(^ > 1» aignlfloantly different from 0 it may be used as a measure of magnitude of de­ formation foross. On the basis of ROP­valuas more oomplex and holistlo deformation parameter was formulated, I.e. the Olobal Deformation Parameter 0DP((£) ­ £ HDP(l(>) (2)

where summation run over all carbon atoms In the overcrowded . region. Then ws could show that ODP­vsluss for 9 molsoular ays­ teas vary roughly parallel to ohanges of V the Charton's bulkl­ ness parameter of substituent /3/.

/1/ Krygowskl Т.Н., Anulewlo» В., Daniluk Т., Drapala Т., Struot. Ohsa. /2/ Doaenloano A., Hurray­Rust P., Tetrahedron Lett., 21, 2263 (1979). /3/ Charton Ж., Toploa in Current Chemistry, Д£, 57 (1985).

со

25­2 ­ 196 ­ X­RAY STRUCTURE OF A NEW INTERMOLECULAR CHARGE­TRANSFER SALT BETWEEN. AN ORGANIC SUBSTRATE AND A FOLYOXOMETALATE, 3 (a~PW1204o)" 3<8­HYDROXYQUINOLINIUM) ­J(ETHANOLE) 2(НгО) D.Attanasio, M.Bonamico, V.Fares, P.jmperatori. and L.Suber I.T.S.E. ­ C.N.R. ­ Area della Ricerca di Roma P.O.B.10, 00016 Monterotondo (Roma) ­ ITALY

Interest in possible CT Interactions between polyoxoaniona and organic substrates, as a prerequisite for the catalytic oxidation of the latter, led us to investigate the crystal and molecular structure of the title compound. As shown in the figure, the anion structure consist» of an or­Keggin­type molecule. The 8­hydroxyquinolinium moieties (three per PW^O^"*3) are stacked approximately along the in­ direction with an interplanar spacing of 3.25 and 3,57 A, alternatively. The hydrogen bonding is through the B­ hydroxyquinolinium oxygens and a water or an ethanole molecule. The second water molecule presents a weak hydrogen bond with one of the oxygen of the anion. The result ia a quite complex packing arrangement in which the polyoxomotalate anions and tho other molecules are weakly bound each other. The most important feature ia the lack of substantive structural direct interactions between the G­hydroxy_ quinolinium cations and the polyoxometalates anions. Apparently the substantial red shift exhibited by the polyoxoanion electronic spectrum does not have a simple structural basis. ­ 197 ­ X­НАГ DIFFRACTION STUDY OF HOMO­ AND MIXED­LIGAND fi­D1KBTDNATBS OF Cu(II) I.A.Baldina, S.A.Gromil'ov, S.V.Borleov Institute of Inorganic Chemistry, Biberian Branch of the UBSB Academy of Boiences, Novosibirsk, USSR

Complex compounds of transition metals with A­dlketons axe being under intensive study and finding extensive praotlaal use. In the present communication the results are reported of X­ray otudy on twelve homo­ and mixed­ligand complexes of Cu(tl) with Л­HkoLona as Uganda. The llgand oubatitutes are ad follows! OH,, CF,( CgH,­ and C(CH,),. Powder samples have been investigated on DR0N­UM1 (R»19? mm, OuK.i.­radiation) dlffructo­ metere at room temperature» Reflections were indexed using data on the preliminary single crystal study. The data for single orystals from Syntax P2.. diffractometer (MoK<|.­radiation, the heavy atom method) allowed to determine crystal structure» for five compounds, I.e., two homo­llgand ­ 0u(btfa)2» Cu(bpm)a, and three mlxed­llgand ones ­ Ou(gfa­aa), Cu(gfa­ba), Ou(pta­ bn). The Ou atom has a plane­siuare coordination with the dlstanoes Ou­0 1,887­1,959 A. In the mixed­ligand oomplexee the molecules are conneoted to form oentroeyometrioe.1 "pewttio— dlmers". The crystal chemical analysis of the Ou(II) Jb ­dlketonates investigated has been carried out. The influence of substitutes on aetal­oyole geometry, packing of molecules, and physioal­ ohealoal properties has been considered. - 198 - CRYSTALLOCHEMICAL ASPECTS OP VOLATILITY OP TRANSITION METAL J3 -DIKETONATES

I.A. Baldlna, P.A. StabnikoV, I.K. Iguoenov, 9.V. Borlaov Inatitute of. Inorganio Chemistry, the USSR Academy of Soiencea, Siberian Branoh, Hovoalblrek, USSR

A general approaoh to &ooount for a high volatility of me• tal oomplexee with organlo Uganda haa not been developed ao far. At present analysing paoklog and intermoleoular interaotlone In iryetale one may predlot temperature dependence of vapour pree- aure of new olaaeee of volatile oomplexea «1th organlo Uganda. The paper glvea the result» of X-ray etudy of tranaltlon metal J3-dlketonates. The oryatal atruoturea of ten oompounda have been determined,and the lnfluenoe of llgand aubatltutea on the geometry of a metal-oyole la oonaldered. Peaturea of lnter- aaleaular oontaota are oompared with volatility of the oompounda. Yan-der-Waala volume* of moleoulea of metal ^-dlketonatea and their packing ooefflolenta In oryatal» have been oelculated. It haa been ahown that the laaa la the packing density,the higher la the volatility of a oomplez. Within the method at aton-atomlo potential» Van-der-Hoala energy in oryatale of aetal ^-dlketonate» ti»a been oaloulated. The dependenoe of Tan-der-Vaala energy value on the of the eubetltut» In a llgand la oonaldered. The energy component given la ahown to agree with aubllaation heat» of these oomplexea. Couloab energy 1* oaloulated for aoae oryatale of metal j9-dlke- tonatee. The value of Coulomb energy la little affeoted by the type of the aubetitute and nature of a metal atom. Thie value doea not exceed 10* of the eubllmation heat. ­ 199 ­

IHf CRYSIAt AND MnLEClPLAR ST.E fit П С HE M1S1 R V OF THE U N5 у Н ME Т RIC AL

Г0МР1 f X: (M n»n)[5(in,15,20­TETRAPHENYLPORPHINA?n) IH О Н(ПП] [(N ­ M E T И Y|_­ 5,in,15,20­TElRAPHENYLPORPHINATO) IR П NOTO] PE R С HL О R А ТЕ , DrCHLORHMETHANE SOLVATE

T.J. Rarlr?^, Л, Viytfnuch* L. Utna­Grnfyrt!*!? M, ntvratfcrul^ К. Orahnnt^ 'bwtttuln of rinnnrnl Chnmlstry, I­J7, Technical Unlvnrslty of tddz, 90­924 tddi, Poland. Hmtitute of Chemistry, University of Wronlaw. 50­3R3 Wrntfaw, Poland.

Crystals nf the title compound observe the snncR group £?i/c ­ Г^^к» ^ lJRit

ml] hm ^ ­ Ifi.fiOSO), b = 16.B270), £ ­ ?n.(VW),/J­ 1ГЛ.МХ2>\ V~ Ъбб A anrt contains Tour оИдотпНс niDlftculnsj thB respective cnlcnlatnrt and experimental rinnslUan erai \. 36 and 1,35 nc.m" rasp. The structure has her>n refined to an £ Inrfnx on F_ nf 0.0743 on tne basis of B39B reflections (133 K, Mokei­) using blocked full matrix tnt:h)t)NR {SHr L X78), The main structural fpaturns nf the Ышл:1счг

N4rnflf nNjfnn^ coordination group are as follows: FeO)­n(t) and Fp(2)­u(2) bond Innpthe ere ^, 767(4) end 1.740(4) A rrap. Thrt Fn­D­Fn nnnjn Is ](Л.ЮУ, I.e. elpnlflcenUy smaller than similar angle In u­nxnhte[ 5,10,15,2CUtetraphenyl porphlnato iron 0TO]i П4.ЧО' /1,2/. The Fo­N distances, ere tram 2.05X5) to 2.079(fi) Д. Tha distance brtwenn Iron and methylated nitrogen b 2.257(b) A; this la presumably the longest Fe­N bond length found in Iron porphyrins so far. The N(123)­r;(45) (methy­ lated nitrogen) bond Is ач1а1 to the plane formed by the three remaining nitrogen •toms et the porphyrin core П. Ferric ions are displaced by 0.4ft and О.ЬЭ Д from the plantn defined by four and three, I.e. N(121), N(12?) and N(124) nitrogen •tons reap, the twisting of 1frw macroring is 30.2* and the angle between planes defined by the rttmgen atoms N(21), N(22), N(23) and N(24) and N(121), N(122) •nd N(124) is 7.4*. As la usual in the crystalline porphyrins, the porphine skeleton departs significantly from planarlty. Bond lengths In the skeleton are in good agree­ ment with those In other trw. porphyrins. The ГЛП" ion jntf the CH_ni_ mnlacule •re disordered. The macroringa of the dimer are perpendicular to the h rttrnction of the unit cell.

Th* t­гау work «as supported financially by the project R.P.n.lO of The Polish Ministry of the National Education.

П/ Hof'man A.B,, Collins D.M., Day V.M., Fleischer E.B., Srivaarteva T,S., Hoard J.L., J.Am.Chem.Soc. ?4, 3620 (1972). v Swepston P.N., Iben J.A., Acta Cryst. C*\, Й71 (l^HM. - 200 - CRYSTAL STRUCTURE OF A BIFURCATED HEMATOGENIC COMPOUND U. Baumeister , Z. Kosturkiewicz Faculty of Chemistry, Adam MJckiewicz University, Poznan, Poland H. Hartung Department of Chemietry, Martin Luther University, Halle, GDR

Studying crystals of compounds fomung mesomorphic phases with several conformationally or constitutionally induced distortions of the classical rod-like shape of the molecules our interest was turned to the monotropically nematic substance 4-Ethoxy-3'-(N- methylidene-4-athoxyani1ine)-4'-<4-rnethoxy-benzoyloxyj-azobenzene, C31H29N3°3* *irat synthezised by VorUnder. It represents an interesting class of bifurcated meaogenic compounds not investigated by X-ray crystal structure analysis till now. The t ni Dund crystallizes in space group P^ with two molecules Per unit cell and lattice parameters a - 10.979(3), b - 12.42717), * - 11.04813) A, a - 110.83(4). 0 - 105 81(4) / - 82.96(4)°, V - 1333.0(1.1) Xе. The structure was solved by duact

methods and refined to( a final R value of 0.038. The methyl ideneam1ine azobenzene moiety of the molecule is almost planar and makes an angle of 76.8*" with the plane of the benzoyloxy group. The most striking molecular feature is a clone intramolecular distance of 2.733(6) A between the csrbonyl слгиип atom and the nitrogen atom of the azomethin group itrongly affecting the molecular conformation. Sheets of molecules parallel (223) are formed within the crystal structure.

on leave from Martin Luther University. Halle. GDR ­ 201 ­ STRUCTURE OF J­PH£NYL­3­PIPERIDINE­2,4­PENTANODIONE MONO­OXIME C. Bellver , A. L6pet­Castro. Instituto d* Ciencias de MstcrlAles dp Seville (C.S.l.C.) у De­ .partemento de Fisica Aplicada > Univ. Seville, Seville (Spain)

Crystals are monoclinic, «pace group P2l/a, with a >­ 14*253 19), b ­ 9.994(6), с ­ 10.468(4) Л, Й­ 93.70(4)', Z ­ 4, D^l.22 0^. 1.2t M« nf3' , ^i­. 0.076 im"1, F(OOO) ­ 592. The structure was solved by direct methods. Final R value wis 0.06 for 2341 observed reflections. Length* and angles agree well with those reported i« simil­

ar compound*. Only the C4rC5 and C2­CI bond length* (1.490(4) and l.$07(S) A, respectively) are shorter because of the presen­ ce of an atom showing s double bond. The molecular conformation of the piperldlne ring la a chair. The puckering parameters (Cremer and Pople, 1975) for th? ssqusne» C3'2­C3'3­C3'4­C3'5­C3'6­N3 are Q. 175(1 > *, f­ Ю0(зГ' and Q • 0.59(U A , and the Nardelli assyimetry parameters t

• Ce(C3'4) * 0.013(2) and ACj(C3'4­C3'3) ­ Q.007O)*. Ttie suba­ titutiit C3 is axial. The crystal structure is stabilized by Van der Waals forces.

CJ'j CJ'S

СУ1 C3'6

0 t. . tjl C3 — CI Ъз —CJ2 I CI /c4 \ OH

26­1 ­ 202 ­

THE CRYSTAL STRUCTURE OF THE S_Y£[­ AND AJ4TJ­6ie­Cr(CO)a COMPLEXES OF TETRAHYDRO­INDENO[2,t­allNDENE

I.E. Bltterwoif, Department of ChemiBtry, University of Idaho, Moscow (USA)i A. Ceccon, F. Manoli, A. Venzo, P. Ganii, and G. Valle, Diparti­ menti dl С him tea, Universita di Padova (Italy).

Аз an extension Л our researche on Cr(CO)3­complexed aromatic sys­ tems having a well­defined molecular rigidity, we have undertook the struc­ tural analysis of the title compounds, (A­svn, and D­antj, respectively). The dihedral angle between the least­equare planes of the two indane­like fragments In the organic moiety is 57° and 110° for A and B, respectively. The chromium atoms are in both compounds nearly exactly centered on the normal to the benzene rings with the Cr­C distances ranging from 2.20 to 2.22 A. The Cr(CO)a groups adopt always an exo­con for mat I on.

Crystal data. A, monocllnic, space group C2/c (n. 15), with л = 18.677(2), A ­ 7.087(1), e 3 3 с a 15.088(2) A, 0 *=9l.t(l) ; V a 1006.7 Л , Z = 4, De = 1.50 gem" . B, monoclinic, apace group P2|/a (n. 1­1) with a - IG..171(2), b = ll.002(1), 3 3 с ­= 11.109(1) A, 0 = 101.0(1)°; V = 1904.5 A , Z = 4, De = 1.03 g cm­ . 203 ­

GROUP THBOHY AND CONFORMATIONAL ANALYSIS OF PUCKKHKD CHKMJCAL KINGS

•J.CA.Uogygns. and Г) G.Kvans Department uf Chemistry, University of the Witwatemand, Johannesburg, South Africa.

The normal atomic displacement modes of a planar N­membered regular polygon provide a basis /1/ for the conformational analysis of a puckered N­membered chemical ring or cyclic fragment. Two linearly independent modes, equivalent to the mutually orthogonal cosine and

eine for mi of each irreducible Em representation and one of the two

poMible mode» of B5 of the U... symmetry group, combine to reproduce

the puckering Conversely, any ring conformation reduces to a linear combination from an N­Э eubeet of independent elements, choaer from an extended basis let of primitive forms, spanning all symmetry­adapted representations and orientations. Orientation refers to the phai relationship between the chemical and group­theoretic identities of the ring. The normalised linear coefficients are independent of the amplitude of pucker and of the chemical ring numbering scheme. For N<6, all primitive forms of the subset correspond to standard low­energy symmetrical forms, familiar to chemists, but this ie not a general condition. The computer program based on this procedure yields the quantitative specification of ring conformation as the unique linear sum uf primitive forms, starting from fractional coordinates. Familiar classical conformations are flagged. Copies of the program will be available at u­­; Conference.

j\f Pickett,Н.Ы. L Strauss,П.L. JAm.Chem.5oc. Щ, 72 В1 (1070)

36­2 ­ 204 ­ SYNTHESIS AND STRUCTURE OF THE BIS (1,2,6,7­TETRACYAN0­3,SU­ MMING­PYRROLIZAKIDE) COPPEH (II) COMPLEX ADDUCT WITH THF H. Bonamlco, V. Pares. A. Flamini, P. Imperatori and N. Poll I.T.S.E.­C.N.R,­ Area della Hicerca dl Roma, Roma, Italy

The dicyanovinyl pyrroles J. oyollze readily in triethylamlne to give the pyrrollzine derivatives 2 /1/. n

In the ооигвв of our studies on tetracyanoethylene (TONE) ohemietry, we isolated the novel stable carbanion Д /2/. In he attempt to determine its llgand properties, we discovered a metal promoted reaction, which strictly resembles the above shown orgonlo onei CN CN . t . CN • HI" ­CN •4 'li

j /n­Fi;Hi"tca"in"> In the presence of a metal (II) ion, the anion Д pyrrollo proton attacks the adjacent nltrile nitrogen atom with the forma­ tion of a highly symmetrical planar jB­dilolne metal chelate £. It la not possible to achieve the Betel ­ free fi ­dilmlne anion, elno» aeaetallatlon reverses­the reaction and regenerates the anion ,£. formula £, or"Its equivalent nesomers with the negative charge on

0e, Is supported by ­T­NMR apeotrum of the Zn(II) derivative and by the aingle­oryetal X­ray analysis of the title compoundi „WHI NI1SI

/1/ «eler H., Top.Curr.Chem., 6±, e5 (1976). /2/ Dessy 0., Fare» V., Flemini A., and Giuliani А.Ы. Angcw.Chcm. 2±. «26 (1985). ­ 205 ­ THE GROUND STATE TRANS INFLUENCE ON BOND DISTANCES. SYNTHESIS AND STRUCTURE OF cle­DINITRATOBIS(DIMETHYL 8ULPHOXIDE) PLATINUM(II).

D. Bostrom,a B. Nor*n, A. Oakarsaon and R. Strandberg*

*Inorg. Chem. Umea Univeraity, 8­901i)7 Umea, Sweden Inorg. Chem. Lund Univsralty, S­22100 Lund, Sveden

Crude cla­Pt (DMSO), (NO,)2 was prepared by the reaction

of allver nitrate with cis­Pt(DHSO),C12 In aqeous solu­ tion. Recryatalllsation from nltromethane gave mono­ cllnlc cryetala, P2,/c, with «­9.032(3», b»14.262(3), 0­10.918(4) A, 0­117.860(2)°, «.«. The coordination goometry of the mononuclear complex la paeudo square­planar with Pt­0 distances in the range 2.05­2.10 A and Pt­e dietancee In the range 2.224­2.228 A. Theae distances may be compared with the Pt­0 distance in KjPtlNO,),­iHjO, 2.01 A /1/ and the Pt­8 distance in trans­Pt(tetrahydrothlopheneljlj, 2.31 А 121. In theae compound» the trans Influence is aero by definition. It may thus be concluded that the trana Influence of О on S haa shortened the Pt­S dis­ tance approximately 0.08 A and the trans influence of 8 on О has elongated the Pt­0 distance 0.04­0.09 A.

/1/ Siding, L.­I., Oskarsson, A,, Inorg. Chlm. Acta 103, 127 (1985). HI Elding, L.­l., Nortn, B.l Oskarsson, A., Svensson, C, Zeitscrift fUr Krlst. US., 362 (198C). ­ 206 ­ CRYSTAL AHD MOLECULAR STRUCTURE OP BIS (1­BEMZlXIttIDAZ0LIN­2­yLIl)EN) COLD (1) CHLORIDE

Bruno Bovlo Dipartimento di Chlmlca, Univerelta di Pavia, Italy flavlo Bonatl, Alfredo Burlni, Blenoa Roea Pletroni Dipartimento dl Sclenze Chimlche, Unlverelta dl Camerino, Italy

Crystal datai C20H20N4C1AU( triclinlcj apace group PT. a­15.746(3). b­11.000(1), c­1l.105(l)A, ^­92.29(2), ^.106.83(1), У*­8В.77(2)°| Z»4. The structure wae solved by yattereon and Fourier methods, Pull­matrlx­least­squarea refinement of 5044 ob­ served refleotlone with I* Эё (1) yielded H­0.047 (Rw­0.050). The cryetal contains two independent cations where gold has approxima­ tely linear two­ooordlnatlon, and the average Ли­C dlBtance ie

2.027(7) A| In each ­(Ph­CH2)M­C­Au­C­ll(CH2­Ph)­molety tho benzyl groups lie on opposite sides. The cation» have virtual 0, symmetry but they exhibit no real oryetallographic symmetry and all the atoms ocoupy general positions. The lnteraotlon between gold atoms la poselble and may be attractlTe or repulslvei here the Au(A)­AuCB) separation la 3.2630(5) A, and the C­Au­C angles are 175.2(4) and 176.6(4)°. The two CI" lone Join the two Independent cations in a dlmerlo unit through four hydrogen bridges, whereas the shortest intormo­ leoular approaohes between this dlmerlo unit and the equivalent ones are normal Van der Waals contaote. ­ 307 ­ CRYSTAL STRUCTURE OF 3,5­DIPHENYL­4­(4­PYRIDYL)ISOXAZOLE

Bruna Bovio Dlpartimento di Chimica Generale, University di Pavia, Italy,

Vllma Buaetti Dipartlmento di Chimica Organica, Universita di Padova,Italy.

In the cycloaddltian reaction between benzonitrile oxide and pyridine in apolar solventa , two blscycloadducts were obtained In fair yield» . Similarly , by reacting the nitrile oxide with the methyl­substituted pyridines , 2­picoline and 3­picoline , aome products deriving from a cycloaddition pathway could be isolated f their NMR spectra show the picoline methyls as ainglet» in the typical CH range , The 4­picoline reacts with benzonitrile oxide giving & cry­ stalline product which separates from the reaction mixture after only few hours. Surprisingly, no signal attributable to the methyl group is present in the NMR spectrum of the isolated product , *hlch only showe aromatic low­field signals , tt was deemed necessary therefore to carry out an X­ray diftractometric analysis to ascertain the structural features of this crystalline adduct .

c H N o Mr 298 3 Crystal data i 20 i4 2 i ' " ­ < '* monoclinic , a ­ 15.768 tl), b ­ 15.6U (1), с ­ 6.0446 (4) A, 0­94.753 < 6 )° j V ­ 1488.5 (2)A j £­4 Space group P2 /n. .

The structure was solved by direct methods , and refined by least­ squares treatment to R ь0.055 (Rw­0.051 ) ­ ­ 208 ­ CRYSTAL .AND MOLECULAR STRUCTURES OF A NEW FIVE­COORDINATE COPPER(II) DIMER AND TETRAMER COMPLEXES M.Buxowska­Strzyzewska, A.Toslk and W.ManluklawIcz Institute ol General Chemistry Technical University of \-6ai, Poland

Tha syntheses and crystal structure determination! ot the two coppar(ll) complexes with chloro and benzlmidazole ligandsi [CujCljl^HgN^CI­iHjO (1) and

CutOCI6(C7H6N,)4i0.75C2H5OH (2) ara raportad. Tha pala green crystals of 11) crystallize In tha orthoromblc ipaca group Pnma with 4 molecules In a unit call of dimensions a­19.506(3), b"17.384(4), e­11.940(2) R at 293 K. Tha pala goldan­orown crystal» of (2) crystallize In the ipaca group PI with two molecule» In tha unit call of dlmernlons a>13.003(2), Ь­1Э.246(2), c­13.892(5)*. ol .66.06(1), £­74.27(1), (•71.43(1)° at 293 K. Tha itructirai wara ulvad by dlr.ci method» to final R.0.047 baud on 213a fndapandant data with I >. 3f (I) for (1) and R­0.069 based on 5Й4 Indapandanl reflections with I) 3f(l) for (2). Tha complex cation of (1) consists of pair» of dlttortad trlgonel­blpyremldal

csppar(ll) centres CuCI3(C7H6N2)2 and CuCI2(C7H6N2)3 connactad by two wide, chlorlda Ions, The trigonal coordination consists of thraa chlorlda Uganda tor ono coppar atom and of two chlorlda and ona benzlmldazole Uganda for tha othar Tha axial sltas ara occupied by tha nitrogen atoms ot banzlmldazola molecules. The Cu­Cu separation in tha dlmer Is 3.986(1)*. The equatorial part of tha dlmar Is strictly planer (C symmetry of the complex with eouatoriel planes situated on tha symmetry plane). The system of hydrogen bonds between complex nation, chloride anion and water molecules Is anallzed. The tetramer complex (2) was cryatellizod from ethyl alcohol solution of (1). Complax (2) is formed by dlmerlsatlon of dlmerlc cations of (1) through dissociation 2­ ol three benzimidaiola Meant» and coordination of 0 Ion to four Cu atoms In tetrahadral geometry. All chloride Ions occupy the bridge positions with tha Cu­Cu separation from 3.11212) to 3.145(2)*. The blpyramldal coordination of Cu atoms Is formed by three equatorial Cu­CI bonds and Cu­0 and Cu­N axial bonds. The trigonal symmetry of the blpyramldal geometry Is here less deformed than In (1). Tha bond lengths end angles ara anallzed fcrt comparison with other blpyramldal coppertil) dimers. Tha magnetism of crystals (1) and (2) will be Investigated. ­ 209 ­ CRYSTAL AND MOLECULAR STRUCTURE OP POUR 1,4­OllllfBROPYRIDIHE DERIVATIVES M.P.Bundule, A.A.Kemme, A.P.Mlshnev. O.J.DuburB Institute of Organic Synthesis, Latvian DSR Academy of Sciences, 226006, Riga, USSR

The wide variety of biological aotlvitlee found among 1,4= dihydropyrldlne (1,4­DHP) derivatives haa oaueed considerable interest In X­ray atudy of their structure. In this connection we determined the structures of the following compounds! a) 2,6­dlmethyl­3,5­diethoxyoarbonyl­4­(5 ­nltro­2'­furyl)­1,4­dl­ hydropyrldlne, J., O^H^HgO^j b) 2,6­dimethYl­3,5­nlmethoxyoarbonyl­4­(o­dlfluoromBthoxyphenyl)­

1,4­dihydropyrldine, 2, 01BH1QNO5P2l о) 2­(2,6­dimethyl­3•5­diethoxyoarbonyl­1,4­dihydropyrldlne:4s oarboxamldo)­4'­methylthlobutyrlo aold, %, С.дЬ^оНг0?3' a) 2,6­dlmethyl­3,5­dlethoxyoarbonyl­4­(o^­nltro­ o(­furyl­2'­ethyl­ ene)­1,4­dlhydropyrldin«, £, C^H^HJCJ. In these compounds, the 1,4­DHP ring assumes a boat conformation, the aubetituent IH­ at 04 1 в in axial orientation to the 1,4­DHP ring. The t/_:.­ lists the cia­ and trans­

orientations of the C0AR­ frag­ ments rfcarbonyl groups with respect to the double bonde of the 1,4­ШР ring and the mean values of some torsion angles. Compound Conformation ТГ(СС­С4­С) T(C­C­NI­C)

1. cis­trans 11,0 5.6 2 cis­cls 16.8 8.9 cia cls 20.1 I r 10.5 £ ciS7trans 33.2 18.6

27­1 ­210­ DIFFERENT MODB 0Г OOOKDINATION OF LIGANDS CONTAININO ГН10­ SEMICARBAZIDE FRACMEHT AND THEIR REALIZATION IH COMPLEXES WITH METALS I.F.Burshteln. H.V.Qerbeleu, T.I.Mallnovskl, А.Г. Yerejan, O.A.Bologa Institute of Applied Physio, Institute of Chemistry of Moldavian Aoademy of Solenoes, Klahiner, 277028, USSR

There ere таПоив,types of organlo moleoulea, possessing в large number of potential qualitatively different donor atoms in their structure. However It le not eeay to predlot whioh of them and In what combination the donor oapaoitlea can be realised in the oomplex formation. Regarding the oomplexlng of the Thio­ eemioarbaxlde 11(1 )Hj 0(5)1(2jHBOJHg and the thiosemioabazids fragment in Uganda on its'baela, it la neoesaary to note that out of the fire nonhydrogen atoms, four are potential donors. The oomplexlng properties of the sulphur atom differ con­ siderably In oomparioon with the other donor atoms of the Uganda in question. This permits to suggest that any combination of the coordinate oentrss lnoludes a sulphur atom, as in the ease of the thiosemloarbazlde. The latter, as a rule, is a (H,S) bldentate ligand. The monodentate coordination la noticed only through the sulphur atom In oomplioated moleoules, ae in the thlosemioarbazl­ dediaoetlo add. A new type of ligand coordination, where the thlo­ semloarbazlde fragment.usee three donor atoms and the ligand ful­ fill» the funotlon of a trldentate =• bridge, has been found in oop­ per oomplex with a tMossmloabezone of glyoxalio acid. The sulphur and nitrogen 1(1) atoas are coordinated to one oopper atom, while the nitrogen I{2) ­ to another oopper atom, symmetrically coupled with the first. This structure is a final example ahowlnc that all the donor atoms of the thiosemiearbazide fragment oan form ooaplexsa,sxoept 1(3). At present.etructures in which 1(3) participates In the coordination are unknown. However, it la neoessary to note that under certain conditions (nature of metal, geometry of oomplexes, compatibility of Uganda etc) nuoh a situ­ ation can ba realized. ­ зи ­ Crystal and Molecular Structure of the Oinuclear Complex,

­ Vi2­CJ) зIFthtllI) 1С1)21Р­|­Ргз)12|ИР­1­Ргз1. У­ an­lntermedlate

In the Synthesis of the Paramagnetic Hydride |RhUV)t>i)2

(С1)21Р­1­Ргз>21, I.

Donatelli capitenl, pasouale Hura and Annalaura Segre.

Recently we reported the synthesis and the caracteriration of

two stable paramagnetic hydrides of iridium(lV)

Considering the stability of those compounds we tried to

extend this chemistry to rhodium. Indeed we synthesized the

paramagnetic complex of rhodiumllVI, l*. Moreover we were

Interested to understand the mechanism of formation of the

paramagnetic dihydrldo complexes of Ir(IV) and RhilV). During

the several attempts to obtain compound £ *• obtained en

intermediate of I the dlnuclesr complex 1. In ibis work we

present the full cartcterliatlon, both in the solid state and

In solution, of. }.

II Hura, P. J. An. Chem. Soc. 19*6, 311­152.

2| Hura, p.i Segre, A. Angew. Cheuls ШС, И, «O­lsJi

International Edition in English.

1) Hura, P.; Segre, A.i Jostero, S. Inorg. Chem. in the prase.

«I Attanasio, D.,' Hura, P.; segre, A. To be submitted.

27­2 212 ­ THE CRYSTAL STRUCTURE OF A NEW THALLIUM!Ill) POLYMER COMPLEX

A. Caatineiraa, W. Hiller*, J. Strahle*, M.R. Bermejo and J.A. Garcia Depto Quim. Inorganica, Universidad de Santiago de Compostela (Spain). •Institut fur Anorganische Chemie, Universitat Tubingen (Germany).

Complexes of the thallium trihalides of etoichiometry T1X­.L­, TlX'X­.L­ and T1KX'X".L ate known |l| ; many of these have distorted trigonal,­bipyramidal geometriea. Bridging halogens is also a feature of several five and six^­coordlnate thallium f III) hallde dimer complexes or polymers. However, in contrast to TlBr,.2PyO (РуО ­ pyridir.e­N­oxide) |2|, the now synthesized TlBr,.PyO is the first oxigen­bridged polymer of т1хз known containing five coordinate thallium atoms.

TlBr3,PyO crystallizes in orthorhombic C2 22. apace group With a ­ 1045.7(51, b ­ 1X26.9(5), с ­ 690.4(5! ргп and Z ­ 4. The structure was refined to R ­ 0.06 7 for 735 reflections with I>3o(I).

The complex (see figure) has a polimeric atructure containing infinite zig­zag chains of O­Tl­0 units where the coordination geometry around each thallium atom is a distorted trigonal­blpyramyd with bromine atoms 'occupying equatorial sites, at 250.3(5) and 253.1(5) pm, and oxlgen atoms of the PyO Uganda in axial positions as oxigen­ bridges, at 2SC.811) pm. The TlBr, groups «how distortion from trigonal symmetry With two large Вг­Tl­Br angles (124°) and a small one (111° ).

|1 I H.R. Bermejo, A. Fernandez, M. Gayoso, Cas t ineiras, Hiller, J. Strahle.­ Polyhedron, 7, 2561(1988) |2| И. Hiller, M.E. Garcia, N.R. Bermejo, Cas t ario ; Act a fry.it. C42, 60(19*6). ­ 213­ X­RAY STRUCTURE DETERMINATION OF DICYANOMETHYLENE DERIVATIVES OP 1NDANE

l.A.Chetkiria, t.G.Popovat V.E.Zavodriik, V.K.Belsky, A.N.Sobolev

Karpov Inetitut* of Fhjeioal ChemiBtryt MOBOOW, USSR

Indane compounds vith dicyanomethylene­groupe are acceptors and donor­acceptor conjugated systems with intramolecular charge transfer. Crystal and molecular structures of I­YI compounds were determined. Unexpected chemical structures were found for IY and YI compounds.

CtCH).

11 З­Вгв(dioyanomethy lent)­indane­2t X = H„

Space group P2./bf Z­4, R­0.031 1,3­Bie(dioyanom§thyltne)­indanon0­2, X=0 Space group A2/a, z­8, R­0.032

111. lt 3­Bie(dioyanomethyt0ne)­8­t4 '­(fttf/­diethyl­

aminophtnyl)phmnylimine)indent, Z=N-Ph-N{Et)g

N(Et)0 Space group Pi, Z­2, R­0.049 b. Space group P2,/a, Z­4, Я­0.0Э2

П. {3­Dioyanom*thy ten* )ind*n* (1, JT­fcJ­ (N­(4­11, N­ dit thy latninopheny I )­2­a­­ino­3~oyano) pyrrol* Space group Pi, Z*2, R«"0.057

У. Tritthylammonium salt of 1,3­biB(dioyano­ methyl4nm)­indana­S Space group I2/a, Z­8, R­0.042 Cryetallin* eolvate,of dipy­ ridinium salt of 2,2*­bi» ff \m . сн$сп П,J­bta(diayanomethylent) indane) with acetonitril*

Space group P21/b, 2­4, R­0.051

In acceptor compounds the molecule I has almost planar con­ formation and the molecule II has more twisted conformation. Geo­ metrical parameters of molecules in triclinic(a) and monoclinic(b) modifications indicate to intramolecular charge transfer betweer electron donor and acceptor moieties of the compound III. New tri­ cyclic system was found in structure IY. The iones of salts Y and YI are linked vt'a the hydrogen bonds NH..'.N(sC). ­ 214­ MOLBCULAR АЙВ CRYSTAL aTHDOTUWJ О? Л3,Б11Н0РН08РН1№В8 A.N.Oiernega, H.Yu.Antipin, Tu.T.Struohkov Institute of Organoelement Compound? f the USSR Academy of Soienoes, Новое "! Institute of Organic Chemistr} lirainlan Aoademy' of Soienoes, Kiev, USSR

X­ray diffraotion studies of a large number of novel J^ ­ iminophoaphinee Z­N.P­lf (X > Ar, Ali, PR2, P(S)R2, PRy Y . Ar,

Hi, NRg, N=.PfU, PR2, OR, BR, Hlg et al.) have allowed to eluoi­ date main regularities and oharaoteriBtlo features of their mo­ leoular and oryatal struoture. Thus, it hae been ahown that the РГОС bond angle la very soft (varying In the range of 114.0­ 17i.7°), whereas the KPT bond angle Is muoh more rigid (100.6­ 115.9°)• Vox the first time it has been found that A* ­lmlnophos­ phlnes may exist either se tranffc­ or as ola­>ieomers depending on the eleotronio and eterio properties of Bubatituttnte. The faotore determining the most favourable oonformation of ^'­Ajulnophosphl­ nee art diaoueeed on the basis of ab Initio UO LOAD 80У oaloula­ tlous. It has been shown that the eleotronlo struotures of double bond in the XNaPX and XH«Fi, systems are signlfioantly different. The theoretioal explanation for the different dependence of the FaN bond length on the PHX bond angle in these two types of com­ pounds has been given. It has been shown that the XJfaPR and RHaPX aolfoulee (X ­ donor or sooeptor group) exhibit essential­ ly different types of conjugation ("nan­olaseloal" in the seoond oaee). The first example of eeoondary P...Big interaction in crystal involving biooordlnated phosphorus atom has been found. The lnfluenoe of eterio shielding of the reeotion oentres on the ohaeUoal properties of A^­ioinophosphines it oonsidered on the basis of the obtained structural data. I­глу structural studies of the A'­islnophosphines trenef ormatlon produote allowed to olarify the pathways of reactions Involving these oompounds. ­ 216 ­ STRUCTURE OP THIS (X­4­ACETYLHEXKNE­1­0NE­5) IRON (III) (X ­ ­CI, ­Br)

P.M.Chyra.gov. R.A.Abdullayev, D.G.Oambarov, M.I.Chyragov S.M.Kirov Azerbaijan State University. Baku, USSR

Fe(CgH1002Cl)­, and 7е(СдН­00­Вг)^ ссдрХехев have been prepa­ red by FeCl^ 0.1N solution interactionwxth the corresponding ГРЧ­ gente ta.4en as 1i3 rafcio at pH­3­ Th»: composition obtained was extracted by carbon tetrachloride. After a month's interval tran­ sparent red needlea have precipitated in the solution.

Fe(C8H1002Cl)3 crystal is mofioclinioi a • 21.047(7), b ­ 10,893(6)» с ­ 26.340(9) A, jft ­ 121.94(3), г ­ 8, apace group

Co, dQ_ll * 1.38 g/carj PeCCgH^OgBr), cryetal is triclinici a ­ 14.254(7), b ­ 12.627(6), с • 7.807(3) A, ofc . 05­21(3), fi ­ 85.94(3), (Г­ 87.28(3), z ­ 2, apace group FT. Experimental Pvui sets were obtained or. a ЭУЛПЕХ diffraoto­ meter. The structure» were solved by the heavy atom technique and refined by the leapt squares Method in full matrix anisotropic approximation (Rfi • 0.12, Rp, « 0,125) High values of R­factor are attributed to the cryetal imperfection. Monoolinic structure has two non­equivalent molecules wh :o iron atoma (Pe. and Pe„), and in th? *riclinic fc^m (Pe), have octahedral surrounding formod by six oxygen atomc with three chelate ligands. Average о о bond length* values for Fe^­0 ­ 1.965 A, for Po2­0 « 1.990 A, 0­Pe,­0 chelate angles » 83°, 0­Pe„­0 ­ 84.6°. In one of the 1 С о molecules c­0 bond lengths are from 1.216 to 1.324 A whereas in • the other one they vary from 1.206 to 1.321 A. For the triclinic form Pe­0 average bond length is 1.995 A» ° ­'e­0 chelate angle is 85.5°, bond lengths of (C­0)aver • 1.2$ A, of C­C In metal cycle * 1.42, and to the substituenta «* 1.5 A. Intermolecular separation does not exceed the sum of van­der­Waals radii. Off­planar metal cycles have envelope conformation in monoclinic forms. Bond length distribution observed in metal cycles points to n­lnternction derealization in these compounds, thus correspon­ ding to the (~00~) type coordination.* ­ £16 ­ X­RAY ANALYSIS ­ MASTER SPY UNRAVELLING THE COURSE OF REACTION

M. Ctechanowicz­ftutkawsk» and P. Serda, Regional Laboratory of Physlcochemical Ana;yeis and Ftructurel Research, Cracow, Poland, end A. Kolasa, Faculty of Chemistry, J*gl»l lont an Untver»ity, Сгасэи, Poland

Attempt» of cyclisatlon of benzoyl acetani 1 Id* under the influence

a of ^0Х3 '* CI, Br) on heating lead t. man, mono­ and two, X­subetttuted, bimolecular product». The latter were the point of Interest and the X­ray method we» necessary to distinguish among a wide variety of their possible stereochemical structure*.

W l У. / * CO­NH­Ph

POX,

Pfc^CH^NH­Ph "^y -^

к ,0 Х>Х=с'Сч> O^K­* H­ PIT" ^H I Ph В The molecular structure» of compound A ix • CI > and & (x ­ Bri were Hetermined tc oe as shown schema11cal1 у in the Figurs. The presence of such structures in the reaction­ products give* an evidence that bimolecular reactions go via head to r\eac cycloadcilion til and condensation.

С1Э M. Ciechrtnowicz­Ftutkowska »t al., Tetranedron, 37, (19811. 217 P0LTTYPI8K PHENOMENON IN COMPLEX COPPEB (II) COMPOUNDS WITH ^.­лгаяо ACIDS Diakon I.*., Chapurina L.P., Kairyak b.N., Domi S.V. Inatitute of Applied Physiea, Inatitute of ChemlBtry of the Holdavia'n SSR Academy of Science». Kishinev, USSR Electron­diffraction data were used to observe polyty­ piam on crystala of coordlnational compomda, in particular, in copper (II) cheletes with treonlne, glycine, serine and a­alanlne: CuTre2, CuGlySer and OuAlaSer. The indicated crystalline compounds had a layered structure. For all com­ pounds the presence of two types or complex layers is typi­ cal since taken separately in structures they can Join one another unamblglously. It was found that the compound cu(D­Tre)(L­Tre) contain­ ing in lte molecule both optical isomers of treonlne is crystallized in two polytypic with single and double layered structures that differ only in relative displacements of layers along b(tjb) axis. It waa proved experimentally that crystalline compounds In each of the pairs

Cu Gly (Ь­Ser) and CUg 01y2 (D­Ser)(b­Ser); Cu (D­Ala)O­Ser) and cugfD­AlaHL­AlaMD­SerML­Ser) are polytypic modifications. The crystals have Identical unit cells and their structures are similar because each of them can be obtained from the same initial layer by only varying means of stacking these layers lit apace.

In the aaalo^oua polytypic xodificationB there takea place cryetalllaation of compounds which are enaatioaorphoue to the above indicated:

Cu Gly (D­8er) and Cu? 01уг (L­Ser)(D­Ser)t

Ou (L­A.la)(D­eer) and Cu2(t­Ala)(»­Ma)(I.­Ser)(D­8er) Conditions of structures formation о the above consi­ dered layers have been found alongside with the possible alter­ natives of reciprocal arrangement of the latter permitting to snMsfy these conditions.

28­i 218 ­

THE CRYSTAL AND MOLECULAR STRUCTURE OF 6­S­ACETYL­4,5­0­ ­DIACETVL­23­S­ETHYL­2­3­6­TRITHJ0­D­MANN0SE­DIETHYL­

­DITHIOACETHAL C2^3606S6

¥L5£Z&£S&E? S.L*J*ld' D.MllJkovldB R. F.zlld? *nd U. Klewent* <> ) University of Kovi Sad, I.DJuriuica 4, Yvj­21000 Novi Sad (a) University of Tuzla, Yu­75000 Tuzla '(•) University of Regensburg, D­8400 Rcgeneburg

Colour1es plate­like crystals of the title compound were synthesized by treating of 1,2­0~isopropyHdene­3,5­0­ ­dibOetyl­e­S­aoetyl­e­thio­a­D­gluoofuranooe vith ethane thiol and oata lytic anion to of a strong mineral aoid, at d°C, and isolated in a high yield. The purpose of the structure determination is to verify the position of the substituento and moleouler configuration and conformation. A single crystal x­ray diffraction analysis was carried оить on an Enraf­Nonius CAD­4 diffTactometer (graphite monoohromator, CuK radiation, room temperature). The oompound о oryi. tallieed in the monoolinio space group P2( with unit cell parameters: a=8.660(5), b=17.155(9) o=9,226(6) *, ^=95.61?

V=1363.6{8) A*, Mr=516.11, do=1.26 Mgm"*, dc=1.27 Mgm'*, for Z=2, F(OQO)=552.00, ^39.8 on'1. Direct «ethods (SHELX 76) have been used to solve the structure, being anlsotropically refined by full eatrix least squares calculations to R=0.076 for 3618 reflection with I>3c(I). The shape of the molecule is shown In Pig.l. The structure was stabilised by van der Waalв forces.

Fig. 1 ­ 219­ PURINIUM SALTS WITH POLYNUCLEAR, MOLYBDENUM CONTAINING ANIONS:

(Hypoxanlhine')4[SiMo12O40]' 10H2O and (Mercaptopurlne'UfMoiCUCIj] E. Dubler, O. Hilnggi, E. Gyr & H. Schmalle, lnsl. of inorg. Chcm., Wimenhurerstr. 190 8057 Zurich, Switzerland

As pan of a program elucidating the coordination properties of око­ and rhiopurinej, we recently reported on synthesis and structure of metal complexes of hypoxanthine, allopurinol and of 6­mercaplopurine [ I )­[3J. Attempts to synthesize molybdenum complexes with purine ligands resulted in salts with polynuclear, molybdenum containing anions and cations with the purines in their protonated form. Formula, crystal data and structural features are: (CfHjNiOblSIMOuOeHOHjOs a = 12.802(4). b = 37.934(8), с = 12.955(4) A; p = 105.25(3)'•; V = 6069.6 A3; space group

P2,/n, Z = 4; dc = 2.749, d„ = 2.74 g/cm'; R/R„ =0.115 /0.077 including 12701 observed reflections (block refinement, 478 and 401 variables respectively), The helcropolyoxomolybdate(VI) anion (SiMo^,,,)*­ possesses the "Keggin" structure of twelve, distorted Mo06 octaheura arranged in four groups of three edge­sharing oclahedn. These octahedra are disposed around a tetrahedral site occupied by the SI atom. Mo­Mo distances within die cluster range from 3.341(1) to 3.368(1) with a mean value of 3.354 Л between edge­sharing octahedra, and from 3.702(1) to 3.750(1) with a mean value of 3.721 A between comer­sharing octahedra. The hypaxanthinium cations all are protonaled at N(1), N(7) and N(9), but not at N(3). Two hydrogen bonding contact» are observed between the heteropolyanion and two hypoxanthlnium cations.

; apace group Cm,

Z = 2; dc = 2.601, d. = 2.60 g/cm'; R/R, « 0.041/0.043 including 2099 observed reflections (block refinement, 103 and 89 variables respectively). The structure contains discrete polychloromolybdate(II) anions of the type КМо^С^ЗД]2­ and 6­mercaptopurinium cations. In the cluster anion, six Mo atoms form an approximate regular octahedron, surrounded by an inner cube of eight CI atoms and by an outer octahedron of six CI atoms.

Mo­Mo distances within the Mot octahedron range from 2.577(8) to 2.616(8) with a mean value of 2.595 A.

IDE. Dubler, G.ИЬад)* W.Btnicti,J.Inora. BHichero. ».U»(1M7) |2| U. Hintzt, H. Schmalle it E. Duster, lnorf. Chon. 21,3131 (lMt) 111 E. Oubkr t, E. Uyr, lnori. Chcm. J7.1466 (198«>

28­2 ­ 220­ STHUCTUHE 0? FYRUVILAMINOACID 0XIMJS3 A.A.Dvoricln. Yu.A.Simonov, T.I.Malinowsky, Н.О.Ьшлрвка, I.O.Fritsky, V.V.Skopenko Institute of Applied Physios of the Moldavian Academy of Sciences, Kishinev, Kiev state University, Kiev, USSR

The oompounde of t!.e CH3­C(N0H)rC<«0)­NH­0HHCO0H ( where H is the residia of irreplaaable d. ­aminoacido) are interesting for blorganio chemistry, as the dipeptldes etruotural analogues, oontaining oxoimino and amlnoaold fragments. Thee» oompounds po­ ssess a marked biologioal activity. The investigation of the»» oompounds as a polydentate Uganda is of interest as well. The oompounde with К • H(A), СНЛВ), СН.­СН.­Э­ОНЛО) have bean investigated by X­ray analysis and NMRsspeotrosoopy, Th» trans­oonfiguration of the amide bond takes plaoe in oxlms­ pyruvllglyoine (A)i the oxime group is in antiposition with re­ ferenoe to this bond and in transposition with reftronos to the amid* oarbonyl. The flat moleoular configuration is stabilised by the N­H...0 and N­H..N lntramoleoular H­bando. The framework is formed in the orystal by means of the intermoleoular H­ bonda. The unoommon case of the triolinio acentrlo space group P1 «ith t m 2 was found in the oxime of' pyruvil­L­alaiiine (B). There are two oonformers in the unit oell with a aaquanoa of torsion angles In the о bain. The oarboxyl group Bakes ­m ang­ le of 90* with th» framework of one moleoule, and «n angle of 30° with the other one. The tranaoonflguratlon of amide group is re­ alised In both Independent moleoules B| the oxime group is in the peptlda bond and In transposition to the amide oxyg.n .There la • a aultlbranohed H­bond systan in the oryatal. The lnter­ •toalo dletonoes, H­bond . the oorrelations between NMR­and IR­ apeotroaoopy and Z­r*ay t ­ruotural data nave been widely disous­ aed.

\ ­381­ ASYMMETRIC SYNTHESIS 0Г AMINO ACIDS CONFORMATIONAL STUDY OF HETEROCYCLIC INTERMEDIATES

M. Dyrbuich and E. Egert Inatltut ftlr Organieche Chemie, J. И. Goethe­UniveraltHt

Nledemreeler Han

Slx­msmbered heterocyclea like lactlde» <»)> blelactlm • than of 2,$­dlketoplb>eratlnea (2) and dlhydrooxazii nonaa (3) hava proved to ba valuable tool» aa convenient intermedlatea In the courae of the aiymmatrla aynthaala ot amine aclda.

fO^0 ^NyOCHj ^NyOCHj

1 2 2 V

We have examined mora than 30 differently aubetltuted heterocyclea by meana of X­ray atructure analyala 1л order to deaorlbe the dependency of the­ ring geometry on the nature of the aubetltuenta and to find out the pre­ ferred orientation ot functional group». Ma were nalnly intareatad In the reaaona (or the occurence ot 'folded* conformation* where an aromatic aubatltuent ahielda the heterocycle. Additionally force­field calculation» were performed In order to analyae the different conformation» and to obtain a profound inaight Into the reaeone why a certain eubatltuent prefer» the conformation found In the cryatal.

1) Schollkopf, U., Toplca in Currant Chanlatry Ij», 69 11983) MOLECULAR gTKUOTUWSB OF N­BKNZOYL DKRIVATIVQ3 OF CIS­DbCAKIimO­ QUINOLIMtt A.A.iiBpenbetov. G.B.Lltvinenko, Xu.T.Btruchkov Institute of Chemical Sciences, Kazakh 8SK Acad;­ Bel Alma­Atai Institute of Organoelement Compounds, UQiiti Acad. Bel. • moecow, USSR

clB­Decahydroqulnolineti (DHQ) may exist in two coni'ormatlonfl (A or B) depending on the nature of substituents at the II atom as well as at the carbon atoms R

I­ИI ^"А >В .I (K'+R" J^) = 0", _R"= H П R'. OH, K'« R". H 1У 01­.МЦ Шjj j „,R'», „.H';. HHt , »­R". 00000 № ^ R m и

' Jor ciejDHQ and its Hralkyl derivatives (H = H.Alk) the A

conformation with an equatorial orientation of С(6)Н2­шо1пу1влв group relative to the piperidine cycle IB preferable. Trie structu­ ral studies of three N­benzoyl­cie­DHQ (I­IIIJ "1th a cle­posltlon of the U(b)tL,­methyleiie and me­groupe have shown that their mole­ cule e have the В conformations and In molecule IX all three suD­ stltuents in plperldln» cycle (0H­, He­, and OCbJH^­groups) are In the eyn­axial orientation. The stability of the В conformation for l­III la evidently due to a tendency to elimination of eterlc ro­ pulelon between acyl groups and equatorial aubetituents at the o^rf­carbon atoaa, which Is characteristic for the A conformation of the atabicyclio system. The acylasine fragments cannot lose pla­ aarity because of a considerable Stconjugationi according to HUH data the conjugation energy is equal to "19­20 keel/mole. In mole­ cule IV for each of the canonic conformations (A or B) one of the substituents always retains an unfavorable equatorial orientation. The structure­ study of IT has shown that its molecular conformatir On is close to the В type with some twisting of piperidine cycle, having a distorted boat conformation with the C(2) and C(IO) atoms

at its bow and stern positions. The C(ti)H?­mtithylene ала «u­^rou^e are in a paeudoaxial orientations! torsion un^ict. o(0)­.!­o­o &re equal to oI,3 and '/'/,i:° rospoctively. ­223­

CRT8TAL STRUCTURE DETERMINATION OF SOKE PTRIDINIUM COMPOUNDS I.S.Ahmed Fare», A. El­Shora, V.B.Rybakov National Research centre, Phys.Deprt., Cairo, Egypt •INoscow state University, Faculty ot Chemistry, Moscow, USSR

Pyridinuim compounds have been known for a wide variety of biological activities, that some pyridinium salts «ere found to be active bactericides, fungicides and herbicides. The target of this work Is to throw light on the stereocheaistry OK some new pyridinium derivatives, namelyi phenyl­0­methyl­pyridyl hydroxy

lmide *c13H12ON2" (I), N­phenyl­2,4.S­triphenyl perchlorata

•C2?H2204NC1'(II) and N­(methyl­2­pyridyl)2,4,6­triphenyl

pyridinum •C29H23C1N204' (111), where the sterlc repulsion la bound to play a large role on the orlentaion of the phenyl group with respect to pyridine ring, the data collection for the three compounds were performed with No К radiation, on an Enraf­Nonlua CAD­4 computer controlled kappa­axl* dlttractoaeter. The cell constants and the orientstlon matrices for data collection were obtained from least~squares refinements, using setting angels of at least 20 reflections. The crystalographlc data for the three compounds aret compound (lb Monoclinic И , m­11.401(4), D­7.7»1(3),

3 3 c­IZ.766(4) X,fl.92.»7(2)°, V­H32.7 A' . X­4. Ож­1.245 gm.cm" , т.ч.­212.25. *»0.050 and R^­0.04». Compound (II)i Ortorohombic Pbca, *­16.611(9), b­16.656(6),

3 3 C­17.SS4(5) i, V­4«5«.« 8 . 1­е, D%­1.322 gm.cm' . m.w.­4«3.*(, R­0.055 and R^­0.056 Compound (III)i Monoclinic P2,/b. a­)s.*41(b), b­1».502(6),

3 1 c­1S.133(S) 8, <­)1S.S»(2). V­5026.7 8 , I­в, 0Д­1.3(» gm.csf , a.w.­49a.*7, R­0.08S and R^­0.042. The structures were solved by the direct methods and were refined by full matrix least­squares using anisotropic temperature factors for all atoms, except for hydrogen atoms which were treated as riding on their carter atoms with fixed distances 0.95 X and with isotropic temperature factor. All the bond lengthes and the valency angles, are consistent with those published in literatures. The plaoarity and the packing of the Molecules were fully discussed. ­ят­ UOLBOULAR­ ABD CRySTAL STRUCTURE 0» SUWOHE 0? THE 4­ACBTOIT­2­ ­HYDROXY­W­BORHAHE BUUOSIO AOID

E. Piaaa. Z. Kaluaki Department of Chenlstry, Adorn Hioklewioa University, Poinah, Poland

The struoture of the tltl« oompounds пае been nolved in order to determine tha lnfluenoe of oyollc aubatltuent at 1 and 2 position*, ai wall aa a aubatltuant at 4 poaitlon on the geometry of norbornane akelaton. Oolorlaaa naadlaa were obtained from sthanol aolution by alow evaporation of the aolvent. Oryutala ara orthoroeMo РЬпв, —1,H{2), Ъ.15.40(1), с«2Э.37(1), Z­8| 2224 unique reflexione measured on P2, Syntax diffraotoBater using Oufc radiation, Struoture was solved by direct method and refined up to H«O,065. Bond lengths of norbornane akeleton lie in the range determined previously for others oamphoree. Unexpectedly the 0(1)­0(7)­C(4) angle (69°) la anion amaller than suoh angle determined for other oyollo darlvatiraa. The view of moleoul» la ahown in rig.1,

In the unit oall the molaoulea are bonded only by ran der Waale foroas. - 225 STRUCTURAL CHARACTERIZATION ОГ THE TITAHOXAHE TETRAHER S |H -C5(CK3)5TiBr(H-o)U F.Florencio, I.Fonaeca Institute de Qulalca-Flsica "Rocaeolano". C.S.I.C. 28004-Hadrid. sapin. J.L.Balctcar Dpto. da Geologla. Univeraidad de Alcala. 28671-Alcala da Henares. Spain.

The Molecular configuration of tltla compound consist of

s four (r) -C5(CH3)5)TiBr Molecular unite linked by four oxo bridgea to produce an eight-aeabered central ring of alternating Ti and О atom*.Tha tetramars geoaetry la conatralnad by a cryetallographic

twofold rotation axis vich paaaaa through 0(1) and 0(2). The four

oxygen atoaa define a plana with tha Ti atoaa up and down thia

plana, alternately.

89-1 ­226 ­ KH FOUR МО FIVE ICWERED RHENIUM CLUSTERS

U. flCrtt and H.­J. Haupt Anorganlicht und Analytbch» Chtarit, Un1vtrtim­«H Ptdtrborn, Uirburgtr Strata 100, 0­4790 Padtrborn, ГВ8

Transition Ratal clutttn and thtlr rtlattd chtuHtry htv* galnad w1da Inttratt In rtctnt yt*r< out to thtlr ability tt hoaogenout cttalyiti. Our own work on rhtnlua clutttr* nil ltd to vtrlout now iiibitancas with тагу Inttrtatlng propertied tl hydroganatton cttllyitl /I/. Tht ba»1c #1tf»»nt of tht»» cluster typts 1» • nearly planar shaped four or f1v» mafcartd ring consisting of rhtnlu» it ом. Th» ring

«dots tr» bridged by (ij­PPhj Uganda, til» Re4­frag»»nt being capped by * Uj­PFI» group. Furthtnuort, (dd1t1onil Uj­X Uganda «1th X • H, 0, and halogen art attachtd to tht rhenium rlngi. Aptrt fro* tht catalytic effectiveness of tht hydHdo bridges, art thtlt p­­X bridges centres for further reaction processes. At typical representatives of thtlt cluster wt will prtitnt and dlicun tht eoleculer ttructurtl (as determined by X­ray diffraction) and hydro­ gtnatlon rates at homogenous catalysts of tht following compounds:

I. М4(С0)в(м2­РРпг)г(рг­Н)г(|14­РРЬ)

И. М4(СО)в(рг­»И|г)3(р2­1)(1.г­0)(иг­И)(рГ»И1)

III. »»4(CO]g(p2­PPhj),(gj­Br)(u2­H)(u,­PPh)

IV. И»5(С0)|(мг­РРпг)4(рг­1)г(и3­1)(Р4­РИ1)

IM Haupt. H.­J., taUta, P., Flarkt, U., Ange*. Ctitult tOO, 280 (ИМ) ­827­ UTKUCTURAL ANALYSIS OF 1 XETHYL­2­PHEt1Yl.­3<2 ­KITKOVIHYDIHDOLB (1) AND l­HBTHYL­2­fHENVL­l)(2 nfclTHYL­2'­NITROVINYL)IHDOLB (U>­ T.Fonaeea», S.Hartlnez­Carrera», J ­ О.Hodrlguez» and J.B.Subiratsb *Uepartasenta de Keyoa X, Inetltuto Rooaeolan , Serrano 118, 2B0U6­r!adrld! bDepertanento de Uuinica, FacuKsd da Ciwnoiaa, Universidsd Autonona da Madrid, 2eo49­Hedrld, Spain.

Title conpounds J and II have been obtained by oondanaatlon of the 1­Methyl 2­Phenyl­3­Pornyllndolo with nltrotiethan* (I), mp. !«7­d«C, or nltroethene (II), up. 142­3°C. Compound I. CITHUNHOII. H»= 27В.Э1, nonoollnlo, P2i/o, »= B.301(1), b = 17.383(1). a­ 8.9fcl4(l)A, ft" 103.79(1)", V= 1409.03(2>A», Z = 4. D­ = 1.312 gen"3, jfcdi К»­ 1.541BA, u,i в.ВВЗ en i , F(000)­ tiB4, room tenperaturo, R*.= 0.051 for 2102 'observed reflections, [I>3o(IJ]. Conpound 11. CmHioHaUa, H,­ 292.34, «onoollnlo, Ca/o, a = 14.8B»(I>, b= IB. 324(1), o= 11.204 (1>A, Be B1.555(3>°, V = 3055.4(4)*», 2= B, Do= 1.271g on­». X(Cu К«,)г 1.5418A. ц= в.397 on­'. P<000)= 1232. roon tenparature, H»= 0.U84 for 2117 observed refleotlons, tl>3e(l)l. Bond distenoos and angles for 1 snd П, show similar and expeoted values to the previously rsportsd nltrovlnyHndolss.1 Th« lndols nuolsus Is planar snd the nitrovlnyl aids chain is sleost plmnmr, within experisentsl srror Units. The nain differenoe found lying in the rotation of the nitrovlnyl chain, indole nuoleus shows dlhedrel anglea with nltrovlnll ohaln lor в.1(1)° in I snd 146.7(2)» in II and with phenyl substitusnt for 118.9(1)" in I and 131.03(7)° in (I. This featuraa oould be responsible for some differenoes In blologios) aotlvity sgaints ;>sr*)SltesB.

1. I.Fonssos. S.HsrtlnsE­Csrrera. S.(3arola­Blenco, J .0. Bodr ifuec, snd J.B.Subirats. J.Cryst.Speotr.Researoh, (1888), IB, 285­276. 2. L.Canoirs. J .A.Rodrlfuex, e.id J .B. Sublrats, lur . J .Hsd .Ch*a>. (18B9), to be published.

0> CO 9

29­2 CRYSTAL STRUCTURES OF 2,3­Dl(2"­FVHIDINYLJ­У,lU­DIMETHYLQUINOXALINE AND 2,3­ DHa'­PYHIDIHYDBENZOQUlNOXALINE METAL COMPLEXES,

H. Font­Altaba and X. Solane

Dap. Criatalografia, Mtnoralogia у Depdaltoe Mlneralee, Unlvereldad de Berc*Lo­ ne. Spain

The complexatlon of 2,3­dl(2'­pyridinyl)­9,10­dimethylquinoxaline (DMQ) and 2,3­dU2'pyridinyl)­benzoquinoxaline (BO) on transition motel» haa been studied on, using a* metals Cu, N1 and Co.

Th» crystal structure of the following complexes nan been determined: The copper, cobalt and nickel complexes of DMQ and Ы»(1,3­trifluoromethy1, 1,3­ dloxopropanediene), the molecule of BQ and the cobalt complex» of BQ and bls(l,3­trlfluoromethyl, 1,3­dioxopropanedlene). The crystallographlc data ara:

DKOCu 0MQN1 ОИЭСо BO BQCo • (A) • 23.643 24.272 19.130 16.990 14.382 b ­ 15.245 15.222 9.248 7.9B2 12.853 0 ­ 9.044 6.964 1B.19B 6.197 9.024 4 ­ ­­­ 96.74 92.55 94.Id 97.61 95.18 94.89 100.80 r ­­­ 102.48 94.54 If­ P2j/« рг^т Рг^. Pi Pi

K - 0.060 0.054 In P 0.056 in Progree*

The metal la linked In BQ llgand by the Nitrogen atoma 4 and a 2' of pyridi­ nyl group, while It la linked to two 2* nitrogen of pyridlnyl group» In the DMQ Metal complexes.

A atudy on the geommetrlcal difference* in DNQ and BQ Uganda according to metal will, be ahown. ­239­ SOME PECULIARITIES OP POTASSIUM XANTHATE CRYSTAL STRUCTURES

N.A. Frolova, V.Ch. Kravtsov, 3.B. Leonov Irkutsk State University, Polyteohnioal Institute, Irkutsk] Institute of Applied Physica. Academy of 3olenoea,Klahinev, USSR

In view of widespread explication of xanthate* to the sul­ phide ore flotation their atructure is of groat interest. Their phyeioo­chemloal activity depundenoe on geometry of hydrooarbon radioal la a specific oharaoterletlo of tbe investigated potas­ sium xanthatea set. Potaealum xanthate oryetals with composition RCOSpK, where R is a hydrocarbon radioal, have been investigated by X­ray analyeia. Transparent eIngle aryatals with prlematlo habitue are characterised by the following parameter*!

I ­ etyl­(02HcC032K), monoollnlo» apaoo group P2­,/o, a»4­40, b­16.46, 0­18.89 A, o­92.1°, Z­8t II ­ propyl­tO^COSgK) .rhom­

bic, epaoe group 0oo2, a­20.16, b­9­92, о­в.25 X, 2­вл H­0.045j III ­ laopropyl­CC^H^OOSgK), monoolinlo, apace group РЭ^/b, a­

6.62, b­19.34, 0­12.46 A, /'­94.9, Z­8, R­0.052( IV ­ but/1­ (O.HQCOS^K), monoolinio, epaoe group P2./o, a­4.37, b­19.60, 0­9.6O X, в­ЭЭ°, Z­4, R­0.107­ Potaaeium xanthate atruoturea ooinolde praotially with one another. Potaaeium lone form different coordinate polyhedre. «ith atoma 3 and 0. In atruoture I two nonequlvalent К lone have dif­ ferent coordinate enoirolament 1 K1 la surrounded by one 0 atom and alx 3 atorasi Kg ­ by one 0 atom and «even S atoma. In struc­ ture II К Ions oooupy particular positions and are surrounded by two 0 atoma and six 3 atото. In structure III two oryatallogra­ phlcally nonequlvalent К lona are surrounded by two 0 atoms and sir 3 atoma. Iu structure IV К Ions are surrounded by one 0 and six 3 «tome. When linking coordinate polyhedrjforms lay«rai In­ side them EC Ions ars arranged, outside ­ hydrocarbon radloals In the ehapc jf algaag ohalna. The main int*r*tomlo diatanoea end valent angles are alaoat the earn* for all structures and agree with literature data. The distances C­3 are in the range 1,656­ 1.699 A, tiat corresponds to the linkage of one and a half. The diatanoea K­3 and K­0 In the polyhedra of К iona are In the rangea 3Л79­3.489 X, and 2.83­ЭНбО X, aooordlngly. ­ МО­ FEATURES OF THE CRYSTAL STRUCTURE OF 1­(4­METHYLPHENYL)­2­ (1',a',Э'­THIPHENYLCYCLOPROPEN­3­VU­BUTANEnl,3­DTONE V.S.rundamenskly, G.L.Starova, V.N.Plotkln, I.N.Domnin, D.S.Yuflt LHPO "Burevestnik* and State University, Leningiad, USSR

Substituted cyclopropenes with 6 ­dicarbonyl fragment in po­ sition 31 of the cycle undergoes theroocatalytic iaomeriiation to cyclopentadienola. It wao shown, that this process depends on the structural features of fi­dicarbonyl group /1/, which we have studied by X­ray method on example of thovabove­mentioned compound. Transparent isometric monoclinic crystals C^2^26°2> «Pace group l> 2i/n, a­». 903(1), b­19.054(1), c­12. 851(1) A, £ ­95. 35 (1) • ,

1*4, DR­1.4 q/cm$. The structure is solved by direct methods and refined to 1Ц,­0.05. The most important bond distances and angles are presented in the Figure « In this compound as well as in earlier studied 3­alkyl­l,2,Э­triphenylcyclopropenes /2/the three­ sMftbered ring is practically symmetric. Phenyl rings, adjacent to double bond are twloted *roe «he ayclopropene plane by 11' end 23\.The phenyl, rinn in posi­ tion 3' and plana through C3'C2C3 atoeie are practically in bisected conformation relatively tu the cyclo­ propane '» plane (84* and 91*, respectively). In ft­dicarbonyl frag­ awnt B,E­conforamtion is established. The plane, costing through carbonyl groups ia b*nt relatively to cyc­ at"^ lopropane by. 47* and Urn fftenyl ring bond lengha 0.01 A of benzoyl group by. 34°. and angles 0.1*

References. /1/ Flotkin V.H. et al., 2h.Org.Chi».23, 1115, (19в7). It Domnin I.N. et al.. Tetrahedron, 41_, 5Э77, (1985). ­831 ­ POSSIBILITIES AND RESTRAINTS ОТ STRUCTURI CORRELATION KETHOD ILLUSTRATED BI THE EXAMPLE О» ТЯ0Р01Д1И АГО "­inTDROXTPHEHALBNOKl DERIVATIVES N.O.Turmanova*. A.V.Leain, L.P.Olekhnovlob", T.0.8hishova»«« •Institute of Crystallography, USSR Aoad.Bol., Moeoow; ••Rostov State University, Rostov­on­Don; •••Qorky Agricultural Institute, Oorky, USSR

Tautomarlo transition in tropolone derivatlvee wan atudled by «fcruoture correlation method using 9 oryabal atruoturae. A gradual transition from tba ayatem with normal van­dnr­Hnale oontaot C.,.0 (2.94 i) to the oovalent bond (1.4? I) in aplro­ oyolio intermediate of the xeaotlon through the formation and gradual,strengthening of the eeoondary bond (2.65, 2.74, 2.59, 2.56, 2.52, 2.45 A) was demonstrated. At the firat etage «ha re­ aotion oonrdlnete was shown to ba a f(motion of the rotation angle у about 0­0 bond of the tropolone nuolaua, ai well aa of 0­0 jiinrt lengths and O­C­0 and 0­0­0 bond angles* *f varying from 01° to 2°. A further shortening of C­O distance should oo­ our in the tropolone nualeus plane. A ahange in the hybridisa­ tion state of oarbon atom from op to яр" in the reaotion oentre ia dasoribed in terms of logarlthnlo dependence based on the Pauling equation. We failed to obtain a similar dependents for 9­hydroxyphe­ nalenone derivatives, in contrast to tropolone derivatives. Se­ condary 0...0 bonds were found only in atruoturee of benzoyl and 2­ohl'>robenBoyl derivatives, while there ware no auoh bonds in 2,4­dinitrobensioyl and pioryl derivatives. This is due tc apaoe reatralots whioh govern the real eoleouler oonformstion in a crystal. This peculiarity of 9­hydroxyphenalenone la due to air­mem­ bered oyoles in eplrooyollo intermediates instead of flve­me:.­ bered nnee in tropolone derivatives. Therefore, the 0...0 dts­ tenoe ~Г.Г A, corresponding to a strong secondary bond, la at­ tained for у«гл , i.e. the conformation oorresponda to sterl­ oellj unfnvaurable one. Instability of eplrooyollo intermediates in the ph*>nalitnnn« series makes the aterioally favourable aon­ format Inn with Y clone tc Oc disadvantageous. ­ 232 ­ STRUCTURE OF N­(2­)METHYL)­2­THIOFURAMlDE J.Garbarczyk, H.Krol ikowska Jnetltute of Chemical Techno)ogy, Technical University of Poznart. PI. Sklodowskiej­Curie 2, 60­965 Poznari. Poland.

In order to find the influence of tioamide substituente on geometry of five­membered aromatic rings. X­ray analyeiB of series furan and tiophene derivatives has been undertaken in our laboratory. These compounds instead their usability in pharmacology are applied In agriculture as a stimulator of growth of vegetables. Thie la firet structure of these series. Crystals are monocllnlc: P2,/a, a­7.900(2). b­9.971(2). c­8.834(2)A. (9­107.01(2)

3 Э V»663.4<21A , Z­4. D ­1.409д.ст" .Л(МоКл)­0.71069Ж,Т­153К,

The measurements were carried out on CAD­4 diffractometer at low temperature. The structure was solved by direct method. The position of the hydrogen atoms Н1.Н2.НЭ were determined on the bee is of geometric calculations, position of remaining hydrogen

•tome were located from a difference Fourier map. Final R­0.048 for 1308 reflections. Bond lengths (Fig.1.) and angles determined for title compound are in good agreement with data presented by Galeslc, et al . II] . The molecules are connected by N­H...9 and N... S hydrogen bonds. The H...3 contact (2.55A) is significantly shorter than the corresponding van der Waais radii sum <2.85A1.

Fig.l. REFERENCES. 1. N.Galesie. A.Vlahov. fl.GaJeaie.Acta Cryst.(1967).С4Э.479­482 This work was supported in part by Polish Ministry of Education. (Project RP II. 10) ­ 233 ­ THE CRYSTAL STRUCTURES OF COMPLEXES OP NICKEL(II), COPPER(II), ZINC(II) AND OXOVANADIUM(IV) WITH 9­(г' ­HY0ROXlfPHENYb)­6­ ALKYLTHIO­ i­ АСЕГГЬт5,7,8­TR1AZANONA­5, 6,8­TRIENE­2­0NES N.V.OerDelou. Itu.A.Simonov, P.N.Bouroeh, V.B.Arlon Institute of Chemistry, Institute of Applied Physic в of the Mol­ davian Academy of Sciences, Kishinev, USSR Template interaction of S­alkylisotbiOBeiiicarbazone of o­oxy­ benialdehyde with aoetylacetone and orthoforaate in the presence of M«(«oac)2, where Ив­Hit Cu, Zn or VO gives polyfunctions! orga­ nio Uganda, whioh are isolated in metal free state (H.LR) In the oases of Zn(ll), VO(IV) and in corresponding oomplexed form (HeLR) when N1(11), Cu(II) are used as matrices, Th« chelates of sine and oxovanadium(IV) were prepared by direct reaction of metal salt with H^IiS in methanol and aqueous acetone respectively.

UK

6 SK 0 X laoksi Пе­Mi, R.CH, (NiLCH,, I) (HjLB, V, where Me­Cu, R­C.Hj (CuLCjH., tl) R­alkyl)

X­O, He­V, R­n­CjUy (VOLn­CjH7, lit) X­Py, Me­Zn, R­n­CjH^ (ZnLn­CjH­'Py, IV) i> X«ray investigation of 1­XV > < showtd that organic Uganda in complexes are quadrldentats independently of the method for their synthesis. In all cases under consideration aquare­planar p., coordination of two deprotonated llgands LR through H1, N4, 01, 0? atoms are realised. The distances Me­01 are equal to 1,84}, 1,879, 1,9*2, 1,950, He­o? ­ 1,647, 1,954, 2,049, 1,992, Me­R1 ­ 1,829, 1,914, 2,079, 2,050 and He­N4 ­ 1.84J, 1,9?i, 2,089, 2,020 X for the 1­IV,.respectively. The coordination number of central atom is completed to five through pyridine N­atoa in IV and through oxygen atoa in III. In contrast to ths ohelates of oopper, tine and oxovanadlua, whioh are built from moneaer ooaplexes, ths formation of centraayaaetrical diaers due to electrostatio intarao­ tion was found in M1LCH­. The diatance Я1­И1 la equal to },4?6 i. The mechanism of conformational tranaformationa of H_LR during the process of complexatfon Is considered. 30­1 ­ 334 LATTICE IICLUBIOR O0NFLKX33 OF Q03SYP0L 1ITU B8NZE» AW CHLOROFORM

H. ddanico*, B.T. Ibragla vb and 8.А. Tallpovb * Faculty of Ohealstry, A Mlokiewiot University, 60­780 Foiuu, Poland; Institute of Bl >organlo Chealatry of the UiSSR Aoademy of Soienoes, Tashkent, US Я

Ooasypol, a natural Polyphenol isolated froa oottonaeed kernels, bas attraoted wc­ld­wlde attention due to its promising antiapematogenlo properties. The oryetallisation works,aiaed at obtaining well onaraoterlsed gossypol samples, dlsolosed that this natural pigment la a very flexible host, taming lattice inolusion ooBplexes «lth ost, polar and nonpolar, organic» sol­ vents. Several о lasses ­>f Inclusion oonplexee of gossypol are known. The presented here ooaplexea of gossypol with ohlorofora and bensene belong to new olasass whloh have not been desoribsd so far. X­Ray struoture anal sis of the 1i1 gossypollohlorofom (apOLP) and 2)1 gossypol) iiumt (QPBN2) coaplexee shows that the orystale of QFCLF are aonoolinio, 02/o and fora an interoa­ late­type struoture while those of OFBNZ are trlcllnlo, FT, and form a olathrate­type atrioture. However, there are striking similarities In ths paoklag node of the host iwleoules In the two structures. It seeas ver: probable that the desorption pro­ oees of the OFCLF ooaplez prooeeds through the dFBNZ type etruo­ ture. ­ 235 ­_ ~~STRUCTURE OF *­(ALKRAMIN0)­4­0XO­2­BUTENOIC ACIO ESTERS " Ивгек L. Gldwka and Iwona Iwanlcka Institute of General Chemistry, Technical University of I6dt, iwirkl 36, 90­924 L6d*, Poland

*,4­(2­Methyl­I,4­piperflzlnedlyl)bls[4­oxn­2­butenoic acid diethyl ester] (D has been found to inhibit the growth of trans­ plantable neoplasms L1210 and 5al80 In nice" and many plperazldes, methylplperazides, oxopiperazldes and amides of et.fS­unsaturated carboxylic acids esters have been synthetiied as potentially active antimitotic and cytostatic agents^ . Characteristic feature of these compounds is amide and ester groups separated by a double bond and the X­ray studies of compounds II and III were aimed at determination of electronic structure and conformation of the «hole conjugated systevi. **»*­. л л

(И ЕЮ—­CJ ­­CH l^i i 0с — сн—CH — c—f(_w—c­сн—TCH­C—m 0 0 0 (II) EtO— C­­CH

,CH—e — r(ji­' —сн=сн— c—OB 1 ­CH (Ш) mi— с ­ 'CH­ —CH=»CH­?­OM« Cry«t«l diti: (П) CJJHJJNJOJ, P2j/c, l-l, ••1.2(2(2), b^».357(2), с­11.2ввМ)А, 0­93.09(2)', R.0.050 for 15«» observations. (Ill) C^H^NjO,, Pi, l'l, «*«.60»(1), b­в.5*3(2), cl<.9»0(»)R, «•«5.<0(2), fi'tJ.il(2), У­»5.?7(г>*, Й-D.OtO for 227« reflections. Tho research was supported by the Polsh Ministry of National Education under the project RP.II.10.

1. Graczyk 0., Pakuleka I., Groerkovekl S., Najnan I., Acta Pol. Pharsi. Ц, 24»­25« (I»«0). 2. Groszkomkl S., Nsjasn I., Pol.J.Pharmacol.Phar». 35, 517­521 U»8J). J. GrosikOHSkl S., NaJ.an I., acts Pol.fhs». «}, 327­330 О»»*).

30­2 ­ 2Э6 ­ NON­TYPICAL CONFORMATIONS OF PYRANOSE RINGS Ш 1.213.4­DI­0­ ­1SOPROPYH DENE­o­»­GALACTOFYRANOSE DERI VATIVE9 P.Gluzlnskl*. A.Kemme**. J.V. Kralewskl* Institute of Organic Chemietry, Polish Academy of Science*, 01­224 Warszawa, Poland Institute of Organic Syntheeie, Academy of Science» of the Latvian 8SR, 226006 Riga. USSR

Basing on the X­ray structural investigations of three selected derivatives of 1;2 t3,4­di­O­iso­propy1idene­e­o­galacto­ pyranose» J6­deoxy­7­C­(2­furyl>­ 1 /1/. б­O­toluene­p­eulfonyl­ С /2/.and l(S)­ecetoxy­3­[6(*)­0~benzyl­l.2i3,4­d1­0­1eopropylidene­ ­a­«»­galactopyranoe­6­yl]­l­(methyl 2, 3.4­tri­0­benzyl­6­deoxy~/>­ ­D­galactopyranosid­6­уПргорупв 3 /3/1 the methods of conformati­ onal calculations of galactopyranose ring» are presented. The conformations of these rings are defined by calculations of puckering parameters, asymmetry parameters and endocycllc torsion angles. The galactopyranose ring in tt may be characterised by e "pure" ivimi I*'* ­J conformation, whereas in i and Э by

T S and 5 7 conformation» twist+serew \ M*° J\ screw*(vtel Г »** ".J * respectively. The hybrid forms exhibit much higher Internal strain energies of pyranose rings than those of the chair forms usually encountered In saturated saccharides. The proper establishing which form is prevailing in a hybrid was possible through tho calculations of least­squares planes characteristic for tvimt and screw forms. /1/ Krajewski J.K.. Glurirteki p.. ОгЬлЛскук­LlpkowBk* Z. , Ramza J.. ZamoJski A., Carbohydr.Res.. In press. /2/ Krajewski J.W.. Gluxinski P.. Urbanczyk­Lipkovska 2.. Zamojekl A.. Andreetti O.D.. Bocelll 0.. Carbohydr.Res.. US. 1 11966}. /3/ Krajswekl J.V.. Gluzlrtskl P.. Jarosz 9.. Zamojeki A.. Bleidelle J.. Miahnyov A.. Kemme A.. Carbohydr.Res.. liA. 183 (198Э1. ­ 23? ­

? 3 ON THE STEREOCHEMISTRY OF THE R,(X.)C(sp )­N(sp )R2Rj FRAGMENT. CRYSTAL DATA, SEMICMPIRICAL AND 'AB INITIO' CALCULATIONS. G.G1111. V.Bertolas! and V.Ferrettl Centre dl StruttuHstlca Dlffrattometrlca, Unlverslte dl ferrara, Ferrara, Italy.

3 The geometry of the R.(X­)C(sp )­N(sp )R?Rj fragment, found In molecules such as amides, enamlnes, anilines etc., tends to be planar. In a crystal environment, however, the geometry 1s often deformed from the ptanarfty and the deformation can be ascribed to two types of notion: a simple out­of­p1ane bending of N{sp )(de­ scrlbed by Хы­0<Хы<оО°) or a combination of the N­bendlng and a twisting around the C­N bond (described by т:0<т<90*). By structure correlation methods 1t was shown /1/ that this motion can be considered to map the geometrical changes of the group along the ds­trans 1somer1zat1on pathway. In the same paper we have proposed for the c1s­trans IsomerlJatlon process the following energetic model:

E(t',xN) • (CTIB*IB)(I­COST'>/.? • QPd.cosT'lx//? • IB(1­cosi')(cos3X|(­1)/» w2?, CTIB­cls­trans Isomerllatton barrier and IB­pyramidal Inversion barrier for N(sp Mln kc»l/mol), OP­force constant for the out­of­plane bending of N(sp?)(tn kcal/mol rad2). In order to support the validity of the model, we have undertaken 'ab initio' calculations (4­3IG balls set) with full geometry optlmliatlon of formamlde, thloformamlde, ethenamlne and formam1d1ne molecules for different values of т and Хц> A typical energy plot at a function of t and

XN obtained by 'sb 1Mt1o' methods 1s shown, for amide, In F1g.1. For the same case Figs.2 and 3 snow the comparison between 'ab 1nK1o'(A) and molecular­ mechinlcsl*) calculated energies for two sections of the total energy map,

E(0,T) and E(0,xN). Values of СТ1Б, IB and QP for the sernlemplrlcal model were calculated by best fitting three singular points on the 'ab Initio' f map (СT1В­ 21.5, 1B­0.7, QP­7.9). The agreement Is to be«consIdered quite good and the same happens for thloamtdes. Specific discrepancies are found for enamlnes and amtdlnes which will be discussed at the meeting.

21,9

1. r 3

0 70 4> «О ЮГ GilH G.,Bertolas1 V..Belluccl F.,F«rrett1 V., J.Am.Chem.Soc. 2420 (1966) ­ 238 ­

STRUCTURE AND ABSOLUTE CONFIGURATION Of (­X3R)5,7DlrlETH0XY­3,9­0l WDflO­EUCOMMALIH­f­p­BROMOeEWOATE . AN UNCOrtlON CASE

Federlco Giordano

Dlpartlmentodl Chlmlca, Unlverslta di Naool!, Italy

The title compound Is a Bromorderivatlve of a chlral homoisof lavavone Isolated from tbxarl species. Crystal data are. C26H25°7Br­tt' 527 3B­ flcllnlc, P\, в- 8 066(1), 0­ 11.044(2), С- 15518(4)A, 4 • 112.3*2),0­76.40(2), •» ­ 11034(1)­, V- 119CK1 > A3, /•2 0,­ 1.47 Ид пГ'.МСиК,)­ 1.5418 А, ц ­273 mm"', Я0001­540, room temperature, final ft- 0.056 for 3517 Independent observed reflections and 361 parameters. As shown In the figure, the two molecules In the unit cell pack simulating a symmetry center, owing to small conformational changes of the ring carrying the chlral centers.

The structure has been refined Imposing a centrosymmetry constraint to most atoms of the molecules, whereas few atoms around the chlral canters were allowed to refine freely. Although the 94» of the electron density Is In a ctrtroeymmrtrical arrangement, an unambigous assignment or absolute configuration has been done on the ground of the agreement between if0 and /if4 of 50 enantlomer

Da* of a nitration process in refining platinum metal* eeuaes an Interest to investigation of nitrite complexes, Th» only paper /1/ nuy be cited as including to* data on crystal structures of potassium complexes. Хчеау powder diffraction study of К3[вп(НОг)6] ­ (I) and Иах1;3_х[1Ц1(И02)Л has been oarried out In the present work. The oompound (I) has been prepared following the general procedures IU, In recrystallisation of (I) fro» MaM02 solution the sodium oomploxoe nave been prepared. BaiK relationship In

samples prepared at Increasing concentration of 5aN02 In •other liquor froa 0,05 to ЧН la given In the Table. Beginning fro* 0,75*1 solution this relationship is constant. t Concern,. HaiK a, * Oonoent. •ail a.l HaH02, U KaNOg, II

0,05 0,34i2,66 10,635 0,75 1,20|1,Э0 10,411 0,2 0,7212,28 10,530 1,0 1,24,1,76 10,404 0,3 0,8612,14 10,490 2,0 1,2011,80 10,394 0,4 0,9712.03 10,456 4,0 1,26,1,74 10,390 0,5 1,0811,98 10,438 X­tfay study of this complex has been oarried out on dif» fraotoaeter DBON­ШИ (B­192 am, CuUs­radlation) in the range 5­ 100° 2w.1e

Eecryetallitatlon of (I) in HaI02 solution oauaed a part of the К Ions to be substituted by the Яа ions of smaller else. It results In decreasing the 0» parameter. An impregnation is achieved at NaiK*>1,25H,75 1. Ferrari A.. Oolla 0. Baodloonti., 1933, v. 18, p. 45. ­ 2«­ OHARAOTBRISTIO BKHATIOUR ОГ OKANURIO AOID IN COMPLBX FORHAIJION WITH HBTAIS И.Z.Ourevloh, Z.A.StarHcova. T.».Sysoeva, M.Z.Branzburg Reeesroh Production Association "IRRA", Moscow, USSR

In the oourse of study of epeoiflo features of oyanurio •old (2,4,b­trloxy­1,3,5­trlasine, H,L) in complexes with various

aetals we performed the X­ray investigation of K2(H2L) H20 (I_),

Li(H2D2,5 H20 (II) and Cu(H2D2 2 H20 (III). Crystals of I and II are built of anions HjL", oatlons of metal vxA molecules of hydration water. Crystal! of III are built of complexes

0u(H2L)2(H2O)2 i where the coordination of Hgl" anlones oocu.fr by'means of К atom (Cu­H 2,002 1). In general the three struc­ tures are similar and oonslst of alternating organic and inorga­ nlo layers. Or(anlo layer* are composed of oyanurate anions united in ohalns by H­bonds F­H...0­0, the latter are packed in layer* due to etaoJtlng Interactions between oyanurlo oyolea. Inorganlo layer* are built of metal oatlons and water mols­ oulee. Thus Irrespective of ooordlnatin type of metal oations with HjL" anion* ­ ionio in I and II and oovalant In III ­ the

hydrated speolee H{H20)n are ooncentrated in the веке spaoe of orystal atruotur* (in inorganic layers). It вау be assumed that structures of cyanurates, ­which oontaln Uganda with similar oomplexlng ability ­ oyanurate>ani on* and water moleoules ­ are conditioned by Interaction mode between oyaourats epeoies. ­ 2« ­ THE MoOj­DIEN SYSTEM. CRYSTAL AND MOLECULAR STRUCTURE OF BIS(DIETH YLENTRIAMMONIUM) HEPTAMOLYBDATEfVI) TETRAHYDRATB

J. M. OmiejTE»­7.nrrili»a. A. Luque», M. Martfnez­Ripollb, P. Roman» » Depl. Qufrnica Inorganics, UPV7EHU, Apdo. 644, 48080 Bilbao, Spain. Ь UEI CrlstalogratYa, CS1C, Serrano 113,28006 Madrid, Spain.

When trying w study the system MoO}­dien in aqueous solution in order to prepare new polymolybdttes, we have obtained the bfs(diethyIenlriammonium) heptamolybdate(Vi) tretrahydrate. Thlt system was previously studied by Marzluff l\l who prepared the trioxcHdlethylentriammlne)molybenum(VI); Cotton and Elder solved the crystal and molecular structure /2/.

Thermogravimetric studies show that the title compound contains four water molecules that are lost between 70­ J 30 °C lr spectra Indicate that the organic bases are proionaled and the polyanion presents the well­known infrwed spectrum for heptamolybdate anion in solid state.

The compound, (СаН^эЫМотОгдИНаО, crystallizes in the monoclinlc system, space poup P2|/a with a ­ 15.633(3), Ь ­ 12.067(2). с ­ 17.557(3) A, 0 ­ 90.50°, V ­

3 3316(1)A , D, ­ 2.68, D0 ­ 2.68(1) Mg/m' and Z ­ 4, The least­squares refinement using 6404 observed reflections gave agreement Factors of R ­ 0.026 and R„ ­ 0.029.

The structure solution confirms that the compound contains discrete (M07O24)6* anions, (C4HieN3)3+ cations and water molecules, connected by several hydrogen bond types. They can be classified u follows: N­H­O, N­H Ow. Ow­Hw­O. Ow­Hw­ Ow, and C­H­O.

The МоОб octahedra within the polyanion are distorted and the distortion has been evaluated using several equations /3/.

/I/ Manluff, W. P., Inorg. Chem. 1 395 (1964). til Cotton, F. A., Eider, R. C, Inorg. Chem. A 397 (1964). PI Roman. P.. Outlerrez­Zorrilla. S. M.. Manfnez­Rlpoll, M., Oarcfa­Blanco. S , Transition Met. Chem. Ц, 143 (1986).

3I­I ­ 242 ­ ORGANOMETALLIC COMPOUNDS AS SELECTIVE REAGENTS IN ORGANIC SYNTHESIS : EXAMTLES FOR THE RELATIONSHIP BETWEEN STRUCTURE AND SELECTIVITY

By К. Нагие. G. Boche and N. Marsch, Faci.bereich

Chemie der Unlversitaet, Hans­Heerwein­Str.t D­3550 Marburg, Federal Republic of Germany

Organometallic compounds are very important aa selective reagents In organic synthesis. There is a lack of Information about their structures and the relationship between their structures and their selectlvities. He have developed some cry­ stal structures of organometallic reagents and try to explain their selectivity from these results. Some examples will be discussed, «. g. i

1 . Structures of lithiated sulfoxides : Substi­ tuenta direct the attack OIL methyl iodide.

2. Structures of an reagent, the lithi*ted reagent and of the product of an stereospeclfic reaction rationalize the selectivity of this reaction. ­ 243 ­

STRUCTURAL AND CONFORMATIONAL FEATURES OF l­PHOSPHABICYCLO[3.3.0]­

OCTANE 1­SULFIDE H. HaMitng, U taimiltttA, f. K\tch Sektion Che: te der Harttn­Luther­OnivereltJlt Halie­Kittenberg, Poetfach, DrRWOlO Halle, German Democratic Republic In contlnuitlon of our previous Investigations on the conformational behav­ ior of phosphublcycloalkane sulfides IV an K­ray structure analysis of 1­phos­ phablcycloij}. .ojoctane 1­sulflde has been perforated. The compound crystallizes 1n space jro. PZj/t «1th a ­ 7.461(1). b ­ 7.841(1), с • 14.508(4) Д, I • 99.96(3)*, Z 4. The structure «as solved by direct methods using the program SHEUS­86 and refined to I! ­ 0.056 for 981 observed reflections. The phosphol­ ant rings of :he molecule are cls­fased and adopt both an envelope conformation. In one ring the flap carbon atom Is potltlcnally disordered. As a result of the non­ststlstlcol disorder, the title compound ealsts in an ако­endo conformation (main occupap­y) as well as an endo­tndo conformation In the solid state (see Fig. belm). Mi rather surprising result Is compared «1th tha conformational behavior of related compounds and the findings of Mt studies.

П1 пТиДма, К., Ъатиюх, (/., Лшек, Я., Клик, Г. Acta Crj >t. C44, 1438 (19М). and references therein.

31­2 ­ 244 ­

NON­CATENATED CHANNEL INCLUSION COMPLEXES 07 TRIHESIC ACID WITH INTERRUPTED AND UNINTERRUPTED HOST MATRIX FRAMEWORKS. P.H. Herbateln, И. Kapon & CM. Reisner Department of Chemistry, Technlnn ­ Israel Institute of Technology, Haifa, Israel 32000

Trineaic acid (benzene­l,3,5­tricarboxylic acidj TMA) сал In principle for» two­ dimensional hydiogen­bonded hexagonal networks with central holes having net di­aawtera of Although such holes In superposed networks would be expected to be natural locations for guest molecules of channel inclusion complex**, catenation of the networks was found to occur In all the varieties of TMA (its polymorphs, hydrates and complexes) studied until 1987 /1/. Than the first channel Inclusion conplaxes were reported, with guasta such as n­tetradecana, n­octanol, octane, cyclooctana and lsooctane /2/. The complexes can be classified in tarns of the repeat In the direction of the channel axla, and in term* of the crystallography of the unit cell. So far two­, three­ and five­ layer repeats have been found among the thirteen conplexea for which crystal data have bean obtained. Room­temperature crystal structures have been determined for

the n­tetradacene, iaooctane, d­camphor (with 2Ha0) and oieyl alcohol complexes| these show details of the TMA framework but only oleyl alcohol la well defined among the guest molecules. In the n­tetradecane and isooctane complexes the guest molecules are not linked to the THA framework» which is thus

1 'uninterrupted . However a new feature appears In the d­camphor.2HaO and oleyl alcohol complexes, where the water molecules and the hydroxyl group respectively Intervene in the TMA framework, which io thus ' taterrupted '. Mm are planning low temperature structure analyses which appear essential for definition of the role of the guest molecules in these complexes.

Referencesi /1/ Herbstain, P.H. "Structural Parsimony and Structural Variety Among Inclusion Complexes (with Particular Reference to the Inclusion Complexes of Trimealc Acid, N­(p­tolyl)­tetrachlorophthalimlda, and the Keilbron "Complexes")." TOD. Curr. Chew.. 140, 107­139 (1987). /2/ Herbstain, F.H., Kspon, G.H. Raisner, "Catenated snd Non­Catenated Complexes of Trimesic Acid." J. Incl. Phenom.. 5, 211­214 (1987). ­ 245 THE CRYSTAL AND MOLECULAR STRUCTURE OF 2­HYDR0XY,2­CARB0XYLl4 4lb PR0PELLANE­6­ENE, AN ECLIPSED PROPELLANE. F H. Herbsteln. И. Kapon 5,6. M Relsner Depanment of Chemistry, Technion ­ Israel Institute of Technology, Haifa. Israel

Propellanes are tricyclic molecules where the three rings have a single bond (the conjoining or propeller bor 1) in common II); the structure of the title molecule has been determined as part a comprehensive study of tneir stereochemistry 12,31 The C12H16O3 molecule crystallizes in space group C2/c, 2 • 16, wim я • 19208(7), /> ­ 19.616(7), с • I3,4I8(5)A, ft ­ 121.35(5)'; 1640 reflections in the last refinement cycle, Rf ­ 0.096. There are no significant differences between iht two crystallographlcally­ independent molecules In the asymmetric unit. The н?хч. /4 ' molecule is eclipsed and the cyclohexene (\^^f ^> „ r,n9 |s boat­shaped as expected, however 1.306(10)4 II )^j (1.f1(2)4) the other slx­membered ring unexpectedly "/ ^SL J has a screw­boat conformation, with HOOC"4^ ^/ large displacement lactors for the two peripheral carbons and an app'.re it shortening of the bond between them by «0 134 This Is presumably due to some inexplelned type of disorder, chemical or physical in nature. A similar effect has been reported and ascribed to disorder between two conformations 14). The crystal packing has a number of Interesting features. The molecules are linked by hydrogen bonds between carboxyl groups to give the typical dlmers, and between hydroxyl g.­oups, with the formation of tetramers. in the tetramers the oxygen atoms are Inked In almost square parallelograms; similar arrangements have been reported e g 151.

Rrtcrocm: I einsturg, 0. "PROPEIUWES ­ Strudureend Reactions", (Monographs in nooarn cnemiairy »7, Srn Editor Hans F. Ebel), Varleg Chemle, GmbH. 0­6940 Welnhelm, West Oormany, 1975; also Sequels I (pp.161; I July 1975­ Jl December, I960) em) И (pp.232; I January l«ei ­ Я Dacemoer 1984) published by the Department of Chemistry, ТеInlon In 1901 era) 1965 respectively. 2. Herbsteln, F.H.. tehkenazl, P., Keflory, ft, kepon, M., Relsner. ft tt. t, Olnsburg, D. "Propellmes LXXIK. Comparison of the ОклМгня of Dlthiat ff.3.3Jpr

M. Hllbers, L. Klrlazla, H. Lelmkilhler and R. Matte», Anorganlsch­Chemisches Instltut der Ifeetfalischen Nllhelme­Univeraltlt, Wilhelm­Klemm­Str. 8, 4400 Miinater, F.R.G.

Using W4e4* aa countarion m aeries of new mono­, di­ and tri­ nuclear fluoro­ and fluorooxoenione of titanium, vanadium, chro­ mium, molybdenum and tungatan were prepared. Some examples are:

m«4(Tl(H20l4rj>TlFe­II20 (NMe4l3Cr2F9

(NHa4)2(Na,R)V]03rt2 INMe4>2M204F6(H20) M­Ho,H

(NMe4)2(N«,R)Ho306F, (NMe4)CsV202Fg(H20)

(NMs4)H2Mo2p2F9­H20 )NMe4)VOF4

Tha atructuraa of moat coaipounda mentioned ware determined by alngle cryatal x­ray diffraction. Tha dlatrlbutlon of oxygen and fluorine Uganda on bridging and terminal coordination sites was establlahed unamblguoaly.

<НМа4)3Сг2Рд and the laoatructural compounds (NMe4l3Fe2F9 and

(lma4)K2Mo202F« H20 la a symmetrical dlmer with a fluoro­bridge and terminal oxo­groupa trana to tha bridge bonds.

me4)2(»s,K)V303F12 and dma4l2(Ns,K)Ko306F9 are laoatructural c­.'cllc trlmera with oxo­ or cla­dioxo groups in their molecular planee.

(HHs4)jHo204F6(H20) and lime4)CsV2o2Fe(HjO) are asymmetrical Si­ men with bridging fluoroliganda and Intermolecular or intramole­ eul. r hydrogen bonds. Tha preparation of theaa compounds aatabll­

ehee tha preaenca of VOT^Ih^O)' and Но02Рз(Н20)~ iona in aaquoua

aolutlona of hydrogen fluoride* V2Oj and Mo03.

/1/ auchnolE, И., LelakOhler, П., Klrlaila, L. and Mattes, It. laorej. Cha*. 1»8», 27, 30J5. ­ 24? A COMPLETE STRUCTURAL ANALYSIS OF COCCINENE: CRYSTAL STRUCTURE, 2D­NMR, AND MOLECULAR MECHANICS STUDIES.

W. HiUef, A. Cantineirati, H. Koiug (lutilut fur Auorgauische Chemie dec Univenitft Tubingen, FRG and L­ Castedo, E. Quinoa and R. Riguera Departamento de Quintica Organic* de la Facultad de Quimica, Santiago de ComposteU, Spain

As part of our investigations about marine natural product! from the Galidan coast (north­ weil Spain) w« isolated from the red algae Ptoctmium еосеЫгтт a balogenated teiracfaira) monoterpeue having the violacenc type skeleton. We report about the absolute structure of coccincne, СюНнОДОг (йве figure) *• **11 •* about ,3 13 the remits of NMR tcchm4ue» (41, C, 41­41 and 4i­ C COSY, NOE) and molecular mechanics calculatiuni (Allingcr's MM2 program).

Cocciueue crystallize» orlhorhonibic in the nonceutroaymmctric jpace group P2|2|2t with th« lattice parameters a = 638.3(2), Ь = 1297.9(2), с ­ 1589,0(2) pm and Z= 4. The final R value is 0.044 (cnantioiiier: 0­UC1). A comparison betweeu the geometry deduced by molecular mechanics cakulatiooa (gaseous state, very similar to tbe geometry in solution as ihown by the coupling constants) and tbe geometry iu solid state is preseuted. ­ 248 ­

REACTIVITY OF ALKENES AT A DIRUTHENIUM CENTRE J,A,K,Howard. S.A.R.Vnox. N.J.Terrtll, and M.J.Yates Department of Inorganic Chemlttrv. Camocka Close, Brlitol BS8 ITS, UK

We have shown /1/ that Пиого­allcenes combine with methylene in (RujfCO)­ (CHj­CHjKfi­CHjM/i­COyTj­CjHj^] (1) under relatively mild conditions <<4fj °C) to give new complexes, l(V) *nd (lil)} мод (bit cMort> and bromo­alkenej react even more readily. The reaction proceed! via hydrogen hallde elimination and In the case of fluoro­ alxenes. Incipient formation of hydrogen fluoride )n the form of H....P hydrogen bonding ha* been Indicated both )n the n.m.r spectra and In the X­ray structures. The remit* of this are lummarlsed In the figure below.

We have reported also /2/ the first synthesis of a dinuclear complex containing co­ordinated metiiyleneffi­CHj) ,n0 ethylene, fJV) which does evolve propylene on heatlnf. However on oxidation the ethylene llgand in the complex U transformed to /(­vinyl allowing synthesis of a p­melhylene/*­ethylldene complex which evolvei propylene more efficiently, suggesting a process for tlkene homologation on a metal lurface. The full details of the structures and the relevant cbemlitry will be reported. tit Yates, Michael I., Ph.D. Thesis, University of Bristol (1988) and Howard. Judith A.K., unpublished results. /2/ Doherty, Nancy M., Howard, Judith A.K.. Knox, Selby A.R., TeMH, N.J.. and Yale», M.l. (19Я9) Submitted to J.Cbem.SocChem Comm. ­ 249 ­

5YMMETRY AND CONFORMATION OF LOW NUCLEARITY RUTHENIUM CLUSTERS S.lenflli, E.Nardelll Tatltulu di Chlmlca Generale ed Inorgenlca dell'Universlta dl Parma, Centre dl Studio per la Strutturietice Dtffrattometrlca del CNR, Vlale delle Science, I­4.1100 Parma (Italy) P.Fredlen'., A.Blenchi. A.Snlvlnl, F.Piacenti Cettedre di Chlmlce Industrials, Dlpartimento dl Chimlca Organlca dell'Universi­ ty di Firanze, Via QihO Capponl 9, \­bQ\2\ Firenze {Italy)

Ли (CO)ACH COO) (Pfly ­)*fl) 1" hydrocarbon solution under hydrogen pressure In the 20­200'С temperature range givea origin to the following compounds: H^Ru (CO» («( JV), H Ru (CO) fPBunj(Pftun ) (Vj, H Ии^(СО)* (МЯ)ГРви ) fr A I (PI (VJ), H fiuI(CO).,(РЙи° РИи" ИРВи" Г(Р) («1», и n «ш*"л{со)*{Рнъи НР & Jjr ft." ) /P) ivrnj О v ly 7 с 3 с. , end a not fully characterized compound. The nature of the (V)­(VIM) compound* haa been defined by X­ray crystal atructure analysla which ahowed the metal cluster nature of these compounds in which hydrldo and phosphide bridges are present. In compounds |УП­(5П1} a bars phoaphlde phoaphorui atom la encapsulated In the metal Ouster. The analysis of the geometry of these cluster molecules show that approxi­ mate local symmetries are present which are characteristic of the building of thea« clusters. From the projections of the figure showing the cores of these molecules the approximate molecular symmetries are quite evident. Van der Weals non bonding potential energy calculation allows to understand the orientation of the terminal phosphlne Uganda.

32­1 ­ 250 CRYSTAL CHEMISTRY OF OOSSYPOL INCLUSIOM COMPOUNDS WITH HYDROPHOBIC QUEST MOLECULES B.T. Ibragimov. S.A. Talipov, M. Odanleo» Institute of Bioorganic Chfouistry, Uzbek Aoad.of Scl., USSR • A. Mickiewich University, Poznan, Poland

It Is well known that phyeioliglcally aotlve polyphenol sub­ stance of cotton ­ goeeypol ­ forma Inclusion compounds practioal­ ly with any small organlo molecule. Unlike the other guest mole­ cules, goeeypol differentiates distinctly the hydrophobic guests from hydrophilic ones as those two types of gueets can not form leostruotural inclusion ooatpounda with gossypol. Qoseypol makes complexes with a large number of hydrophobic guest molecules for­ ming inoluelon compounds of seven different types. Crystallograp­ bic parameters of one representative of those types of gossypol inclusion compounds between which there is a morphotroplc transi­ tion are given in the Table.

т7> 6ue»t >,* g,& Ctl j у Г­ fey jM­ A CH^jClg 21.320 19.129 15­765 90 113.05 9U uil/u 1i1 В 0ЫСЦ 26.693 9.068 26.262 90 10a.6b 90 C2/o 1i1

0 CC14 8.647 13.221 14­504 70.05 91.12 71.64 VI Ш

D toluene 20.615 19.32* 16.150 90 90 109.13 ^2t/| 2i1 Я benzene 11.24! 14.9B6 17.360 9b.Ь9 dJ.14 1Л.09Р1 2.1

Dichlorinethane and goaeypol form inclualon compound of ohannel type, илеtable under ordinary condition*. On decomposing It Into ••parate components, elngle crystal» axe well preaerved. Triohlor­ nethane can be plaoed In channels, and an inoluelon compound of B­type la formed where the layers composed of the gueet and hoat moleoulea only are alternating. If one more hydrogen atom in * gueet molecule will be 0hanged for a chlorine atom, then again a morphotropio transition occura and an inoluaion compound of goaaypol of C­type is formed. The gueet molecules are localised again lnaide the channel, but now. however the channel Is between the layers of goesypol molecules. In such channel в molecules of all isomers of xylene are placed as well. On decreasing the mem­ ber of methyl group in a xylene molecule by о.ш, a futher mor­ photroplc transition to D­type structure takes place. ­ 251 ­ COMPARATIVE ANALYSIS OF THE STRUCTURES OF

PENTASILACYCLOHEXANES XSl5Ph,0,X ­ 0, Ti(nf­Cp>z V.A. Igonln. V.V.Dement'ev, T.V.Tlmofeeva, V.E.Shklover, Yu.E.Ovchlmlkov, Yu.T.Struchkov Nesmeyanov Institute of Organoelement Compounds, USSR Academy of Sciences, Moscow, USSR

An X­ray diffraction study оГ two heterocyclic poly­

sllanes (if­Cp)gTlSl5Ph]0 (I) and 0(SlPhg)5 (U) was carried out. The Sl­Tl and Sl­Sl bond lengths in molecule I are.0.02 Я greater as compared to isolated bonds of these types. The Sl­0 Lond lengths in heterocycle II exceed the standard value by 0.03 Й. The О atom has an opposite influence on the Sl­Sl bond as compa­ red to that of *ie metal atom the average Sl­Sl bond length In IT is 2.381 %, which is 0.02 % snorter than In (SlPtiglg and (SIPhgJg. The S1S1S1S1 torsion angles In cycles I and II are in the range 40­50° and their average value Is close to 47.6°, which almost exactly colncldel with the torsion angle observed earlier In highly symmetric cycle (SlPhj,)g. Heterocycles I and II have a chair and a boat conformation respectively. Significant differen­ ces of the Sl­0 and Sl­Tl bond lengths In these cycles and the presence of Cp­llgands at the Tl atom result In essentially different non­bonded interactions determining the conformations of the cycles. Thenfore,results of molecular mechanics conformati­ onal calculations of Me­analogues or I and II are In agreement with the experimental X­ray structural data.

§

32­2 ­ 252 BKHKf!­.!> CYCLOI HfXAOIIiNliS

И. imKartmflcr. K. Jahn, IX KullCass, i'. Осьсг

Insiiiuie of Organic Chemistry, University of Heidelberg,

tm Ncuenhcimcr |­eid 270, O­64U0 Heidelberg, (.KG.

In the course of our structural program of strained polycyclic compound* we iyuihc*i/cd bridged dicyanocyclohcxadieitcs and determined (heir structurci. Because of stent «rain in tlie compounds 1 with а кто bridge (Dcwur­bcn/ene derivative), 2 with otic (.'Hj­group (norborna­ dicne derivative), 3 with two CHj­groupi and 4 with eight ("Hj­g'oups (one ело, one endoj HI hridgci between the I,^­positions of the cyclohcxa­l,4­dien«i tho «p1­hybridised carhun monii «re pyramidali/cd. The direction of these, der/or it mi ion» depend on the length) of the bridging groupt.

/r-ZH fl~CH

CN

(сн), г mu

//—CN < CN

^CN CN s

The cyclohcKa­1,3 dicne 5 (art anti­Brcdt compound} hat a itrouyty dvlunucd double tiuud on the bridge head carbon atom. ITie detonmiioni ol" I ­ 5 and their photochemistry will he discussed. ­ 253 - THE STRUCTURE OF s­TRIAZINE DERIVATIVES A3 COMPARED WITH BBHZENK ANALOGUES

Iwona Iwanlcka end Marek L. Qlowka Institute of Oenerel Chemistry, Teohnioel University of Lodfc, Lbdl, Poland Three e­trlaslne derivatives! 2,4,6­triiisthoxy­1,3.5­tria»lne (I), 2­oyclohoxylamlno­4, 6­dlmethoxy­1,3,5­trla»lne (II) and 2­(2,2­dlmothylpropiurK)ylo3[y)­4, 6­dies< i­«y­l,3.5­trle»ine (III) have been studied by X­ray method.

R 0 ""TOT R= ­0M» ­NH­(H) ­О­С­Ъи оме i п ш

Results of these studies showed ohareoterlstlo features dif­ ferent than those observed in analogous beniene structures due to presence of trlasine system. The sain differences oonoern asyn­ очtry of bond lengths in aromatio ring, enhanoad conjugation of aronatlo AT electrons and lone pairs at adjeoent atooa, and dif­ ferent spatial orientation of substituents. Сьу­*;.! datai (I) OJHJNJOJ, orthorhombio, Pnma, г»4, a.8.474(2), b«6.719(1), o«14.409(2)A, dlffraotoipeter, Mo, up to 0­24°, 780 unique reflectlone oolleoted, 677 used in the refinementi R­5.0».

Ш) 0nH,8ll402, triollnlo, PT, a«2, a­6.894(4), Ь.8.13в(4). o.12.20l(6)A, 4. .106,67(2),^ •90.420). ^"•105.41(1)", Ho, dlffraotometer, 9*25", 2564 unique reflections oolleoted, 2225 used In the refinement, R.6.9%.

(Ill) C10H15Nj04. Bonoolinio, P2,/n, Z­4,a­10.317(3).b­e.665(4). 0­13.639(5)A, Л.100,45(2)°. Cu, diffraotoeeter, max e­75", ­50°C (in a capillary), 2523 unique reflootiona oolleoted, 2277 used In the refinement, R.4.6*. Support from the Polish Ministry of National Education (projeot W.Il.lu) IB gratefully eoknowledged. ­ 254 ­ aotlD­SOLID AHD 0/.3­SOLID REACTIONS WITH A DIOI. HOST

1. Johnson. D.R. Bond, L.R. Haeenbeni Department of Chealetrjr, Unlrerelty of Cape Tom Cap* Tom, Rondeboeoh, 7700, South Africa Г, Tods Department of Induetrlal Chemistry, Feoultj of engineering Bilme University, Hatsujraaa 790, Japan

The klnetlos of the solld­eolld reaotlon between the dlol hoet ooapound H and bensophenone /1/ nave been Investigated uelng various speotroeoople techniques Hi

/1/ Toda Г., Tanaka K., Seklkawa A., J. Che». Soo. Chen. Oonraun. 279 (1987) /2/ Qavessotti A., J. An. Chen. Soo. 10£, 16, 5220 (1983) ­ 255 ­ PREPARATION AND CHARACTERIZATION OF PbjS^YClljOfl end

Pb25r2HoCu3Oe. J.­E. Jergenean, Department of Cheeiatry, Aarhua Univeraity, DK­8000 Aarhua C, Denmark. UimlM Haeeel Andersen, riae National Laboratory. P.O. Box 49, DK­4000 HoeJtilde, Denmark.

The titla compound h«a bean prepared by reaction of PbO with precuraora of composition s^LnCujO^j with Ln ­ Но, Ч, The prepared aanplaa have been characterized with X­ray and neu­ tron powder diffraction. The cryital itructure contains Cu02 ahaata airailar to what it found in e.g. YBajCujOg md Cu layara without oxygen, oxidation at low temperature reaulta in incor­ poration of oxygen in the laat mentioned layera. front X­ray powder diffraction it waa found that oxidation lowera the ayn­ rnatry froa orthorhomblc to triclinic. ­ 256 ­

CONFORMATIONAL MAP AND APPLICATION OF THE PRINCIPLE OF STRUCTURAL CORRELATION TO RING­FLIP PROCESSES IN VARIOUS SYSTEMS CONTAINING 1,1­ AND 1,2­DIARYL HuIETIES.

Hanaheffi KeftoryCw>. Silvio B. Bieli*"*, and Zvi Rappoport***1 .

^'Department of Chemistry. Technion­Isrsel Institute of Technology, Haifa 32000, Israel. 4h>Department of Organic Chemistry, The Hebrew University, Jsruaslem 91904, Isrsel.

Correlated rotation in 1,1­diarylvinyl systems is usually snslyted In teraa of flip mechanisms, all of which involve hallclty reversal. The zero­ and the two­ring flip processes involve conrotatory rotation of the aryl rings, while the one­ring flip Involve* dlsrotatory ­­ot*tion. The lower energy path* which determine the most probable conformational mechanism can be analyzed by conformational вара produced either Ъу Molecular Mechanic» theoretical calculation* or by the uae of the structural correlation oothod. We have obtained the conformational aaps for various systems containing 1,1­ and 1,2­dlaryt moieties using the torsional angles of the aryl groups deduced frost a large number of crystal structures, ss well aa by Holsculai Mechanics calculstions for the perent 1,1­ and 1,2­dlphenylethylane frame. The poaeibla paths for hellclty reversal are clearly displayed by these «ape and conclusions regarding the preferred flip Mechanism in 1,i­ dlarylathylenea, benzophenonee, cis­stllbenea end in '., 1,2­triarylethylene systems were drawn out.

Variations of othar structural parameters, such aa bond lengths and angles, which occur during the hellclty reversal process are alno demonstrated by t ­.« use of the structural correlation method.. ­ 257 ­ STRUCTURES OP THREE MOLYBDENUM (IV) CLUSTER COMPLEXES V(ITK THE CORE

E. Kamcnar, 3­ Korpar­Colig, M. Bruvo and I. Vickovic Lab. of General and Inorganic Chemistry, Faculty of Science, The University, Zagreb, Yugoslavia

In the last decade a number of triangular trinuclear cluster complexes with Mo­Mo bonds have been intensively studied /1/. In the continuation of our research on Mo complexes with 0 donor li~ gands we have prepared three complexes of the general foimula

Mo304(acac)3(OC0R)(H20) with R=(I)H, (II)CHj. (IllJCjhy All three complexes crystallize as 1:2 solvates containing molecules of the corresponding solvents (methanol, ethanol and propanol).

R Crystal data. (I): a»10.130(2), b=1B.133(5), I c­7,901(2)A, £=105.95(3)° sp.g. P2.,/m;(ID: /C\ a=19.346(6), 0=13.413(4), c=8.146(5), sp.g.

1 ач 1 a S Prima; (III): a­19.180(3), b=18.410(4), Ко ­Mo > c=8.004(2) A, sp.g. Pnma. In all three •|\^n^ n \ I / n x struct1*1"63 "the cluster molecules have a mir­ x ;r/ ° ror lane Mo P symmetry and consist of the tri­ I 0 angle of Wo atoms with Mo­Mo bonds ranging \ I from 2.472 to 2.523 A. Above the plane of three Mo atoms (I) 1,486; (II) 1,418; о (III) 1.499 A is a triple­bridging 0 and below thie plane three double­bridging 0 atoms bond lengths vary from 2.006 to 2.045 A, those to double­bridging 0 atoms from 1,901 о to 1.947 A. Two Mo atoms, related by a mirror plane, are additio­ nally bonded to the acetylacetonato ligands with Ko­0 bond lengths ranging from 2.052 to 2.126 A as well as to (I) formato, (II) ace­ tato or (III) propionato ligand with Mo­0 distances from 2.116 to 2.166 A. The third Mo atom (on a mirror plane) instead of being bonded to carboxylato ligand its octahedral coordination, apart of the acac ligand (Mo­0 from 2.071 to 2.115 A), is completed by wa­ ter molecule at the Ko­0H9 distances varying from completed by wa­ ter molecule at the Mo­OHp distances varying from 2.041 to 2.204A. The acetato complex is anieotropically refined up to RsO.047 while the refinements of the other two structures are in progress. /1/ Cotton P.A., Polyhedron, £, 3 (1986). 33­1 ­ 268

CRYSTAL UTO MOLECULAR STRUCTURE Of THE NICKEL (II) PROPYLDITHIOCARBAHATE

J. Kamenitalc. R. Pastorale, 7. ВfeeInn Department of Inorganic and Phyeloal Chemistry, Palaclcy University, Olomouo, Czechoslovakia

The orystal and uoleoular structure of nickel (II) die

H (propyldithiccarbamata) NlGoS,N2 i'6 wae solved oy the heavy atom method and the structure was refined anlaotropioally to final residual faotor value of R « 0,029 (wR ­ 0.037). for 715 observed refleotions. The crystal Is monoolinio, apaoe group P2,/o with Iattloe parameter» a • 946,3 /2/, Ь ­ 776,9 /2/, о ­ 1167.4 12/ рю, fim 125,14 /2/°l Z ­ 2. The moleoule contains two four membered N1S0S rings with approximately planar configu­ rations, where the N1 atom la situated In the centre of inveraion. The molecules propagate the chains along the c­axls of the unit cell. ­ 259 ­ CRYSTALLO0RAPH1C STUDIES ОГ A*­HYDROXY~P1ЫАЫ-3 ONE AH7NES. CHIRAL AUXILIARES IN ORGANIC SYNTHESIS. J. ^nroliih-Wrijc i#ch.ow?hti. W._Kw±a t ho*vshi _ /ns( Ku(* of G&n&ral Chemist ry. Technical Lfniv&rsi ty, Z*»\i rhi 36, QO-Q?4 bod±, POLAND

When uai ng optically unref i ПР^ 2<*- P ' none ( e . e . 63%) to obto i n 2да­hydroxy pinan 3­cne (1) and then respective Schiff bases (2). was observed [1] that mother liquors are optically pure epimers whi)<*h& crystals are pure racemate.The results of X tay structure analysis of Schiff raceinic base (S) (with R­Ph) showed.

^0H NR P ­ $­ raacernate fi5% e.e. 100% (crystals) (Uqutd,)

that eelf­purification is due to easy dimer formation between two epimers (by H­bonds).Heduction of optically pure SchifT bases (2) to respective amines (3)does not l«Ad to the obtaining two stereoieomeric secondary amines (3c or 3/3J but to one particular

«OH U0H $=° — &

et­ucture .The crystn 1 lo­?raphic investigation confirms the correctneg of the аввишеЛ course of the reaction being the source of potential chiral auxiliaries in the organic synthesis.

Ill biAri'.^wiez W. ."arolnk Wojciechoskn J . . Kwi atkows'K iW. , J . Cryst . Sj'ectr Ren. H9R9). in picae • ttjrlufM r«*icl> w«i* Cirsa­iced by Яр. II. Ю r'O^remm* of *oli< Mi"\»lrv o< tdiienUon.

•ЯЗ­2 ­ 260 ­ CRYSTAL AND MOLECULAR STRUCTURE OP ORTHO­IIITRO PHENYL ETHER OF 2­AMIKOETHAJIOL

V.E, Kataev, O.K. Kataeva, I.A. Litvinov Institute of Organic and Physical Chemistry, USSR Acad.Sci..Kazan

Several papera аг.э known where the attempts had been made to correlate ganglion stiraulant activity and molecular conformation of some substituted phenylcholine ethers /1,2/. We determined the structure of analogous compound, ortho­nitro phenyl ether of 2­ aminoethanol (1), which is the base, not salt, in contrast to the above mentioned molecules.

The conformation of the molecule (1) is defined by three torsio­

5 4 3 1 4 3 1 2 nal angles С ­С ­0 ­С ( Г0), с ­0 ­С ­С (Г,), O^C^­N (^2>.

0 that are equal 1Q*172.5 , £.,=91.2°, ^2=l73­7°. The observed geometry is compared with the structural data of highly potent ganglion stimulants /1,2/. The extraordinary molecular structure of (1) ie discusBed, especially the existence of the planar five­ membered cycle including 0% С , С5, Н , 0 atomB as well as the ac­conformation around the С ­CJ bond.

/1/ Celikel R., Geddes A.J. et al., Cryst.Struct.Commun., 9_, 111 (1980). /2/ Kneale G., Ceddeo A.J., Sheldrick В., Cryst.Struct.Commun., Д, 351 (1974). 261 ­ X­RAY STRUCTURAL ANALYSIS OP BENZOIC ACID COMPLbXES AMD ITS

DERIVATIVES WITH BIOGENOUS METALS (Mgf Ca)

Z.3h. Karayev. P.N. Musayev, V.R. Cherkezova Azerbaijan Medical Institute, Baku; Institute of Inorganic and Physical Chemistry, Academy of Sciences AzSSR, Baku, USSR

Crystalline structure of /MgCRgO^/Cp­HgNCgH.COO^CHjOjgCl).

/Mg(H20>6/(p­02NC6H4COO)2(Hg­Ojg(II) and /CaCCgBgCOOHHjO^/CgHgCOO (III) complexes nave been studied by X­ray diffraction. The crystals I and II are built of oentrosyrametric hexaaquan cations of Mg, two outerspheric acid anions and two moleculeв ol crystallization water. The compound I Is completely lsostruotural with analogous octahydrated p­oxybenzoate Mg* In the crystal la being formed a three­diraeixtional lattice of H­bonda, in the for­ mation of which participate 9 out of 10 Independent active hydro­ gen atoms. Hexaaqua­magnesium cations form the walls In the faoe of (у и о) and (у z 1/2), and in the interspaces between them «re being placed acid anions and molecules of crystallization water* As distinct from octahydrates p­oxy­ and p­anlnobexusoates Kg in the structure II are being taken place only intramolecular H­ bonds, combining hezaaqua­cations of Mg with nitrobenfcoate anion and crystallization water molecule­ In the crystal of в indepen­ dent hydrogen atoms only three take part In the formation of H­ bonds. Thus, the substitution of ­OH and ­NBg groups in the ben­ zoic ring into ­N02 group completely destroys the system of H­ bonds and results in other molecule packing In the oryetal. In the structure III one of two bensoate anions is on outer­ spheric and the other exhibits tetra­dentatno­bridged­cydio structural function between Ca atoms. All three water molecules intraspheric and one of them is simultaneously coordinated by two adjacent Ca atoms* The main structural unit of the compound ­ a layer, by the periodical repetition of which along the axis b is formed the crystal. The layer consists of the irregular polyhed­ rons chains of eight­coordinated Cat lying parallel to the axis c. The bond lengths in the investigated compounds are ordinary. ­ 262 ­ CRYSTAL STRUCTURE AND PHASE TRANSITION IN jl ­TRAM Я PdtNH^Clj STUDIED BV RTETVELD METHOD S.D.Klrlk A.I.Kruqllk, A.A.Kraplvko, I.S.Yakimov , Institute of Chemistry and Chemical Engineering L.V.Kirensky Institute of Physics, Krasnoyarsk, USSR

The crystal structure of A­trans rd(Nfl, )_cl2 has not been determiner! yet due to the impossibility to obtain a single crystal of a proper quality. In the present study such determination has been undertaken by the powder method. The X­ray diffraction experimental data have been obtained at 25, ­50 and -1CG с on an automated powder diffractometer equip­ ped with a low­temperature chamber. CuK ot­radiation has been used. The data were processed by Rietveld analysis according to the program [lj. The powder pattern was successfully indexed at 25 с on the basis of a tetragonal unit cell with a=B,151 8. c=7 797 л, 2=4. But the further modelling and refinement showed the orthorhoroblc structure with the space group Pbca. The Pd atoms are arranged in square centered nets,which are parallel to th« xoy plane. The arrangement of square complexes Pd(NH,),ci, is such that the Pd­N О Л Z £. bonds t'^ie distance is 2,00 A ) are normal to the net, and the о о Pd~Cl ones (2,28 K) lay on the net plane at 45 to the axes X and Y. The nets alternate along Z by the translation (0,5 Q o,5). The refinement of the chlorine positions has shown that there happens a disordering in the alternation. About 10% of nets are shifted by the translation <0 0,5 0,5). Partial disorder In net stacking is responsible for the stability of a pseudotetragonal cell in a wide temperature range. At ­62 С a phase transition and a gradual monoclinlc distor­ tion are observed. The phase transition is described by an inclina­ tion of the axis t in the plane XQl. Nets shift one from another in the direction of the X axis, and the diqtancon between nets decrease. The parameters of я unit cell at ­flO°r are: a=8,115;

Ь­а,Юб; с­7,75в A, fi*92t49°, 2=4. fl]. KiriV S.O., Sorisov S.V., Fedorov V.E., J.Struct.Chem., 22, 730, 1901, 263 ­

NEUTRON DIFFRACTION STUDY OF THE VERY SHORT HYDROGEN BOND IN LITHIUM HYDROGEN PHTHALATE DIHYDRATG."

Thomu F. Koetzle(a) and Herat Kuopqra(M (a) Chemiatry Department, Brook haven National Laboratory, Upton, NY 11973 USA,

Th« crystal atructurea at 213 К and 22 K. war* refined from IS6S 11508) reflection!. Initial coordinate* wera taken from the X­ray atudy 111. In contrast to 121, the apaca group (Pnmal la found to be maintained at low temperature» (a­ 16.804 [16.7671, b • 6.76316.68S1, с • 8.203[8.2041 Я), la. the hydrogen phthelate anion ramalna planar on cooling. The geometry of*the Intramolecular hydrogen bond la a* follows (values not corrected for thermal motion))

O­O* O­H O'­H

22 К t 2.393W17) 1.2093(23» 1.1846(231 213 К i 2,3837(23) (.2024(33) 1.1621(35) 248K(X­rayJ((] i 2.38S<2> 1.20012V) I.IVH2W

The hydrogan bond la nearly symmetric, but doea ahow a significant deviation from the symmetric geometry which can be explained from bonding characteristics within the crystal structures О la acceptor of a weak hydrogen bond with the water molecule, whereas O' le not Involved In any Intermodular linkage. The temperature behavior of bond lengths and angle* Is dJacuaaed In comparison wltb other examples of very abort Intramolecular hydrogen bonda.

(If Conachorek. W„ К Upper*. H , Act» Cryst. B3J_, 1068 (IV7SI. [21 Bart), H , KUppera, H., Acta Cryst. АД, S 174 (I97S).

• Work at Brookhaven National Laboratory was carried out under contract DE­AC02­76CH00016 with the US Department of Energy, Office of Basic Energy Sciences. ­ 264 ­ THE STRUCTURAL ASPECTS OP STABILIZATION OP OOPPER(II) RELATIVE TO COPPER(I) IN COMPLEXES

И. Koman. H. Hariassy, G. Ondrejovic

Department of Inorganic Chemistry, Slovak Technical University, 812 37 Bratislava, Czechoslovakia

Copper(II) is usually reduced to copper(I) by thioure (tu) and Ph,E (E • P, As, Sb). However Cu(II) can be stabilized re­ lative to Cu(I) by chelate ligands or by the dimeric structure oi copper(II) oarboxylates /1,2/. We have examined the stabilizing effect of the chelate dl­ oximate.ligands on Cu(II) relative to Ou(I) by preparation and structural characterization of copper(II) dioximate complexes with triphenylarsine, Cu(Hbd)2(Ph,A3)j(Hbdobutanedionedioximate) and thiourea, CutHhd^tu^ (Hhd«3,4­hexanedionedioximate),

Cu(Hbd)2(tu). The etruoture of the oomplexea consists of the molecules. In each molecule four nitrogen donor atoms of dioximate ligands are placed in the tetragonal plane, whereas arsenic and sulphur atoms occupy apical positions of tetragonal bipyramidal (Ph,Ao, tu) and tetragonal pyramidal (tu) coordination polyhedra. The stabilizing effect of dioximate ligands on Cu(II) rela­ tive to Cu(I) is associated with the formation of strong hydro­ gen bonds between dloximates ligands, assuring a peeudomacrocy­ clic'stability of the planar configuration of this part of the molecule. The PPh, AsPh, and tu ligands are restricted to the apical coordination sites, unfavourable /3/ for the reduction process.

/1/ Koman M., Vsligura D., Ondrejovic G. Acta Crystallogr., Sect. C4_4, 601 (1988) /2/ Koman M., Valigura D., fiuroanslra E., Ondrejovic. J. Chem. Soo. Chem. Commun., 381 (1984) /3/ Nefedov V.I., Pozdeev P.P., Ondrejovic G., Valigura D., Gazo J. Koord.. Khim. 10, 1332 (1984) ­ 265 ­ THE CRYSTAL AND MOLECULAR STRUCTURES OF FIVE ACYCLIC NtTRQALDlTOLS Junen AW». Peter К6Н*\ Beint B­nmdenbury** and Willy Seelhorst^ *1 Inetitut fur Anorg. und Angew. Chemte del Univereitat Hamburg, Martin­Luther­King­PI. 6, 2000 Hamburg 13, West­Germany; *> Fschbereich Chemie der Uuiversitat Oldenburg, Poetfach 2503, 2900 Ol­ denburg, West­Germany In continmtson of our recently «taxied reee&rch program", we have de­ termined the structures of five nitroalditols. The principal aim of these in­ vestigations is the determination of the preferred conformations of heptitols, which are almost unknown*). We also include nitropentitola and nitrohexitols in our structural analyses, although the conformations of the corresponding pentitols and hexitols are extensively investigated^. The names of the determined nitroalditols are: l­Deoxy­l­nitro­D­axabino­pentitol, 1, СдНцгЮ#, 1­Deoxy­l­nitro­L­manno­hexitol, 2, CfHuNOr, l­Deoxy­l­nitro­D­geiacto­hexitol, 3, CtHnNCb,

T­Deoxy­T­nitro­D­grycero­L­guIo­heptitol, 4, CrH|5NO« and 1­Oeoxy­l­nitro­D­glycero­D­gulo­heptitol, 5, CTH^NO?,. The crysti Lk jraphic results are summarized in the following table:

1 3 3 4 A

a (A) 4.858(1) 5.022(1) 8.398(1) 8.792(1) 4.746(1) b 13.500(1) 5.382(1) 6.379(2) 23.351(4) с 6.077(1) 61.373(4) 10.206(1) 19.070(3) 4.848(1) 0 91.73(1) 97.04(1) 91.42(2) 105.48(1) apace group «i P6. P2i C2 P2i Z 2 6 2 4 2 obs. data 863 931 1055 1197 1070 p&nmeteri 153 179 179 193 193 Я­vnlue 2.9» 2.9% 4.6% 7.2» 6.9% refinement ш progress In progress in progress

All five compounds except compound 4 adopt the extended, planar, ug­ sag arrangement. Together with the four, recently determined structures1', only 7­Deoxy­7­nitro­D­glyceio­L­gulo­heptitol1 4, exist» in a bent ("sickle") conformation. Compared with the corresponding conformations of pentitols and heritob this result is rather unexpected and till now assumed to be very unfavorable. 1) J. Kopf and P. K6U, Abstract PS» 3.2.MO, ECMM, ZeiticAn/l fir KrutsllcfrBsMt 185 (1988) 230. 2) S. ). Angyal, J. K. Saaidsrs, C. T. Grainger, R. Le Per sad P. O. Williams, CorsoAioV. Ra. 150 (1986) 7. 3) G. A. Jeffrey and H. S. Ют, CartoAyaY. Ru. 14 (1970) 207.

34­1 ­ 266 ­ STRUCTURES OF COMPLEXES WITH "«SYMMETRICAL TETRADENTATE SCHIFF BASES

J.Kopf, J.Loub Institute of Inorganic and Applied Chemistry, University of Hamburg, FRG; Department of Inorganic Chemistry, Charles Univer­ sity, Praha, CSSR

The structures of three complexes with unsymmetrlcal

tetradentate Schiff bases were determined: /CufCgH N^O)/CIO .H20

/1/ (I), /Ni(C11H16N30)/NCS (II) and /Cd(CuH16N:10)/C104.C2H5OH (III). The tetradentate Uganda are bonded to the metals through one 0 and three N acorns. The structure of I and II consist of complex cations and anions (resp. water molecules), the 2* structure of III consists of /Cd(C,.H.,N~0)/_ complex dlmeric 11 It J с cations, perchlorate anions and ethanol molecules. The coordina­ tion polyhedron around Cu and Ni is a distorted square, the coordination number of Cd atoms is 6 (4 from the Uganda, 2 from the ethanol molecules). In the compound II are two independent molecules A and B, between them statistically significant differences are found only in the one N1­0 and one Nl­N distances and In the angles of rhodanlde anions. In I the conformation of the Ri ring is an unsvmmetric envelope and of the R2 ring a half­chair. The torsion angles r'l­Cl­C2­N2 are 49 and ­49°. In IIA both rings have the unsymraetric envelope conformation, in IIB the Rl ring has half­chair conformation and the R2 ring has the unsymme­ tric envelope conformation. The torsion angles T1A, T2A, TIB and T2B are ­48, 44, ­53 and 46°, respectively. In III both rings have the half­chair conformation and the torsion angles Tl and T2 are ­63 and ­54°,respectively. I 1 X и T ' N Г 7 N1 TM N2 CI—C2 /1/ Huoer V., Loub J.. Podlahovd J., Kopf J.. Weiss £. : A^'ta Cryst. 44, 1905 (1988). ­ 267 THE ABSOHJTE CONFIGURATION OP AH UHSIMKETMCAI, DITHIOPHOSPHATE : MenO( EtO) P( S) SHorph А.Д. Kozloi. Haria Curie­Sklodowaka Onlverslty, 20­031 1яМ1п, Poland, and G,J. Palenik,'University of Florida, Gainesville PL 32611, USA,' and A. Siopusineki, L. hiczak and J. Michalaki, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90*362 Uil, Poland

Wenthyloxy< e thoxy) ( thloraorpholino) thlophosphorus( V) [o16K­2NO_PS2] was synthetlsed as a model for the nucleophilic substitution at the bivalent sulfur atom. The optically active compound crystal­ lite» in the space group 22,2^, with B­12.503U), b­12.820(2), о­13.259(5)Я, Z­4. The structure was solved by C2Hs0 direct methods and refined to R­0.0506 (R^­0.0305) for 2586 reflections collected with Ho Kf radiation. In order to determine absolute configuration of the mole­ cule, intensities of 26 sele­ cted Frledel pairs were measured using Cu (U radia­ tion. The absolute configuration at the chlral P atom is S while the menthyl group has the configuration 1R,2S,5R , which is con­ sistent with the configuration established for (­)­menthol used In the synthesis. The P­0 distances of 1,376(5) and 1,566(3)8 are similar to other reported values. The P­S and P­S bond lengths, 2.091(2) and 1.915(2)?, compare yell with the theoretical values: 2.116 and 1.9168, respectively. Although the theoretical S­H single bond dlatanoe Is 1.755%, in a few sulfur "­substituted morpholins and piperldlne derivatives published to date this type of bond has the length between 1.620(3) to 1.683(3)2. So, the S­H dlatanoe observed in the present struoture, 1.700(3)1, Is o­ie of the longeet.

34­2 ­ 268 ­

1Ш5 ROLE OP AMMONIUM ION IN THE АЛМОО (OEDP)jJ.n H?0 (A? ­

+ + 1 ­ 51ffl4 or 4Na + lffl4 ) CRYSTAL STRUCTURE FORMATION I.A.Krol. Z.A.Starikova Reaearoh Production Association "IREA", Moscow, USSR

In the crystallization process of the (NliJ .MoO.^Og. ­ OEDP ­NH.OH (OEDP ­ 1­oxyethyliden diphosphonic acid, H.L) aqueous solution complex (NH.)c [Mo02(Hl)(L)].5 HgO (I) precipitated. However, the analogous Na^ealt is not formed under the same conditions, and complex Na^jNH,, [Mo02(Hl)(L)] .15 HjO (II) is obtained only when NH.OH solution is added. The crystal struc­ tures of I and II ore determined from V­ray diffraction data. The composition and geometric parameters of the [MOO­CHLHL)] anion in I and II are almost Identical | the Mo­ ratoms hav« a distorted octahedron coordination typical for oxocoomplcxas. The OH­groups participate In the "overcrosoed" intramolecular H­bondinga (HL)O­H...0(P0,). The H­atom is sta­ tistically distributed between the two Uganda (HL and I, ). The speoiflc peculiarity of the I and 11 structures is the ([ЫоО„(Щ,)(1,jtffl.J ~ anions layers formation; in these layers the HH.+­lons are bound to anions by H­bonds N+­H...0(P0,) (H...0 2,757 ­ 2,662 I) lying within the layers. ­ 269 X­RAY STRUCTURE OF TRANS­DICHLORO­CIS­DICHLOROBISil­ETHYUMID­ AZOLE) PLATINUM. fcL Kublak, J. Kuduk­Jaworskd, T. Olowlak and B. Jetowsk*­ TrzebtaLowska Institute of Chemistry, University of WrocUw, Joiiot­Curle 14 ВО­ЭвЗ Wroclaw, Poland The precis» estimation of molecular structure of compounds which are promising to be drugs is always important, but eepeciaXy In case of neutral platinum complexes because their configuration decides 'about biological activity. Though we can plan the stereospecj f 1c synthesis of the desired platinum compound, but It may undergo ieomerixatton during preparation or purification­ Is this communication we present tns crystal and molecular structure of platlnum/JV/' complex containing l­ethyllmldazole as neutral llgand. So far there Is only few neutral platinums'! Vs* complexes, PDD analogs, which structures have been described. The crystal and molecular structure was determined by use of a Syntex P2 diffractometer with monochromatic MaKa radiation. The compound crystailzos in th* mono­clinic system. with four formula units in the unit cell, space group P2 /n *nd lattice parameters е­12.749<*>, Ь­».217СЗ>, a­14.8vet3>A, ^­110.0й<П>* The structure was solved and refined using the heavy­atom method and subsequent least­squares techniques. Refinements using 3110 observed reflections led to final values for R and К of 0.036 and 0.046 respectively. The coordination around Pt is octshedrel. The two 1­ethylimldazole Ugands are cis­coordlnated to Pt, the Pt­N distances are 2.007 and 2.OS5<10M­ The Pt­Cl distances range from 2.30­4 C4> to 2.3toi3>A. These values are typical for piatinumCIV> complexes. This work was supported by the Polish Academy of Sciences (Project CPBP.0i.l2>. ­ 270 ­ THE HYDROGEN BONDS IH SALTS OF CINCHONA ALKALOIDS WITH DIPHENIC ACID DERIVATIVES

HacjeJ Kubicki, Teresa Borowisk and Marian Gawron Faculty cf Che«lstry, Adam Mickiewicz University. Grunwaldzka 6, 60­780 Poznari, Poland

The structure 1 invest igat ions of the С t nchona alkaloids salts with dlphenlc acid derivati­ ae have bean undertaken in order to explain their high Л ton effect. A probable reason for this effect is the axclton Interaction between the UVractive chrorrjphoree and/or the lnternolecular hydrogen bonds •• abilizing the stereostructure of the salt. Here we present the X­ray structure о two 2:1 salts namely (1) of quinine with the diphen ­• a^id and (2) of qulnidine with the 3.5'­dinitrodiphen acid, iu both of them interesting interactions via hydrogen bonds between the base and acid «olercles have bee" found. ­ 271 ­ CRrsTAI. STRUCTURE О? GUANIDINIUM HIBROCBN ACETYLENE­ DICARBOXYLATE I. Leban and A. Rupnik

Department of Chemistry and Chemical Technology, £. KardelJ University, РОВ 537, 61001 Ljubljana, Yugoslavia,

In the course of the systematic studies on acid salts of dicarboxylic acida the crystals of guanidinium hydrogen acetylenedicarboxylate have been prepared and its crystal structure has been determined from X­ray diffractometer data.

Crystal data. CCNHj^.HC^O", Mr­ 173ЛЗ, monoclinic crystal system, space group KN/c, a­ 8.837(1), b­ 18.961(2), c­ 9.067(2) X,p. 9i?.09(1)°,

} 0 V. 1518.2 X , Z ­ 8, Dcalc­1.515 g со"? at 20(l) Cj

MoK

1?«(1), conventions! R and Rw were 0.04* and O.OW respectively] computer programmes: SHELX 76 and GX.

There are planar guanidinium cations and hydrogen acetylenedicarboxylate anions in the structure. The acetylenedicarboxylate groups are linked with the inter­ molecular hydrogen bonds ( O...H...C being 2.415(3) and 2.<*64(3) it) into the infinite chain. The contacts between guanidinium and hydrogenacetylenedicarboxylate groups are established by the interoolecular hydrogen bonds of the type N­H...O, ranging from 2.8OU0) to :>.933(5) X.

The financial support of the Research Conmunit;/ of Slovenia, Yugoslavia, ia gratefully acknowledge. 272 ­ STRUCTURE OF TWO LIGANDS BEARING HETEROBIARYLIС UNITS AND THEIR Eu(IlI) COMPLEXES

by Janusz Llpkowskl and Kinga Suwihska institute of Physical Chemistry. Polish Academy of Sciences. Warszawa. Poland

and Giovanni D. Andreetti Institute of Structural Chemistry. University of Parma, Parma. Italy

CifHjoNjOzd). orthorhombic Рг­,2.,2. a ­ ) t ""V b ­ 10.605. с ­ 5.242 Я, Z ­ 2. V ­ 780.1 &>. •• • ) 'c.9 gem"*. Mo Kot. The structure was refined tc j • '5 , for 396 reflections with F„ »3o (F0). The ."i.icule has Cj symmetry.

2C« HJONJOJ­EUICIO^J•3/2CH3CN. nonocllnic P2(/c, a ­ 12.792. Б ­ 17.642, с ­ 43.89 A. 0 ­ 91.30\ Z ­ 8. V ­ 9891.9 A1, D„ . 1.366 gem"', Cu KM. The structure was refined to R ­ 0.13 for 8576 reflections wjth

r„ > ;

CsoHi,, NI04(ID. monociinlc P2­(/n. a ­ 9.B3B. b ­ 12.446, с ­ 18.445 А. В ­ 101.26°. Z ­ 2, V ­ 2214.9 A1, d, <= 1.291 gem"', Mo Kot. The structure was refined to R « 0.061 for 1616 reflections with F„ * 304F„). The mole­ cule Is centrosymmetrlc.

CwH4,N.OVEu(C104), • CH5CN, monocllnic C2/c, 3 ­ 50.13. b ­ 19.97. с ­ 27.97 S, В ­ 117.9', Z ­ 16, V ­ 24729 A', DK ­ 1.419 gem"1, Cu Ka. The structure was refined to R ­ 0.17 for 576B reflections. There is two inde­ pendent complex molecules in the asymmetric unit.

Detailed conformation of the ligands in both complexed and uncomplexed forms will be discussed as well as the geometry of the coordination spheres around the Eu(III) cation. Л

CD (II) ­ 273 ­

CRYSTAL AND MOLECULAR STRUCTURE OF THE P(lll) OITHIOACIOS' М1ХЕП ANHYDRIDES I.A.LItvlnov. M.B.Zuev, O.N.Kataeva, V.A.NaumoVj •A.E.Arbuzov Institute of Organic end Physical Chemistry, USSn Acad, Set. Kaian, USSR

Struchkov Yu.T. I\l and Light R.W. 121 determined the structure of two dlthlocarbamlс acid derivatives la and lb. The molecules were found to have e, short contact between the central phosphorus atom and thfontc sulfur atoms. To reveal the nature of this contact an X­ray study of the compounds contai­ ning the P­S­C­S, P­S­P­S and P­S­C­0 fragments was carried out

S S S II II X

P(SCNR2>3 PhP(SCNEtj)2 PhjPSCNEtj

Ic) R­Et II III lb) R­Me S S 0

PtSP<0MaL,i3 . P(SC0Et>3 P(SCPh>3 IV V VI о The short Intramolecular contact P...S (2.97­3.18Л) was obsei— ved In all compounds. Ab Initio calculations of the model mole­ cule H_PSC(S)H showed the preference of Z­conformatI on and the absence of the P*­S­ dative bond. The decrease of the P­S­C velunc* angle In I, II, IV­VI to 94­97 4S compared to that In 111(101°) with the slmu I tartec us enlargement of the P­5 bond lengths up to 2.177 A In comparison with 2.123 A In III may be explained by n­* Interaction of the (S­) lone pairs with antl­ bondtng orbltals of the P­S bonds. The observed conformation, In which the S­ (00 atoms lie on the continuation of the P­S bonds. Is favourable for suet nteractlon.

/I/ Yuflt O.S., Struchkov Yu.T., Pudovlk M.A. et al., Dokl. Akad. Nauk S5SR. 25J5, 1190 (1980) /2/ Light R.w., Hutchlns L.D., Paine R.T. et si., Innrg. r.h„n. _T>, J597 И900)

35­1 ­ 274 ­

STRUCTURAL CARACTERIZATION OF W) TH10IMIDAZOLE DERIVATIVES A. Lopez­Castro, M.D. Estrada and M.J. Diane* Instituto de Ciencias de Materialee de Seville, C.S.I.C., у Depar tamento de Fiaica de la Materia Condensada de la Universidad de Seville, Seville, Spain.

The t о thioimidazoVa (I and II) sintetlzed by Fernandez­ Bolanos (Organic Chemistry Department, Seville University), have been studied by X­ray difraction in order to corroborate the structure and/or stereochemistry of these compounds. The crystal data arei

Space Dcalc. »(K) b(A) : (A) &("} gruup g.an"­' i

I 313-4 6.V79/3J 7­125(2} 14­6<М( 5) 'W.­Ш) P2X l -42 2

И 440.6 10.877(2) 22.529(3) 8.887(2) 100.98(1) P2t/n 1­37 4

The phenyl, p­tolyl, auger chain and thioiroidazole group» are planar. Bonds in both compounds indicate some electronic delocali­ ratioo in the thiolmidazole and the thloimidazole carbatdehyde groups. In the compound (II) we have observed a distance S­S of о 2.068(7)A, that correspond to л disulfide structure.

/ HC—NCJ? не—NC~^ II >=s ^_ .sc—s — С—NH I CHO (CH0H)3

CH20H

(I) (Ю ­ 275 ­ MODELS OF THE S^2 NUCLEorHJUC SUBSTITUTION AT THE 31 ATOM: X­RAY STRUCTURAL STUDY OF NOVEL DERIVATIVES OF PENTACOORDINATED SI A.A.Macharashvlll, у .$, Sh,klover• Yu.T­Struchkov, Yu.I.BaukDv, V.A.Pestunovlch Nesmeyanov Institute of Orqanoelement Compounds, Academy of Sciences of the USSR, Hoacow USSR

X­ray structural studies of a number of pentacow J mated silicon derivatives with different coordination geo»etr* oC .it SI atom but with the same CI subatltuent, occupyinq one с r.h­ axlal positions, provides the experimental basis foe the napping of the SN2 reaction pathway usinq the method of structural corre2afclona /1/. The results of the x­ray study of three.novel derivatives of pentacoordinated SI, viz, S­(dimethylchlorosllyl­ methyl)lmldato­2­pyrtplldlnethlone (I), bis(O­Sl)chelate 1,2­bls­ (dlmethylsllylmethyl)dlacetylhydrazine (II), and (H­Sl)chelate methyl phenyl(phenyl­N,N­dlmethylhydrazonato­0,N >­chloroellane(III) are reported In the present work.

Ms Me T Л И ie ш ме м,

The S1*N (S1*0) and SI­C1 distances (1,942(3) and 2,423{1)Ъ, respectively. In I, 2.142, 2,219(8) and 2,223, 2,19l(4)X in II, 2,264(2) and 2,19211)* In III) and bond angles at the SI atom de­ monstrate unequivocally that in molecule I the SI atom has a trl­ qonalrbtpyramidal 13+2] coordination, whereas In molecules II and III Its coordination belonqe to a allqhtly distorted [4+1] type. The SI atom In I Is displaced from the equatorial plane towards the N atom by 31=0,050(1)£ and In molecules II and III the displacements of the SI atom towards the CI substltuent are equal to 31=0,146(1) and 31=0,187 and 0,205(3)1 respectively. It is clear that the nature of the 5­membered 81­contalnlng chelate cyc­ le and of the axial sustltuent haa a considerable effect on the bond lenqths distribution In the axial fragment and causes the shift of the structures II and III along the reaction coordinate towards structure I. /1/ Butql H.­B., DunLtz J.P., Ace.Chem.Res, 16, 153 (1983).

35­2 ­ 276 , STRUCTURAL INVESTIGATION OF DIOXAPHOSPHEPANE AND DIOXAPHOSPHORINANE DERIVATIVES ON SACCHAftlOE BASE

N. S .Magomedovaj A. N. Sobo lev, V. K. Be I 'akii

L.Ya.Korpov Institute of Physical Chemistry tHoeaout USSR

M. P. Koroteev,N.H. Pugaahovat E. E.Nifant '«u *

Chemistry Department of V.I.Lenin State'Pedagogical Institute,MoeaoutUSSR

In present work we report the structures of novel dioxaphos­ phepanea(I­IIX) and dioxaphosphorinane(IV) derivatives of saccha­ rides (the preparation technique was published earlier/1/). The eeven^merabered fragments A in structures I­III have an asym­ metrically distorted "chair ?i6) "­conformation. The dioxa­ vhoephorinane ring A in IV adopts a slighly flattened chairs­conformation. The orien­ tations of P­07(H)(I­III),P­07 (IV) and P­X(X«0,S,Se) bonds are quasi­axial and quasi­equa­ torial, respectively. The glucose configuration of monosaccharide backbone re­ mains unchanged in compounds I­III» ^C605(H)­gcoup in IV directed under ring A and is In "tcan*"­position to ОЛ­СЧ­ bond In at D­glucofuranoae ring B, The ВС­fragment in all struc­ tures have a distorted "but­ terfly" ­ configuration.

/1/ Nifant'ev E.E.«Koroteev M.P.,Pugashova N.M.,Bekker A.R., Bel*skii V,K.,Magomedova N.S..Kochetkov N.K. izv.AN SSSR «er. к him. 9, с. 219И198В) ­ 277 ­ CRYSTAL STRUCTURES OP PHOSPHONx"LHY])RAZONES 0? SOME KETONES

T.I.Malinowaky, V.N.Biyuahkin, O.N.Hebrova, L.I.Zdanovaf L.Q.Mosyak, V.M.Ovrutsky, L.A.NeAalskaya Institute of Applied Fhyaloe, Institute of Chemistry, Moldavian Aoademy of Solenoee, Kishinev, SSSR The compounds with antitumor activity have been found among the phoaphony1 hy&razonea. The substances reported in this com­ munication have not a marked activity, hut are of interest in the investigation of the dependence between the «txuoture of the sub­ stances and their anticancer effeot.

The crystal structures of [_Q­phenyl­NIN­di(2­ohloroBt.hyl)­ amidophoephonyl]hydraz­onea of aoetophenon* (I) and paru­ohlox­o­ aoetophenone (II), ro­para­ahloraphenyl­itf,N­di{2­ohloroethyl)­ amidophoaphonyl] hydrazone of ben^ophenone (III) and (0,0'­dlyh.e­ nyDphoaphonylhydrazone of pinaooline (I?) hare been determined by I­ray analysis* The phosphorus atom haa a distorted tetrahedral ooordlnatlon ir all studied oompounda. The angl* deviations from ideal value for regular tetrahedron are typioal of compounds with the >iame phosphorus coordination. The interatomic distances F»0 and P­0 in all the compounds are nearly equal (1,460­1,470 and 1,583­1.593 1). The bonds bet­ ween the phosphorus and hydrazine nitrogen in moleoules I­III (1,641­1,656 A) are longer in ooiaparlsoh with analogous in the two independent moleoulea in the etruoture Xi (1,616 and 1,621 I). The same bond in II coincides with the phosphorus ­ amino nitro­ gen bond, while in I and II the latter is praotioally equal in both moleoulee (1,627­1,632 A) and shorter than phosphorus ­ hyd­ razine nitrogen one. The interatomio dietana ее in other fragments of studied molecules are correspondingly oloee and agree with known data. There are differences in conformation of ohloroethylamin* moieties. The bonds 0­C1 in the oompound XI &r« on the one side of the nitrogen atom plane, but in molecules I and III ­ on different sides. The conformations of the other moieties of these raoleaules ooinolde. are linked The molecules form diraers in oryatals^by means of hydrogen bonds with hydrazine Ш­graup and phoaphoryl oxyg*u of neighbou­ ring molecule. ­ 278 ­ THE STRUCTURAL AKD ABSOLUTS CONFIGURATION OP ЗОНЕ DITERPBN COMPOUNDS •allnovslty 3.T., Dragalln I.P.,2adorozhnaya L.A., Vlad P.Ph. Institute of Chemistry, Moldavian Academy of Sciences, Kishinev

The natural dlterpenold­eolareol le the Initial product for ob­ taining aromatio substanoea. A rerios of five­ and six­membered oxide compounds, with a now oarbon skeleton"a part of which poee­ eses valuable aromatio properties» were produoed on its basis. ФЛ ФЛ л ФФФ«, /**•, <•­* 1 13 4 5

The X­ray analysis of some produots obtained on the basis of fl ­lactone (1­3), dlol (4) and acid (5) was oarrled out for the correlation determination between the aromatic properties and structure. j­laotona with the same composition are different in physlco­chenioal properties. It wae found the oyclea A and В in compound (1) have a trans­coupling, while in (2) and (3) ­ a cis one. The orientation of the methyl group bounded with C. le also characteristic of the compounds (1­3). An uncommon structure was established for oompound (J), where crystallographlc independent nolecules are bounded one with another in couples forming a dljner, which le due to the H­bonds (2,70 and 2,69 A). An absolute configuration waa determined for all the Investiga­ ted compounds.

I) DAI 083», 1987, Т.294, • 1, ».111« 1988, v.229, • i, Р.1Э9П 1968, v.301, V 1, ». 99. ­ 279 ­ CRYSTAL STRUCTURES 0* COPPER(II) HXLOOElUDEb «^u THIOCARBOHYDRAZOlffiS OP PYRUVIC ACID ANILIDE T.I,MaHnovflky, L.A.N&aSelacaya, V.Ch.Kravteov, V.N.Biyushitin Institute of Applied Physios, Institute of anemiatry* Moldavian Academy of Sciences, Kishinev, USSR

The orgaolо molecule L oomes out as monodeprotonated tг­i«ro­ tate RWO­ ligand In ооordination compounds of oopper(II) h ^.oge­

nlv.d CuI(L­H) with thloaemioarbaaone OH3­0(­»­NH­CS­HH2)­C(­0> ­

­NH­CgH5 (I) and (methyltblo)thiocarbonylhydreBone CH^­C(=R­NH~

­C3­SCH3)­C(=«0)­NH­C635 (II) of pyruvic aold anllide. The proton break* loose from the nitrogen е'от of the hydrazine residue* The oopper atom Is pentaooordinaied In a slightly distorted squa­ re pyramid, In the base of which there are donor atoms of the chelate ligand and halogen atom (CI,Br), whereas in the apex­ the halogen atom of the neighbouring oomplex. The oentrosymmetrlo dl­ meru are formed In the structure. By an Interaction between oopper(II) chloride and S­uitthyl­

lsothioeemloarbaBone of pyruvic add anllide CHy­0(­N­NH*CSCU3 ­

­NH2)­C(­0)­NH­CgHc (III) two oompounds are formed 1 brightly­gre­ en о rye tale CuCl^tL) and brown oiu.es OuOl(L­U)* The Z­ray struotur*4 determination shows that in the first case the organlo moleoule is in the iraino­form as the terdentate NNO­ligandj one hydrogen atom of the thioamide fragment UH^­group passes to the hydrazine reseWN­atom, The sulphur atom does not enter the metal coordination. The coordination polyhedron, as in case (I), le also tetragonal pyramid at­ the base of whioh there arc ligand donor atoms and a ohlorine one, the eeoond ohlorla» atom is in the apex* The formation of the dlmer does not take pluoe. In the second oase the organic ligand is monodeprotonated

while the complex is planar. Thus ф the replacement of the amlnogroup iu the thloamide fragment SOH., does not change the structure of the complex and Its Interaction In the orystal. At the same time the roethybtlon; of sulphur in the ligand changes the donor ability of the atoms and leads, under the same cuTuditioti, to the formation of the adduct and chelate salt. ­ 280 ­ /NTHRACENO­CRYPTANDS AND CROWN­ETIIERS X­RAY STRUCTURE AND FLUORESCENCE EMIS3I0H ANALYSIS

P.Harsau.H.fiouas­Laurent,J.P.Deevergne,F.Fagee,J.Hinechberger U.A. 44etU.A.348 CNRS­UniY.de Bordeaux 1­33405 TALENCE Cedex(Fran­

It la well known that a number of polyeyelie aromatic hydro­ carbons exhibit a high fluorescence efficiency as well as a dual fluorescence (monomer­excimer) which can be "modified by structural factors /1/. The remarkable fluorescence properties of the anthra­ oene ring were ocnblned to the oomplexlng ability of сготт­ethere to synthesize anthraoeno­oryptands and bieanthraceno­crown­ethere /2,4/. The structural and physical properties of these moleoulee were determined essentially by X­ray analysis and fluorescence «mission spectroscopy /2,3/­ In order to increase the selectivity towards alkaline earth cations, oarbonyl groups have been incorporated into the linking chains, to mimic natural naorolidest this also made easier prepa­ ration of larger rings than with the preceding series* Crystal structures and fluorescence spectra of this new fa­ mily of compounds (Fig.1) will be described and comparative re­ sults dlsc­issed.

/1/ Bouas­Laurent H., Castellan A., Desvergne J.P., Piue and Applied Chem., 5.2, 2633 (1980). /2/ Ouinand 0., Harsau P.* Lehn J.M., Desvergne J­P., Bouae­Lau­ rent H., Acta Cryst., C£2, 715 (1986). /3/ Cuinand Q., Marsau P., Bouae­Laurent И. , CaBtellan A., Desvergne J.P., Acta Cryst., C4_2, 857 (1987). /4/ Bouae­Laurent H., Castellan A., Daney M., Desvergne J.P., Мчгяяи P., J.Am.Chem., UJO, 315 (19^6). - 281 - ALKYL AND ARYL AMMONIUM DIHYDROGEN MONOPHOSPHATES. LAYER AND CHAIN STRUCTURES R. Masse, M.T. Averbuch-Pouchot, M. Bagieu-Beucher, A. Durif. Laboratoire de Cristallographie, associe1 a l*Univereii6 J. Fourier, C.N.R.S., 166 X, 25, Avenue des Martyrs, 38042 Grenoble cetfcx, France

The chemical reaction at room temperature between aminoacids, primary or secondary amines and the first acidic function of orthophosphoric acid yields Baits where the atlcyl or aryl ammonium cations are anchored between sheets or chains of (H2P04~)n anions. The layer structure of these organic-inorganic salts may be used as model for molecular engeneering. The most attractive is the use of chiral cations to ensure the formation of non centric crystals and in the best case polar crystals. The two reactions:

Xe ip* + Inorg" -* x€ 'Р In°rg %ъ ip* + Inorg" + solvent -+ fc€ ip . Inorg . solvent

where x« 'P* - chiral cation, are illustrated by numerous examples. The authors show through the structures of the Lct-butylammonium dihydrogen monophosphate (СзНдгЧ+.НгРО-*-), the sarcosine dihydrogen monophosphate (C3HRNO2+.H2F04">, the L-histidinium dihydrogen monophosphate monohydrate (CeH|oN302*.H2P04"-H20), the Lov-alanine dihydrogen monophosphate (CjHgN02+.H2P04~) and some other materials the relation between chirality of cations and anionic aggregation.

36-1 ­ 282 ­ THE STRUCTURE OP METHYUMMONIUM UHDECABROMODIBISKUTHATE J. Matuazewskl Department of Inorganic Cbeniatry, Academy of Economics Wroclaw, POLAND

The structure of a novel compound [NH,CH,]c[Bi,Br1 j] hae been determined using single­crystal X­ray data. The compound crystallises in the form of pseudo­hexagonal prisms. The struc­ ture is orthorhomblo; diffractometer refined unit­cell parameter» are: a ­ 13.405(4), b ­ 14,462(4>, с . 16.006(6) 8. Space group

Pca21 confirmed during succeslvs refinement utilizing 1976 (i 3 (i)) data oorrected for absorption. Pinal discrepancy factor» are: R ­ 0.063 and wR ­ 0,05? (anisotropic thermal para­ meters for Bl and Br atoms, isotropic thermal parameters and constrained С ­ N bond lengths for С and N atoms). The structure comprlsee methylammonlum cations and discrete ^Bi^Br..] anlonfl each of then being composed of the two oorner­aharing octahedra. The bridging Br atom forms two bends with central Bi atoms (nean length: 3.073(e) 8) that are longer than the two In­line Bi ­ Br(terminal) bonds (mean length: 2.699(e) A). Further distortion in the complex Oimer is introduced by the immediate cation environment round t'.ie brotolne Uganda. Two of the five methylammonlum cations occupy the positions at which stabilising H ­ H*»**Br hydrogen bonds seem to be formed. Two further [NH­BC11 1+ cations are disordered to various extent.

However, on the ь tunds of the D­P pyntheses results as well as on the geometry considerations several prlvli.3«ed positions may be postulated for thobo two cations, fhe last cation may adopt either of the two indistinguishable orientations, The whole structure la Btrongly pseudo­symmetrlcally related to the Pcab space group. ­ 283 ­ THE STRUCTURE OF СУАЖХШМЕ LIGANPS AND THEIR COMPLEXES

M.D. Mazue, Yu.A. Simonov, A.A. Dvorkin, T.I. Hallnovaky, N.N.Gerasimchuk, O.A. Domashavskaya, V.V. Skopenko Institute of Applied PhyeicB of the Moldavian Acad.Sci..Kishinev Kiev State University, Kiev, USSR

Acidoligande of HONC(CN)­R type, where R • C(0)NH2, C(S)NH2,

C(0)N(CH,)2 due to their ambipolydentate properties and marked biological activity are interesting for the coordination chemistry. The problem of the mode of theirs coordination by the metal be­ comes actual because of the presence in such compounds several donor groups and the possibility of tautomeric transformations in them. Using X­Ray analysie the following compounds were studied: HL3(A), KHLVCB), RbL1, CBL^C), (N1(2,3.2­tet)L2Jci0 (D), A<:>J. (­­ЪО^/li J4,J•v^ui. 4 fcuBrL2 Dipyl (E), where NC X Hi/ (x=o, R== H) \ « HL* (X=S, R=:H )

3 HL (x=o, R== CH3) HON NR2 In (A) a chain structure with NO­H..* 0«C ixvtermolecular H­bond a 1B realized. Two flat fragments NONO(CK) and C(0)R marking a de­ hedral angle of 27 can be selected in the molecular framework. (А) possesses a trans­anti configuration of ­CBOH­group relative­ ly to the carbonyl one. The similar configuration of the ligand is found for L in (B) and (C) complexes. And what's more, in the first case the К coordination includes the nitrogen of the cyano­ oxime group ana the oxygen of carbonyl one. In Rb (isostructural Cs) compound in addition to the named donor groups an oxlme group enters SB a dumb­bell. The configuration of the ligand is being changed by transition to the (D) and (E) complexes. In can be des­ cribed as cls­anti. The ligand Is bidentate and is bonded to the metal through the H of oxime group and the S of sulphur one. The peculiarity of (D) compound is the cie­J5­form 2,3.2 *tet. The in­ teratomic distances, the peculiarities of the structure formation of the el' ili and transition metals with L type Uganda are so being widly discussed.

36­2 ­ 284 -

Cu(SCN)2

Crystal Btructurea of Cu(II) binuclear complexes with bridge

ljgoods are interesting to study for their magnat ic

properties. Recently, systems made up o* Cu(ll) atoms bridge

bonded by 2,2'­bipyrimidine (bpm) ha^e been synthesized/1/.

Two structures, at room and low temperature, of. the

CutSCNJgfbpi,;) (a) and Cu^tSCN),, (bpm) lb) compounds, will now

be presented. Both, compound (a) and (b) from green and brown,

respectively, became blue when the temperature is lowered. At

room temperature, the structure shows that (a) consists of

Cu (bpm) (SCW) g units which are bridge bonded by S aLOitis to form

a ld­copper{II) chain. On the other hand, compound (b) is made

up of Cuglbpni) (SCN)^ units, bridge bonded in a

threedimensional arrangement by means of bpm molecules and SCN

groups. In both compounds the Cu(II) atoms are in a distorted

octahedron geometry, with the same chromophore (CuN^Sg I •

Substantial differences are to be found, at .room temperature,

in the distortion towaids л tetrahedron geometry in compound

(a) and a lengthening of the Cu­s bonds in respect to (b).

Structural «eaauremente at low temoerature were performed in

order to relate the color change with the Cu­S distances differences and the angular distortion around the Cu(ii) atom.

/1/ Julve M., De Munno G., Bruno B­ and M. Verdagger, Incrg.

Chem. 21* 3l6° (1988) 286 ­ COMPLEXES OP BmZOlC ACID DERIVATIVES WISH NICKEL AMD COBALT; STRUCTURE AND CATALYTIC ACTIVITY IN PROPYLENE DIMERIZATION P.N. Muaayev. D.B. Tagiev, G.V. Tsintaadze Institute of Inorganic and Physiaal Chemistry, Academy of Scien­ ces of the AzSSR, Baku; Georgian Polytechniaal Institute, Tbilisi, USSR Crystalline structure of NKp­HgNC^COO^HgQ (I),

Ni(o­02NC6H4C00)2'6H20 (II) and CoCo­ClCgH^COO^­SR^O (III) com­ plexes have been studied by X­ray diffraction. The crystalline structures of II and III consist of discrete molecules involved by a two­dimensional network of hydrogen bonds. The carboxyl groups are monodentate, ootahadral coordination ot niokel and square­pyramidal georaotry of cobalt are supplemented by water mo­ lecules. The substituents in the benzene ring (O^N and CI) are only involved in hydrogen bond formations, while in I the NH^ group is the second aotive site in the organic ligand responsible for lamellar polymeric structure of the complex. N1 atom ie In the center of symmetry and Is coordinated In the main coordina­ tion plane by four oxygens of whioh two belong to COO and the other two to HoO. Coordination of Ni la supplemented to ootohed­ г*Л by two nitrogens from the amino­groups of the neighbouring on. О г те a whicb form a lamellar polymeric structure. The water &oj. 1*1» i.a involved in the H­bond with non­coordinated oxygen* •boxyl groups belonging to the adjacent layers, thus ensu­ v \t polymeric layers are mutually croealinked. The bond s< . in the complexes under study are usual.

r, i'he complexes with •­ t2Cl were ueed to oatalyze propylene

Hj—j.'isation reaction. C^,Jt>ler . turned out to be of the highest aotlvity. It tas found that л+ь oatalytio system offered the highest selectivity to 2­methylpentenee (81 wt.&) at a propylene conversion of 855C It is seen from EFR studies that the forma­ tion of a catalytically active aite is attended with destruction of the polymer structure of I under the action of a Lewis acid and the formation of paramagnetic Ni­Al complexes /1/ which are responsible for the catalysis.

/1/ Tkao A., Sta^fco A., Coll. Czech. Chera. Comm­ 21» 10°6 (1972) ­ 286 ­ PECULIARITES OP CRYSTAL STRUCTURE OP THE NEUTRAL COMPLEX

[Ni(DDDT)2] AND THE PRODUCTS OP ITS OXIDATION­ CATIONIC

COMPLEXES (Ni(DDDT)2] ,(C10,)2 AJID [Hi(DDDT) j ,(BP. )?

S.S.Hahapetyan, V.E.Shklover. Yu.T.Struchkov, L.Yu.Ukhin, A.I.Kotov, E.B.Yagubsky Nesmeyanov Institute of Orgar.oelement Compounds, USSR Acad.Sci., Moscow, USSR In search of new highly conducting eystems, analogues of BEDT­TTP (superconductivity was found In the molecular metal

(BEDT­TTF)?I­ /1/) chelate complexes of transition metals [M(DDDT)­] with mixed valence are synthesized.

The similarity of SEDT­TTP and M(DDDT)_ molecular structures la obvious, molecular packings of neutral BEDT­TTP and Au(DDDT)2 are also Bimilar. We have synthesized three novel nickel complexes

[Hi(DDDT)2l(I), [Hi(DDDT)2]3(C104)z(II) and [H1(DDDT)2]3

A. E. Obodovskaya. Z.A. StarikoTa Research Production Association "IREA", Hosoow, USSR

With the aim of studying several peculiarities in the structure of N-aryl substituted hydroxamlo acids there have been studied compounds I-III of the type R,-C(«0)-N(OH)-R2 where R, - S-NOg-CgH.-C-C- (I), 0gH,-15-orown-5 (II), C6H5-C-C- (III)i Hj - 2-Cl-CgH.(I), CgH- (II,III). Ill contains one HjO raoleoule. An analysis of the obtained and literature data has shown that only one of two extreme conformations vols and trans) is observed. The only exception is ois-conforaiation for III. The ole-conformatlon in III la stabilised by the intramolecular component of a three-oentre H-bondlng 0-N-C-O.. .H.. .0' whiah binds the moleoulee In dlaers with a propeller orientation of benzene rings. I and II have a chain structure. The obalns in I are built up by means of an lntermoleoular H-bondlng N-0H..-0*C oharaoterlstlo of hydroxamio aoida. The ohains In II are formed by the H-lnteraotlon between HgO moleoule and the ether 0 atoms and OH-groups (0^-H...0| 0W. ..HO-N). I and II mo• lecules are nonplanar. The bulky substltuent in III inoreaaes the rotation angle of Rj with respeot to the hydroxamlc group to 85°. The values of valence bonds in I and III indicate to the absenoe of an extended ^conjugation between the multiple C-C bonds -C-C-

niCHLORO(l,3­DIAHIHO­2­^ROPANOL)PJ.AT)N!JM(II), f Pt (NH СИ^СИОНС! | , AND Dl I0DO( 1 , 3­DTAKINO­2­PROPANOL)PLATTNUM( II), [ PUNh^CH^CHONT^

А. Oksanen8, R. Itvekee8, T. Laltalainenb, E­L. Pulkkinenb and P. Lumrne8

eDlvtsion of Inorganic Chenletry, University of Helsinki, Vuorlkatu 20, SF­00100 Helsinki, Finland, bDivlslon of Organic Chemistry, University of Helsinki, Vuorikatu 20, SF­00100 Helsinki, Finland

Studies on ollgoaterlc antitunoral platinum complexes raized a question about the effect of the ааш1пе ilgand size on the tendency towards oligo­ •erlzatlon. The title compound's were prepared for further studies on olfgo­ •erlzatlon reactions of platinum. Both compounds crystallize in oonocllnic centrosymmetric space group P2 /n with cell dlBenalona: a­8.497(3). b­8.784(2), c­10.735(5) A, g* 105.79(3)° and Z­4 for the chloro compound and a­10.756(2), b­7.211(1), £.­12.113(1) A, 0­91.20(2)° and Z«4 for the iodo compound. The final К vultiea ere 0.056 fot 1456 reflections (chloro) and 0.044 tor 1080 reflections (iodo). tn both coapounda the four llgend atoms coordinate to the central metal ion to give в сla­planar environment and the diamine ligand forms a six­ eenbered ring in chair conformation with axtally oriented hydroxyl group. Packing of the nolecules la quite different. Two molecules of the iodo comp­ ound for* palra through 0­H***0 hydrogen bonds [0­­­0­2.58(2) A) while the shortest tnterrotecular 0"*0 distance In the chloru compound is 3.84(2) A.

Fig. I. Some relevant bond leg the of f Pc(NH2C»2)2C)IO»Cl2 ] and (PttHHjCHj^CHOHljl. The 0­H hydrogen atoss are omitted. - 289 - THE STRUCTURAL INVESTIGATIONS OF THE INNER COMPLEX COMPOUNDS OF THE DERIVATIVES OF 8-MERCAPTOQUINOLINE L.J.Pech, Yu.A.Bankovsky, A.N.Sobolev, A.P.Sturls, I.R.Berzina Institute of Inorganic Chemistry, Latvian Academy of Sciences Riga, USSR

Practical significance and theoretical interest have led to a wide and systematic investigation of the analytical reagent 8» mercaptoquinoline, its derivatives and inner complex compounds formed by them (ICC). The aim of the present investigation is the consideration of 20 ICC of 8-mercaptoquinoline derivatives, comparison of their molecular and crystal structures and clarification of some regularities of their spatial structure depending on the nature of the metal as well as of the nature and position of the substitu- ent in the quinoline nucleue £lj. It was established that the greatest changes of the structure of the central coordination knot and the geometry of the complex, on the whole, are observed upon transition from complexes of B-mercaptoquinoline to the complexes of its 2-substitutes. With introduction of substituents of other positions of the quinoline ring, these changes are negligible. In the series of S-mercaptoquinoline derivatives, 2? carboxy-8-mercaptO'Tuinoline, as a tridentate linnd, is distlngul shed by its capacity to form not only the bond* "metal-sulphur'' and "metal-nitrogen", but also the bond "metal-oxygen", which leads to an increase in the number of elements interacting with these reagents. Zirconium and hafnium belong to such elements. The results of investigation of physico-chemical properties (absor ption spectra, composition, stability in two^phase systems and in dimethylformamide solutions,solubility In organic solvents otc.) are discussed in this study as regards the inner complex compounds of 2- and 7- alkyl, 2-, 5- and 7- alkylthlo-, 2- and 4-phenyl-, as well as 2-carboxy-8-mercaptoquinallnee and their '.ntercemection with the structure.

[lj B&nkovsky Yu.A., Sturic A.P., Pech L.J., Berzina I.R., m Izv. Akad. Nauk La*rv. SSR, Ser. Khim.,6, 146 (1987). cv - 4j»

37-1 - гэгу - CRYSTAL STRUCTURE OP TWO SESQUITERPENE /"­LACTONES: COMPARISON WITH SEVERAL SIMILAR COMPOUNDS

A. Peralea C.S.I.C. Institute Rooasolano, Deparatamento de Crlstalografia, Madrid, Spain

In this study 32 sesquiterpene ^­methylene­ ^­lactones have been analysed. The ^"­lactone ring ie fused to the other ring (whloh noraaly has six, seven or more carbon atoms), through the C6­C7 atomst the fusion can be either trans or cis, but more freouently the trans fusion is present. As it is know /1/ there is a correlation between the CE (Cotton effect) and the type of fusion of the T ­laotone ring, and between the CE with the chlrelity of the 0»C­C«0 ormophore /2/.

Pig. 1

/1/ W. Stooklln, Т.О. WBddell and T.A. OeiSBman. TETRAHEDRON. 26, 2397 (1970). /2/ A.T. MoPhail and Q.A. Sim. TETRAHEDRON. 29., 1751 (1973). - 291 -

STRUCTURE AND REACTIVITY OF SOME OXO MOLYBDENUM COMPLEXES

M. Pierrot. F. Djafri, F. Ridouane, R. Lai and H. Arzoumanlan, Cristallochimie-Esipsoi, UA126, Centre Saint-Je"rdme, 1339V Marseille Cedex 13, France.

in spile of an abundant literature on the chemistry of transition metal complexes involving the oxo-ligands, ii is only recently that the око complexes bearing other functionalities (alkyl, aryl or carbene groups) have received much aitention. During ihe past few years we have been interested in both ;-,e oxo ligands and metal oxygen bond reactivity in metal oxo compounds.

1- Mo(0>2(mes)2 (mes= mesityl: Сд^Мез) belongs to the rare class of metal oxo aryl complexes and its structure will be compared with the Rh and Os analogs. Under a few atmospheres pressure of CO, the pyridine solutions of this compound yield an unexpected formation of dihydropyridine dimer : this is an unprecedented example of carbonylation mediated by a d° transition metal complex.

2- During the study of molecular oxygen activation by bimetal tic system such as Mo-Pt, we were able to point out the transfer of dioxygen from one metallic center to another one. The structures of two compounds have been

established : [PPh4)(Mo(0)3(mes)l and fPPh^ll^Og]. The latter complex exhibits a desordered structure which may result from the equilibrium between peroxo and superoxo forms.

3- The reactivity of [PPhl3(Mo(0)(CN)5l towards molecular oxygen or orthonitrosotoluene and the lability of the суало group in "trans" position with respect to the oxo afford the opportunity to prepare new complexes which will be described.

Si

37-2 ­ 292 ­ CRYSTAL STRUCTURE AND INTERMOLECULAR INTERACTIONS IN liESOGENIC SHIFF BASE COMPLEXES OF TRANSITION METALS

A. P. Poliahcb.uk, T.V.TimofeoYB. U.Yu.Antipin, Yu.T.Struchkov Neameyanov Institute of Organoelement Compounds} USSR Academy of Sciences, Moscow, USSR

In a search of the correlation between the structure of Shiff base complexee of metals and their mesogenic activity the X­ray study of oompounda I­VIII has been carried out.

R' I II III IV V VI VII VIII

UOu .Oil Ou CuCuCuFdNi

!?1 / 0 0 R '^ ^ ~?" 4^' rf­OCb^ ? OC9Hig СИ Ш? N02 Offlj OGH3

CH 2 ягД5Г I,II,IV­VIII. I^­OCt,^! IIIiH ­^

On the bads of X­ray data the calculations of the energy of In­ termolecular interactions (In atom­atom approximation) in theoe crystals were performed, which allowed to find the moet etable molecular associates. It was shown that mesogenic activity is moat pronounced in the complexes with a planar metallochelate unit and, thus, with the most elongated shape of the molecule. The crystals, which are built of layers whose thickness is compa­ rable with the length of the molecule, form, as a rule, smectlc phases on heating. In this case the energy of interlayer interac­ tions is usually 3­5 times greater than the intralayer energy. The crystals with chain­layer packing, wherein the layer thickness is comparable with the length of the metallochelate unit, do not form emectic phases but may form a nemetic meeophaee. It is found that the additional coordination of a metal atom usually inhibits formation of а meaophase or causes the eaaentlal narrowing of the temperature area of ita existence. ­ 293 ­ THE SHORTEST INTRAMOLECULAR HYDROGEN BOIW IN 8­OXYQUINOLINES. CRYSTAL STRUCTURES OF TWO 8­0XYQUIN0LIHE DERIVATIVES

I.H« Polyakova, Z.A, Starikova Research Production Association "IREA", Moscow, USSR

In the course of systematic studies of 6­oxyquinoline deriva­ tives X­ray crystal structures of I and 11.0,5 Py have been investigated.

In the propellerlike molecule I dihedral anglee between oxy­ quinolinio (oxin) and phenyl­lactonlc cyclee are 72,4­84,0°. Two oxin groups have different geometry. In one of them bond distan­ ces and angles correspond to the values in unsubstltuted 6­oxy­ quinoline and molecules II. The structure of the other one is des­ cribed by none of the canonic forms, nor by their superposition. The most striking features of the fragment are equal C­N bonds (av»1,353 A) with a somewhat decreased angles CNC (116,2°) and a о very short for 8­oxyquinolinee bite distance 0...M, 2,622 A. A po­ ssible interpretation of this structure is the formation of a mo­ lecule with H(0) atom common for both N. and 0 atoms, resulting In a short intramolecular H­bond 0...H...N. H­bond "activation11 may come from the stacking interaction uetween two neighbour molecules, о d ­ 3,6 A, In the normal oxln part the intramolecular H­bond О­H...N is formed, 0...N 2,650 A. In the two molecules of the asymmetric unit of II oxin frag­ ments are tied up to flat systems orthogonal to the planes of Ph and lactonlc cycles. All the OH­groupe take part in bifurcated H­bondв 0­H.,.N(N) ordinary for 8­oxyquinoline derivatives. Bite о dietances 0...N range from 2,713 to 2,?36 A. Rather long intermo­ o lecular components, 0...N 2,623­2,966 A, bind molecules to chains. ­ 294 ­ SBGOMURY BONDINGS IN TUB d­UBTiL COMPLEXES WITH LINEAR AMD CYCLIC LIGAHDS M.A.Foray­Koshlts, G.A.Kuklna Ir.atltute of General and Inorganlo Chemistry, Academy of Soiences of the USSR, Hosoow There have been carried out X­ray structure and other physical studies of Hl(II),Cn(II) and Cr(III) complexes with acyclic and

oyolio aliphatlo tetraamine Hgandai H2N(CH2>1NH(CH2)lnNH(CH2)n­ HHg (l,m,n­tet) where l,m,n­2 or 3, tetramethylcyclam (IMC) and anlonlo Uganda Including tetraethynyl borate B(C­CH)7 (teb~). In Ml(II) and Cu(II) compounds of the type M(2,3,2­tet)teb I the square coordination of the metal by the (2,3,2­tet) ligand la completed te a square pyramid through the covalent long distance interaction of one of the teb~ ethynyl fragment. The change In the H­C­C­B tilt to the Mil. square normal axis and slippage of its projection in the

nerlee I*teb"lCl",Br")J",C10T is shown In the figu­ re. With X»teb~ U interaots with the C­C fragment at a distance of 3,2Aj according to "o and В HUR the long distance interaction is predominantly dative (HI— teb"). With Х­СЮ7 U interacts with H atom (with H­C bond electrons), the interaction la agostlc, donor (from C­H to M). The axial long distance Interaction maintains in solutions. Li­ gands X»Cl~,Br~,J~,Clor complete the H coordination to a blpyra­ •ld.

Or(III) ooaplexas with l,m(n­tet and TMC have trans­ or cis­£ ootahedral structure depending on the nature and denticlty of ooncoiBltant Uganda* In intermolecular H­bondlngs Cr­N­H...X with X­I'.CjO^ ,Br~ the charge transfer occurs from X to Cr­N­H fragment which results In the shortening of N­H distances and re­ levant oharge of phyaloal and ohemlcal properties ­

The possibilities of formation and character of th* secon­ dary bonds in Au(I) complexes have been studied. Potentially bidentate Uganda with two hatегоatошв capable of coordination to the sp­hibrldized Au atoa of the AuL­cation with the formation of 5­membered cycle usually form one 6*­ and one secondary bond. The choice of the particular (Г­bond of the Au atom ­ either with the X or with the Y atom ­ is determined by the delicate balance of electronic properties of the X and Y atотв. In 8­hydroxyquinolinate AuPPh, the Au atom refer to form 6*­bond with N atom. The molecule of thia compound shows ooncide­ rable structural variability in solid state. In different crys­ tal modifications it has different geometry of the central frag­ ment Cj}^>Au­P. This difference corresponds to the shift of the AuPPhz cation between two positions bonded to different he­ teroatome. Some decrease of nucleophility of the N aton in azo­B,2 ­ diphenolate (AuPPh^)g leads to the shift of the AuPPh, moiety from X to X atom. The same effect has been found in mercaptoqui­= nolinat» AuVPhj. In some complexes instead of potential intermolecular secon­ dary bonds Au...heteroatom either apostle Au...U­C interaction or secondary Au...Au interaction 1в observed. In orgauogold compounds with unsaturated organic Uganda intermediate between fr and *r type of bonding was found. In general a largo variety of different typeв of secondary bonds is characteristic of the stereochemistry of the Au(I) atom. Some of these bonds are typical for transition or nonwtransition metalB and some of them do not have any analogues in the structu­ ral cheuiiBtry of other metals. ­ 296 ­ PSCULIARITIES Q? CHEMICAL STRUCTURE OP d°­ AND d^­TRANSITION HBTALS OIO­COMPLEXBS WITH BONO­ AND FQbYUEiraATE LIGAHDS M.A.Poray­Koahitz, V.S.Sergieiuca Institute of Inorganic and General Chemistry,USSR Aoad.

Scl; Moccow.USSR

She etructurea of oxo­complexea of d°­ and d ­transition metals of Y­VII grovDB (V,Nb,Mo,tf,Re,Tc) have been compared. Two types of Isomerism in d ­complexes have been conside­ red! a) the isomerism of trans­influence (elongation of the N•0 double bond in going from one Isomer to вл­cther is accora­ ponlefl by the shortening of the H­L(trans)) and b) the isome­ rlm of a double bond (elongation of the M=0 bond is not accora­ pUnled by the shortening of the M­L(trans) bond). It has Ъееп shown that for d°­matale the choice of a trane­ paxtner among the oontyv­eting Uganda is determined by the aelf­ oonsistenoy prlnoiplet trans­position to double bond is first of all ocoupled by a neutral atom or ligand (less polarixable d­donor) and only In second time by aoidio (charged) atom or ligand. In this oast the H­L(trans) bond is elongated due to the trans­lnfluenoe of double bonded oxo­llgand. о For d ­metals this rule becomes more complicated and the ohojoe of oxo­llgand trans­partner depends on the nature of the trans­llgand (ita й­ and 'JT'­donor properties). If the oxo­11­ gar'1 tT vis­partner is capable of ^f­donation to metal atom the " , as) bond may even rather become chorter than longer.

' • Л the complexes of d°­Mo02 and d ­ReO with the chelate IT Uganda of the same type as an example,it has been e. u that the Uganda are coordinated by metal atom in a dif­ ferent wayi in case of the d ­Ыо02 complexes the trans­position relative to the oxo­—cigand is occupied by a neutral donor ligand and In d ­ReO derivatives ­ by acidic sit* of a bidentate ligand. Охоэрегохосо>ф1ехев of V45+) are treated as an example of atruotural manifeatatlon of the Og­ligand trans­influence and alternation of geoMtrlc parameters due to the redistribution of aleotron density of the V(OgK* group. ­ 297 ­ URYSTALLOCHEMICAL RUBIK'S' "MAGIC CUBE" ?0R THE MODEL

3+ OP [M(OCN2H \'] OCTAHEDRAL COMPLEX CA_ ION

V.G. Rau, V.I. Bonder'» T.P. Rau, S.V. Stepanov

Vladimir State Pedagogical Institute, Vladimir; Yu.T. Struchkov

Institute of Organoelemental Compounds, USSR Academy of Sciences, Moscow, USSR

Single crystal X­ray atructurel studies of heterooomplex compounds containing the octahedral JVHOG^RA)^ cation for di­ and trivalent metala revealed the regularities of intra­ complex hydrogen bonds formation of the type N.­Hj.­.O... It al­ lowed to suggest the mathematical model of the structure of a complex cation as an oriented graph with six vertices and to enumerate for 1'; the results of H­bonde rearrangements possible. It was found out that the transfer from cne configuration to another can be performed by rotating carbamide around metal­oxy­ gen bond and because of this transformation the model cation stands in a row with a well known mathematical game ­ Rubik's "Magio Cube". Prom the practical point of view the model suggested allows to propoee the mechanisms for the reactions proceeding with the formation of final product oontalning [УКОСИ^Я*)^* from the initial one and to predict the configuration of a complex cation which were not found earlier. Of 72 possible structure variante of octahedral complex (among them there are 54 with point group 1, 1 with point group m, 1 with 1, 8 with 2, 2 with 32, 4 with 3, 2 with 3) only a few were found 1л the real struc­ ture» but neither of the configurations found ie in oontradlo­ tion with the mathematical model suggested.

3B­I ­ 296 ­ THE РЛОВЬЕМ OP "STRUCTURE БКИСБЙ" CREATION V.G.Rau, L.G.Parkhomov, N.A.Kotov, A.V.Maleov Vladimir State Pedagogical Institute, Vladimir, USSR

We will name aa a "structure seeker" a mechanism, a system of rules or an algorithm which could answer the question: wheth­ er the given molecule (or a group of molecules) is a figure which divides ^­dimensional space R­3. As it is known the nature solved the problem of structure seeker in favour of lattice for solids. In this саве if the shape of о molecule is approximated with some spaclal polymln^ consisting of N point seta of supor­ lattice we can note (the subdivision criterion) thut the selec­ ted model of a molecule divides the space with packing coeffi­ cient k, only in those cases whon there exist N/k parallel poi­ nt rows of su^urlatticc which fill the cell of main lattice with the periods a, b, o. Kach of N/k paral1el point rows constructed contains one and only ono point of suporlattice belonging to the polymino under study. for tho calculation of the variants of filling the piano with polymino^moleculea it is necessary (a) to calculate the number of different pencils of parallel point rows of a super­ lattice (which ie determined by the sum of divisors of the number N/k), (b) to iduutify N points of polymino solving the definite system of comparisons and (c) to obtain (or not obtain depending on the results of solution of tho ystem) the necess­ ary piano division. The culculutional programs are realized for 2D version on JSC computers. For the hoinomulecular compounds with the number of molecules in u cell Ъ > I it is necessary to carry out the preliminary step of counting of the variants of surroun­ ding for conventionally chosen one molecule by the others. For the heteromolecular compounds the stages aro suggested to create tho structure seeker on the basis of counting the "weighted" (coloured) cyclotomic point sots. .. 299 ­ tiTiiUCTUHE OF Tilb NIOiCfcL(II) AND COBALT(III) COMPLEXES CONTAINING PHENYLAZOTHIOALiCYLCARBOXIMIDb ANION­RADICALS AS LIGANDS M.D.Revenko, Yu.A.Simonov, N.V.Gerbeleu, P.N.Bourosch, L­P.Batta^lia» A.Bonamartini Corradi, G.Peloai Kishinev State University; Institute of Applide Physics of the Academy of Sciences of Mold.GSR; Institute of Chemistry of the Academy of Sciences of Mold.SSR, Kishinev, USSR; Institute of General and Inorganic Chemistry, University of Parma, Italy S­clkylisothiosemicorbazides (L) form three types of comple­ xes with the nickel ions: the paramagnetic octahedral ­[NIL^X^] and [NILpAnlXp., and also the diamagnetlo square­planar [Ni­L_ijXp­. 1­Phenyl derivatives behave themselves differently "f­rom 'those non­substituted. The Complexatlon with nickel (and ­oofcaVt) eml*fcB is •Bcco.'npuinea by redox reactions with the formation ©f free ra­

1 11 dicals R l>J'(1')­M'(y)­C(3)(S­AlK)­N(4)R (У) which are stabilized after the coordination by the metal ion. The results of the x­ray

structure determination of the complexes NIY­CA), CoIY2(li).v (H -

11 I II C^l^Alk­CI^.R *!!), NiY2(R =p­K'02­C6H4,Al(c­CIl­j,R ­C6II5) (С) are reportea here. The compound A has a aquare­zplinar structure with practically total derealization of the eleotron density in the five membered metalring. The medium bond distances are: Nl­M(1)« 1..825, N(1)­N(2)=1,354, N(2)­C(3)»1,345, C(3)­N(4)­1., 305, N(4)­ D N1^1,835 A. The diamagnetism of the chelate results from the qua­ ziaroma'tic character of the formed system having 1UTT ­electrons (2n+P, n=4). The complex В is square­pyramidal with iodine in the apex and an unusual for cobalt(III) five coordination. The geome­ tric parameters for the metalring are close 'to 'those of the A­ complex. The substitution of the hydrogen atom off N(4) by the phenyl radical and the introduction of the nltrovgroup In the R causes the tetrahdrisation of the chelate* The dihedral angle be­ et tween the two ring is close to 90 . The medium bond distances are: Ni­N(1)­l,895, N(1)­N(2)­l,336, N(2)­C(3)­1.353, C(3)­N(4)­ о 1,317, Ni­;,(4)«1,911 A* These parameters show the reduction of the electron derealization. The compound 0 la psrsJiaJtnetle and represents the first example of the tetrahedral nloltel chelate with ligands derived from S­alkylieothiosemlcarbazlde. The obtai­ ned parameters have been compared with those found for the initi­ al non­oxidised and final total oxidized forme of Uganda. 38­2 ­ 300 ­ CRYSTAL STRUCTURE OP 3­HYDROXYHETHYL­CJS­4a,5,6,7,6,Ba­HEXA­ H№RO­2H,4H­1,3­BEHZOXAZm­4­OHE

B. Ribar Inet. Phys., Faculty of Sciences, Novl Sad, Yugoslavia A.Salman, Gy. Argay Central Research Inat.Chem., Hungarian Acad.3d., Budapest P. Piilop, G. Bernath Inst.Pharmao.Chem..Albert Sjent­Gyorgyi Med.Univ..Szeged,Hungary

The crystals of the title compound were prepared as described by Piilop et al. IM.

Cryetal dates CgH15N0,, Мг­1в5.22, враое group Рг^с, а. 12.775(2), b­6.577(1), 0­11­377(3) A, £­97.76(2)°, V­947.2 P.

3 Z­4, Dx­1­298 gem" , A.(UoK^)­0.71073 A. The structure was solved by direct oiethodB (SHELX 76) and re­ fined to R­0.047 for 2068 observed reflections measured with CAD­4 diffractometer using "oK,­ radiation. The six­membered oarbo ring exhibits a perfect chair confor­ mation. The hetero­ring assumes aljBoet perfect half­chair confor­ mation as shown by its puokering parameters Q­0.531A, />­330.1» and «­47.5°. The puckering amplitude y5 is lnversly proportional to the out­of­plane amplitude of 06 /refered to the least squareB plane of ring atoms C2, N3, C4 and C5/ governed by the eame rulee found by Ribar et al. /2/ for different 1,3­oxazin­4­one deriva­ tives. Molecules are held together by hydrogen bonds forming in­ finite ohaina parallel to c­axls. ^­s02

Dl /1/ Piilop P. , Pihlaja K., Mattinen J. , Bernath G. , Tetrahedron Letters, 28, 115 (1987). /2/ Ribar B., Kapor A., Kalman A., Argay Gy., Pliiop I'. Bernath G. J.Mol.Struct., i2g (1989). ­ 301 ­ STRUCTURE OF PENTACARBONYL(N,N­DIBENEYL­BENZENESUL­ FENAH1DE)CHROHIUN<0) M. L. Rodriguez. C.Ruiz­Perez and I.Brlto C.P.N.O.A.G., Unlveraidad La Lacuna ­ C.S.I.С 38206 La Laguna Tenerlfe Spain C.Diaz, J.Cuevas, G.Gonzalez and V.Manriquez Facultad de Cienclaa, Universidad de Chile Caeiila 653. Santiago (Chile) In spit's of the coordinative characteristics expec­ ted for sulfonamides because of the lone pairs on sulfur and nitrogen atoms, the A­{S)­(ethylendi­ astne­(R)­cystelnesulfenamide)cobait(III> perchlo­ rate is the only seta! complex reported with this kind of ligands /l/.­ The X­Ray crystallofraphy analysis of this compound reveals a N­?ulfen&mlde coordination toward the metal. As part of studies about the coordinative properties of sulfur­ nitrogen compounds /2/./3/./4/, we report now the crystal structure of a new sulfonamide metal com­ plex, the pentacarbonil(N.N­dibelzyl­benzeneaul­ fenamide)chromlum(O).

/I/ 0.J.Qalnsford, W.G.Jackson and A.M.Sargeson. J. Am.Chem.Soc. 99, 2383 (1977). /2/ C.Diaz and G.Gonzalez. inorg. Chlm. Acta. 85. 61 (1984). /3/ i.Chadwlck, C.Disz, a.Gonzalez, H.A.Santa Ana and N.Yutronlc. J. Chem. Soc. Dalton Trans. 1986, 1867. /4/ G.Gonzalez, C.Diaz and H.Binder. Z. Naturforsch. 42 B. 513 <1988). Acknowledgment.1.8. thanks the AIETI for fellowship ­ ЗСЕ ­ CKTSTAUiOCHEMICAb IPBCULIARITIES OF THE STRUCTURES OF Co(II), Ni(II), Cu(II) Ш> Zn(II) COMPLEXES WITH ENAMINOKETONE DERIVATIVES OF 3­HUIDAZOLINE HITROXYL RADICAL G.V.Romanenko, S.V.Pervukhina, n.V.Podberozskoya Institute of Inorganic Chemistry, Siber, Branch, Academy of Sciences of the USSR, Novosibirsk, USSR

The structures of new class complexes of 3d­metals with pa­ ramagnetic Uganda on the base of 3­imidazoline hove been studied. There were some bis­chelated complexes with the total formula Ml| I Mb} (lb Ni, Cu, Zn ), Hil| , CulJ , Nil£ , Ml|

Hi ," Zn) , [Ю^(ИеОН)2] (Ifc Co­, Hi) ana ;[NiI^(BtOH)^. The L bidentated Uganda are connected with the central M atom by the donor 0 and N atoms, forming distorted tetrahedron almost in all bis­chelates ("trans"­tmgles 0M0 and HHN 127­144°) except MLg (M=

Uln Di, Cu) and N1L| with the square­pla­ nar coordination of the metal atom (£OMO and IMS 167­177°). It should V* be noted that two isomers ( with tet­ tahedral and square coordination of 0­N .I I the Cu atom) have Ъееп found for CuLg upon recrys^allization of the substan­ ce from different solvents. Metal­cyc­ les and Imidazoline rings ( including the 0 atom of a paramagnetic fragment Ш? >JWD ) are almost planar ones, setting at a small angle. The Ir ligands pro­

R= CH,(1), C2H4(2), duce an equatorial plane of octahedron CF,(3), t­C„Hq (40, in mixed­llgands complexes with alco­ C6H5 (5) hols, axial positions are occupied by the 0 atoas of Hethmnole or ethanole. tritraaolecu!lar distances M...iO from the И to the 0 ato» from XT^O group is ~5,5 X, but lntermolecular distances M. ..O*­ in bis­chelate3 are ~5,3 X, the sane distances in the mixed­ligand complexes are significant­ ly shotter and , perhaps, that is the reason of their unuslal magnetic properties. ­ 303 ­

CRYSTAL STRUCTURES OF HRuCo3(CO)llSe(CH3)2 AHO

WluRh3(CO)9[M­Se(CK3>2)3HKuRh3

S. Rossi, J. iPursiaioen, M., Ahloren, T.A. Pakkanen Department of Chemistry, University of Joensuu, Joensuu, Finland

Hixed­setal clusters are currently under intensive investiga­ tion because unique properties are expected owing to the possible different metal site reactivities. Dialkyl sulfides are rather common ligands in metal complexes but metal clusters with SR2­type ligands are virtually' unknown. In our studies of tetrahedral mixed­Beta! Ru­Rh­Co clusters dimethyl sulphide has been proved to be a versatile ligand. It can act as a two electron or four elec­ tron donor, bind terminally or bridge metal atoms /1,2/.

In this paper we describe the reactivity of SeMe2 towards mixed­metal clusters HRuCoxRh3_x(CO)j2 (X­Q­3J. It substitutes readily one or more carbonyIs at Moderate reaction conditions.

This ia apparent in the structural examples af HRuCo3

HRuR c Fi

Figurm 1. figure 2.

/1./ Ahlgren M., pursiainen J., Pakkanen Т.Л., 2. Krjstallogr. lfiS, Э12 (1988). /2./ Rossi S., Pursiainen J., Ahlgrmn H., Pakkanan T.A, submitted. ­ 304 ­ THE CRYSTALLINE STRUCTURE OF A NEW ORGANIC SALT HeCioSeOalS­ Rozhdestvenskaya I.V... Kartenko N.F., Usov O.A., Abashev G.G., Russkikh 4.3., Vlasova R.M., Semkln V.N., Priev S.Ya. USSR, 194021 Leningrad, A.F.Ioffe Physico­Technlcal Institute Polytechnical sir.,26.

The crystal structure of а пен organic salt bistoxapro­ pylenedilhio) tetrathiofulvalene pentaiodide ­ (BOPDT­TTFJIs have been determined. X­ray diffraction data were collected on a. Syntex P2j diffractomeler with graphite monochromator, MoK^ radiation, (sin &/Л)м}Г 0.806. (BOPDT­TTFHs crystallizes in the eonoclinlc system, space group C2/e, with the following cell constants; a­20.253(5) A , b=16.116(3) A , c­16.116(1) A, A «(17.63(1) , V­2456.5(2) А3, z = 4, F(000) = 1908 , Пх­2.в4 g/св3, f* (MoKfli) «70.6 аь~\ measured 2393 reflexions, oj­ khem Я067 reflexions with 1 >1.98бЧГ). The structure was solved by the direct method and refined by FMLS procedure to a value R«0.035 for 1788 observed reflections (|F| > Ae(T)), with 134 parameters for 132 atoms, room temperature. The structure contains two different anion types: linear I3, located a center of symmetry with I­I^contact 2.846(1) A, and pairs I2 with I­I contacts 2.764(1) A. The shortest I­I con­ tact between anions in linear and pair positions is 3.383(1) A. Cation^radicals BOPDT­TTF oriented along diagonal of unit ол" that hinder fonation of sheet­like structure of anions.These structure peculiarities are considered to affect some physical properties: semiconductor with conductivity about 2.5­10­5o"'cm_I Л 300 К and activation energy 0.1 eV. ­ 305 ­ X­RAY STUDY OF Ni(II) COMPLEXES WITH SHIFT BASES DERIVATED FROM SALICYLALDEHYDE

C.Ruiz­Perez, M.L.Rodriguez, F.V.Rodriguez­Romero C.P.N.O.A.G., Univ.La Laguna­C.S.I.C. Ctra.La Esperanza, 2 38206 La Laguna, Tenerife, Spain M.S.Falacios, P.Matin­Zarze, P.Gill Dto.Quimica Inorganica, Univ.La Laguna, La Leguna Tenerife Spain

Complexes of TJ­sallcylidene­L­aminoaclds with transition me­ tal ions have received much attention in recent years, specially reepect to their structure and magnetic properties. We have studied the compound (N­5­3r­salicylidene­L­trypto­ fanate) triacuo Nickel (II) dihydrate. Crystal data:

[(CieH13N203)(H20)3] Ni(II) 2»H20» Mr­534.0, Monoclinic, P21, a­7.379(1), b­7.636

3 Dx­1.596 gr/cm" , Z­2, F(O00)­544, X(CUX^)­1.541B А, у*ССиК^)« 37.70 cm"1. Room temperature. Pinal R­0.051, R^­0.05 for 1820 unique observed reflections (I^3<£(I))* The structure consists of discrete molecules with octahedral metal ion bonded to one terdentate Shift base and three water mo­ leoules and is characterized by the presence of polar cavities in which water molecules are located. There are two additional non­ coordinated water molecules which play an important role in the formation of inter and intramolecular hydrogen bonds. The metal­ carboxyl oxygen bond is longer than the metal­phenolic oxygen distance (2.065(6) A vs. 1­998(5) A). The angle 020­Ni­021 is owl less than 180° (173­6(2)°) because of the dimension of the central ion with reapect to the tor­dentate ligand. Each dis­ crete molecule is taking part in two chain, which are built by hydrogen bonds.

39­1 ­ Э06 ­ CRXSTALLIC AND .MOLECULAR STJlUCTURKJ OF ШЕ COPPISK(II) COORDINATION COMPOUNDS WITli oHii­'F'J UAdiS OK TjiE SEWICARHA^IDE I.D.Samus, (j.G.Taran, V.I.'faapkov, и.'Г..За/nua Kishinev Polytechnical institute S.Lazo,Kishinev State University V.I.Lenin, Kishinev, USSR

It is known that copper(ll) sal to react with the eemicar­ bazoncs of aldehydes and ketones forming different in tnc com­ position and struoture coordination compounds. Some of these complexes poseos medico­biological properties. 1'he data on the structure of the complexes are mainly baaed on the reaults of the physico­chemical investigations, their structural studies be­ ing limited /I/. The results of the X­ray diffraction investigations of the coppor(ll) coordination compounds with semicarbnzonen of

the selycilic aldehyde 41 ,Sura) and pyruvic ncid (li?:Jpu):

Си(НгЗян)|Л.^120 (I),CulH3sn)i;0j.ll./) (11), 0u(iUpu)C1.2M2^ (ill) are presented in this work. The crystals of tho I composition belong to the triolinic syne.ony, of tho II composition ­ to the raonoolinic one. The first oomplexfe a monomerio planar compound, the second ­ dimeric, in which the copper atoms are linked toge­ ther with the phenolye oxygen of the uulycilic aldehyde, 'i'he Shift*» base in these complexes is the tridental ll^and 01,N1,02, forming on ooordlnation five ­ and sixring metallocyclos. Vhe Interatomic distances are i for I ­ Сп­01=»1,9У7( 6), Cu­Nit. 1,960(7). Cu­02=I,9I7(6)A; for 11 ­ Ou­OI =1,493(4), Cu­Ill=I,939(4), Cu­02»I,962(3), I,963(3)A. In the third complex oopper(II) ion hm square­pyramidal coordination) llSpu is tridental monodeproto­ nated llgond bounded up with copper through 03 atom of the carbo­

xylic group(Cu­03=l»969A.)# carbonylic охуцеп 01 of the aemicarba­ eide (Cu­OI=2,O0UA) and nitrogen of the hydrazine group (Cu­b2= 1,915л*) • The tridental liUpu forma on coordination two fivering helate netallooyclee. It is obvious that the studied complexes structure depends not only on the acid residue nature, but also ,the Uhiff'e base nature.

/I/ Taran G.G., Samus H.U., oamus I.D., Zavodnik V.E., itelskii V.K., Bodiu V.Ci. Izvestia AW KSSH. iieria physico­technicheefcikh 1 mate«a­ tiaheekikh nauk, №2, 27 (1984). ­ 307 ­ THE X­RAY INVESTIGATION OP THE CuOl) AND Mi (II) COORDINATION COMPOUNDS WITH 2­HYDR0XYETHYLIMIN0­2­HYDR0XY­1­BBNZALDEHYDE

N.M. Samue*, Yu.U. Tchumakov, V.I. Tsapkov. V.N. Biyuehkin, M.S. Popov, T.I. MalinovBky V.I.Lenin Kishinev State University, Kishinev, USSR

It wae shown experimentally that M(NO^)2.6H20 (M • Сц, N1) interacts with Shiff base obtained from 2­hydroxyethylamine and 2­hydroxy­1­benzaldehyde. The antimicrobic active coordination compounds /1/ with various composition are formed, depending on PH reaction media and the nature of the protonacceptor reagent. The X­ray structure determination for complexes: Cu(HL)N0~

(I), Cu(3­pic)(HLjN03 (II), Cu(4­pic)(Ht)N03 (III), Cu(L) (IV) and Nl(HL)g (V), where HgL ­ HO­CgH ­CH ­ N­CHj­CHg­OH wae under­ taken. The coordination polyhedron around the central atom in I­III compounds ie an extended tetragonal pyramid. The I and III compound* are pol­ymeric, while II ­ dimer. The nitrato­group piaye the role of the bridge In I­IV compounds, while the pheno­ lic oxygen atom carries the bridge function in the dimeric oomp­ lex. The nitrato­group is monodontate in the dimer, in III ­ bi­ dentate, and in I ­ tridentate. In the IV compound the copper atom coordinates the twice Ueprotonated H„L molecule through the phenolic and alcoholic oxygen atone and the imlne nitrogen. The totгелеric cubic complex ie formed in the structure* In the V compound two approximately flat single deprotonated HL molecules are bound with the nickel atom and come out as trldentate Uganda disposed In the two mutualy perpendicular planes. The nickel coordination polyhedron is a distorted octahedron with the imine nitrogent phenolic and alcoholic oxygen atoms in its aplcee.

/1/ Samus N.M., Shlyahov E.N., Slba Kulemu, Burdenко Т.А., Chaika T.S., Teapkov V.I., Popov U.S., Khimlко­formatает­ ticheeki Zh., ±, «6 (19B7).

§

39­2 ­ 306 ­ X­llAY 3TUUX OF COBALX(III) AJJU RHOUIUhl(III) WITH SULPHUR^ MITROUEK­AWD­SELISMIUMCONTAINING LIGANDE3 I.D.Sainua, W^E.Rugcmovsk.y.K.M.Samua G.Lazo Polytechnical Institute, V.I.Lenin State University, Kishinev, Moldavian iJSU, USSIl

An X­ray study of coordination compoutida of Go(IH) and Rh(lII) face and edge isomers with thiouemicarbazide of both general formula [_fih,Co(T3G') Jui^.niy) end [Rh.CotDioxinOpL,, 1 N0,.nlIgO is carried ou., where Та С is thioaeinicarbazide Dloxi­ me­dimethylglioxime, methylelioximc, L­thio­(oelenium)=carba ­ mide, acethylthiocarbomide, n = I, 2 /I/. The complex cation packing analysis allowed us to determine the character of coordination of Ti>C raoloculeswtth the coinlex­ forming atom , Typical intramolecular hydrogen bonds are char­ acteristic of coordinated J-— dioximines. The moot interesting result of the (structure investigation wua the proton "moving" alone the 0 ­ U«.,0 coordinate /2/. It is shown that the oxime proton localization is determined by If ­ interaction between the coordinated thio(selenium)car ­ bamlde and the raetal cycle of the plane dioxime fragment. Hydrogen and molecular bonds play a main role in the cryatal ^rmation. The crystal structure of the rhodium(III) dichlor ­ ..r.e dlthiouomicarbaaide chloride monohydrato contains two ory­ stallically independent complexes which are related to each other by a second order supersymmctry axis (i.e.,the axis is not parallel either to node ro.v, or to node plane with small indexes) ; the shift components are 0,13 a; 0,2? b; 0,09 с /3/. Both cations have the symmetry nuii2 with an accuracy of 0,14 X for the cation Л, and 0,10 ft for the cation B.

/I/ I.D.yamus, M.E.Husanovsky, O.A.liologa, N.M.Samus. .Koordina­ tioiumya chimya. 7,120(1900). /2/ U.K. Husonovs ky, I. D.Somas, V. К. Zavoanik, N.M.S anius, G. I.tihpa­ kov,.Koordinationnaya chimya,12,1703(1906). /3/ I.U.Sumuo, M.E.Ruaenovsky, H.J.Chernicova..Thirteenth Inter­ national Congress of Crystallography. Hamburg.P.311(1Ув4). ­ 309 ­ STUDIES IN MOLECULAR STRUCTURES AND CONFORMATION OP N­PH03PH0N0­ METHYL­L­TIfflEONINE AND N­FHaSPHONOMETHYL­L­PROLINE

И. Sawka­Pobrowolaka. T. Glowiek, J. Ba. Institute of Chemistry* Univsi­sity of Wroclaw, P, Joliot­Curie H, 50 383 Wroclaw; *Instltute cf Organic and Physical Chemistry, Technical University, 50 370, Wroclaw, Poland

Aminophoaphonic acids are analogues of amlnocarboxylie acids in which a ­C00H group ia replaced by a ­PO­jHV, group. These acide are of considerable interest because of their occurrence in many living organisms. Their biological activity Is mainly displayed through the inhibition of various enzymes having amino acid sub­ strates. The differences in size, shape and 'oaaicity of the car­ boxy late and phosphonate groups may play roles .a the differences in the enzyme­substrate interactions. This coraciunicatlon reports the X­ray structures of N­phosphonomethyl­L­threunine (I), and N­phosphonomethyl­L­proline (II). Crystal data for (I): С­Н^НО^?, orthorhombic, £2,2,2,, a­ 5­381(1), b­10.558(2), c­15.542(3) A, Z«4. The structure was solved by direct methods to R­0.038 for 24­77 reflexions. Crystal data Tor (II); CgH^MbP, orthorhombic, 1*2,2,2^ a­ 5.623(2), b­7,857(2), 0­19.635(5) A, Z«4. The structure was solved by direct methods to R­0.038 for 1009 reflections. The rooleoulea I and II exist as zwitterions with the amino groups protonated and the carboxyl groups un­ionized, the phos­ phonlc acid groups being ionized. The molecule I is in an exten­ ded conformation. The crystal structure is stabilized by five intermolecular and one intramolecular hydrogen bonds. In molecule II the pyrrolidine ring adopts the half^chair conformation. This work was supported by the Polish Ministry of Science and Higher Education (Project RP. 11.10). ­ ЗК) ­ THE CRYSTAL CHEMISTRY OF Ho(vt) DIOXOCOMPLEXES WITH "OLYDKNTATE LIGAHDS li.T.Sharipov, H.K.Machnudova, A, B.Hudoyarov Ifistitute of Chemistry, C­bek Academy of Scienceo,Tashkent, USSR

The determination of th*. crystal structure of some Mo (VI) dloxocomplexes with anions of hydroxamic acids and hydrazones has been carried out. The coordination of Uganda botn in ketone and henol tautomeric forms has been determined. The formation of pentanomial helatic cycles aa a result ^f coordination of ltgand via oxygen atoms in bis­hydroxamatic, bis­hydroximatic and hydro­ xarohydroxlmatlc Mo

X-ray structural analysis of a wide rann? of complexones, in• volving different functional groups (acetate, propionate, succi• nate , amide, • ' h •1"— >t-hy1 ihn^phnn* "^ ind b^t-oro-

atoms (N,Pfs), and also different metal coroplevonates has been carried out. The study-of our own results (the structures of 30 complexones, 5 hydrohalogens and 40 complexonates have been inve• stigate') together with literature data enables one to state the regularities of the structure and functional behaviour of the complexones and also their cationic and anionic forms. The idea of the aminocarbonic and aminophosphonic family co- molexone structure has been prorosed. It was shown that the bull- ding unit of molecules are H-cycles of different sizes. The cycles Imitate metallocycles in complexes. The cycle closing agent are

intramolecular H-bonds N-H,..X (x=NrO,S). The cycle systematization in given and the factors effecting their geometry and conformation are discussed. The genetic relationship is found between stereo• chemistry of complexones based on mono-, di- and trlanines. The crystallochemlcal classification of complexones has been suggested. The possibility of carrying out the orototropic tautomeric change in complexones and the ways of its existence have been shown. The relationship between the cationic form structure and acid group properties has been stated. It was found that the complexones can play th role of the geometrically prepared matrices for the for• mation of metal complexonates with the replacement of intramolecu• lar H-rcycles for metallocycles. Biologically active gen-diphosphonic complexones structure and the structure of their netal complexes have been investigated. The relationship between biological activity and molecule confor• mation has been confirmed. The foundation of the coordination sphere in metal complexo- nates has proved to favour the Hrbond formation, resulting in the closinti metallocycles of a new type called H,M-cycles. ­ 312 ­ STRUCTURE OF THE «TRANSITION METAL COMPLEXOKATES INVOLVING ALAHINATB CYCLES AND THEIR PHOTODi'XIARBOXTLATION PRODUCTS L.M.fihko}fnikova, Л.L.Pozniyak, A.В.Иjuhin, К.D.buyarov All­Unlon licscarch Institute of Chemical Reagents and Jiigh lure Substances, Ministry of Chemical Industry, Moscow, UiioH

While studying siatematically the structure of the comp­ lexonates and their photolysis products X­ray structural analysis of 11 compounds was carried out. Compounds include,­ Jool,.,bipy].

(ClO^)­, (1), fCoL^phenJCClO^.ail^O (11), [CoL20H]2(С10У|)я­'*Н2°

(111), |coL20Hj;3C1^.6H20 (1V), JCoL.OU^.bJL.O (V), fUuL,NOLi].

H20 (V1), [CoLnbipyJ(C10A)2 (V11), [CoL/lpJionJ([J10/|)2 (V111),

Са[Со1.5Ь1ру)(СЮ4),.5И20 (1Х), (CoL^pbenJCI 0^. 2H20 (X), [NiLg. ОЦ0)р).­?Н­,0 (Х1), where L^ ­ 1^diethylenctriaminemono­^­propio­ nate, lip - '4­diefchylenetriamineaono­3­propionate, L, ­ etiiylene­ dlamine­N,N'­di­3^propionate, 1^ ­ 1­ethyldietnylenetriamine, lit­ ­ 1­othylethylenediamine­4­(^­proplonate), L,­ ­ ethylenodi­ amlnensonosuccinate. Jn the compounds 1­V, 1X, X there are alaninote cycles CoH(;(1)0(2)C(5)6, havins a planar fragment CoNC(a)C(3). C(1) atom goes out from this plane for the distance of 0,63*0,71 X. The choice between chair and boat conformation is due to the value and direction of 0 atom deviation from the plane of the fragment mentioned above (from 0,09 in 1V to 0,19 % in V). In compound V1 the alaninafce cycle doesn't close and the propionate branch coordinates the neighbouring Cu atom to givft rise to r.arboxylate cycle. The complexes V11­X are photodecarboxylation reaction pro­ ducts­ The complexes obtained as a result of reaction 1 have

hS CoOOCOII2Cii2N(R1)n2 c[) *­ Cocii2-r bond breakage) or redox Lranr.f orni.­i t.i •m ('­о­С bond horaoly ci­ nni breakage). The ligand in complex x 1 rPiSulLa from homolylical !­оП'.) breaka^o вод is shown «jroottrlpx AJU; Г">(>1.'.­ ­ 313 ­

POIIKBDHAL ISOHBRI OP FACT[WiIS­(/?­AMINO£THH,ATB) COBALT (III)] ттвигажлТБ S.O.Shova. A.P.Culea, ll.D.IIazua, Yu.V.Kokunov, Yu.A.Buslaev Kishinev State University, Kishinev; Institute of Appl. Physios or the Academy of Sclenoes, Moldavian S3R, Kishinev; Institute of General and Inorganic Chemistry of the Academy of Solence of the USSR, Moeoow, USSR

The crystal and molecular structure of the red^violet modifi­ cation of [trls­(,6­aminoethylate) oobalt(III)] threehydrate (fao­ [^«(HgH­OKg­OHgOj.^JHgO was determined by the method of the X­ray structural analysis. Crystal is trygonal) a»b. 14,668(7), о ­ 4,9550)i, X ­120°­ SP808 group ВД. R­0,051. The statietlo desorder of the ligand oxygen atom was reve­ aled In the struoture. As a result of It, two different environ­ ments for the cobalt atom are realised. In one oaae the central

atom has an octahedral ff In an another oaee trygonal^prisnatlo environment. There are two equaly probable polyhedral Isomers In the crystal struoture of fao­[4rie­(j3­aminoethylate) cobalt (III )J threehydrate with a) octahedral and b) trygonal­prismstlo coordination of Co(III),respectivelyi

b)

Each of the isomers has a six­coordination number of the central atom. There are tree bldentate H2»­CH2­CH_0" Uganda, co­ ordinated by 0 and > atoms. The orystal struoture of the complex Is determined by the system of 0­H...0 and М­Н...0 hydrogen bonds. It is of great Interest that the trygcmalajiriematlo coordi­ nation for Co(III) was first: established In fao­fcodyUCHg­

СНгО)ЛзН20. Moreover the polyhedral isomer у i octahedron ­ tri­ gonal prism is realized in the orystal structure. 40­1 ­ 314 ­ COMPARATIVE STEREOCHEMISTRY OP SOME COORDINATION COMPOUNDS OP S­AND­D­BLEMENTS WITH DEHYDRAZIDES OP CARBONIC ACIDS

A.E.Shvelashvili, Т.О.Vardosanidze, E.B.Klninoshvili, E.N.Zedela­ shvili, I.A.Beehkenadzs, N.B.Jorjolianl, L.Sh.Charelishvili Institute of Phyeical and Organic Chemistry, Academy of Sciences, GSSR, Tbilisi, USSR

Structural studies of metal complexes with dehydrazidee of carbonic acids show that dehydrazidee function as chelate bridges. According to the means of combination of metal atoms with bridged /DM/ Uganda the structures may be divided into two typesi struc­ ture e with single and double bis­bldentate cyclic bridges between each pair of metal atoms. The analysis of solved structures permits ue to make a hypo­ thetical conclusion that the choice of bridges depends firstly on the anionic composition of the compound. Comparison of linear and ang ular parameters of a bridged ligand with those In a molecule of non^coordinated DM shows that bis­bldentate coordination of me­ tals does not lead to somewhat definite (systematic) redistribu­ tion of electron density on #" and <£ bondings between hydrazide atom i.e. no sterio requirements of metal ions are observed inde­ pendent of their behaviour. The stereochemistry of the ligand is predetermined by the energy of interligand repulsion only. At stereochemical ratio Met DM • 1i2 bridges of the first type form the nets with four­membered loops in which coordination sites are dodecahedra. At ratio Me: DM*1:1 chains of the direction with octahedral coordination sites remain. The bridges of the second type at ratio Hei DM»1:2 form chains (with double bridges) with octahedral coordination sites and at ratio Me: DM­1:1 these chains break into dimerlc complexes with cle­octahedral sites. ­ 315 ­

THE STRUCTURE OP PERCHbORATE <<.­130ЬЩ>А!»1!?В /C^H^OHj HC10+/

J. Slmlnslcl. E. Figaa, Z. Kaluski

Department of Chemlati7t Adam Mloklewics UniTereity, Orunwaldzka 6, 60­780 Pocnan, Poland

This work ia a part of a aeries of X­ray etudles of spart­ eine derirativea. *­leolupanine conslete of two rigid quinoll­ tldine moieties. The orystals are monoollnlo, apaoe group P2.,, Z­4, a«8.663(1), b­15.000(1), c«13.006(1) A, 8­99.38(1)». 2590 reflections were oolleoted on a Syntax P2. difractome­ ter. Struoture waa aolTed with program ЗНВЬХ­вб' and refineraened with ЗНЕЫ.­76. The final R ralue waa 0.056 for 2390 independent reflections. There are two molecules in asynnetrio part of the unit oell. One of the perchlorate anions is strongly orlentatio­ nally disordered. In both symmetrically independent oatlons rings А, В, С and D пате a distorted half­ohair, ohalr, ohair and ohalr conformation, resppotirely. The configuration for the rings Junotlon A/B Is quasi­ rails and trans for junotion C/D. There are two similar hydrog n bonds linking the oations and perchlorate anion»: N(16 A). .02 of 2.933(8) X and R(16 B)...05 of 2.961 A. Ring A in molecule (b) is partly disordered.

40­2 ­ 316 ­ STRUCTURES OF HTGH.NUCLEAR CAHBOiraLfHOSPHIME CLUSTERS Yu.L.Slovokhotov, yu.T.Struchkov, E.G.Mednikov Neemeyanov Institute of Organoelement Compounds, USSR AcacL Sot, Mosoow, USSR.

X­ray structural study of the neutral high­nuclear oluaters of palladium and platinum with close packing of metal atoms In cluster oore has been carried out! Pd­j^CO)­,,!^ (I, lcosahedral

paoking), РЬ17(С0)12Ьв (II, icosahedral), Pd2,(CO)20L8 (III, distorted body­centred cubic), р42з(00)221Ю ^IV' £ace oen*1'ed

d oubio), P }4(«>)wLla (V, icosahedral) ond PdJe(C0)28L12 (VI, very distorted "amorphous" packing). Different packings In the olustere I­VI, proved by the analysis of radial distribution funotians, agree well with Chini's assumption of small differen­ ce* In their energy. A model of large cluster as eleotronically saturated "droplet" within the ligand shell can be suggested. The oonditlon of electronic saturation allows one to predict the existence of "ateric barrier" which terminates the enlargement of oluetere with ligand shell t after this barrier metal polyhedra appear to be eleotronioally unsaturated and therefore termodinsmioally unstable. Numbers of valenoe electrons at the interstitial metal atoms in I and II correspond to llingos' rules, whilst other dusters III­VI dieobey these rules /2/. In agreement with thaoretio&l predictions /}/, average radial metal­natal distances in the olueterB I, II and V with iooeahedral peaking are 0.10­0.15 A shorter the» tangential distanoes and equal to them in foe IV and b.o.o III olusters. We are grateful to Drs. S­B.Kuraeov and N.K.Kremenko (Institute of Coal Researches, Kemerovo), who provided us with the oryetale of II. In the all clusters studied x, с PBt,.

/1/ P.Oiinl, J. Organometal. Chem., 1980, 200, У!. /2/ D.H.P.Hlagoe, Ohem. Commun., 1985. 1352. /J/ H.R.Hoare, P.Pal, Adv. Phye., 1971, 20, 161. ­ 317 ­ STRUCTURAL STUDY OP THE LABILE OHIRAL CENTRES OP Pt AMD Pd AMINO ACID COMPLEXES O.P. Slyudkln, I.A. Baidina, 3.V. Borisov State University» Institute of Inorganic Chemistry, Siberian Branch of USSH Academy of Sciences, Bovoeibirek, USSR

Recently there is growing internet in the chemistry of chiral complexes with biollgands. The action of metal complexes in vivo occurs among the opti­ cally aotive fragments. Thus the determination of absolute confi­ guration of asymmetric atoms and ring conformation of coordinated Mollgand ie of great interest and importance. X­ray study of several L­histidlne and sulphur­containing amino acid Pt and Pd complexes has been made.

The conformation of rings in [Pt HisH I^ and [Pd HlsH Cl2] has been shown to depend strongly on the hydrogen bond system. Planar coordination in Pd HisH Cl„ is symmetrically complemented to the octahedral one by the interactions between adjacent mole­ cules* In [Ft Methy­L­CysteineH С1л bond length of uncoordinated carboxyllo group "C­^Q­H Provei* *° °a similar.

Other spectral and structural correlations of the complexes in eolide are being discuaeed. ­ 318 ­ STRUCTURAL STUDIES Of CHIRAI, LrHlDROKPROLIHB PLATINUM COMPLEXES O.P.sl.TurtUr^ L.Kb.Hlnachera, H.A.Poral­Koahits

3tate Univeralty, naToeibirsk, Institute of General and Inorga­ nic Chemistry, Aoadeay of Sciences, Hosoow, USSR

The study of reactiona of the chiral Ft complexes with naoro Moaoleculea aa well aa elucidating of the relation be­ tween the stereochemistry and optical actlrlty of suoh compound* are the great practical and theoretical interest. The X­raya atudles were performed for different types of L­hydroxyproline Pt complexes: Ce[pt(HHypro)Clgl (I), trane(K.N)­

[Ft(Hy]iro>2].2Il20 (II), tranedC.N^l.CDJPtCHypro^Clg^HjO

(III) and trano(M,H;S,S)[pt(Hypro)2 |s»C(NH2)2l2].4H20 (IV). The Mollgand la H­aethylated and coordinated through N,0 donor atoaa in I| in bldentate coordinated in II ahd III; is monoden­ tate coordinated through H aton in IV. In the compaunda I­III the asymmetric atoa II haa aa usually the forcad S­absolute configuration. In the aonodentate coordinated ligand (the com­ pound IV) the ohlral atoa N haa H­abaolute configuration. The complexes here different size and possibility of con­ nection to bloatoleculea through hydrogen bonda and by aubatitu­ tlon of chlorine atoa*. Th* character of the hydrogen bonds in structures I­IV is different. In tha eryatala I th* hydrogen bonds occur direotly between th* complexes. In the compound* II­IV the complexes are connected by the hydrogen bonda through the water aoleoules with the participation of the oxygen atom of the carboxylate gro­ up, the chiral nitrogen atoa and the oxygen atom of the hydroxy­ group.ufhlch coabined to an asymmetric Cj» atom of the pirrolidiny ring. Th* ap*otral behavior of the complexes in aolld atate and the different character of the abaolute configuration of nitrop gen atoa, conforaation* and th* hydrogen bonds in these crys­ tals пате ъ*еп discussed. - 319- ROTATIOHAL CONFORMERS IN CRYSTALLINE 1,7-DICARBOLLIDE Hi (IV)

B.V. Sobolev. K.V. Kradenov, V.V. Volkov, S.G. Vasiljeva Inat.I^org.Cheit. USSR Acad,Sci.,Siberian Branch, Novosibirsk,USSR

The Raman study of nonlonic 1,7-dicarboIllde Ni(IV) (Pig.1) •hows that the usual picture with several rotational conformers in liquid or gas, but only one in solid is not a rule. At least two confonuers in cryetal result in doublet p(M-L) (L-J^-1,7-

1 C2B„H..) 175 and 186 am' in Raman spectra (Pig.2a). One from them (1) may turned ou.t in a laser beam (Fig. 2b) and no restora• tion occured during a long time, so the rotation in solid pt-eea is excluded. At contrary, the conformer (1) is more stable lr. solution (Fig.2c), but it is not a oase for solid benzene solu• tion (Fig.2d), obtained by rapid freezing. The benzene solution in porous glass give the picture as for solid solution (Fig.2e). The strong line (447 sm ) belong to both of the conforaera and has perhaps ERS-nature. This line disappears in parous glass.

Fig.1. Possible oonformere Fig.2. Raman spectra

of (•jr-l,7-02B9Hl1)2Ni(IV) ­ 320 ­ SOLID STATE ГАОТОМШИС TRANSITIONS IH MOHO'JUBSTITUTED GUABI­ DINES E.V.Sobolev, L.A. Beboludyakova Inetltute of Inorganlo Chemistry, IteSK Aoad, 8Iberian Branch, Novosibirsk, US8H

X­ray studies of soma guanidine derivatives (oyanoguanldlne, nltrogusnldlne eta.) both at rooa and low (80 K) tanperaturae show the only molecular fora In orystals with rather equal lengths (1,34 A) of СИ double and single bonds. Our optical da­ ta baaed on tasting (solution, ueuteratlon (Pig.1b), composi­ tions with porous glass) of extra vibrational lines in spaotra (for exeaple doublet V (0*1) in oyanoguanidine) give different results ­ at least three Individual atruotural forms in oyano­ guanllinti We oan vary oomposltions of solid oyanoguanidine on the «urfaos of porous glass and observe these varia­ tions 1» spectre (Tig. 1a,o,d). This Is also a rea­ son for exoludlng the well­known hypothesis of Fer­ al resooanoe nature of doublet and Davydov reeonan­ oe ae well. These results axe In good agreement with the solution studies. So we have suggested the solid stats tautomerto traneforn&tions In gua­ nldlne derivatives with the nlgratlon of double CB bond on guanldlne fregnant both at 300 end 80 I and perhaps at lower tenperatures• (fig. 2). This prooese is shown to be forbidden on the surtaoe of porous glaaa up to $00 K.

ГСУ ©­C FlK. 1 • ­N

^ О B-l Pig. 2 etc ­ 321 ­ THE CRYSTAL STRUCTURES OF SOME SUBSTITUTED CYCLOPROPANE COMPOUNDS I. S0tofte Structural Chemistry Group, Chemistry Dept, B, Technical Univer­ sity of Пептагк, DK­2800 lyngby, Denmark

The crystal structure of 2­p­Chlorophenyl­3,3­dimethyl­l­ methoxycyclopropene has been determined /1/. Since the substi­ tution pattern of this compound differs from that of other cyclopropene structures, a close comparison was not possible. Therefore, investigations of substituted cyclopropane and cycloprnpene compounds were carried out. The present three structures are part of this work.

The compounds are: 2­p­Chlorophenyl­3,3­dimethyl­l,1­dichlorocycloprDpane 2­Morpholine­3,5­dimethyl­l,l­dichlorocyclopropane 2 ­p­Chloropheny1­3,3­dimethyl­1,1­dimethoxycyclopTopane

A comparison of the crystal structures concerning the geometry of the cyclopropane rings will be presented.

/1/ Sdtofte I., Crossland I., Acta Chem. Scand. B£3 (1989),

4I­I ­ 322 ­ CRYSTAL STRUCTURE 0? A NOVEL COMPLEX OF Nd AND Ba WITH Лг ­PIOOLIMIC AC IP

P. Starynowlog Institute of Chemistry, the Wroclaw University, 14 P. Joliot­Curie Str., 50383 Wroclaw, Poland

Crystals of tetraaquahexsdecakls(2­pyrldineosrboxylato)dl­ barluatetraneodyadu» 7.8­hydrate were formed by addition of freshly precipitated neodymium oarbonate to a water solution of bariusi 2­pyridlneaarboj^late ( цб­pioolinato), and free <=t­piooli­ nio aoid. The crystals are monoolinio, P^/n, a»15.495(7), b> 20.296(12), 0­19.309(11) A, e­110.75(3)°; present R­4.1* based on 6250 non­iero refleotlons. The struoture consists of large oentrosyw»trlo oomplex aggregates and water moleoules. In tbe ooapla* there are four Nd and two Ba aatlons. The Nd ions dis­ play two different nodes of coordination. All are nine­coordi­ nate and surrounded by four <£­ploolinate anions bonded via oar­ bc^rlate o^rgen and the nitrogen atoms, whereas the ninth site .is oooupled either by a water molecule or by a oarbo^rlete oxy­ gen bridge. The barium coordination environment is entirely dif­ ferent and oonslsts of a water moleoule and 6 oarboxylato oxygens.

The distances (Hd­0OBT.b ­ 2.41 ­i..51 A, Nd­N ­ 2.63­2.73 A,

N4 2 5 я 2 ­°wat.r ­ ' * *• ^°ошЛ " ­70­3­16 A. Ba­0wat()r ­ 2.77 I) are within normal range. The waters of hydration are partly dis­ ordered] out of their nine sites fire are oocupled by less than one moleoule. ­ 323 ­ CRYSTAL STUDIES OF HETEROCYCLIC COMPOUNDS COHTAIBTHQ OBE OTYQES AHD TWO SITROCfiN ATOMS

A. Stepleh, tf. Derewenda, M. J. Grabowski Depart, of Cryet., Inst.of Chem., University of i6dfc, Poland R. Glinka Inst, of Chem. and Techn. of firu^s, School of Medicine, Zi6d&, Poland A. Tbozet Laooratoire de Kineralogie­Crlstallographle, Unlverelte Claude Bernard Lyon I, Vllleurbanne, France

Of the group of the title oompounda the last one has been H, »,­ditoeyl­6,7,B,13­tetrahydrodlbenBOl [b.g'J [1,4,6] oxadlaso­ nlne Investigated. There are two different aoleoulea in the asym­ metric unit. The tosyl groups are in an ezo, exo conformation In molecule 1 and In an exo, endo conformation in molecule 2 (Fig.1). The nine­membered ring is In a quasl­ohair conformation in both molecules. The compound shows a Diologloal activity.

Fig. 1. Comparison of the structures of molecule 1 (bold line) and molecule 2 (fins line). The coincidence of the two molecules was obtained by fitting together the hetero­ cyclic of the two molecules by least squares. The ato­ mic numbering scheme is given for molecule 1.

«­г - 324 ~ MOLECULAR STRUCTURE OP THE PRODUCT OF DESULFHUKAT10N UP A 9-MEMBERED OXADIZONINE

A. Stepien, E. YUajiaman, M.J. Grabowski Department of Crystallography, Institute of Cheinietry, University of Lodz, B. Brzezineka Institute of Chemiatry and Technology of Drugs. School of Medicine, Lodz, Poland 5. Lecocq Laboratoire de Mineralogie-Cristallographie, l'Unlvereite Claude Beraard 1, Villeurbanne, Prance

A tetrabenao-;'b,g,k,pJ [1,10,4,6,13,15] dioxuletraazacyclo- octadeca-!2,7,11,16 1 tetraene-6, 19-dione ia forming during the proceea of desulphuration of 6,7-dihydro-5H, I^H-dibenzo-Jb.gj Ll»4»6^J oxadiazonine-6-thione (1) /1/. This double molecule pro• duct, with respect to (I), possess a IB-membered macro-heterocyc- lic ring, showing a "saddle"-like conformation with two non-linear diimino eysteme. Two of four, fused to the macro-cycle, benzene rings are nearly parallel to each other. Tho product ahowa no biological activity,

/1/ Cllinka R. , Fiatoweka E. , Pol. J,Che'n. , £b, 259 (19B4). - 325 - THE CRYSTAL STRUCTURE OF 2,2,4,4- TETRAMETHYLGLUTARIC ACID

MR. Sundberg*, R. Kweras*, T. Stuiunen and T. Laiialainen

Division of Inorganic Chemistry, Division of Organic Chemistry, Department of Chemistry, University of Helsinki Vuorik. 20, SF-00100 Helsinki, Finland

Methyl esters of gluiaric acids liuvc frequently been used us models [or polyrocidyl mein-auylaies. On ihe other hand, variously substituted gluiaric acids ore known to form either helical or planar chains. The reasons leading to heliciry arc unknown, which prompted us •" the present study. The title compound was obtained as an oxidation product of 3,3,5,5- teuamethykyclopenune-l^-dione. The structure of the uifc compound was determined by single crystal diffraction methods. Crystal data for С Н О : M -IS8.22, onhorhombic, space %n>u\> Pbca (no. 61), d=12.160(3), fr-11.746(3). c=14.793(4) А, У-2Ч2Щ) A , Z-4, D =1303 gem , monochiomuted MoA'u. F(000)-888, Л-0.049 for 650 observed reflections. In the present compound the asymmetric unit forms helical polymer к chains running along \hc с axis, with methyl groups bent outwards. ­ 326 ­ STRUCTURE OK ГЧ , W, N**, N"­TETRAKTS [THIENYL METHYL­2 | ­ 1 , 4 , 8 , 1 I ­ rETRAAZACYCLOTETRADECANE AND ITS Си С I I ) COMPLEXES

Kinga Suwinska Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa. Poland

The macrocyclic ligand derived from J, 4, B. 11 ­tetraaza=­ cyclotetradecane (cyclam) is a very qood complexlng agent for Cu(II). The ligand shown below crystallized with Cu(NO^)2. The mixture of three types of different crystals (green, blue and violet) was obtained.

The crystal structures of the 'free' ligand and the three complexes will be presented. An attempt to expla­ ne the colour beheviour will be undertaken.

Crystal data: (1) 'free' ligand, monoclinic Pc, a ­ 11.^89. b ­ 6,018, с ­ 21.899 A. Д ­ 92.09°, Z ­ 2: (?) 'green' complex, tnonoclinlc P2^/c, a ­ 16.562, Ь ­ 19.394, с ­ 13.596 Л, 0 ­ 93.21'. Z • 4: (3) 'blue' complex, monoclinic C2/c, a ­ 14.912, b ­ 23.747, с ­ 24.352 A, fi ­ 99.06*, Z ­ 8; 'violet' complex, monocllnic Pc, a ­ 10.976, b ­ 8.850. с • 19.8B9 Д, D ­ 97.96*, Z ­ 2. In all the cases 1:1 complex forma­ tion Is observed.

,N N С ^ *'UO U^ ­ 327 ­ STETCTURE OF THE МОШЯЛАЙ COMPLETES OF AM&OSVLPURIC ACID WITH 18­ AND 15­MEMBERBD CROWN ETHERS a b K.Suwineka , Ya.Lipkowaky, Yu.A.Siiaoaov , A.A.Dvorkin, T.I.Malinowsky, M.S.Fonar, Bd.V.Ganin0, S.A.Katlyar aInstitute of Physical Chemistry, Polish lead, Sci. Warsaw, FPH; ^Institute of Applied Phyaics, Uolti^ Acad, •3ci^ Kishinev, USSR; CResearch and Design Institute of Uoполета, Tula, USSR Crown ethers form molecular complexes (host­guest type complex) with N­H, Q­H­, C­H neutral molecules. Strong КН...0 and 0H...0 and weak CH.,.0 interactions are responsible SOT the complex formation. We have studied the complexation in aminoaulp burlo acid ­ crown ether system» The crystal structurea of ami­ noacid inclusion compounds with cis­rsyn­cis­dicyclohexano­ld­ crown­6 (A), oie­antl­oie­dicyolohexano­18­crown­6 (B), l5rcrown ­5 (C) and monobenzo­l5­orown­5 (D) have been determinated by X­ray methods. The complexes exhibit 111 host­guest ratio* ,In all oases aminoacid exists in the form of 1ЦЙзо7 zwitter­ion, A and В are connected with the guest by NH...Q bonds having length interval from 2.81 till 3*04A* NH­­rgroup topologlc oor­ respondenoe to the 18­membered crown­ether (boat) cavity results in an energetically stable enough boat conformation. The lata*is characterized by 12 anti­ C­0 and 6 gauche­ C­C гоtamera respec­ tively. For the 15­membered crown ether oomplexes there is no topo­ logio correspondence with NH~(0Ht) groups and only two guest pro tone take part in boat complexatlon.Intramolecular Hrbonds can be interpreted as bifurcated ones, their lengths being in 2.74­ ­2.98A interval (C and D). for the l5­crown­5 (G) the arrange­ ment of 0­C fragments ie gauche^, 7 C­0 bonds present anti­, and remaining 3 C­0 bonds­a gauche­ conformation. D ie charac­ terised by 8 anti­ and 2 gauche­ C­0 and 4 gauche­ and 1 ois­ rotamererrespectively. The third gueet proton takes part in intermolecular H­bonds. ­ 328 ­ CRYSTALLOCHENICAL ASPECTS OF COORDINATED COMPOUNDS OF НЕТЛIS WITH AMIDES AND HYDRAZIDES OF PYRIDINE CARBOXYLIC ACIDS'

G.V. Tsintsadze. T.I. Tsivteivadze, Л.Р. Norinmnidze, T.N. Turiaehvili, R.Sh. Kurtanidze, Л.1. Kvitashvili V.I.Lenin Georgian Polytechnic Institute, InBtitute of Inorganic Chemistry and Electrochemistry of Acad.Sci. of Georgian SSR, Tbilisi, USSR Among numerous biologically active compounds and drugs which contain peptidic groups, amides and hydrnzides of picollne­, nico­ tine­ and isonicotinic acids (РЛ, NA, PH, NH and INH) attract attention as ligands. The aim of this work was to deter­ mine the structure of comploxee of manganese (II), cobnlt (II), nickel (II), copper (II), zinc and cadmium with the mentioned or­ ganic Uganda and acidogroups (halogenides, paeudohologenideo, cerboxylate, nitrates, sulphates) by method of X­ray structural analysis, establishing the type of coordination of acidic and neut­ ral Uganda dependent on the central atom nature, it wae of inte­ rest to trace the dependence of complexes structure motive from nature end eterio peculiarities of ligands, search for correlation between structure and biological activity of complexes, which one enables to establish possible fields of their practical use. On the basis of structural date, analysis of the mentioned metallic complexes it is shown that organic ligande may fulfil tnonodentate (NA, INA ­ nitrogen of heterocycle), bidentate (PA ­ nitrogen of heterocycle and carbonyl oxygen; NH, PH, INH ­ nitrogen of amino­ groups and carbonyl oxygen, i.e. fivemembered metallocycles) and threedentate (INH ­ nitrogen of aminogroups), carbonyl oxygen, i.e. five­membered metallocycles and nitrogen of heterocycle) func­ tion, whereas dependence of composition and number of central atoms­complex formings, acidoligands ­ monodentate (halogenides, carboxylats, nitrates, pseudohalogenides) or bidentate functions (peeudohalogenides, carboxylats, nitrides, eulphateB). Cryetallocheolcel aspects and bioactive properies of studied compounds (ligand surrounding of central at опт nnri blonctivity) are considered. ­ 329 ­ STHUOTUHii AND CONTORMATIONAL STABILITY OP B.ErGEHMAGRANOLIDES K.M.Tard,ybekoy. S.V.Idndoinan, T.V.Timofeeva, Yu.T.Struohkov Neameyanov Institute of Orgaxjelenent Compounds, UBSB Academy of Scienceв, Moacow, USSR

Ал X­ray diffraction stiiy of 5 sesquiterpene lactones with the germacrane famework, viz. ealonitenolide(I), hanphilline(II), 8­(4­hydroxy)­angelathydroxy­i ,E­gerniacrB­l(10),4,ll(l})­triene­ ­6,12­olide(III), tamirine(IV.. and 6­acetoxy­l;5­meto3cy­E,E­ger­ .was carried out. macra­l(lO),4­dMepojqr­B,12­ol: deWV^In the molecules I­III the germacrane cycle Is linked to the lactonic cycle via a оошшоп 06­0? bond and in the molecules IV­V via a common 07­C8 bond. Ihe 10­membered cycle in I­III anc* V Is in a chair­chair conformation

( D513D ), whereas in IV it ms a boat­boat shape ( D,­, Dlif). Ihe Isotonic oycle in all cases has the 7* ­envelope conformation, the only exception being observed for I, wherein this oyole io in a bfi ,7•<­halfmohair conformation. Ihe equatorial eubstltuenta at the 0} and OB atoms in I­III со not exert any influence on the conformation of the lCb­membar 1 cyole. Earlier /1/ it has been :ound that germacranolides may ad­ opt either chair­chair (^D,­, Э14'), ohair­boat (IC^P V) °r bo­ 14 1 1; at­»boat (­.Л^ЦС and ^D5i 14) conformations. The force field calculations oarried out in tl e present study have shown that a chair­ohair conformation of б£ ,7л (H)­germacra­6,12­olidee Is more stable than any other ooi_foi_»ation of the 10­membered cycle, the energy differences дЕ being in the range of J.7­5<5 koal/mo­ le. For 6 4 i7ot (H)­?germacra­6 12­olldes the ohair­boat conforma­ tion ie the most fovourable, ith лК=2.0­4«9 kcal/mole. For 7 Л ibA (H)­germacrar8,12^olld 3 all abovameationed conformations have approximately the same e orgy (дЕ*1.5 koal/mole), whloh ag­ rees with a higher lability с the lO­membered cyole in this se­ ries of oompounds. On the ave age .the conformational energy of 7d. ,8m(H)^germacra­B,12­olid3a is by 6­7 kcal/mole higher than tuat of the ?•< ,Hp (H)­isomer J.. Probably it is one of the main геааопв for an absence of 7

/I/. Samok 2.,Harmathe J., Oc 1.Czech.Cbea.Oommun. £J, 2779(1978}

42­1 ­ зэо ­ STRUCTURAL STUDY OF 2­DBVfETHYLAMlNOETHANOLATO BRIDGED TETRANUCLEAR СОРИЩП) 3­BROMOBENZOATE COMPLEX: [Oi^^BiO^C^gNO)^ U. Turpemen, L Mutikainen, R. Hamfllainen and P. Lumme Division of Inorganic Chemistry, University of Helsinki, SF­O01O0 Helsinki 10, Finland

In a systematic investigation of tbe reaction between Сц(П) carbaxytaes and 2­dialkylamino­ ethanols, mooomesic, dnneric, tetramerie, hexameric and nonameric complexes have been synthesized and structural})' characterized by X­ray crystallography [1,2]. The title compound WHS obtained by stew evaporation of etbanol solution containing Cu(Q) 3­bromobenzoete and 2­dimethylaminoetnanoL Dark

blue crystals of Cui(C7H4BrOi)4(CtHloNO)4 are triclinic, space group PI, a=l4.487(5), 6=14.978(6), c­15.081{5) A, a­118.46, 0410.19(3), 7­8M6P)0, Z=2, K­2664{2) A3, final R value 0.049 for 3251 significant reflections.

The «гостите consists of discrete molecules, which may be considered as constructed around eight­

membered Cu4Ot rings of cubane­type structure. Within tbe Cu404 core tbe Cu­Cu distances vary between 3.119 and 3.795 A. Each Си atom Is surrounded by two ethanolato oxygen atoms, a cnrboxyl oxygen atom and an amino nitrogen atom in a nearly square­plinar arrangement with avciage Cu­O and Cu­N bonds of 1.94 and 2Л5 A Tbe axial sites rt acb Си atom are occupied by an ethanolato oxygen atom and an oxygen atom of tbe carboxylate group with Cu­O distances of Z44­2JS9 A.

[1] Turpemen U, HlmlUinen R, Recdijk J. Inorg Chim. Acta 134, 87 (1987). [2] Turpeinen U„ Htmillmen R, Reedijk J, Inorg. Chim. Acta 154, 201 (1968). - 331 - AN ENERGY HODBL POR PROTON ORDENINC IN SBQRT INTRAMOLECULAR BTDKOCEN BONDS P. Vanhouteghem, A.Т.Н. Lenstra. U.I.Antverpen, Dept. Chemistry, Universiteitsplein 1, B-2610 tfilrljk, Belgium

Most reviews on short intramolecular H-bonds are restricted to a phenomenological partitioning scheme. McWeeny, e.g, has pointed to a relation between H-positions and the overall acceptor(A)-donor(D) distance. This correlation has been investigated further by Olovsson and coworkers. Apparently, a large variation in the shott H-bonds occurs (see e.g. hydrogen fflaleate studies with D...A-2.4A). They are symmetric or very asymmetric, suggesting a large sensitivity of the H-bond to external or coordinative influences. We studied these effects more closely. The dominance of ionic interactions vas our first hypothesis. Using the Coulomb logic the sequence

43-2 332 ­ CRYSTAL AM) MOLECULAR STRUCTURES OP TWO CARBONYL CLUSTER

COMPOUNDS IjH­ H)(JU­ OH)OB3(CO)10 AMD (_/U­ OH) Oa2Fe(CO)10

A.V. Virovetz. B.V. Podbere2skaya, V.P. Klrin, V.A. Makeakov Institute of Inorganic Chemistry, Acad.Sol. of the USSR, Siberian Dept., Hovoeibirak, USSR

Two trinuolear cluetera (JU­H)(_/4­OH)Oa,(C0)1o (I) and

(JU­OH)2OBgPe(0O)10 (II), have been studied by a single crystal X­ray structure analysis. Both clusters contain reactivable J4 ­ OH­groupB which allow complexes to be chemically fixed on a eur­ faos of inorganic bparers ав well as organlo ones for using in catalytic ргосеввее* Single crystals I and II have teen prepared from a mixture

(111) C6H12 ­ CHjClj and from CHC1, respectively. The data have been obtained using automatlo diffractomcter "Syntex P2," (9/29

eoan type with variable speed, 20иах «50°, A HoK ). Unit cell parameters arei t 0)( ­107,06(4)», V­1593t1) Я3, space group

­3 (ацн^кьт, P2,/n, Z­4, fc&lc-3,be g.cm , R­0,035 for ТЖ ­itqg T 10'° '•hkl' j Ft(60), 8­14,009(6), Ь­1Э.ЗЗО<4>, c­9,511(2) X, /i Л ­103,69(2), Ji­8'l,83(2), <".1o2,22(3>°, 3 (COIjin^^onEn, V.1699(1) X . врасе group PT, Z­4, f calc­ m ­3 2,96 g.cm , R­0.091 for 2004 Ihkl. Tha unit cell in the crystal structure II contains 2 Independent molecules with the ваше geomntry. The cluster I has Nvai­40 and closed metal frame. The unit cell parameters of I are simular to

tHbee of (jU­H)(^<­OCH3)Oe3(CO)10 /1/, but the molecules have unlike arrangement about symmetry elements. The cluster II has И ,­50 and opened metal frame. The Os­Os bridge* bonds are 2,809(1) and 3,050(1) X for I and II, respec­ tlr«ly. An Influence of nature of bridged ligand on crystallocheml­ oal peouliarltlea of M«­cluster os discussed in comparison with

(j*4­H)2Oe3(CO)10 (Os­Oe bridged 2.683 ff)/2/ . /1/ Churchill M.R., Waeserman H.J., Inorg.Chem. ^J., 2391 (19i">). /2/ Broach R.W., lillisme J.B., Inorg.Chem. W, JH (1П7Ч). ­ 333 ­ STRUCTURE OP 3­(BESZYIiO!KCASBOirCLMETH,n.)­BEN2;OTKlAZOI.INE­2­OHE

V. Vrabel. J. LokaJ, E. Kello, V. Koneony Department of Analytical Chemistry, Paoulty of Chemical Techno­ logy, Slovak Technical University, Bratislava, Czechoslovakia A.C. Batsanov, Yu.T. Struchkov A.N. Nesmeyanov Institute of Organoelement Compounds, USSR Aoademy of Sciences, 28 Vavllov str., Mosoow 117B13, USSH

Derivatives of the benzothiazole present a new group of ooa­ pounda exhibiting a biological growth aotivlty of plants, excep­ tionally in higher concentrations the retardation activity as well. Prom the above given derivates the 3­(benzyloxyoarbonyl­ raethyl)­benzothiazolln­2­on haa some remarkable properties.

Crystals of title compound are monoolinic, space group P21( unit oell parameters a­4.714(0.5), b.10.914(1), o»14.419(2) I, *> 3 3 94.29(1)°, V.739.7(D X , Z­2, Dm­1.33, Dx­1.34 Hg.m" measured by flotation In гпЗОд solution. Intensities of 1006 independent reflections were measured on a Hilger * Watts Y/290 dlffraotome­ ter (Mol^t, graphite monoohroraator). Struoture was solved by dl­ reot methods employing 151 reflections with )E/ >1.3, refined by full­matrix least squares with anisotropic thermal parameters for nonhydrogen atoms, using 786 reflections with I>2.0(T(I). Hydrogen atoms were located by a difference synthesis (coordi­ nates and thermal parameters has been fixed). The final R­0.043, wR.0.041. The crystal contains disorete molecules of the title oon­ pound. The shortest lnter^olecular non­bonded aontacts are 0(2)...H(82) 2.28 and 0(2)...H(61) 2.48 t. The benzothiazolin» system is practically planar, the maximum deviation from the least­squarea plane being tor N 0.046(6) St. This plane Is tilted by 145.4° with rsspeot to the phenyl ring. The six C­C bonds in the phenyl ring vary in length from 1.280 to 1.390 A, thus indi­ cating a significant distortion from a standard benzene ring. ­ ­ 334 ­

SrEREOELECTRO NIC ДНП STfRtC INTERACTIONS IN 2­A MINO­1, 5,2­ОГО X A­ PHOSHHORINANE5 W.H.Wplf, T.J.Bartczak Institute of General Chemistry, Technical University of Lodz" ­ Palitechnika tddzka Zwirki 3:., 90­924 Lodi, Poland.

Stereoelectranic Fffects are among the most important factors governing con­ formational properties of 1,3,2­dioxaphosphorinanes. They outweight in most cases the usual steric interactions. In present work we report analysis of these effects in

2­amino­l13)2­dioxaphosphorinanes investigated Dy x­ray crystallography. Eleven structures have been solved by us. Twenty structures were selected from literature data using C50B. Several statistical tests have been applied to compare conforma­ tional parameters between compounds with equatorial and axial amino substituents. 5tereoelectronic effects «ere firstly explained on the basis of dipole­dipole inter­ actions. However, this theory could hardly explain the characteristic pattern of conformational parameters observed in dioxaphophprinanes. Presently, these effects are explained using frontier orbitals or hyperconjugation. ЛД these theories as aoplied to dioxaphosphorinanes will be presented by us in detail. In dioxaphospho­ rinanes with axially oriented P­N bonds the most stajilizing interactions are those between endocyclic oxygens np­and antibonding €* orbitals of exocyclic P­N bonds. This effect increase electron density around N atoms. Elertron withdrawing sub­ stituents bonded to nitrogen stabilize this additional charge, increase anomeric interactions and therefore tend to occupy axial position in respect to the dioxa­ phosphorinane ring. On geometry grounds there are also possible interactions between lone pair ortatals localized on N atoms and anti­bonding orbitals of exocyclic P = X bonds (X = 0, S, 5e). However, the latter bonds are highly polar with X atoms carrying negative charge. Therefore, further growth of electron density around X strongly destabilizes molecule. Stereoelectronic effects in dioxaphosphorinanes with equatorial P­N bonds are much weaker. Orbitals n^­ of exocyclic oxygens interact with antibonding orbitals of adjacent P=X bonds. These interactions increase nega­ tive charge on X and are disfavoured because of reasons mentioned above.

This work is a part of Polish Ministry of National Education project RP.n.10. - 335 - THE CONFORMATION; OV 2-CYAHO-2-PKENYL-SPARTEIME CATIOH

Irena Wolska and Teresa Borowiak Faculty of Chemistry, Adam Mickiewicz University, Gnmwaldzka 6, Poznan, Poland

The crystal structure has been eolved in order to determine the configuration of A/B and C/D quinollzidine ring junction, the orientation of the substituentB in A/B quinolizidine system and protonation of the free base. The X-ray data show that the configuration and conformation of the 2-cyano-2-phenyl-cation are as follows: trans A/B chair/ chair - cis C/D chair/chair, the phenyl substituent adopts the equatorial orientation and the 'cyano-group the axial orientation» Unlike in sparteine perchlorate, the nitrogen atom N{16) has been protonated. As a result of protonation, an intramolecular hydrogen bond N(16)-H(161) ... N(I) has been generated and its parameters are comparable with those of sparteine perchlorate. ­ ЗЭ6 ­ KAXH FEATURES Of CRYSTAL OKSMISTRY OB 1IETAL ALKOXIDES H.Ia.TuroVB, E.P.Turevakaya, V.G.Kossler, N.I.Kozlova, I.V.Hogova, A.I.ianovaky. Yu.T.Struchkov Moscow State University, Chemical Department, Йовсож; Nesneyanov Institute of Organoelement Compounds, tioacow, USSR

Practical applications of metal alkoxidee tt(OR)n ав etartlng ooapounds for preparation of widely used in modern technology me­ tal oxide materials have had lately a stimulating effect on the structural etualos of alkoxides. Several hundreds of alkoxide struotures have been reported to date. Heverthelesa oaly a limited number of structural types accommodating "simple" or bimetallio alkoxidee, alkoxooomplexee etc, have been found, • 1, Uonomerlo alkoxide moleoules are known only for bulky R groups or for polydentat* alkoxygroupa capable of formation of •table chelate complexes, e*g. octahedral MoOp(OC­,H^OMtO^.

2. Dimerlo molecule» with two bridging 0H­groups(/Mb(0MeW2 type) or blnuolear complexes with the UsM triple bond, e.g. vari­ ous dimolybdenum compounds, are most numerous. J. Cluster triangular and cyclolinear chain molecules, such as

XAl/(0Pr^)2(AlX2)/o, where XcOPr or 01, are moet remarkable, among trimeric oomplexes* 4. Xetrameric alkoxldes belong either to cubane­like comple­

г+ xes, e.g. /Ц(54(ОМе)6(иеОН)10/ (/ТЮМеД type) or to the comple­ xes of Ai(0Ue)4/4 type, such as /U."fb(OEt)5(OHV2« /NaWO(OEt)5 • StOHA,, differing from the cubanee by the arrangement of two pairs of fused pairwlse coordination polyhedra of metal atoms. 5. Oligomerio molecules with n>4 may be represented by metal oxo^alxoxyderivatives, e.g. PbgO^OPr1)^, octahedral cluster with oxo­ and alkoxvgroups centering alternately triangular faces,

1 А /SaMo204(OPr )5'Рг ОН/г, involving two dimeric MOgC/n­OR), groups, or decamere lllo4w4­O)2yw}­O)20vi­OEt)14(OBt)b (a=Al,Fe), products of partial pyrolysia of corresponding athylataa.

6. Alkoxidee M(OS)a with R=l!e,Et, L!=Ll­08t Mg­ba,Cd,Ni(II), Ie(II),kn(II)t Al,Qr(III),Fe(ITI) form polymeric layered structu­ re» analogous to etructuree of LiOK, Hg(0H)2, and Al(OH),, respec­ tively, the separation between the MO^ or M06 layers being in­ creased by approximately double linear size of the alkyl угоир. ­ 337 ­ CRYSTAL AND MOLECULAR STRUCTURE OF CRYSTALLINE COMPLEX

^[NS(O)NSO?] 3.SO^ (PNF2>4 Z.Zak. T.Qlowlak", and K.Sernik Department of Inorganic Chemistry, J.E.Purkyne University, Kotlarakii 2, 611 17 Brno, Czechoslovakia ; ^Institute of Chemistry, University of Wroclaw, r.Joliot­Curie 14, 50­383 Wroclaw, Poland

The crystalline complex of (PNF2)4 (I) with [NS(0)NS02]3.SO, С J Г > w*e obtained ae one of the products formed uy the reac­

tion of (PNF?), with­SO­,. The crystals are monocllnlc, и»

14.026, Ь»15.61У, c=21.852 i, p­100.98°, apace group P 2г/с, Z=8. The molecular structure of (t) agrees well with the

. ,'ucture of pure (PNF2), /1/, but (JI) repreeenta a new structural type amongst sulphurrnltrogen Gompounde. The cage­ like molecule of (JI) conslate of one Bix­ynember«d (NSO), and one eight­membered (NSO?).S03 ringe Joined oy N­S bonds. The six shorter N­S bonda (av. 1.573 R) in the (NSO), ring belong to N 'e with a coordination number 2, each of the three N atoms of the (NSOjKSO, ring form three N­S C­bonds (av.1.726) and carries a lone electron pair. If the ­0­S(02)­ linkage were removed from the (NSO2)­S0, ring, the resulting (NSO),

H n (NS02), cage would be comparable to icaane , a recently prepared hydrocarbon C12H1B /2/.

/1/ H.UcD.Kcaeachln.F.R.Trooans, J.Chem.Soc. 1461. 4777 /2/ C.A.Cupae.L.Hodakowakl, J.Am.Chem.Soc. 21,4668(1974)

43­1 ­ 338 ­ ГНВ STRUCTURE О? ЯИГ 1IETAL COMPLEXES OP o­SEMIQUIHOHE AHD CATE­ CHOL ТЕ LIGAHDS WITH UHUSUAL PHYSICAL PROPERTIES. X­RAY STRUCTURAL IHVE3TIGATIOH. L.K. .iakharov.Yu.H.Saf'yanov.Yu.T.Struchkov.H.I.BochkoTa Inst tute of Organometallic Chemistry,Acad, Sci. of the USSR, Oorlcy; Phyt co­technical Institute, Gorky, USSR

AB a part of our systematic «tudy on crystal structures cf met' ^ complexes with o­semiquinone and catecholate ligande, the X­ray structural investigations of seven new complexes have been carried out: JA ­4,4 ­bipyridyl­bls(3,5­di­t­outyl­1,2­semiqui­ none)Cu (I), tetra (pyrldine)(3,5­di­t­butyl­1,2­catecholate)Cu (II . ( 3,6­di­t­butyl­4­chloro­1,2­catecholate)(3,6­di­t­butyl­ 4­cl Loro­.1,2­eemiquinone)(t6trahydrofuran)cuprate bis(I,N'­di­t­ but; l­1,4­di»*»buta­1,3­disne)Cu (III), (2­methoxycyclocctene­ 5­У H3,6­di­t­bu­tyl­1,2­semiquinone)Pd (IV), (triphenylphos­ pnii. э) (2­methoxyoyclooctene­5­yl) (3,6­di­t­butyl­1,2­semiquinone )­ Pt (V), tricarbonyl(triphenylphosphine)(3,5­di­t­butyl­1,2­ o«ml quinone )Ro (VI), dicarbonyl(3,6­di­t­butyl­4­chloro­1,2­ »«m­quinone )Rh (VII). The oryetal structure of I consists of polimerlc chains in

which the planar Cu(3,5­di­t­butyl­1,2­semiquinone)2 fragments are bonded through 4,4t­bipyridyl molecules. The molecule of II has the tatramaric structure. The unusual five­membered coordi­ nat on of the Pt atom was found in the molecule of V. In crys­ tal structure of VII the planar molecules are packed in columns with the Rh...Rh bonds directed along the packing axis. The investigated crystal and molecular structures are discussed in terms of their relations with the physical proper­ tie of crystals (dichroism of I, antiferromagnetic exchange int raction in II). ­ 339 ­ i­RAY INVESTIGATIONS OP THE PRODUCTS OP INTERACTIONS OP

H~Ge­H£­GeR3 (R=Ph,C6P5,CP3) WITH COMPLEXES OP TRANSITION METALS LaJ.Zakharov.Yu.T.Struchkov^.I.Bochkova^u.H.Saf'yanov, A.I.Yanovsky. Institute of Ortianometallic Chemistry , USSR Acad. Sci, Gorky; Institute of Or^ano­Element Compounds,USSR Acad. Sci. iloscov/, USSR

X­Ray investigations of the products of interactions of

К­,Се­Д_,­Сс­Й.­Н0­£з!*,3 CR=Ph,CgPc,CP­(R=Ph,C6P5,CP , ) with complexes of transition tals have been carried out: GeK­, I 3 NiCp / \ lit; „ Щ* HK \ / X, NiCp GeR,

^ u

1­ is suuv.:., t:.,••. . ­lit proauctjj of these interactions may oe i.eul.al aii .;ел1 иь ±чли.с. uoi.tpum.d.;­. J. .ч.а ±i ­л­шь.^. ^ , and -j-aieutber laetallacAUin .ърсс eiioiy. C^:.<;.uimd;; III­V1 wave

r.he union with v.ri^ui.al ^oo­dij^tLii­ui ^Г u:.o HtJ uiui.i.

43­2 ­ 340 ­ STRUCTURAL PECULIARITIES OF MOLECULAR CRYSTALS OP CYCLO (meta­ AND para) PHENYLENESSULHIIDES

I.A. Zamaev. I.V. Razumovskaya, T.V. Timofeeva, V.E. Shklover, A.V. Astankov, V.I. Nedel'kin, V.A. Sergeyev Nesmeyanov Institute of Organoelement Compounds, USSR Acad. Scl., Moscow, USSR

The X­ray structural investigation of the molecular crystals of cyclopoly(ra­phenylenesulphldes) I­III and cyclopoly(p­phenyle­ neeulphides) VI­VIII hae been carried out (the structure of penta­ mer V was studied ez ­lier: M.L.Kaplan, W.D.Reents, C.S.Day. Cryst. Struct.Commun., 11,1751(1982), Crystals VI and VIII are the host­ gueat type I: I complexes (gueot­CHCl, and (Me2N),P0 for VI and

VIII respectively; in the ТаЫб dcalc without guest is given; dc with guest in bracke a). The bond and torsion angles of indepen­ dent molecules in structures Г and VII differ by 1° and 2­20°, respectively. In II and III of different crystal modicstionB of the same compound the corresponding differences are 1­20°. Accor­ ding to the force field calculations each of the molecules I­VIII has only one minimum cf potential energy corresponding to the con­ former observed in a cryetal. Optimization of conformation of ­iso­ lated molecules I and II started from the geometry of symmetri­ cally independent molecules in crystals has led to the same con­ former corresponding to the energy minimum in both cases. The den­ sity of crystal modlfic scion III is higher than that of modifica­ tion II due to the stac. lng interaction of molecules.

Compound n Space Z Bond angles Bond distances d„ (g/сщ*) group CB0 (°J 8­0 (X) " I 3 00 16 98.1­104.4(4) 1.763­1.801(8) 1.43 ^•Sfall 4PI 4 103,7­105.0(2) 1.757­1.799(5)1.37 Jill 4 P2,/n 102.6­104.9(2) 1.761­1.740(5) 1.41

IV 4 Ргх/о 4 98.4­ 99.0(1) 1.776­1.792(3) 1.40 KJ=­i V 5 G2/o 8 100.1­104.0(2) 1.772­1.783(4) 1.37 t>^"JilVI 6 P2J/0 2 101.9­103.0(2) 1.772­1.783(4) 1.21 [I.43] JVII 7 Pl 8 00.7­107.4(4) 1.752­1.801(8) 1.43 Vlll 8 P42J/0 2 ­01.7­105.6(4) 1.773­1.789(8) 1.12 |1.43] ­ 341 ­ STRUCTURE PECULIARITIES OF fAROILOXIMETIIILI DI= AND THRF.EFLUORO s. II LANES ­ COMPOUNDS OF PRNTACOORDINATE SILICON, r:.A. Zelbst, A.A.Kashaev, M.G.Voronkov Institute nf organic Chenlstry, Siberian Branch of USSR Academy of Sciences, Teachers Training, Institute, Irkutsk, USSR

The results of x­ray structure analysis of compounds with в

general formula X­CgH^COYCMjSlF­j fx=4 ­H,­F,­CI,­Br, 2­Clt Y­0f

4r NCH­), derivative of nentacoordln.ite silicon with the bond Si ­ F and the inner ­molecular bond С ­ о ­ SI, have been analysed. The influence of substitution character in silicon atoms and carbonyl group as well as benzol cycle the inner­molecular bond 0 ­ Si value has been teefced. The lenqth of the bond varies from о

1,913(4) to 2r216(6) A. In all our compounds the silicon atom Ьав a somewhat distor­ ted trygonal­bipyramidal fTBP) coordination, the bond о ­ Si being axial. The other axial bond in all cases in one of the Si ­ F bond». As it was predicted,the 0 ­ Si bond lenght is moat influenced In distorted molecules located in the vicinily of the silicon atom. It Is shown, that the decrease of fluorine atoms in silicon reduces the О ­ Si bond strength. The pentacoordination of the silicon atom in (aroiloxiroet­ hil)dl ­ and threefluorosilanes can be explained more decently in forms of the three­centre four­electrons bonds theory! in molecu­ les F and 0 atoms form a hypervalent bond with a silicon atom. In terms of this theory the geometry properties of the coordinative oolyhe ron of the silicon atom can be easily explained. S;nce molecules are of an approximately equal size and have stretched gabitus they are stretched alonq one direction. For a number of compounds there li an intermolecular interaction, and \t is eer­scially significant in CH.SOCMjCH­SiF^ molecule. ­ 342 ­ STRUCTURE ADD POSSIBLE WAX'S OP FORMATION OP HITRILES BASED OH SYMH­TETRACyANOETHANES AND ITS DERIVATIVES

A.B.Zolotoy.A.I. Prokhorov, S.V. Removalokhin, Р.И. Lukin, O.E. Kasakin and L.O. Atovmyan Institute of Chemical FhyBicB of the USSR Academy of Sciences, Chernogolovka, Hoscow Region, USSR

Continuing a series of studiee on the structure, properties and ways of formation of nitriles based on tetracyanoethane (TCET) /1,2/ we have determined the X­ray structure of (I­VI)­ products of the following reactions: R )c=o • H,N. ,­N* (I) ffl) ce P.* C\N / CN ii­C­ ­tf­H + ­Ph­=­C0R­ / CN NH, CN CNCN/.V«­H, ' CN РМШ) Ph ЫС CN ^w NC CN M A ­ HC­C­CH(Ph) —­ Jl II l4 Y~jf (лп- IMF i* CNN=C(b)Ph Ph =C(H)Ph H (Ufa) CN CN

CN ff " XjwLcOjft

NH? H Ж NH ff»i­C3H7/ ?

С0гСгН5

The following questions are studied: stereochemistry and re­ gioBpecificity of reactions in the (I­III) formation, structural factors enhancing cycle opening (III) and anionic intramolecular migration of the Fh(n)C=N~ group leading to (IVa), conformation of moleculas (III), (V), (VI), display of conjugation effects in the geometry of (I), (II), (IV), the role of the structure, me­ dium and base for the formation of (V), (VI), /1/ S.P.Zilberg.Q.E.Hasakin et al.ah.Organ.Khimii,24,1014 (1988). /2/ A.B.Zolotoy, S.P.Zilberg et al.In: Problemy kristallokhimii, Kauka (1989). 4. BIOLOGICALLY ACTIVE SMALL MOLECULES AND BIOLOGICAL MACROMOLECULES

Oral presentations ­ 344 ­ ТЬе Strucuture of Fooi­and­Mouth Disease Virua

D. Stuart, R. Acharya, E. Fry, D. Logan, Laboratory of Molecular Biophysics, University of Oxford, Oxford OXt 3QU, England.

G. Fox, D. Rowland», F. Brown; Wellcome Biotech, Langley Court, Beckenham, Kent, ВЕЗ 3BS, England.

Tbe structure of cry it all of FMDV (serotype 0, BFS I860) baa been determined at 2.flA resolution (Acharya el a).,1989a). Refinement against all data (Including weak and negative intensities) in the range Б­2.9А using XPLOR, has reduced the R­factor to 16% with an RMS deviation in bobd lengths from ideal values of 0.017A , with no manual rebuilding of tbe model.

The overall structure of the capsid and the arrangement of the proteins within it are similar in gross terms to that described for other picornaviruies, however, there are a number unique features. The canyon or pit found in other picomaviruses appears to be absent; this has important consequences for cell attachment. The major immunogenic sit* (the so­called FMDV loop, residues 140­160 appro*.) forms a disordered protru­ sion. This offers a satisfying structural explanation for the peculiar success of synthetic peptide vaccines against FMDV which might have broad implications for the design of such vaccines (Acharya et al. ,1989b). Several lines of evidence from our work and that of others have implicated this FMDV loop in cell attachment and there is evidence that the cellular receptor for FMDV is a member of the inlegrin family.

Recently we have determined the structure of two mutant viruses which escape neutral­ isation by a monoclonal antibody thought to bind tightly to the FMDV loop. These results will he presented.

References

ЛсЬагуа R., Fry E., Stuart D., Fox G., Rowlands D. and Brown F. (1989a) The three dimensional structure of foot and mouth disease virus at 2.9A . fl»ture (London) 337, 709­716.

AchexyaR., Fry E., Stuart !>., Fox G., Rowlands D. and Brown F. (1989b) Implications of the three dimensional structure of foot and mouth disease virus for its antigenicity and cell attachment .Vaccines B9. Cold Spring Harbor Laboratorv^in press). ­ 345­ CRYSTALbOORAPHY OP 1ЯТАСТ RIBOSOHAL PARTICLES

A. yonath1*2, Г. Prolow1, 3. Welnetein1,3, Z. Berkovitoh­Yel­ lln1,J, K. Bartela2, W. Bennett2*3, 0. Weber2, H. Hansen2, U. Evers2, N. Volkmann2, K. 3te,;en and H.G. Wlttmann3 Dept. of Structural Chemistry, Welrmann Inst., Rehovot, Israeli Hax­Planok­Reeearch­Unlt for 3truo. Hoi. Biol. Hamburg, FRO; 3Hax­Hanok­Inst., for Hoi. Genet lea Berlin (West)

Diffracting cryetale have been grown from aotive bacterial rlbosomes (2.3x10 daltone), their large (1.45x10 ) and email (8.5x10 ) aubunlte. Crystallographio data are currently being oollected with eynchrptron radiation at cryo­temperature (85 K) from the following systemBi whole rlbosomes; large eubunits of wild­type and mutated bacteria; ohemlcally modified large and small subunlts (which epeolfloally bound heavy­atom clusters); and complexes of rlboaomal partlalea with oomponents of protein biosynthesis, namely tRHA and short nasoent protein chains. The beet crystals are grown from rlboaomes of extreme halo­ phi lea and thermophllee. The highest resolution recorded so far о as single­crystal rsfleotlons is 4.5 A, and as "powder ring" or "fiber arcs" • 3.5 A. Monofunotional reagents prepared from heavy atom clusters, undeoagold and tetralridlum, have been used for soaking experi­ ments as well as for apeolflc binding either to expose ­SH groups on the surface of the ribosoaes or to an Isolated rlbosomal pro­ tein which was, in turn', reconstituted Into mutated ribosomea, lacking this protein. The modified partloles have been crystal­ lised, and crystallographlo data have been collected. Approximate models have been reconstructed at 30­47 A , using diffraction information obtained from tilt series of two­ dimensional sheets examined by electron­aicrosoopy. These show the overall shape of the ribosome as well as separation between the two subunlta; the presumed location for protein biosynthe­ sis; a possible binding site for mRHA and tRHA and a tunnel which nay be the exit path of the nasoent protein chain. Attempts to place these models in the various unit­oells will be discussed.

44­1 ­ 346 ­ CRYSTALLIZATION OF OLIGONUCLEOTIDE IN DIFFERENT CONFORMATIONS ВТ PHASE DIAGRAMS TECHNIQUE Lucv Ha}ini:\a and Valya TereshXo Institute of Crystallography Academy of Sciences of the USSR, Leninsky pr. 59, Moscow 117333, USSR

Experimental phase diagrams revealing the region of existance of aicxocrystals in some oligonucleotide duplex­­spermine systems

mere obtained in coordinates Sn,D, «here Sn and D„ are concentrations of spermine and duplex in a system. All diagrams are wedgelike. The slope of upper branch is determined by oligonucleotide length 2ц (in base pairs) as k='/(n­1). The upper and lower branches when extrapolated to D =0 and S =0 respectively give the solubility of the precipitated complex. The presence of №D, MgCl and KaCl was shown to change the shape of diagram in specific way.

The model explaining the features of the diagrams for oligonucleotide duplex—s'permine system is proposed. On the basis of the model the analysis of the experimental phase diagrams has been carried out and the parameters which characterize binding of spermine and Hg * cations to duplexes have been estimated. The multiparameter crystallization space has been shown i:o be divided into subregions, each of which corresponds to the precipitation of a given duplex complexed to a certain number of spermine molecules (sometimes this complex also contains Mg *).

These results were used in crystallization of (pCpG) . Five crystal forms of the hexamer have been obtained which belong to different space groups. The space groups and the unit cell parameters of these crystals, as well as the location of the base­ stacking reflections, indicate that the oligonucleotide is able to assume different double helical conformations. It seems quite likely on the basis of the preliminary consideration that among these crystals there are examples of Z­like and B­like ^NA. ­ 3*7 ­ DEPENDENCE OF ЬОСАт, DNA CONFORMATION ON BASE SEQUENCE. COMPARISON OP OLIGONUCLEOTIDE CRYSTAL DATA AND RESULTS OP DUPLEX ENERGY CALCULATIONS V.I.Poltev, A.V.Teplukhin Institute of Biological physics, USSR Aoademy of Sciences, Pushchino; Computer Research Center, USSR Academy of Sciences, pushchino

The X­ray studies of oligonucleotide crystals have revealed the dependence of lecal duplex conformation on the nucleotide sequence. These data allowed a suggestion about "conformational code" for nucleic acid­protein interactions. The regularities were formulated for the dependence of double helix parameters on sequence of purines and pyrimidines. However the questions arise as to what extent this conformational heterogeneity is determin­ ed by the base sequenoe, what is the contribution of intermolecu­ lar interactions in crystals and if it is possible to apply the regularities obtained for restricted set of oligonucleotide orys­ tals to any base sequence. in this connection we carried out calculations of base­base interaction energy for all pairwise combinations of the comple­ mentary pairs as a function of the double helix parameters. The minimum energy regions corresponding to B­ and A­conformation right helices were found. These regions differ in the shape and size for different base pair combinations but have oommon parts. The significant differenoe was found for the two repeating (Д*Т) and (GfC) sequences. The deviations of the position of energy minima from base positions in standard B­ and A­forms were ana­ lysed. These deviations reflect the tendency of the step to adopt a certain conformation. As a rule pyrimidine­purine stopfl as compared to purine­rpyriraidine ones have larger helical twiat angles, smaller interpalr and base pair canter­to­helix axes distances. The calculation results allow опз to interpret the Хтгау data for oligonucleotide crystals and polynucleotide fibers. The dependence of local oligonucleotide conformations in crystals on the sequence reflects the tendency revealed in the interaction en energy calculations for combinations of two pairs but not for ?i all the Ьаве pair steps. This is the consequenoe of the influen­ ce of the conformation pi neighbouring nucleotide pairs. 44­2 ­ 348 ­ THE MOLECULAR STRUCTURE ANV CONFORMATIONAL ANALYSIS ОГ COME N-PYRIDYL -PHCNYI.SUCC I HI MI DCS.

I rxst ifule of G&r*.t*ral Ch&mis try. Technical Uni versi t y, Zu/irh i 36 90-924 t^idi, POLAND ф _.N

<©S}­CH СНг 16 X = H V= —

Y The pha rmaco 1 og i ca.l screen i ng has shown that two N­pyridyl­phenyl­succinimides. 110 and 111 , have clinicaly accepted anticlconvulsant properties HI.The X­ray examinatione of these two compounds and 10 .being pharmacologically inactive,(with R about 0.04) have showed that the anticonvulsant properties in this case are clearlly connected with conformation of the molecule.The negat ive charge on both oxygen atoms, estimated on the basis of HOSE­model 12.3],is elightly higher in 110 and 111 than in 16 .It can be a reason for an easier connection of two pharmacologically active molecules with receptor via H­bonds. The conformational alysis (for Ift and HO) was performed by MM2P programme with rotation round two torsional angles

) in both discussed molecules are observed for different* values of 6­and the freedom of rotation for IIO is considerably bigger. (UWilimowski.M.K*dzierska,L..Arch.Immunol.Therap.Exp.27,389(1979) UlXrygowski M..XnuVewicz R..Acta Cryst.B3e, 732(1963) [3|Karolak­WojciechowsKa J.,Acta Cryet.8*3 ,374 (19671 Struclurol r***rch» w*r* flr«irw:»d by HP. II. to programm* of FoUeh Hintvlry ot education. ­ 349­ 8TRU0TURE­FUN0TICM АШ,У31Э OF THE NAD­DEPENDENT FORMATS DBHYDRO0EHA3K 12 1 g.H.Harutyunyan: V.S.Lsmzin, A.E.AieshinJ I.N. Bezrukovn? V.O.Popov2 Institute of Crystallography, USSR Aoad.Soi., Hoaoow| Institute of BloohemlBtry, USSR Aoad.Soi., Moscow| nloeoo* Stat* University, USSR, Moscow. Using three ieomorphoua heavy stem derivatives the eleotron density naps of the ternary oomplex of the bacterial MAD­dependent formate dehydrogenase (PDH­HAD­ acide) were obtained and the struoture has been orys­ tallographioolly refined at 3.0 A resolution. The en­ cyme molecule comprises two identical subunits each oonalatlng i of two domains ­ the ooenzyae binding and the oatalytio one. The NAD­blnding domain of FDH has a conservative tertiary structure and oomprleee two Rosaman folds and an additional A­p element. The basic structural motif of the enzyme catalytic domain is the 6*stranded parallel Л­oheet. Conformation of the HAD molecule in the holocomplex of FDH is similar to other dehydrogemmes. Only one out of the three amino acid residues, previot sly considered to be invariant in the coenzyme binding regions of dehydrigenaeea ie preaerved in PDH (Ajp­,221). Two'"oonaervative" glyoine residues are substituted in FDH by Ala­198 and Hls­258. The organization of the enzyme aotive centre is dis­ cussed. - 350 - CCFLANftR ALIGWDT OP CRYSTALS IN TURKEY TEMXW COLLAGEN FIBERS

Wolfia Traub Talmxi Arad and Stephen Miner Departments of Structural Chemistry and Isotope Research The Helanann Institute of Science, Rahovot 76100, Israel.

A study of mineralized turkey tendon, using electron diffraction and electron microscopy, has shown that the plate-shaped apatite crystal? are arranged In parallel arrays across the collagen fibrils. Furthermore, there is a pronaunced tendency for the layers of crystals to be coneiantiy aligned in adjacent fibrils. This provides direct evidence for highly asymmetric molecular assentoly in collagen fibrils. These observations nay also be important for understanding the mechanical behavior of bone at the «olecular level, as such extended, aligned aggregates of flat crystals could develop into natural fracture planes in mature bone. 4. BIOLOGICALLY ACTIVE SMALL MOLECULES AND BIOLOGICAL MACROMOLECULES

Posters ­ 352 ­ ON THfc LIMITS OF ISOSTRUCTURALITY OBSERVED AMONG CAhDENOLlDES AND ANALOGOUS EUFADIENOL1DES

Oy. Argay1, A. Kalman1, В. Ribar2, S. Vladimlrov5 end D. Zlvanov Stakic3 Central Research Institute for Chemietry, Hungarian Anaeittmy of Sainnaeitj

Budapest^ Hungary t Institute of Physios, Faculty of Sciences, Novi Sad' and Department of Pharmaceut, Chemietry, Faculty of РИатчзу, Rvograa, Yuyoatavia •

The limit! of "nrnln­^part" laostructurality dlecovnred between dlgitoxfganln dlgireziganin, 21R­ and 21S­methyl­­dlgltoxlgenln and Jd­optdtgitoxlgenin /1­2/ have boon acrutlnlxed by the atructure determination of uiarigenln (differs from 3rt­epldlgltoxlgenln In lta A/B ring Junction). The gis ­>trans change of the A/3 ring Junction la accompanied by a rotation of the у­lactone ring around the C17­C20 bond which, in accordance with our earlier conjecture, excludea leostructursllty. * The pretence of equivalent amount at H,0 molecule* In the crystal lattice of teloclnobufagln (Эр­Oil bufalln) not only hlndera the expected /3/ laostruc­ turallty of tetoctnobufagin vrlth bufalln, but results in th" oppoaite position of the £­lactone ring relative to that aaaumed tn bufalln (Те' ­= ca. 90° v* ­00°). The water molecules participate In the formation of a complicated hydrogen bond network In which, beyond the expected Intramolecular 0(5)­H.. .0(3) hydrogen bond /3/, 0(9) acta simultaneously as an acceptor for H­0(14) positioned to molecule at x,y,a by a twofold acrew axla 2. (J.J­8)* Despite of repeated efforts no water free teloclnobufsgln crystals could be obtained hitherto, however. The third example of the Umtts of iaoatructurallty served by lia­arte­ bufogenin In which the usual els C/T) Junction is replaced by a trans annota­ tion. Although the rotation of the ft­lactone ring is similar to that of bufalln, Its relative position to the steroid skeleton la significantly altered (C14­024: T.7 va 7.0 Я and 03­CM­024: 131° vs 168°). Consequently, no such toleration of Isoatructurallty as shown by bufalln together with Its precursor ecillarenln /4/ can be expected, fit KalraAn A., Argay Qy.. FOlop V., Ribar В., Lasar D. Acta Cryst. A43, 366 (1987). /2/ Argay Gy.. Kalman A., Ribar В., Z. Kriet.. 185, 133 (1838). /Э/ Ка1тал A., Fttldp V., Argay Gy., Ribar В., Laiar D., Zlvanov­Staklc D., Vladlmlrov 3., Acta Cry it., C44, 1634 (1886). /4/ Ribar В., Argay Gy.. К aim in A.. Vladiroirov S., Zfvancv­Stakic D.. J. Chem. Res. (S) tO (1*83). ­ 353 ­ INTERACTIONS OF ANTHPACYCUNE ANTIBIOTICS AND DNA. 7hE CP.YS.AL STRUCTURE. Or A MOKPHOL1NO DERIVATIVE OP DOXORUBICIN CCMPLEXED TO d(CpGpTpApCpG) .

F. Bachechl, M. CitiHi and G. Ughetto. Istituto di Strutturistica Chimica 'C.N.R. ­ C.P. 10 ­ 00016 Monterotcndo Stazione (Rcrr.al ­ Italy. F.P. Colbnna and M.L. Capobianco.­ Istltuto del compost! del carbonio cor.tenenti eteroatomi CNR ­ 40064 Ozzano Emilia ­ Italy.

Daunorubicln and doxorubicin members of the anthracycline class of antibiotics are among the most widely used anticancer agents and the mechanism of their anticancer action la believed to depend on intescalative binding to duplex DNA, The wocpholinyl anthracyclines are a series of aemisynthetic поп;Ьлз!с analogues which exhibit a greatly modified biochemical «ctivity compared to that of the parent drugs. The morphollnyl moiety provides the molecule with an increased potency and with the ability to Inhibit RNA synthesis to a greater extent than DNA synthesis. In an attempt to investigate If these properties are related to a different Interaction with DNA we have solved the crystal structure of 3'Tdesamino­ 3,­(2­methoxy­fl­.i!orpholinyl) ­doxorubicin complexed to a DNA fragment d(CpCpTpApCpG), at 1.6 A resolution. The complex crystallizes in space group Pl with cell costants a * 18.01 Л, b « 16.83 А» с ­26.75 Д. а ­ 52.В», Ji­ 100.S', У- 94.9', г ­ 2. In the cell unit there are a DNA duple* with two bound drugs. The crvstal structure shows the interaction between the drug and the DNA molecule in great details. These interactions *r* similar to those formed by doxorubicin c^mpiexed to the same DNA hexamer/1/ but there are some significant differences due to the presence of the morphollnyl ring. The paper discusses these aspects of the interaction and the possibility on the basis of molecular struct" re tr­ ' active substituents on the morpholinyl ring may form an adduct with the DNA molecule.

ill G. Ughetto. X­Ray Diffraction Analysis of Anthcacycline­Oligonucleotide Complexes in Bioactive Molecules. Vol. VI. Anthracycline and Anthracedlone­based Anticancer Agents. (J.W. Lown ed.), pp. 29b*333, Elsevier, Amsterdam 198S.

CD

45­1 354 - CRYSTAL AND MOLECULAR STRUCTURE OF A Rh-Cu POLYHYDRIDE.

F. Bachechi'. U. Stadler" and L. M. venanzi7

'istituto di Strutturiatica Chimica, CNR, 00016 Monterotondo St., Rome, Italy aLaboratorium fur Anorganische Chemie. ETH, Zurich, Switzerland. Transition=rjnetal polyhydrides can form a wide range of heterometallic complexes containing coinage metals. This tendency appears to be particularly marked for the mononuclear hydrido complexes of the tridentate tripod-like ligand СН2С(СН2РРЬ2)з , triphos. Mononuclear complexes of the kind [(triphos)MH3] , M = Rh, Ir, were found to give a large variety of heterometallic compounds with bridging hydrides containing copper, silver or gold depending on the reaction conditions and the ratio of reagents /l/. Each polyhydride unit can be regarded as a triple donor ligand to a metallic ion like Cu*, Ag+ and Au*, which act as acceptor. When a [

[(triphosJHs-nRMji-H),, CuLn]* with n - 1, 2, 3, can be expected. The X-ray analysis of the binuclear complex [ (triphos)RhHj

Cu(PP*)] [CF3SO3], where PP* is the bidentate ligand o-CeH4(CH2

Р(СвНи)г)г, has been undertaken. The crystal structure revealed that the Cu atom lies on the C3 idealized axis of the triphos ligand and that the three P-Rh-Cu angles are equivalent. This arrangement should bring all three hydride ligands, which were not located by X-ray analysis, equally close to the Cu atom in bridging position on the Rh-Cu contact. The structure will be discussed and compared with those of related compounds.

/1/ Bachechi F., ott J., Venanzi L. M., J. Am. Chem. Soc. 107, 1760 (1985). ­355­ SYNTHESIS AND X­RAi CRYSTAL STRUCTURE OF 25:rDESACETYL­21,23­PROPYLIDEN­ll

С Bartolucci1, V. Brizzi2, M. Brufani3, L.Cellai1, S. Cerrini1, D. Lamba1, A. Segre1

4stituto di Strutturistica Chimica, CNR, Roma; 2Universita­Siena; 3Universita­Roma, Italy. . Rifamycin SV is a well­known antibiotic, specific inhi­ bitor of the bacterial RNA polymerase, very active on Gram­positive bacteria and mycobacteria, undergoing rapid elimination via the biliary route /1/. Hundreds of derivatives, mostly at C(3) and/or C(4), were synthesi­ zed with the aim of increasing the inhibition power, of extending the range of action, and of modifying the pharmacokinetic behavior. Many derivatives displayed promising properties in vitro, but only few of them proved to be of therapeutic value (Rifampicin, Rifabutin, Rifapentin, Rifaximin), and displayed impro­ vements only in the pharmacokinetic behavior. On the basis of the well­established structure­activity relat­ ionships, we are exploring the possibility of preparing new series of derivatives at C(ll) and/or C(25). There­ fore we synthesized the intermediate 25­desacetyl­21, 23­propyliden^ll(R)­rifamycinol S, protected at C(21) and C(23), and functionalized at C(ll) and C(25). Its X­ ray crystal structure was then determined in order to ascertain the sterical requirements of the subsequent derivatization steps.

Rifamycin S

1) 2,2­Dimethoxy­ propane 2) OH"

3) NaBH4

4) K3 Fe(CN6)J

/1/ Brufani M. Topics in Antibiot. Chem., 1, 91, (1977) ­ 356 ­ MAPPING OP IHB IMMUNODOMINANT REGIONS IN THS FORMATS DEHYDROGENASE. 1 11? A.V.Bogdonova, I.A.5humilln, V.S.lomzln, A.B.Aleshin, E.II.Harutyunyanf T.V.Cherednikova, Tz.A.Egorov? V.O, РоттоУ Institute of Biochemistry, USSR Aoad.Sci., HOHCOWJ n •"Institute of Crystallography, USSR Acad, Sci., Moocowj ^Institute of General Genetics, USSR Acad,Sci«, Moscow, A panel o'f four monoclonal antibodies and ветел polyclonal antisera to the NAD­dependent formate de­ hydrogenase (­FDH) from methylotrophlo baoterium Pseu­ doraonaB вр.101 чтя obtained. A dot^blot technique was used to Investigate the Interaction of the parti­ ally overlapping peptldee produoed by the proteolytic cleavage of the FDH polypeptide ohain with the mono­ clonul untibodieB and polyclonal antisera. The immu­ nochemical studies and the results of the X­ray stru­ cture analysis of the ternary complex FDH­NAD­aside о at 3.0 A resolution revealed the major antlgenio re­ gions in the protein molecule, facilitated the loca­ lization of the epitopes of the respeotive monoclonal antibodies on the surface of the ГОН and helped to quantify the interactions between monoclonal antibo­ dies and the native protein on one hand and peptides oomprizing its antlgenio determinants on the other. ­ зет ­ DYNAMICS OP ACTIN FILAMENT TENSION UNDER BXCITED H­BOND ACTIO!» IN THE MYOSIN HEAD TURN­OVER MODEb

3.V. Beapalova. K.B. Tolpygo

Donetek Ohysioo­Technioal Inat., Ukr.SSR Aoad.Sol.,340114 Donetsk

1. According to the muscle oontractlon model, proposed by one of the authors, the Initial momentum event might lead to ln­ oreaee in value and range of action of H­bond forces provided by excitation through release of ATP decay energy. The myosin "head" eliding model, considered in our earlier paper oould not explain the faot of considerable value of actln filament tension (oa,100­ 200 A) due to eaoh ATP decay event as well as transfer of nearly all ATP decay energy ДВ to potential (not kinetic) energy of »o­ tln filament tension and also the considerable period (oa. 10~^­ 2 10 a), during whloh the act in filament is maintained In strai­ ned state. 2. Using the supposition that the H­bond pulling force is generated at aotln­myosin oontact, or at a Joint,whioh conneots the myosin head with ite thlok filament,the relations of motion for the myc­ln head and aotin globulae are derived and solved. To obtain solution we also suppose that the H­bond foroe value Is constant 1л accordance with the initial condition (at the ao­ ment of exoltatlon of the first H­bond), when all actin globule» are Immobile, the filament Is not strained, the myosin head is normal to the aotin filament. 3. Tine dependence of displacement of the aotin filament end part as well as the value of force, acting on sarcomere •»»­ brans are estimated. Comparison of these values shows that the wave of tension reaohes the membrane afore the myosin head had completed its turn­over. This provides transfer of considerable part of H­bond energy to potential energy of polymer tension. 4. After turn­over.the myosin head Is maintained in the In­ clined position fixed by the whole system of' H­bonda reduced to the ground state. To break them,* considerable activation energy oa. 0,4 eV Is needed, this faot is responsible for rather long period of time (up to 10" a), during which the aotln filamxnt is maintained In strained state. This is due to low velocity, at which the saroomere membrane moves to ooVer the segment, at whloh the actin filament la extended ~10 cm. - 356 - THE STRUCTURE OF O-AMSA, AN INACTIVE STRUCTURAL ISOMER OF THE ANTI-CANCER DRUG AMSACRINE (n-AMSA) J. S. Buckleton , G. R. Clark and W. A. Denny University of Auckland, Auckland, New Zealand. Department of Chemistry. Medical School, Cancer Research Laboratory.

The single crystal x-ray structure of o-AHSA free base has been determined far comparison with that of AMSACRINE fra-AMSA) free base /1/ in an attempt to identify features of the structures which might be responsible for the differences in biological behaviour.

ОШ

NHSO2CH3

(OlQLQ)

C-AMSA ID^AHSA (AMSACRINE] Inactive against L1210 leukemia Active against L1210 leukemia even at very high dose rates at very low dose rates

Crystal Data: o-AMSA, C21HlgN303S.CH3OH, И - 425.49, Triclinic, Space group PI, a - 9.545(2), b - 14.338(1), с - 8.375(1) A, a. - 106.03(1), (3 - 103.23(1), т - 70.96(1)°, V = 1029.04 A3, Z - 2. Intensity data were collected on a Nonius CAD-4 difftactometer using Mo Ka x-radiation. The structure proved difficult to solve, but eventually atomic positions were determined using the extended options of the SHELXS-B6 direct methods package. Refinement by full-matrix least squares returned R - 0.039 far 2169 unique observed reflections [l>2.5a(I)]. The bond lengths and angles are very similar to those in m-AMSA but the torsion angles about the acridine - anilino linkage are different. The cause of the contrasting biological activity is presumably steric in origin, tbbonding to the methanol solvent molecule and stacking of the acridine rings contribute to the crystal stability. These effects are not present in ro-AMSA.

/1/ Buckleton J.S. and Waters T.N.M., Acta Cryst., C40, 1587, (1984). - 3S9 -

XYLOSE ISOMERASE STRUCTURE AND BINDING H Ь.Саггс11, JJ.Glusker The Institute for Cancer Research, Fox Chase Cancer Center, 7701 Burholme Avenue, Philadelphia, PA 19111, USA. V.Burger, RManfre, D.Tritsch, J.-F.Biellmann Laboratoire de Chimie Organique Biologique, UA-CNRS 31, Insntut de Chimie, Universite Louis Pasteur, 1, rue Blaise Pascal, 67008 Strasbourg, France

The structures of crystalline D-xylcse isomerase from Streptomyces rubiginosus attd its complexes with various substrates and their analogs have been determined by X-ray diffraction techniques and each refined to 1.9A resolution. Details of the binding of metals and sugars will be described and their implications for the catalytic mechanism will be discussed. The nature of the conserved side chains in the various forms of diis enzyme camhen be explained in most cases.

This research was supported by grants CA-10925, CA-06927 and RR-05539 from the National Institutes of Health. - 360 - TEN-MEMBERED CYCLOTRIPEPTIDES; THE CRYSTV. STRUCTURES OF CYCLO(-NMeftAla-L-Phe-L-Pro-) AND CYCLO(-NHeftAla-L-Phe-D-Pro). By S. Cerrini*. E. Gavuzzo*, G. Lucente+ and P. Pinnen+ . *) Istltuto di Strutturlstlca Chlmics 'G. Giacomello' C.N.R., C.P. 10, 00016 Monterotondo Stazione, Rome (Italy). + ) Istituto dl Chimica Farmaceutlca, Universita' La Sapienza , Rome (Italy).

It if well known that cyclic peptides are important aa sim• ple nolecular models for gaining conformational information on the more complex blomolecules aa well as for mimicking the bio- active sit?s of macromolecules. In previous papers we reported the molecular structure of ten-membered eyelotrlpeptides containing L-Phe, L-Pro and a 0- amino acid reslduei cyclo(-NMeAnt-L-Phe-L-Pro-) (I) III and cy- » clo(-/l Ala-L-Phe-L-Pro-) (II) 171. In these two models the NMeAnt and A Ala moieties represent the most rigid and the most flexible fragment inserted in the cyclic backbone. 7n order to Investigate the influence on the backbone con• form^ 'on of the relative chirality of the residues and of the substitution at trhe amide nitrogen, we determined the crystal structures of cyclo(-HMa/lAU-L-Fhe-L-Pro-) (III) and cyclo(-N- Me0Ale-L-Phe-D-Pro-) (IV). Crystal data, of (III): Cjgh^NjOj, H.W. 329.«00, S.G. P2j . •-5.117(2), b«P.059(6), c-9.514(3) A, 0-99.18(3)', Cu-Ko. radia• tion, Dc-1.284 g cm~3,Z-2j the current R value Is .05 for the 1491 observed reflections. Crystal data of (IV): CjgHjjNjO^^HjO, P.M. 365.430, S.G.

P2j2,21, a-8.797(2), b-19.440(9), c-21.605(10) A, Mo-Xa radia• tion, Dc- 1.314 g cm"3 , Z-8; the current R value is 0.08 for the 2887 observed reflections. Along the sequence -Xaa, -Phe2-Pro-j- the ( u>j , u>2» W3) dihe• dral angles of the peptide bonds correspond to a (els.els.els) and (cis.cis.trans) conformation in I and II respectively. In both the new models III and IV the ebove cited (o angles have been found to be (trans.cis.cis), irrespective of the chirality of the Pro residue and of the different overall shape of the cy• clic backbone.

Ill Cerrini S., Gavuzzo E., Lucent» G. and Plnnen P., Int. J. Peptide Protein Res. 31.,447(1988); and references quoted therein. /2/ Cerrini 5., Gavuzzo E., Lucente G., Pinnen F. and Zanottl G., Int. J. Peptide Protein Res., (1989), In press. ­ 361 ­ REFINEO STRUCTURE OF MnP COMPLEX OF YEAST INORGANIC PrROPHOSHATASE AT 2.7 A RESOLUTION H.Chtrgad^e Jr..J.Kuranova.a.Strokopytov.E.Harutyunyan.U.Hohne G­Hiuioorf tnit. of Crystallography.USSR Academy of Sciences, Hoi cow,USSR, ln»t. for Biocheml«try,HumboId University,Berlin,DOR

Inorganic pyrophosphatase (PPite) is one of the main enzymes of phosphorous me l tie bo li am. In niture binding and hydroxy lit of pyrophosphate occur*• in presence of Ho ions. In the active site of the enzyme up to three divalent metal ion? can be bound. However up to now it was possible to obtain crystal complex with magnezium ions with only one binding site. Only recently we succeeded in preparing complex of PPase with Mn ' and P., ions, which contained three bindLng sites for Mn Molecule of yeast PPase hn moleLUla г weight of 6 4 kO and consists of two chemically identical tubunttt, Crystals of native apo­enzyme belong to the space group P2 , crystala of MnP. complex of PPase belong to Che space group P2Z2 with unit cell parameters 5Б.2 x 106.в х 118.0 A. The structure of the apo»enzyme was solved before by MIR method at 3.0 Д resolution, we have determined the crystal structure of HnP complex of PPase by the method of molecular replacement at 2.7 A resolution. A distinct peak of denalty has been observed at the difference electron density map tF ­ F , lexpiip in the region of active site, which can not be interpreted unamblguouely. Three binding sites of Mn* ions in active altes of each aubunit have been localized using anomalous scattering in the range of 30.0­5.0 A. The cample tee atomic model of MnP ­PPse complex, with the exception of five residues at C­terminua, was refined up to crystallographlc R­fictor equal to 0.29 in the range of 6­2.7 A with rmt deviation from ideal geometry 0.020 A and 2.9 degree for bond lengths and bond angles correspondingly. Atomic coordinates of apo­enzyme and MnP complex of PPase differ from each other inalgnificantly with the exception of some atomic shifts in the regions of active sites and intermolecular contacts. Three Mn ­ ions are concentrated at the distances from 3.7 to 5.1 A in one subunit . and three ions at the distances from 5.4 to 6.7 A In the other one. This fact made it possible to suggest conformational difference between two subunit's. Further analysis of the protein structure will give us more detailed knowledge of active site con f ormit t ion " о t MtiP t «riipj ex of PPase . 46­1 ­ 362 ­ REFINED STRUCTURE OF CALF EYE LENS У­CRYSTALLIN Illb AT 2.5 8 RESOLUTION

Yu.N.Chirgadze, N.A.Nevskaya, E.A.Vernoslova, S.V.Nikonov, Yu.V.Sergeev, E.V.Brazhnlkov, N.P.Fomenkova, V.Yu.Lunln and A.G.Urzhumtsev

Institute of Protein Research and Research Computing Center, USSR Academy of Sciences of the USSR, Pushchino, Moscow Region, USSR

Protein crystals were grown from 1% solution with 50 mM potas­ sium sodium phosphate buffer, pH 7 and 5 mM glutathione. The dlf­ fractioi limit was equal to 2.5 8 on a conventional X­ray rotating anode generator. The protein crystal was kept in a capillary at 20 C. The crystal surface was always wet during data collection. The crystal belongs to space.groun P2.2.2, with unit cell parame­ ters 58.7x69.5x116.9 8 and two molecules per asymmetric unit. An initial model of the protein molecule was obtained by the MIR method at 3.0 A resolution. The phases were then Improved, expand­ ed and refined up to 2.5 8. Since the exact sequence of y­crystal­ lin Illb is not known, we used a tentative one deduced on the basis of known preliminary chemical sequence data, as well as the closely related rat and human y­crystallin sequences. The final R­factor was about 26% for the range of 6­2.5 8. The final atomic model of the protein had average deviations from ideal values equal to 0.023 R for bond distances and 3.6 deg. for bone? angles. The main chain pathway of calF r­cryatallin Illb is very similar to that of r^^rystallin II with the exception of the linker pep­ tide. However, there are 26 amino acid replacements for these two sequences. At six positions the hydrophobic residues are replaced by hydrophilix; ones, or vice versa. Three of them, 101, 103 and 155, were shown to be essential for packing of molecules in crys­ tal medium. Possibly they play an important role in the organiza­ tion of the eye lens'medium of vertebrates. ­ 363 ­ STRUCTURE REFINEMENT OF "DRY" CRYSTAL FORM OF CALF EYE LENS Y­CRYSTALLIN Illb AT 1.9 ft RESOLUTION 11 2 2 Yu.N.Chirgadze, N.A.Nevekaya, E.A.Vernoslova, A.G.Urzhumtsev, P.Lindley3 and M.Bibby Institute of Protein Research and Research Computing Center, USSR Academy of Sciences, Pushchino, Moscow Region, USSR; Department of Crystallography, Birkbeck College, University of London, London, UK

The crystal structure of calf eye lens ­f­crystallln Illb has been refined at 2.5 ft resolution earlier. We have expanded the diffraction limit up to 1.9 ft using the synchrotron radiation source at the Daresbury Laboratory, UK» During data collection the T­cryatallin crystal was kept in a capillary and cooled by a +10°C air stream. In these conditions the protein crystal was de­ hydrated quickly despite the existence of solution droplets. We аввите that the relative humidity in the capillary decreased only slightly and was equal to about 92­95%. We denote this crystal form as "dry" in contrast to the initial "wet11 crystal form. Both forms belong to the same group p2i2;i2­.. Tne "dry" form has unit cell parameters 57.4x70.1x115.4 ft while the "wet" form has 56.7x69.5x116.9 ft. There are two molecules in an asymmetric unit for both cases. A data set of the "dry" crystal form was collected by the rota* tion method with an SRS beam (A =0.91 ft) for the rotation angles from О to 65 degrees abou't the c­axis. The data set included about

(F c9% Tne x 75» of all possible reflections, Rmerge ' > ­ray diffrac­ tion patt >f the "dry" crystal form differs from that of the "wet" form with R(F) «25.5%. Thus, we really have a new crystal form of 4­cryctallin Illb wlti< a slightly different arrangement of protein molecules In the unit cell. The refined model of the т­crystallin Illb "wet" form was taken as an initial one for structure refinement of the "dry" crystal form. The. R­factor was 64* for 20­6 ft. Restrained least*­square crystallographic refine­ ment decreases the R­factor to 29% for 6-2.2 ft. Stereochemical parameters of the obtained model differed from Ideal ones at about 0.06 ft for bonds and 6° for bond angles. Refinement at 1.9 Л is now In progress.

46­2 ­ 364 ­ CRYSTAL STRUCTURE OF FIVE TRITERPENES EXTRACTED FROM AUSTROPLKNC1UA POPULNEA (Celaetraceae) A.S.CotaV J.Rego**, G.D.F.Sllva** end Y.P.Mflacarenhaa •tnecituco de Ffeica e Qulaica de Sao Carlos­USP ­ C.P. 369­13.560­Sao Carlo* Sac ?aulo, Brazil ** Depertamento de Qufolca, ICEx, UFMG­30.000­Belo Horlzonte­HG, Brazil

The structural foraula of the studied triterpenes are praaented in Pig.l.Naning the five trlterpetenea aa ТА, ТВ, ТС, TO and ТЕ they can ba individualized by the respective residues and ring conformation. In TliRl­R2­R3­R6­R8­R9­CH3, R4­R5­R7­R10­H. R12­0, Rll­OH;. in T2!R3­RS­R7­R9­R10­CH3, R1­R2­R4­R6­R8­R12­H, R11­0H[ In T3:R1­R3­R> R7­R9­R10­CH3, R4­R6­R8­R12­H, All­OH» In T4rRl­R2­R3­R6­R8­R9­CH3, RW5­R7­R1D­R12­H, RU­O* in T5:K2­R3­R6­R8­R9­CH:\ R1­R4­R5­R7­ R10­H, RU­OH, R12­0. Data collection «as performed using a CAD­4 autonetic single crystal dlffractometar, graphite «ono­ Pig­ 1 chromatited MoKa radiation. Crystal structure ШО1УШЛ by direct aathods ualng SHELXS­86, refinement by full Matrix least square aethod using SHELX­76, Crystal data, no, of reflections and final t '/«lues sre auaaarized in Table I.

ТА ТВ ТС TO ТЕ

S.G M\/n C2 F2,2,2, PI "l "3> 6.697(2) 12.109(2) 6.813(2) 14.695(2) 7.271(2) ) 14.714(6) 7.346(2) 16.127(3) 13^4il2i_ 12.390(8) ^c(a] ) 13,8*6(3) 30,570(6) 24.695(4) 6,622(3) 15.632(2) 90" 90* У 90* 90* 74.95(2) a? > 8(e) 103.52(2) 99,13(2) 90° 104.45(2) 87.55(2) 90* 90° 90° 90* 86.76(41 oV{A*»h > 1328(1)' 2679(2) 2714(1) 1288(1) 1357(1) Hr 184.73 468.73 470.74 472.71 456.73 ilmlnul 2 4 4 2 2 Г^ООО) S32 1032 1040 520 504 u(cmrl) 0.726 0.675 0.668 0.733 . 0.651 No.r.fl. No.I>3c(I) 1430 773 1454 865 1922 Final 1 o.oiei 0.0574 0.0545 0.0420 0.0996 ­ 365 ­

Th« aolacular Tint с on format ton of each trltcrpene I» presented In Tabia II

Table II V. ГМс.г Rlril*\pana ТА TC 1* T«' na«a ^^^ TB

t half­boat chair chair chair chair

II chair chair chair chair chair

III chair half­chair chair half­chair chair

IT chair chair chair chair naif­boat

¥ chair chair chair chair chair

In «11 itructurit the aolacula* »ta interlinked In the cryatai nnly by van e**r Vaal Interaction!» ажсарг Т6 vara the two independent aolet lai preaent In tht «aeyaautrlc unit are dlmerlEed by hydrojen bonda from t a d hydroxyl to tha C2 carbonyl of *«h aolecul*.

Work fupportad by CKPq, PAFESP. PINEP and CAPE*. ­ 366 ­ ТИС STRUC7URB ОТ SACCHARIDB­BINDIBG SITE OF OONCANAVALIN­A

t. Derewenoa1, J. Iferlr2, J.R. Helllwell3,4, A.J. Kalb (Qilboa)2, I.J. Dodeon', H. Z. Papls4, T. Nan1 and J.f. Campbell4 1 12 A (York , ganoheater , Helsmann ft Daraebury') Dapartaent of Chealatry, Univeralty of Manohastar, •anoheator «13 9PL. UK

A ooaplex of oonoanavalin­A with methyl cL ­D­mannopyrano­ elde baa been oryatalllaed In apaoa group K.,2^,2^ with a ­ 12).9 i, о • 129.1 X and о » 67.5 A. X­ray dlffraotlon lntenel­ tlaa to 2.9 A hare bean oollaotod on a Xentronlca/Nloolet area datactor. Ihi atruoture haa been aolved by aolaoular replacement wtere tha etartine aodal waa baaed on refined ooordlnatea of an 1222 oryatal of aaooharld«­fre« oonoanaralln­A. The atruoture of the amooharlde ooaplex has been refined by reatralned leaai­ aquarea methods to as R­faotor of O,19. Data (450,000 neaaure­ Mnt) haa alao bean oolleoted and prooeaaed to 2 J reaolutlon and a prallainary analyala conducted. ­ 387 ­ ссжлилгоя or тнв ЗЯНЮТОЙЕ or ьвонвмооьови» I» ЮТРЕЯВВТ? STATES, ОВТАНГЕЮ PRO» CRY3TAL3 GROW 1Я HIGH AUD 10» IOMIO STRBMOTH MEDIA

112 2 Га. Oavedjlar . B. Atanaaor , ?. Safonova , 8. Harutyunyan Central Laboratory of Blophysloe, Bulgarian Aeaaeny of 2 Solenoee, Sofia, Bulgaria) Institute of Crystallography, Academy of Sciences of the USSR, Mosoow, USSR

Retinae, structure of acetatefervlo leghcnoglobla ( .(> i resolution) obtained from orystuls grown in polyehtylr •; ,• yaol of НЯ 400 in 0.1 H acetate buffer, pH 7.0 has been oc.ipared with the structures of legbesraglobln In deoxjr­, oxy­ and aoetatsfsr­ rio states, refined to 1.8 A, 1.8 A and 2.0 A reBpeotirely, on the basis of orystale grown In aianonlum sulphate solutions (2.3 M) in the rime pH. Conformational ohanges will be discussed In terse of the roov­aeon­square deYiatine of helloes, turns, C^c ­ and ASMS atoa positions In different leghemoglobin complexes. ­ 368 ­ PROTBIH U>i«UIS­BLODOETT ?ILM3i STRUCTURE, PROPERTIES

T.V. Erokhin, H.L. Kayuahina, Yu.H. Lvov, L.x. Jelgin Inititut« of dryota biography, USSR Aoad. Sol.., Новое*

Langmulr­Blodgott (LB) teohnique poxnlte to form a monomo­ leoular protein flla on • water aurfaoe and to transfer it to any eubatrate. By repeating the deposition prooedure It la poe­ albla to oonatruot mono­ and multilayer ayatems. The saohanlan of a protein monolayer formation on a water aurfaoa wae itudled, taking a protein ­ baoterlal luolfaraaa as an example. Preeervaslon of a funotional aotivity of the protein waa estimated by analysing the luoiferase lumlneaoanoe. LB films ал membrane proteln­reaotlon oentrea of different baoter&a vara ooastruotad too. The protein «as ahown to preaerve Ita aotivity in a film. Two­compound fllma, oonaletlng of alter­ native la/ere of the protein and fatty aolda, «era produoed. Suob. LB superlattloee poaeeaa a better ordering. LB fllae of laaumoglobullne >.>ra produoed. The etruoture and the ability to apeolfio binding antigen­antibody *ere ana­ lysed. Tat struotur­ of Bono­ and multilayer Illae aaa investiga­ ted by neene of email­angle X­ray aoatterlng, pleioeleotrlo re­ aonanoe davloea and analyst» of 3!­ к ieotherm». The possibility of utilising auoh films aa eenaing ayatema Is dlaouaaed. ­ 369 CRYSTAL STRUCTURE AND CONFORMATION OP MODIFIED NUCLEOSIDE FROM THE tRNA WOBBLE POSITION! 5­METHOXYCARBONYLMETI10XY­2­THIOURIDIHE

. Z. Ooideckt Inet.of. General Chem.(Technical Univ. of Xodz, £odz, Poland

5­Subatituted uridines and their 2­thioanalogues occur in the firet ("wobble") position of tRNA antlcodon loop, where uridine itself 18 only found exceptionally. It eeeme that modified uridi­ nea influence conformational dynamics of "extended anticodon re­ gion" and modulate on this way codon (mRNA) ­ anticodon (tRNA) binding energy. In this context, the studies on their molecular structure in eolutlon and in the crystalline form are of special interest. The title compound was synthesized by Malkiewicz et al. /1/. It crystallizes as monohydrat C^H^NgOgS.HjO in the monocli­ nic space group P2, with a»4.856(2), b­15.204(2), c»11.035(1) A, (5­100.97(2)°, Z.2, UMoK^.2.03 cm"1. The structure was solved by direct thethode (SHELXS86) and refined by full­matrix least­squa­

гев to a final R­0.031 for 1910 observed reflections with PQ> ЗгС {? ). The pirimidine ring is significantly nonplanar, the devia­ tions from the mean plane ranging to ­0.029(3)A for ИЗ and 0.028(3)A for C2. The conformation about the glycoayl

bond is +syn­periplaner with ^CN­29.6° (C6­Nl­Cl'­04'). The ribose ring is in an envelope conformation corresponding to a СЗ'­endo­puclter. The phase angle of peeudorotation (P) is 16.1°, the minimum amplitude of puckering ( t) is 40.7° and the asymmetry parameter дС^ 0H is 2.1°, The conformation of the ­CH2" side chain J.B gauche • This rotamer is stabilized not only by the gauche effect of the C4'­04'/C5'­05' interaction, but also by the intramolecular C6­H..05' hydrogen bond. Such hydrogen bonds probably play a significant role in determining of the overal conformation of в nucleoside. In addition to this intramolecular hydrogen bond there are seven intermolecular ones« in which participate all potential proton donors including water moleoule.

/1/ Malkiewicz A., Nawrot В., Z.Naturforsch., 42b. 355 (1987). 47­1 ­ ЗТО ­

PEPTIDES CONTAINING THE SULFONAMIDE JUNCTION. THE STRUCTURE OF Cyclo­(­N­Ke­ Tau­L­Phe­D­Pro­).

E. Gavuzzo, F. Кагга, G. Pochetti. Istltuto dl Strutturlstlca Chimica "G. Giacomello" CNR, СР. п. 10, 00016 Honterotondo Stazlone, Roma. A. Calcagni, G. Lucente, F. Plnnen, D. Rossi. Dlpartimento di Studl Farmaceutici, Unlversita "La Sapienza", P.le Aldo Moro 5» 00135 Roma.

Continuing interest is centered on the structural modifications of the peptide backbones and the investigations of the chemical, conformational and biological properties of synthetic analogs /1/. P­.1M; .ely scarce examples of peptide bond modifications involving ref.'^­int of the carbonyl group of the amide bond are available /2/. l>\ tr ­> coi.iext we started recently to examine linear peptides containing the tauryl (2­amino­ ethane sulfonyl) residue. The presence in the backbone of the 502 group In place of the normal amide carbonyl leads to a folded conformation due to a cisoidal arrangement of the aC atoms around the S­N bond /3/. As a contln uation of our research in this field, it seemed interesting to examine the conformation adopted by the sulfonamide junction when inserted in a highly strained ring system such as that of a cyclic trlpeptides. Cyclo­l­N­methyi'tauryl­L­phenylalanyl­D­prolyl­) has been synthesized and the molecular conformation and crystal structure have been determined. Crystals are orthorhorabic, s.g. P l\2\2i, with a « 5.454(1), b ­ 13.486(1), с ­ 24.025(5) 1, Z = 4. The structure has been solved by direct methods and refined to R = 0.039 for 1974 reflections with l>1.5 a (I), The sulfonamide junction maintains practically the same conformation as that found in­ the linear dipeptide N­Ac­Tau­L­Phe­OMe ill; the torsion angle around the S­N bond, including the aC atoms of Tau and Phe residues is 70.8(21°. The other two peptide bonds, namely the L­Phe­D­Pio ind D­Pro­ Tau, are trans and cis with ft) values of ­167.9(2) and ­11.8(51* respectively, both deviating significantly from planacity. The ten­membered ring adopts a chair conformation with a pseudo­mirror plane passing through the N atom* of the sulfonamide group and the proline С atom. The Pro residue presents a half­chair conformation with 0 and у С atoms out of the plane of the other ring atoms. The packing is characterized by a weak intermolecular hydrogen bond between the NH group and one sulfonic oxygen.

/1/ Fauchere J.L., in "Advances in Drug Research" 15_, 29, Ac. Press inc. London (1986). /2/ Spatola А.Ё., in­^Chemlstry and Biochemistry of Amino Acids Peptides and Protein (Keinstein, B.ed) Ь 267, Dekker, N.Y. (1983). /3/ Calcagni A., Gavutio E., Lucente G., Магга F\, Pochetti G. and Rossi D., Int. J. Peptide Protein Res., in press. ­ 371 ­ PEPTIDES CONTAINING THE SULFONAMIDE JUNCTION. THE STRUCTURE OF N­AC­Tau­L­ Phe­OMe.

C. Gavuzzo, F. Ma2gj. G. Pochetti. Istituto dl Strutturistlca Chlmica "G. Giacomello" CNR, C.P. n* 10, 00016 Monterotondo Stazione, Roma. A. Calcagni, G. Lucente, D. Rossi. Dipartiroento di Studi Farmaceutici, Universit* "La Sapienza", P.le Aldo Hoto 5, 00185 Roma.

The modification of the peptide backbone, by replacing the amide bond with unnatural Junctions, is among the most promising approaches adopted to improve potency, selectivity and stability of bioactive peptides /1/. The replacement of the CONH with a SO2NH group presents several points of interest: the new Junction mimics the tetrahedral intermediates formed during the hydrolysis of. the CO­NH bond J2h, it should Introduce relevant conformational constraints likely to modify receptor recognition; both solubility and resistance to normal proteolytic processes should be Improved. N­acetyl­tauryl­L­phenylalanine methyl ester has been synthesized as suitable model for initial studies. The crystal structure and molecular conformation have been determined. Crystals are monoclinic, s.g. P 2\, with • ­ 5.08B(2), b ­ 17Л12Ц71, с ­ 9,561(6) A,/) ­ 92.34(4)°; Z ­ 2. The structure has been solved by direct methods and refined to R ­ 0.043 for 2279 reflections with I ­ 1.50(1). The peptide backbone adopts a conformation folded at the sulfonamide Junction in a way which resembles the presence of a cisoidal CO­NH bond with laxge deviation from planarity. Tht torsion angle around the S­N bond, including the aC atoms of Tau and Phi residues, is 65.4(31'. The Tau residue is extended with the Ca­C0 bond intiperiplanar to the S­N bond. The Phe side­chain conformation correspond* to the g~ rotamer. The packing is characterized by Inttrmolecular hydrogen bonds which the Tau and Phe Nti groups form with the «c«tyl cartway! and one of the two sulfonamide oxygens, respectively.

/1/ Spatola А.Г., in "Chemistry and Biochemistry of Aeino Acids Peptides •nd Protein» {Neinstein, B.ed) 2, 267. Dekket, N.Y. (1983). /2/ Schlosi J.V., Ace. Cheo, Res. Ц, 348 (1988).

47­2 ­ 372 ­ MODIFIED CHEKOTACTIC PEPTIDES. THE STRUCTURE OF N­I(N­FGRMYL­4­ AHINOTETRAHYDROTHIOPYRAN­4­CAFBONYL)­L­LEUCYLj­2­AMrNO­INDA4­2­CARBOXYI.IC ACID METHYL ESTER.

E. Gavuzzo, F. Mazza, G. Pochetti. istituto dl Strutturistica Chimica "G. Giacomello" CNR, c.P, n. 10, 00016 Monterotondn Stazione, Roma. G. Lucente, G. Paganl zecchini, H. Paglialunga Paradisi, I. Torrini. Dipartimento di Studi F2rmaceutici, Universita' "La Sapienza", P.le А. Лого 5, 00185 Roma.

Chemotactic peptides are extensively investigated /1/ in view of their relevant biological role. Several studies based on the introduction of stericaUy restricted aminoacid residues into the backbone led to the isolation of analogs with high biological activity and put in evidence the importance of the conformational features on the potency and selectivity of action /2/. it seemed interesting to examine the conformational properties of analogs having the general structure HCO­Xaa­Leu­Yaa­OHt­ where Xaa and Yaa are achiral stereochemical^ restricted residues. Here we report the crystal structure and molecular conformation of HCO­Atp­Leu­Ain­ OHe (Atp = 4­amincterahydrothiopyran­4­carboxylic acid; Ain ­ 2­aminoindan­ 2­carboxylic acid), analog of N­formyl­methlonyl­leucyl­phenylalane which is accepted as the standard for immunological investigations. Crystals are orthorhombic, s.g. P Zyltfi, with a ­ 21.934(B), b ­ 10.856(2), с »­­ 10.380(2) A, z = 4. The structure has been solved by d'.rect methods and refined to R = 0.071 for 2300 reflections with I> l.So(I). Complete folding characterizes the peptide backbone. The

/1/ Sauve' G., Rao V.S., Lajoie G. and Belleau В., Can. J. Слет. £3_, 3089 (1985). '. /2/ Bardi В., Plazzesi A.M., Toniolo С Raj P.A., Ragothama S. and Balaram P., Int. J. Peptide Protein Res. 2J, 229 (19661. /3/ Gavuzzo E., Mazza F., Pochetti G. and Scatturin A., submitted to Int. J. Peptide Protein Res. ­ 373 ­

THE INTERACTION OP SPERMINE WITH DNA: HJOH RESOLUTION SINGLE CRYSTAL STRUCTURE ANALYSIS OF DNA­SPERMINE COMPLEXES

R.V. Gessncr, L.D. Williams. A. Rich. A.H.­J. Wn^r* and С.А. Frederick

Department of Biology. Massachusetts Institute of Technology. Cambridge, MA 02139 and ­ Department of Physiology and Biophysics. University of Illinois at Urbana­Champaign

Spermine (NHjfCH^NHtCHj^NHlCHj)^­! and «veral related polyaminei play im­ portant roles In шалу biological processes such и ­'­'cation, transcription and translation. Polysminu an specifically involved in vivo in the dense packing of DNA In bacteriophage md •perm heads and have also been shown lo condense DNA Ы vino. At micromolar concentrations,

spermine ii known lo Induce the conformational transition of d{CG)n from the right­handed B­DNA lo the left­handed Z­DNA conformation. Although several crystallographic studies of iRNA and DNA fragments have shown thai (he presence of spermine in often crucial for the crystallization process, none of these structural analyses has provided any detailed information on the exact molecular interactions between this polycation and nucleic acids. Thus, very Utile is known about the structural features responsible for the biological effects of polyamines. We present here three high resolution uryslnflographic studies of DNA­spermine complexes which give a detailed picture of the specific hydrogen bonding pattern between the basic amino groups of spermine and either the acidic DNA phosphate groups or the hydrogen bond acceptor sileiof.the bases. In Z­DNA, as shown by (he 0.9 A structure of d(OOCOCG), we find iwo prinlcipal modes of binding ': One spermine molecule spans the entrance of the deep minor groove, forming one direct and several indirect (through one intermediate water molecule) hydrogen bonds to the phosphate groups. The second spermine curves along the convex surface of the Z­DNA helix (which corresponds to the major groove of B­DNA), forming direct hydrogen bonds exclusively to the base keto and tmino groups. In addition, both spermines also interact with other, sym­ metry related DNA molecules, forming a network of polyamines and DNA. In solution, this Interaction facilitates the aggregation of DNA and thereby promotes tfie crystallization ртосеи.

In B­DNA, as exemplified by two 1.5 A structures of d(CGATCG) with either daunomycin от adrianrycin intercalated between the outer two base pairs at both ends, only one principle spermine binding mode is found in each structure 3. Although the DNA has similar confor­ mations In both structures, the spermine molecules assume two different conformations: In the daunomydn structure die poryamine wraps along the edge of the major groove, with the first two amino groups forming indirect hydrogen bonds to the phosphate groups and with the remaining two amino groups forming direct hydrogen bonds lo the base Imino and amino groups. All interactions are with only one DNA strand. In contrast, in the adriamydn structure, the spermine molecule bridges across the major groove, forming indirect hydrogen bonds to die phosphate groups of each strand. However, the Inner two amino groups do not Гогт any hydrogen bonds lo the bases.

The most striking differenc; between E­DNA and Z­DNA is the tighter binding of sper­ mine to Z­DNA: Only in this DNA conformation are direct hydrogen bonds between phosphate oxygens and spermine amino groups observed. The total number of direct and indirect oydmgen bonds per spermine molecule is ahoH twice as high in Z­DNA compared to.in B­DNA. This is consistent with the thermodynamic stabilization of the Z­DNA conformation.

1 Owner R.V.. Frederick C.A.. Quigley H.J., Rich Д «ml Wang AH. F.. Г ВЫ. Окт., 1л pre» (l°fl9) 1 Frederick C.A.. Willi«nt» L.D., Upheiio G..

S OEOFFRfi M COTRAJT, C. COURSE1LLE, 0. PREClOOUX

Laboraloire dc CrLstaiiographie et de Physique Cristalline University de Bordeaux 1 ­ 33405 ­ Taience • France

Neurotensin tf a tridecapeptide isolated from hypothalamic extract*. Il could produce hypotension, increase vascular permeability, pain sensation and a variety of smooth musde effects. Its aminoacid sequence is < Olu ­ Leu ­ Тут rHu ­ Лап ­ Lyi ­ Pro • Arg ­ Arg ­ Pro ­ Tyr ­ lie ­ Leu ­ OH­ Partial sequence oj neurotensin were synthesized and their biological effect tested II was shown that the biological «ction of this peptide reside* essentially in Us carboxyuc terminal group and the smallest peptide with a atUl quite important activity is the pentapeptide Arg • Pro • Тут ­ lie ­ Leu. We report here the conformational studies of Ac ­ A/g ­ Pro ­ Тут ­ Ue * Leu. The molecule crystallizes by slow evaporation of an aqueous­ dtnuthyumlfoxid solution, in the monocunic space group C2, with a ­ 11558, b ­ 21.368, с ­ 18.766 A, fl ­ 9437 ' and Z ­ 4, with one DM SO and four water molecules ш the asymeuic unit. Crystals air. *r/ шшаЫе and almost all the atoms are affected Ы very high thermal parameters. The molecules crystallizes at a zwitterion (juanidino group of argmine +, carbciyt group of Leucine ­ ). No strong interaction between me charged groups are observed; the X ray conformation does not show any turn and can be described as extended. ^ 375 ­ X­RAY DIFFRACTION. QUANTUM MECHANICS. AND MOLECULAR GRAPHICS APPLIED TO THE STUDY OF PERIPHERAL AND CENTRAL BENZODIAZEPINE RECEPTORS UOANDS. О GEORGES. O. EVRARD. V. LUC. D. P. VERCAUTEREN and P. DURANT. UnJveriHy of Nemur, Dept. of Oem.. rue de Bruxeltet, 61, B­5000 Nam», Belgium.

Interest for benzodiazepine receptors bu pown considerably in the last few yean. The biochemical differentiation between Ihc centnl and peripheral itonptor attests nowadays well known. Concerning pharmacological activity, the centrary active Uganda are wed as arukrfytics, aedativts or hypnotics. For the peripheral ЬегшкВагерЬк receptor tigandt, so pharmacological activities associated with the high specific and competitive binding have been reported; their interest Is however obvious at they aright be anpUcated within the cardiovascular system, die pulmonary disorders, the kidney regulation,....

Among the benzodiazepine­like analogs, one may find a few compounds that are adequately substituted to show specific affinity for peripheral or central binding she*. We herein consider PK 1 f 195

PK 11195 (I) tod L 16317 Ш molecular structure» have been aolved by X­ray diffraction; others (2,4) were retrieved from the CambrWge Cryttallographk Database, Mo)e<^ar propcrijfe fJ^omk: cnargea, faiteralomk maps) have been computed using ab Inlto MO method*. By molecular topermipoftrJons based on the structural and electronic properties, we attempt to differentiate peripheral and central llgmds. ­ 376 ­ COMPARATIVE AMAMSIS OV ADKKSODOXIN PHOTEIN GLOBULE STATE

WITH RESPECT TO ТЫ1РЕНАТШШ AND OTHKH РАСТОКУ ACCOKUINU

TO 0&=aPB0TROSCOPY

Govorova A.A., Gailtsky H.M.

Institute of Bioorganio Chemistry of Acad. Sol. ЬИьк, Minsk

Method of clroular dichrolsm (CD) waa ueed to studu ­he

effeot of temperature on conformational state of adre .toxin (AD7,

bovine adrenal oortex protein with moleoulax weigh' 12 500 I).

Protein was ueed with the purification index AdU/2B0' °«!,6<

To> study the effeot of temperature on protein gJobula atate, adrenodoxin CD­epeotra were measured ini 1) 0.05M Na't­i

2) 0.05M lla­P buffer with 50% aumonium sulfate (Am­ti)i }) 0.05M

Иа­Р buffer with 70* Aa­S In distal "peptide" (200­250 nm), and proximal "aromatic" (250­650) areae. Computer analysis ba­ sed on the OD­speotrosoopy /1/ showed that pronounoed changes in the AD secondary" structure were not observed with temperetu­ re alterations* Although, changes were observed iu Cu­spectra depending on the buffer and time of storage. The results obtai­ ned were further used for growing of AJ) monocryetals suitable for Xrraying.

/1/ I.A.Bolotlna, V.O.Chekhov et. all , J.feil. Biol., }±, 891­901 (1980) ­ 377 ­ PRELIMINARY STUDIES Olf ADRENODOXIN PROTEIN MONOCRYSTALS

WITH ИШ X­RAY METHOD

Оотогот* A.A., Galltsky N.M,

Institute of Bioorganio Chemistry of Aoad. Sei. BSSR, Minsk

The release and Identification of adrenodoxin (AD)э as

on» of tb» components of the electron­transport ohaln from

NADPH to P­450, were first made in search for reductase for

P­450 in steroid hydroxylases. Crystallisation of AD was used

by Kstabrook /1/ and Suhara /2/ to obtain highly purified AD.

Crystals obtained by this method of crystallization are not

•.Tillable to be used for X­ray structural analysis. We sugges­

ted a nethod of obtaining large AD monocrystels which allowed

to grow AD orystals with the following dimensions.' 0y3 x 0,4 x

2.0 mm (tetrahedral prisms), and 0f3 x 0,3 x 2,5 mm (hexahed­

ronal prisms). X­ray structural experiment on AD monocryatale

produoed X­rayograms from an Immobile monoorystal with preoes­

eion ­ 10 . Maximum resolution ­ 4K. Spaoe group R3, a —131 &,

о ­103 Я.

/1/ Batabrook R.W., Suzuki X. et al. In: In.n­rul.iur proteins.

New York, 193­223 (1973). /2/ Suhara K., Takemori S., Katagiri M., B.tochim. Biophys.

Acta, 26Д, 272­278 (1972)

48­1 - 378 - THE EFFECT OF IONS METALS ON THERMOSTABILITY OF ADREHODOXINE FROM BOVINE ADRENOCORTICAL MITOCHONDRIA

V.I. Gritsuk

Institute of Bioorganic Chemistry, Bielorussian, Minsk

Recently evidence has been obtained for direct correlation of the stability molecule of protein in solution and the stabili• ty of protein's crystals /1/. To investigate the effect of ions of metals in these ab• stracts I report a study of the effect of the influence ions Fe , Th , Cu , Hi , p-hydroxyraercuribenzoate and ionic strength on thermostability of the molecule of adrenodozine in the buffer solution by method CD. First, this study clearly indicates that in the temperature

+12°C CD spectrum differs drastically from the same in +2°Cf +5DC, +9°C. Secondly, It has been found that cupric ions are effective• ly in protecting of the molecule adrenodoxlne in the buffer for crystallization from the influence of temperature, 0.1 M NaCl is protecting the same. Reagent, p-mercuribenzoate, for preparation heavy atom deri• vatives suitable of the protein crystals, decrease thermostabili• ty of adrenodoxine and provoke the deep conformation transition of the protein molecule. The effect of red shift of main band in far-UV CD spectrum aa well.as few bands in near-UV and visible CD spectra resulting from th: temperature increase has been determined.

/1/ Gritsuk V.I., Govorova A.A., Galitsky N.M. Vest. Akad. Nauk BSoii, N 5, 66 (1988) ­ 379 ­ INFLUENCE OF 5a AND 17c SVBSTITUENT5 ON THE A­RJNG CONFORMATION OF THE 4­EN­3­ON STEROIDS. FL. Grochulski*. Z. Wawrzak*, Z, Gaidecki*, W.L. Duax* and P. Strong* Institute of Physics* and Institute of General Chemistry" Technical University of bid*, Lddi, Poland £ Medical Foundation of 3uffaIo*, Buffalo, USA.

In 141 of 182 steroid structures [1) having 4­en­3­one compos:.ion the Д ring has normal conformation in wich CI is below and СГ is above or in the plane of the conjugated double bonds­ Only 32 structures have the unusual 1/3,2e»­half­chair conformation. Since besides three main groups of steroids possesing the inverted A ring i.e. those having an additional double bond at the C9­C1C position, those with nonstandard 9/3,10a configuration, and those having 20 substituent, there are two steroids having inverted A ring with 6a methyl and 17a substituents. In order to explore the influence of other 6a and 17a substituents on the A­ring conformation, the X­ray analyses and юо!­п; ,•• mechanics calculations of the three compounds were unci^r'._i 6a­chloro­4­pregnen­3.20­dione­17a­y1 acetate 11J . 6a­me^h­.­ ­pregnen­3, 20—i.ione­17a­y 1 butanoate (II), and 6a­methyl­4­pri­ •;;. ­1 ­ ­3.20­dione­17a­yl pivolate (III)­ The compounds have normal A­rir,j conformation with азитте1. .• • parameters: ЛС'­IO.9 and AC*'Z=15 ­1; AC1,2­3.7 and AC* = 19. J-, в 2 i a AC*'z­6.8 and ДС*'2 = 18.2 for (I). (II) and (III), respectively. The molecular mechanics calculations show that the inverted A : ; r conformation is energeically less favouriable than the normal on". It seems that 6a and 17a substituents cause a slight lowering the energetical barrier between the two conformation ot ­„he A r:n This research was supported by RP.II.10 project from the Pol; Ministry of National Education (to PG, ZW & 26) and by NIAA>.: Grant Wo. PK26546 (formerly AM­26546) an i Dr?R Grant N­;. J­:.'­: 03" (to WLD Я PS).

,r MI Dua>: W . .. Cri" J.Т., Rohrer V.C. Wee'­:: v 4. «;

.4. :n Piw­hemv.a! A.'*,­.­ "f K­'­i .-..-,••.,. V . ! . X1 . I87­.V": ;i­: 4'. 380 ­ STRUCTURAL ASPECTS OF SPECIFIC AND NON­SPECIFIC INHIBITORS OF THE DNA SYNTHESIS G.V. GURSKAYA, E.N. TSAPKINA Institute of Molecular Biology of the USSR Academy 4 of Siencea, Vavilov Str. 32, 117994 Moscow, USSR

In recent years 5'­triphosphates of 2'­deoxynucleoaide analogs substituted at 3'­pOflltLon have .become an impor­ tant tool for the study of the properties of DNA­polyme­ rases Cl]­ These analogs have been established to be able to bind to synthesizing DNA complexes (matrix­primer + DNA­polymerase) replacing natural substrates of dNTP. The monophosphate residues of the analogs when incorporated at 3'­position of the DNA chain terminate their further elon­ gation because of the absence ot the З'­hydroxyl. The af­ finity tor this or that DNA polymerase depends on the na­ ture of eubatifcuents at З'­position. At present such high­ specificity analoge aa 3 ' ­azidor­2', Э ' ­dideoxynucleosidee have been found. They are abLe to inhibit the DNA synthe­ sis only in the presence of retroviral reverse transcrip­ tases. At the same time, 5'­triphosphates of З'­amino­ 2',Э'­dideoxynucleosides, 2'/Э'­dideoxynucleoeidee and 2*,3'­dideoxy­2­3­didehydronucleoeides inhibit the DNA eynthesis catalyzed by a great nunber of DNA­polymerasee. We have performed an Хягау structural study of the high=epecificity analogs of azldothymidine (dT(3'­N )) [2], capable of inhibiting the reproduction of the HIV­1 virus, and that of a nonspecific analog of 3'­amino­2',3'­ dideoxythymidine (dT{3'­NH_)) [3]. Structural peculiari­ ties of these compounds and those of other nonspecific analogs will be analysed. 1. A.A. Kiayeveky. Molecular Biology, i?87, £L, ЭЭ

2. G.V. Gjtsfcaya at al. Dokl. Akad. Nauk SSSR \986, 291,654 3. G.V. Gur taya At al. Dokl. Akad. Nauk SSSR in Prase. ­ 381 ­ STRUCTURE OF THE COMPLEX OP CHYHOTRYPSINOGEN WITH MODIFIED HJ№~FARCKEAT1C SECRETORY TRYPSIN INHIBTT5E (PSTI)

H.J. Hecht fD. Schomburg

GBF (Gesellschaft EUr Biotechnologlsche Porachung), Hascheroder Ueg 1, D­ЗЗОО Braunschveig, PRG

Aa part of a project of Improving binding of PSTI to ••viral protectee other than trypsin tw© modified versions of humeri PSTI with enhanced specificity against chymotrypsin v«r« found and crystallized as a complex with chymotrypslnogen. Both crystallize lsomorphously fro* ammonium sulfate solutions in space group P 41 21 2 uith lattice constants a ­ 84,4 А с ­ 86.7 A and diffract to at least 2.3 A resolution. Structure solution proceeded via no1eculare replacement. As model coordinates vere used independently coordinates of chymotrypsinogen ( Brookhaven protein data bank ) and of к. complex of chymotrypsin vith PSTI4 modeled vlth AMBER. A reciprocal space rotation function yielded for both model coordinates compatible solutions vith a unique peak for the orientation. Translation functions calculated fora both aodel coordinates also gave compatible solutions and a clear peak for the positional parameters of the molecule. For convenience the accordingly orientated and translated model coordinates of the complex chynotrypsln ­ PSTI4 vere used for refinement. The final It­value after refinement of 8 ­ 2.3 A data vas 19.5 % for both complexes after inclusion of зоне bound vater.

The overall three­dimensional structure of PSTI,. Is very similar to the structure of porcine PSTI in the trypsinogen complex /1/. Host of the substitutions caused only minor local variations of the main chain atoms as evidenced by the rns deviation of 0.47 A over residues I 15 to 1 42 and 0.35 A for residues I 14 to I 22 oE the binding loop. Major Differences to porcine PSTI occur in the N­terminal part up to Asn I 14 and In the turn at the end of the helix froa Lye I 43 to Ser I 47. At the N­terninus the first three residues are disordered and not visible In a difference fouriermap.

The chyaotrypsinojfen structure fives a ras deviation of 0.9 A In a comparison vlth all veil defined backbone atoas of free chyaotrypainogen A /2/ and 0.3 A in a comparison vlth chymotrypsin froa the coaplex vith OHTKY /ЗЛ The active site conformation especially is different from free chysratrypainogen and nearly Identical to chymotrypsln.

/1/ Bologneel H., Gatti G,t Henegattl В., Guarneri M. > Harquart H., Papemokoa В., Ruber R. , J. Hoi. Biol. (1982) 162, 839­868

n /2/ Wan» ­t Bode W.f Huber И. t J. Mol. Biol. (1985) 1Й5, 595­624

/3/ Fujinag» M. , Sielecki A., Read R., Ardelt V., Laskovski M., James M. J. Hoi. Biol. (1987) 195, 397­418 - 382

THREE-DIMENSIONAL STRUCTURE OF AN HEXAPEPTIDE DERIVED INHIBITOR OF HOMAN T-LYHPHOTRd'IC HTLV1 H.Hospital. О. Frecigoux, S. Geoff re Labqratoire de Cristailographie - UA IbU CNRS, Universite Bordeaux I, 33405 Talance Cedex (France)

Analysis of the sequence of KTLV1 -roviral protease led Co the suggestion that this enzyme was meat oi the aspartyl protease faaily, on the basis of the conserve i characteristic Asp-Thr-Gly active site sequence and the observed in vitro inhibition by the protease-specific inhibitor, pe* -atIn A /1/. Different putative protease inhibit rs have been synthesized. One of them, which sequence includes a statin residue at the cleavage site, was crystallized by the vapor phase diffusion method,at pH6. The hexapeptide sequence correspond to :

Prolyl-glutamyl-valyl-statyl-alanyl-leuci:

The crystal structure was solved v direct determination using the random start multisolution у jcedure in the SHELXS-36 computer program /2/. The crystal state conformation is characterized by a N-terminal £-pleated sheet -or.:Qr:aatior. followed, ac the level of the hydroxyl group, by .mother exTer.ded structure.

/1/ Katoh.1.. Yasunags,T.. Гл^'-.т,.'-". . Yoshinaka.Y. (1987) Nature, Я:г-, 55а-С56. : ' Sheid-i-k.G.M. , (1986) S-.-.'_KS-86, Program for crystal struct •": -ieT-riainacion. Univ •' C-jtriigr-, federal Republic of - 383 - STRUCTURE OF DRY HEN^EGG LYSOZYME AT 1.8 A RESOLUTION.

G.S.Kachalova, E.T.Myachin, T.Ya.Morozova, V.N.Morozov B.V.Strokopytov , A.A.Vagin .

Institute of Biophysics, USSR Academy of Sciences, Puschino, Moscow region; Institute of Crystallography, USSR Acadeny of Sciences, Moscow, USSR

Three forms of hen-egg lysozyme with different content of water in the unit cell have been obtained: 100*.-, ЗОЛ- and 5V huaidity (comparing to the native state). The crystals belong to space group P . X-ray data for three lysozyme forms were measured ona'Syntex P2 • diffractometer up to 1.8 A resolution using Cu-Ka radiation. Structure of native triclinic crystals (10D\-huoidity) was determined'by molecular replacement method [1]. Subsequently we refined the atonic models of all three forms of lysozyme using CORELS [2] and Hendrickson-Konnert [3] programs. This appraach allowed us to reduce all systematic errors in these structures as well as most of local errors. Final R-values for the refined models are about 22* at 1.8 A resolution. Caipful analysis of these three models gave us an opportunity to estimate translational and rotational shifts of lysozyme domains. It should be emphasized that the structure of lysozyme becomes more dense under the removal of water molecules from the protein surface and the number of hydrogen bonds and поп bonded contacts dramatically increases.

/1/ Crowther R.A. Fast rotation function. In: Molecular replacement Bethod, ed. Rossmann M.G., Gordon & Breach, N.-Y., 1972, p.173. /2/ Sussman J.L., Holbrook S.R., Church G.M., Kim S.H.-Acta Cryst., 1977, v.A33, p.800-804. /3/ Konnert J.H- Acta Cryst., 1977, v.A33, p.614. ­ 384 ­ TR1S(TIHOCYANATO­S)COPPER(!) AND BROMIDE SALTS OF 6 AMINO­U­DI)rtETHYL­5­(ortho­ETHVL)PHENYLAZONIUMURACIl, CATION

R. КЬ/еКаУ, MR. Sundberg", J. Ruiz , and E. Colaclo

*DMslon of Inorganic Chemistry, Department of Chemistry, University of Helsinki, Vuorlk. 20, SF­00100 Finland Departmcnto dc Qulmka Inorganlca, Facuttad de Cknclas, Unlverildad de OrRneda, 1Я071 Qrnnadfl. Spain

To continue out studies on biological activity of metal compJexet of uracil derivative». we determined the crystal ilructure of 6­arnlnol3­dlmelhyl 5­(orTAoelhyl)phenylamnlumurecll irla(thkvcyanain­5)c°. У­ТЙ8ГЧ4) A1. Z~4, Я­0.14 (Л ­0.11) tot IR20 reflections (IndMduat atoms refined). Crystal data for II: trklfrtlc, л в ЛТ. Я­7.1731Ц8), fr­7o.MO(2), £­13.394(2) А, о­70Л4(1),/?­75Л1(Ц,Т­79.54<1)а, K­R80.6<2) А*, />2, R­n.052 (R ­0.040) for 2640 refledlom. The protonatkHi'of the catkin takes place и the nitrogen atom N(ft). The additional proton on the N(R) participate* In a short Intramolecular hydrogen bond between N(R) and the carbonyl oxygen atom 0(4) |N(R)*"0(4) 2.578(4) A for lit. Each of the calkins Is essentially planar. The planar Ihrecjcoordlnatlon for the two non­equivalent Cufl) кии Is clearly distorted (see Figure). ­ 385 ­ SIMILARITIES IN THE THREE­DIMENSIONAL STRUCTURE AND IN THE ACTIVE SITE STRUCTURE OF ASPARTATE TRANSAMINASE IN SOLUTION AND IN THE CRYSTALLINE STATE V.M.Kochkina Institute of Molecular Biology, USSR Academy of Sciences, Moscow, USSR

The structures of aspartate transaminase (AAT) from the cytosol of chicken heart were shown by three independent methods to be similar in the crystalline state of the enzyme and in solution. The spectra of linear dichroism for crystals of the free enzyme and its complexes with eubstrates and their analogues were found to have typical abeoroance bands with maxima at the same wavelengths as for the enzyme in so­ lution /1/. The rate of transamination was determined as a function of the substrate concentration to show that the en­ zyme had quite sirailar properties in the crystalline state and in solution.In both physical states, AAT was characteri­ sed by two sets of kinetic parameters for 2­oxoglutarate and aspartate, which differed by a factor of 3 to 6 /2/. The enzyme activity of crystalline AAT was taken using micro­ crystals grown in a PEG 6000 (20%, w/v) solution. The micro­ crystals ( less then 0,5^um wide) did not restrict the rate of substrate penetration inside them. The catalytic activity of AAT microcrystals taken in a 20% PEG solution was 8о£з% of the enzyme activity in. solution.

/1/ Makarov V.L., Kochkina V.M., Totchinsky Yu.M. Biochim. Biophys.Acta, 6Щ, 219, (1981). /2/ Kochkina V.M., Kuznetsov D.A. Biochimiya, £1,921,(1986).

49­1 ­ 386 ­ PHOTOCYCLIZATIOH IH GIBBERELLINS INVESTIGATED BY X­RAY ANALYSIS

L, Kutsohabaky. 0. Adam, B, Voigt Central Institute for Koleoular Biology, Academy of Salenaee of the ODR, 1115 Berlin­Buoh; Institute for Plant Bloohemletry, Academy of Solenoee of the ODR, 4050 Halle/S., Weinberg 3, GDR

Ultraviolet Irradiation of some derivative» of gibberellin A* produces very unusual novaj polyoyolio photoproduots. The photo­ oyolizatlon products vary considerably, even though the starting materialв are olosely related to eaoh other. By X­ray analysis combined with potential energy calculations the structural formulae aa well as the molecular geometries oould be established. By Irradiation of the GA­­oxo propyl eater' 1_ a 15« ­funotlonall­ zatlon has been observed, leading to the formation of an additional 7­membered lactone ring /1/. In oontrast to this result It oould be shown by X­ray Analysis that upon n­*n ­exoltatlon of QA, phenaoyl ester a rearragement ooouriand a 6­membered АЬхл­lactone Is foraed /2/,/3/« The reaotion meohanism for these two different photooheel­ oal elde­speoiflo funotlonalltatione will be dlsoussed.

­оде AcO о II о­сн2­с­сн3

/1/ Adam, Q., Prelss, A., Hung, Ph.D., Kutaohabsky, L.: Tetrahedron *3_, 5815 (1987)

/2/ Volet, В., Porssl, A.r Adam, 0., Kutsohabsky, L.: Z. Chsm. in the press /3/ Kutsohabsky. L., Volgt, В., Adam, 0.: Cryst. Res. Teohnol. in preparation ­ 387 ­ LOCALIZATION OP THE ESSENTIAL THIOL OP THE NAD­. DEPENDENT FORMATE DEHYDROGENASE 11 9 V.S.LamzlnJ I.A.Shumilin, E.H.Harutyunyan, A.E.Ale­ .shin? T.B.Ustinnikova] Tz.A.Egorov? V.O.Popov1 Institute of biochemistry! U3SH Acad.Sci., Moscow; Institute of Crystallo^raphy, USSR Acad.Sci., Moscowj ^Institute of Go.ieral Oenetlcs, USSR Acad.Sci., Moscow. (ySSH Studies in solution revealed that one of the eix cysteine residues present in the subunit of the NAD­ dependent formate dehydrogenase from Pseudomonas sp.101 is essential for catalysis and stability of the enzyme /1/, The presenoe of the coenzymes ­ NAD or NADH pre­ vents both the enzyme inaotlvation and modification. Aooording to the results of the X­ray structural studi­ es of the ternary complex FDH­NAD­azide two of the cys­ teine residues ­ Gya­!) und Суэ­255 are located in the vicinity of the enzyme aotive centre. Only one of these residues (Cye­B55) la blooked in the aposnzyme by the radioaotlve or fluorescent labels based on iodaoetamide. The projective effeot of the coenzymes is supported by the structural data aocording to which in the holocomp­ lex Cye­255 is soreened from the modi float or, while Оув­5 is readily aooeselbls to the solvent. PDH may be used in various areas of blotoohnology for constructing NADH regeneration systems. The possibi­ lity to lnorease the operational stability of the bac­ terial PDH by substituting its cysteine residues by site­directed mutagenesis is discussed.

/1/ Bgorov АЛ., Avllova T.V., Dikov H.H., Popov V.O., Rodlonov Yu.V., Berezin I.Y. Bur»J.Bioohem. 99. 569 (1979).

CD CM

49­2 388 ­ SPECTROSCOPY AND CRYSTAL STRUCTURE OF THE Kd(III) DIGLYCINE COHPLEX,

Nd(Gly­Gly)2(ClO/4)3^H20

J. Legendziewicz , I. Cso'regh , E, Huskowska* and P. Kierkegaard .

Institute of Chemistry, University of Wroclaw, Joliot­Curie 14,50­383 WrocZaw, Poland; Dept. of Structural Chemistry, Arrhenius Laboratory, University of Stockholm, S­106 91 Stockholm, Sweden.

In order to investigate the interaction between lanthannid ions and amino acids, the neodymium complex with the simple dipeptide glycyl­ glycine (Fig. T) have been studied by X­ray diffraction and spectros­ copic methods.

# Net © 0 © N О С о Н

The NdJ ions are nine coot ­inated: seven of the ligand oxygens are provided by the peptides and the remainig two by the water medium. There are two types of gly­gly residues in the crystal: one of them is coordinated to a pair of neodymiun ions and also chelates one of these cations while the second t,ne coordinates to chrte Nd ions through its three oxygens thus forcing infinite nolymeric chains. Absorptions spectra of a single crystal wem mebsmed ac ro^­a tempe­ rature and the intensities of th

The three­dimensional structure of pea lectin car­ bohydrate complex (*­52000 Da) has been studied by X=­ray method at atomic level. The molecule is the diraer consi­ sting of identical monomers. The organisation of ea^h monomer is characterized by the well­developed fi­ structure. It includes two basic contacting Q ­sheets (flat and curved}, consisting of six and seven antiparallel /3 ­strands correspondingly. The "third nonidea.l five strand ,<3 ­sheet shields the region between basic sheets and is formed by their elongated loop parts. The structure of the dimeric molecule is stabilized by a number of intermonomer hydrogen bonds i- г­ and salt bridges. The Ca and Mn binding site is in the depth of the hole rich in negatively Charged groups. The carbohydrate; binding site of each monomer is localized in a cavity formed by loops 78­81, 98­102, 123­123, 215-21S near Ca' and Mn . The arrangement . of the binding site ligands towards the carbohydrate has been determined. ­ ЗАО­ X­RAY INVESTIGATION OP NATURAL, AND SYNTHETIC PROSTAGLANDINS N.V.Nizlmov*, G.N.Tiehchenko Institute of Crystallography. USSR Aciffemy of Scuncti, Mo•cow. USSR

Wide ipectrum of biological ictlon of prostaglandin» (PG ' * ) ­ ragulitori of ctllultr mitiboliim attract* big inttrtil to thtif compound». At trie ват* tint* thvil particular f»itur»i of natural PG ' • lead to пит* rout ndi ef f*ct * on the unga of PG'a. Coniaquvntly, thli circumstance l»d to inttnuv* itufliti of modified PG'a, po**ea*lng а тисП mora prononcao main «ff«ct • nd, at the iiin* time, po*****ing l«*a *ide tfftcti, Thar* ar* two

principal waye for obtaining PG'• 1} «xctriction from natural lourcin Z) complete cntmicil aynthaaii. The ncond w*v i* much mora economical than the firat on*. It l» poiaiol* to control th* principal itagoi of chemical tyntnul» of PG' i by a careful atudy of aynth**** iot»rmiaiotn, poataftting biological activity. X=rey etudl** of a f*w compound* of Ре­family w*r* carried out. Рог on* of th*m, mod ifi#d P6f. , it WII found that th* epimerizatlon of th* molecui* during th* cnemical tyntheti* took pl«c*. It followed from th* imlyili of a diagram of poaalbl* ld*al conformation* of cyclop*nt*n* that PG activity of th* whole ITID1*CU1* la determined priman)y by cyclop«ntan* earring fragment of the mol*cul**. ft**ult* of itrucruril «tudi** of different ciyatallographlc modtficationa of PGE allowed и» to «vilutU qualitatively th* conformational mobility of the PG mol*cul*a. Taking into account th* result* of X­ray itudiai of th* intermediate* of th* chemical ayntheais of PGF and carbacyclin th* d*gr**, of it«>­«oitl«ctivity th* syntheses of the»* mol*cul*t WII evaluated. This i* of principal vaiu* for th* correct control of *y'nth**t» of the product*, possessing strong P6=.ac t lvity . ­ 391 ­ MOLECULAR STRUCTURE OF HUMAN IMMUNODEFICIENCY VIRUS PRDTEARE

I.V.Fee hi к. A.E.Gustchlna end N.S.Andreeva

Institute of Molecular Biology Academy of Sciences of USSR, Vevilov Street ?2, MOSCOH 117"J04, USSR

Retroviral protegee» play an important role In pro­ cessing of viral proteir.B by the specific cleavage of their polyproteln precusor proceeding the formation of mature virtu particles. ­This protegee» belong to the cUti of «spartic proteases, three­dimensional structu­ ••i of HlV­^proteame, established at 3 A resolution, has а high decree of homology Hlth the *.tr­uctur# of pep»ln do­ main* [1­3]. The molecule 1* a dirtier of subunlts with molecular 1Q к DA, the two­nfold «HIS of the dlmer relate* the tnwo halfm of the active site of the eniyme. Molecular model of HIV»1 protease make* it (rosslble to investi­ gate the structural grounds of the enzyme specificity, to describe the groups critical for the formation of the dlmer *nd to develop studies on the de«ign of Inhibitors. for Hiv­l protease.

1. Pwchilc I.V., Buetchina A.E., Andi­eeva N.B., FedoroV A.A. (1789) FEB8 Lettr. in press 2. Pec hi к I.V., Qustchina A.E., And<­eeva N.S., Fedorov A.A." (198B) in "Btructure and Biosynthesis of Proteins" ed.A.S. Bpirin, v.3, p.87­96 3. Navia M.A.,Fitzgerald P.M.D.,McK%ever« B.M. , Chin­Tal Leu, Meimbach J.C.Herber U.K., Sig«l I.S., Darke P.L. , Springer J.P. (1989) Nature in prevs ­ 392 — NUCLEATION AT POLYMORPHIC TRANSITIONS IN ORGANIC CRYSTALS i' N.Petropavlov Institute of Biological Physics, VSSTi Academy ci Sciences, Pushchino, 142292, USSR

Polymorphic ' sniper at ure transitions (?T) in organic crystals have been considered as a growth of daughter phase crystal inside the parent crystal (p) proceeding by way of nucleation and fur­ ther development of new phase nuclei. The nucieation occurs on the P defects that are localized on the habit faces, boundaries between blocks and domens, on the slip planes and phase boundary and appear as line and point dislocations, imperfection of mole­ cular packing, lattice vacancies and inclusions. The number of the new phase nucle* (;•;) determines the type of ?T: monocrystal*­ ­•polycrystal, monocrystal»monocrystal, polycrystAl­*rnonocrystal. Nucleation JS a temperature­dependent process of a threshold

character proceeding; with the hysteresis д 'Л,­ IT..­T ( * where Тл is the temperature of the thermal equilibrium of the phases.

aT. increases with i' perfection an:' upon temperature relaxation of the cryatel, and at д".\, > ^«"­jl the rcetastable phase melts without the P?. NuclentJon depends on crystal habits and cleav­

ability. In lamellar crystals, a TTr is lower than in homogenous samples. Nucleation exhibits "memory" effect. The definition of the dimensions of the nuclei is limited by optical resolution of a microscope. At the early stages of crystal growth, the nuclei undergo deformation until they reach the size of tens of microns. At the next stages, the nuclei become more perfect, but some steric hindrances appear that influence the orientational rela­ tions of growth phases in both daughter and parent crystals and thus the morphology and mechanism of рт. ­ 393 ­ TWO STRUCTURES OF TOSYLOMETHYL DERIVATIVES OF PIRIOAZINE M. Ratajczak­Sitarz, 2, Kalueki Department of Chemistry, Adam Mickiewicz University, Grunwaldzka f>, '60,780 Poznari, Poland.

This Х­гву structurbl determination oi 3­chloro~6­methoxy­5­ ­tosylomethylenepiridezine (I) end 3­chlora­5­tosylamethylenepiri­ zlazine (H) was undertaken mainly to establish their structural formula ­ in particular the site p? the tosylomethylene substituent In the piridazlne ring ­ end conformation of the molecules. The interest in piridezlne derivatives in pharmacological chemistry dates from early fifties when their biological properties were discovered; the plrldaztne derivatives have been also found in •ntiblotlcs produced by Stre.'tomices Jama icons is. Crystals I end II were recrystallized from ethanol solution. The measurements were carried out on a Syntex P2, diffTactometer using graphite monoohrometftd CuK^ radiation. Crystal data: I ­ CJJHJ ^Cl 0­jS, monoclinlc, P г^с, a=12.365(2), b«5.524(1), C­2J . 646(4) R, /5*106.98(1)*, 1>4. II ­ С j2 HnN2Cin?S, orthorhombic, P 2^2^ a=9.888(2), b=25.Ci5(4), c = 5.411(1) 8, Z>4. The structures were solved using SKELX5­B6 program (Sheldrick,1986i The final cycles of the full­matrix least­squares refinement gave for I R.0.049, wR=n.0*9 for 1470 reflections, for II R­0.067, wR=0.064 for 867 reflections. It was established that the tosylomethylene substltuent is present at C(5) in the pirldazlne rings. The bond distances and velency angles are in good agreement with the expected values for these molecules. The benzene end piridazine rings are planar within error. The conformation of the molecule can be conviniently described by three torsion angles measured along the bonds bridging the phenyl and pi ldazine rings, the central of these three torsion angles describes the mutual position of these rings and two side ones ­ ­ their orientation. The conformation of molecule I as a whole can be described as a cis­conformation. Molecule II is nearly planar and the angle between the planes fitted to its two 'ring is 3.7(3)'. No shorter than van der Waals intermolecular .Interactions were found in tnis structure.

50­1 • ­ 394 ­ PREDICTION AND B6TABLISHMBNT OF A NEW CRYSTALUNB PIROXICA*

MODIFICATION, C15H13K3O^S Q. Reek. 0. Laban Central Institute of Molecular Biology, Aoademy of Solenoee, Berlin and VBB Arsnelmlttelwirk Dresden, ODR

The analgeelo and anti­inflammatory agent plroxloam exists In different crystalline forme /1,2,3,4/. Detailed Investigation* of special diffraction phenomena led to the conclusion that the orthorhombic ot­modlflcatlon /3/ belongs to a family of disordered structures with at least two structures of maximum degre» of order (MDO). The crystal structure of "a." should be one of the possible MDO's. Significant differences in powder dlffraotion pattern of some samples were explained by different ratios of MDO1и. Using the structural parameters of "oC" symmetry, approximate lattice constants and atomlo coordinates of a second MDO named " *C" were derived by geometrical packing analyses.

л Я Qulnler photograph of a powder sample oontainlng mainly " г" was used for a least squares refinement of the unit oell. A rigid­ body refinement using the powder diffraotion data oonverged with

R ­X

Crystal data: oN­forti ot p­fonn

a ,11.801(2) X 17.489(7) % b 17.357(5) 11.794(4) о 6.981(3) 6.910(3) В 97.38 (8) ° spaoe group Рса2^ Р2^/о Z 4 4 /1/ Kojlc­Prodlo В., BuBid­Toroe' Z., Aota Cryst. В Д8, 2948 (1982) /2/ Bordner J., Richards J.A., Weeks P., Whipple Б.В., Aota Cryst. С 40, 989 (1984)

/3/ Raok Q.„ Diets Q.t Laban Q., OUnther, V., Bannler G., HBhne, E.t Pharmasle kjt, 477 (1988) /4/ Cccrdas Ь., Medgyasay M., 11. ECK (Wlen 1988) Abstract p. 158 STBUCTUU or no MW oiTunms пюи KARIHI aouacis H.L.Rodriguez, C.Rulz­perez. L.Porta• J.D.Martin, .M.zarraga. H.Norte and P.Arroyo. C.P.N.O.A.O. Unlveraidad La Laguna ­ C.S.I.С Э8206 La° Laguna, Tenerlfe, Spain

Cyclic dlterpen»» »ТФ the typical aetabolltea laolated froa brown alga*, aalnly fro» the Dlctvo­ taceaa faaily. Owing to «lnor atructural difference* ehowed by thla kind of natural produca, X­Ray analyala haa ahown to be a ueeful tool for elucidating their aolecular atr'jcturea.

The atructure of two new diterpenea laolated froa a Qloaaohora ID. and a Dvctlora ao. will be dla­ cuaaed. The cryatal data for both coapoundu are aa follows Coaoound л Compound В roraule C22H34°5 C20H32°3 gyatea Orthorhoablc Monocllnlc Space group C2 «1*1*1 16.687(1) 9.424(1) 6.2605(2) 10.236(1) 21.231(1) 22.675(4) В 120.38(3) П V 1913.3 2117.2 I 4 Ob*, refl. 1857(20(1)) 1554(20(1)) Solution Direct aethoda Reflneaent In Го with 1 block • 0.045

50­2 ­ 396 ­ THE CRYSTAL STRUCTURE OF THE ANTITUMOR PROTEIN­ MACROMOMYCIN AT 1.3A RESOLUTION. Patrick Van Roey, Medical Foundation of Buffalo, Inc.. Buffalo. NY 14203. USA.

The antitumor antibiotic auromomycin (AUR) consists of an

apoprotein called macromomycm (MCR, Mr» 12.000) and an as yet

unidentified chromophore (Mt «=650). The chromophore is capable of causing single and double slrand breaks In DNA but is very unstable in isolated form. MCR is inactive but protects the chromophore from

degradation by reducing agents. Monoclinlc crystals of MCR (Р2г. в ­ 36.29A, b = 35ЛЛ. с = 38.04Л. В •= 99.59*) have been obtained from a 25 mM Tris. 5 mM CaCI,. pH 8.0 solution with 68% MPLt as the precipitating agent. The structure has been determined by multiple isomorphous replacement methods. The molecular structure consists of two domains: a highly ordered seven strand antiparallel f)­barrel and two less well ordered 0­sheet loops. The chromophore binding site is located in the deft between the two domains. It is assumed that the two flexible loops would wrap arovmj the cftromophore when it Is bound but they are not large enough to completely enclose the chromophore. Two MPD molecules have been located In the binding site. The overall structure is very similar to that of the partially homologous analogue actinoxanthln (AXN) /I/, but significant differences are observed In the shape and content of the binding site. The MCR binding site Is narrower than that of AXN. Prominent residues in the MCR binding site include HisJ2, ile42. SerSI. Ser94 and the disulfide bridge Cys36­Cys46. The first four of these residues are not conserved in the AXN sequence. Implications for the binding and nature of the chromophore will be discussed. Research supported In part by PHS grant СА­Э4769 from the National Cancer Institute.

/l/'Pletnev. V.Z., Kuzin. A.P.. Trakhanov. S.D.. and Kostelsky. P.V. (1982). Blopolymers. 2]. 287­300. ­ 397 ­

С,Ruiz­Perez. M.L. Rodriguez, M. Norte. F.Cataldo end A.G. Qonzalez C.P.N.O.A.G.. Univereidad La Laguna ­ C.S.I.С 38206 L* Lacuna, Tenerife, Spain

Slphonarla are gastropod molluscs found In the high lnterdltal region. These animals are characterized by producing antimicrobial netaboil tee presenting a "poly­ proplonate skeleton", which are believed to be emplo­ yed in a chemical defence against predators, gjphopa­ rla dlemenenals. S.lesmoni: S.pectlnata and S. saura /1/, contain metabolites with т­ругопе, furanone and hemiketal Moieties. у QH Single crystals of the title compound, C2lH28°3' Mr­ 328.5 were grown from methanol/ether. They are of­ thorhomblc. space group Рг.2,2., z«4 and а»ю.412(6) b­ 12.900(5}, c­l5.606(u)A Three­dimensional diffrac­ tion data set (Siemens AED, CuKct radiation) consists of 1916 Independent and significant reflections (Ii3o(D). The structure was solved by.direct methods using HULTAN 80 program and refined to R­0.08e with XRAY­80. THe absolute configuration of the Pectlnatone was de­ termined by comparison of 19 BlJvoet pairs with Fo>10o, which are in the ranges 5.

The title compound Is the flrts л­ray study in the se­ ries of antimicrobial metabolites with an (S,S,S) absolute configuration in the alkanyl moiety. All the other related compounds isolated before have had (S,R,S) configurations which "ere established on the basis of their ozonolysls.

/1/ D.c.Hanker, D.J.Faulkner, X.chang­Fu and J.ciardy J.Org.Chem., 51. 614 (1986) /2/ M.Martlnez­Rlpoll and J.Fayos Z.KrlStallogr., 1S2, 189 (1980) Acknowledgment: F.C. thanks the AIETI for fellowship ­ 398 ­ THE CHARACTERISTIC FEATURES OF TAUTOMETIIC FORMS AND CONFORMATION

ОГ PYRIDOXINS (VITAMIN Bg) IN COMPLEXES OP TRANSITIONAL METALS K.Kh.Sablrov, S.Lltvinov, A.N.Yunuefchodjaev Teachers' Training Institute, Tashkent, USSR

Pyridoxlne (PN,2­methyl­3­hydroxy­4rS­dl(hydroxymethyl)­pyrl* dine) 1* a biological stable form of vitamins В.. The biological activity of PN depends on its conversion into pyrldoxal­5­phosoha­ te, l.e, on oxidation of 4­hydroxymethyl qroup Into aldehyde and etherlficatlon of 5­hydroxymethyl group by the phosphorate acid, that provides the binding of vitamin with the apoferment. In the complexes the biological activity of PN Increases by tvo and more orders. Supposing, that the increase of biological activity of PN is duetto the effect of coordination by metals on electrons and PN space structure we discuss in this report PN structure neculiarltl­

es in the following compoundsi HBr­PNII) ,[cu (PN)] [cuCl4]2H2n 'in,

[Cu(PN)2] (N03»2(III),[cu ^­PN­H)]*03 2,5H20(IV), L^V/V 1 1 PN­H>3 (V),[Cu(Q> tPN)ClJCl04­H20(VI) ,[C0{QJ2(PN­H>J (СЮ4> (VII)

(0­2,2­blpyridyl), f Ho02fPN­H)2] OHjO (VIII). In t lie to complexes chelate coordination with oxygen atoms of nhenollc and adjacent 4=. hydroxymethyl groups Is typical of PN ligand. Different tautomeric forms of PN are realized in the following compoundsi HO­W, HO­CH, m'c*k "O­CH,

HHV (PNtn tt­atm (M­H in IT; ;PN­Miffl,mj In compound I both hydroxymethyl groups are cop1anar with py­ cycle. But In complexes with metals the hydroxy1 groups of 4­ and 5­hydroxymethyl groups are strongly taken out from the plane of py­ cycle. The deprotonlzation of 4­hydroxymethyl group In V, VII and VIII proves, that coordination of metals ions brings about labill­ xation of protons of coordinated hydroxymethyl group. The unfolded conformation with labllization of protons of 4­ hydroxymethyl group makes the hydroxynethyl groups more accessible for the attack of*cubstrate and makes easier the transition of ­PN into tha pyrldoxal­5­phosphate. 1 . Sudhakara Rao S.P., et al. ­ Inorg. chem,, V.25, p.734­740. ­ 399­ STRUCTURE OF LEGHEMOGLOBIN COMPLEXES AT 1,7 Я ADD 1,8 i RESOLUTION. T.H.Safonovo, G.V.Obmolova, A.V.Teplyekov, I.P.Kuranovq. A.B.Popov, S.V.Rubinsky, A.A.Rusakov, в .Н .Harutyunyan Inetitute of Crystallography, USSR Aoademy of Sciences, Moscow, USSR

Two llgand states (oxy and isoquinollne) of leghemoglobln (Lb) from lupinus luteus root nodules have been studied by lira; diffraotion technique. Data sets inoluding 14436 and 10893 Independent reflexions up to 1,7 X and 1,8 % resolution respectively for oxy­Lb (LbOO at ­20° 0 nnd looquinolino»Lb (Lb­rlQ) nt +25° 0 have been colleoted using CARD­diffTactometer. Struotures have been refined by the Hendrlokson ­ Konnert restrained least­square method to R­faotors of 15Я and 18%.

Models comprise 254 (LbO?) and 167 (Lb­IQ) solvent molecules.

In LbO_ the oxygen r:oleoule Is bound to the Iron with best geometry, Pe­0, 2,00 Я. The oaoupanales for oxygen atoms are 0,4 (0.) and 0,5 (On). Low oooupanoies are probably due to some disorder. The dlsplaoement of Pe atom from the heme plane is 0,3 Я towards His P11 (proximal), this displacement io greater than in deoxy­Lb (0,08 8)» Oxycenntion leads to rotation of the imidazole ring of His F11 by 30°, as a result of this rotation the hydrogen bond between Kj­ His F11 and 0 Leu P7 is broken. In Lb^IQ the llgand is bound to the heme through the oarbon atom (Fe­C 1,71 X), the isoqulnoline molecule Is at an pi­;­­ ­» 104° to the heme plane. The Inclined disposal of the ligand is probably due to the bulky size of isoquinoline. There is a'short eontcot between the ligand and Phe 310 (2,95 X). The displacement of Fe atom from the heme plane is 0,08 £ towards His F11. The conformstlonal changes between LbOo. Lb­IQ and deoxy­Lb are discussed. ­ 400 ­ CONFORMATIONAL FLEXIBILITY OF 1.4­01ЕИ­3­0ИЕ STEROIDS

D. SCHARFENBER6; И . BOH.; K. SIMON

Acade* of Science of the OR, Central Institute of Molecular Biology. Berlin. Central Institute of Microbiology and Experimental Therapy, Jena; Chlnoln Research Centre, Budapest, Hungary

The 1,4­dlen­3­one structural element Is a common feature of several dlffe­. rentlу acting steroids. It belongs to the fundamental structure of the anti­ inflammatory steroids such as prednisone, prednisolone, dexametasone etc. It It also found In anabolic steroids like methandlenone and In some aroma­ tase Inhibitors useful In the treatment of estrogen­dependent breast cancer. Two X­ray crystal structures of steroids I and II were solved by direct methods and refined by full­matrix least­squares procedures:

(!) 1J6l.21­dlhydroxy­1,4­pregnadlene­3,20­dlone (C21H2g04, '2,2,2,, Z­4, ••7.727(1), b.10.095(2), c­22.876(4) t, R.0.05 for 1850 obsd. reflect.), (II) 17<*­ecetuxy­2l­hydroxy­l,4­pregnadlene­3,20­dione (C^HJQOJ, '2,2,2,, Z«4, «.10.950(3). b.H.B57(4), c.15.634(6) X, R.0.05 for 1325 obsd. re­ flections). A comparison of these two and 18 other relevant l,4­dlen­3­one structures retrieved from the Cambridge Structural Database as well as MM2p molecular mechanics calculations on a model steroid Indicate a relatively high con­ formational flexibility In the region of A and в rings. Contributions can be found, e.g., from the variability In A­rlng boning relative to the plane of B­rlng atoms (the angle ot, between the corresponding normal vectors varies from 29.3 to 42.3 °), from different B­ring orientations with re­ spect to the CO­rlngs plane (the angle В between these normals varies from 2.8 to 14.5°), or fro» some dlstorslons In the en­3­one planarlty. Thus, It turns out that the structure II adopts a relatively flat confor­ mation («.32.5°, B.2.80). Due to this mobility, the 03 oxygen atom of 1,4­dlen­3­one steroids can occupy positions which are similar to those of Inverted and normal A­rlng conformations of 4­en­3­one steroids with the energy­minimum structure of the dlenont being close to the inverted one. This oxygen location Is con­ sidered to be Important for drug recognition and/or binding by receptors and enzymes. ­401­ LLLCTRON MICROSCOPY ANALYSIS OF CRYSTALS OF 70S RIBOSOMES AND 30S RIBOSOMAL SUBUNITS FROM Thегтив thermophilue Yu.V.Sergeev, V.A.Shlrokov, S.N.Ryazantsev, V.O.Vasiliev, S.D.Trak,hanav, M.M.Yusupov, S.V.Tischenko and M.B.Garber

Institute of Protein Research, USSR Academy of Sciences, Pushchlna, Moscow Region, USSR

Electron micrographs of thin sections of 70S ribosome and ЗОЯ riboaomal eubunit crystals were analyzed by computer filtering. Rod­Like and hexagonal barrel crystal modifications of the ЗОЯ aubunit were studied.•Unit cell face parameters 410x360 A, Y ­= 100° and 340 x 170 R, у = Ю1п have been revealed by thin sec­ tions image .malysis of rod­like crystals. Thin laminar(pseudo two­dimensional) microcrystals and large blpyramtdal crystals of 70S ribosome were analysed. The mlcro­ cryatals are suitable for three­dimensional reconstruction at about 45 a resolution. The parameters of the two­dimensional lat­ tice are 480x480 K, y=90°. Large bipyramidal 70S ribosomal crystals were examined by X­ray synchrotron beam. Dimensions of its tetragonal unit cell were a=b = 510 8 and с = ЗВ0 8. Unit cell parameters a ­ 50O й, с ­ 380 8 have been revealed by computer image analysis of thin sections. These values are close to those obtained from X­ray data. Such an analysis could permit the determination of the particle position in the unit cell.

i I

5T­I ­402­ STRUCTURAL FEATURES OP BIS

A.N. Shnulin. Т.К. Oasanov, l.R. tyatlfov, V.I. Shllnikov, Т.К. Kurbanov Institute of Theoretloal Problems of Chemical Teohnology, Institute of Inorganic and Physical Chemistry, Aoad. Sol. AzSSR, Baku, USSR

The crystal structure of the titled compound (He,Cp»(CO),)2 has been determined by X­ray crystal struoture analysis. The com­ pound crystallizes in monoclinio system,speoe group 02 with unit celleparametera: a«17.125(2), b­9.0925(2), o­9.3755(7)X, e. 115.687(6)°, Z»2, RaO.0399. The isostruotural oompounds of the similar composition suoh as (CeH.J.IMCOb (M>Cr,Mo,W) are well laiown /1/. In the crystalline state all the moleoules take trans­ configuration. These iroleaules are exceptionally eterloally orow­ ded because of Internal Interactions between their oentroeymmet­ rlcal halves • By means of PMR studies there has been indioated the existence of both anti­ and gauoha­rotaaera in solutions of the compounds. Inspection of a model of the moleoules has shown /1/ that the energy as a function of rotation about the M­M bond has three minima (gauohe­conformatlon) and three maxima (ois­oon­ formatlon). Prom this point of view the replacement of Cp­rlrg by Cp(Mc­) cycle made even more Implausible the suggestion about the possibility of performing the oomplex with оis­arrangement.There­ fore, the striking and unexpected fact is the observation of this configuration in the coupler under study. The two halves of the molecules are related to axle 2. The computations of energy of the two isomeric forms with minimisation is in fact Indicative of the values of the energy proved to be the same. The results obtained point out the possibility of existence of trans­mole­ cules, although not'explaining the absence of cis­moleoulee In the compounds previously studied /1/. The possible explanation may be associated with great height of the rotation barrier, se­ parating the gauche and ols­oonformatlons and being nonovercome at the temperatures used.

/1/ Adams R.S., Collins D.M., Cotton P.A., J. Am. Chem. Soc. 96, 749 (1974); Inorg. Chem. _y, 1086 (1976) ­40Э­ R&TINEMENT Of PEPSIN MOLECULAR STRUCTURE IN MONOCLINIC CRYSTALS AT 1.8 A RESOLUTION

• *.R. Sleleok*, A.A. »edorov*«, M.N.O. Jamea*and N.S. Andreeva*» •Bioohemioel Department, University at Alberta, Edmonton, Canada T60 2H7t ••Institute of Holeeular Biology, Academy of Sslencea of the USSR, Moaoow 117984, USSR

«onoollnlo papain crystal» with the dlffreotional field ex­ tending up to 1.8 A resolution hare been grown from water­etha­ nol solutions. Intenaltlea of about 24,000 Independent reflec­ tion* hare been measured with the uae of area deteotor. Hendriok­ •on­Konnert prooedure of the refinement haa been applied. Silicon graphlos atatlon haa been uaed for the refinement work. The final result of the refinement of papain atoalo­ parameters with several hundreds water oxygen* as well a* bound athanol moleoulea will be presented.

51­2 -404- CRYSTAL STRUCTURE OF THERMITASE AT 1.4 A RESOLUTION.

A.TBF-LYAKOV, l.KURANOVA, E.HARUTYU>' N FROMMEL*, W.MOHNE*. K.WILSON+

Institute of Crystallography, Academy of Scicno JS5R, Lcninsky pr. 59, Moscow 117333. USSR,

•Institute for Biochemistry, Humboldt University, Hcssische sir. 3-4, Berlin 1ГМ0, DDR'? 'European Molecular Biology Laboratory, Hamburg Outsiati'on, NoiJccsir. Я5, 2000 Hamburg 52, FRG

The crystal structure of ihermitase, a subtilisin-type serine proteinase from Thermnactinomyces vulgaris, was determined by X-ray diffraction at 1.4 A resolution. The structure was solved by a combination of (he molecular replacemeni and the single isomorphous replacement methods /1/. The starting model was thai of subtilisin BPN' from the Proiein Data Bank, determined at 2.5 A resolution /2/. Two X-ray data sets were used in the study. One of them (to 1.7 Л resolution) was collected on the diffractomcter KARDr3 with the muJtiwire area defector (Institute of Crystal log rapby, Moscow). The other (to 1.4 A resolution) was collected on the Fuji image plate on the synchrotron beam (EMBL, Hamburg). The model of thcrmitase refined with the Hendrickson restrainsd_-lcasl-_squares program to a conventional R factor of 14.9 % contains 1997 protein atoms, 182 water molecules and 2 Ca ions. The tertiary structure of thcrmitase is similar to that of the other subtilisins although there are some substantial differences in details. The central P-sheel contains 8 parallel and 2 anliparallel Д-strands. The N-terminal fragment of the chain which is absent in the other subtilisins forms a number of contacts with the main Ca-binding site and may provide the very light binding of the Ca2+ ion. The carboxyl oxygen of Asp5 is involved in the coordination sphere of Ca2* ion instead of Gln2 in the Bacillii subtilisins. This site (residues 82-89) is the same as in subtitisins BPN' and Carlsberg, but is absent in proteinase K. The second Ca-binding site in thermitasc formed by residues 57-66 is unique among the four subu'lisins. The potential third Ca-binding site which is common for the other three subtilisins is occupied by a water molecule. This fact may be the consequence of the lack of Ca2+ in the crystallization solution. The Ca2+ ions are known to play an important role in the stabilization of the structure of subtiltsins against heating and autolysis. The existence of the three potential Ca2* sites in thermitase and the observed mode of their binding suggest that the Ca2* ions may be the major reason of the relatively higher thermal stability of thermitase compared to die other subtilisins.

/1/ Teplyakov. A.V., Strokopylov, B.V.. Kuranova, LP., Popov, A.N., Harutyunyan, E.H., Vainshtein. B.K., Fro'mmel, С Htfhne, W.E. (1986) KristaJlographia 31,931-936. W Wright C.S., Akten, R.A., Kraut, J. (1969) Nature 221, 235-242. -405- STRUCTURE AND PHYSIOLOGICAL ACTION OP DSFSIFEPTIDK IONOPHOHOUS ANTIBIOTICS

G.N. Tiahchenko Institute of Crystallography, USSR Academy of Sciences, Moscow, USSR

Physiological function of the ionophorous antibiotics of en• niatin and valinomycin series consists in the inducing of the al• kali and alkali-earth lone transport though the biological mem• branes. These antibiotics are also used as a tool for the inves• tigation of biological and artificial membranes and of the mechanism of transmembrane ionic transport. By the method of X-ray structure analysis the crystal con• formations of a considerable number of enniatin and valinomycin compounds including native antibiotics and their various analo• gues with the 6- to 36-membored depelpeptide cycles in free state and in metal complexes are determined. Several new conformational types for the cycles of various size were found, the correlation between conformations in crystal In dolution and calculated ones was studied. Conformational fea• tures of antibiotic molecul s responsible for their ionophoric activity ware revealed and changes of molecular conformations under binding releasing of the ions at the membrane surfaces were trac sd. Structural aspects of alkali metal ion transport across biological membranes by enniatin and valinomycin antibiotics were considered and a mechanism of that transport on the atomlc- molacular level was suggested. ­406­

ACETYL­tGLYCYL­BETA­ALANYL» ­N­PROPIL­AMIDEI A HELIX SIMILAR TO POLYGLYCINE­II

J. Tormo, J­ Puiggall, J. Aym^ml, . Flta, J.A. Sufcirana Dept. Enginyerla Qulmica, FTSEIB, Barcelona 08028, SPAIN.

The title compound crystallizes lti an extremely narrow cricllnlc cell with a­4.84 A, b­4.ee A, c­45.38 A, «­89.89" ^«90.02*, /­119.73'. It contains two molecule* In the unit cell along the c­axis. Thus two alternating layer* are generated, one with right handed heli­ ces and the other with left handed. The helices are similar to polyylycin*­TI /1/, each helix making hydrogen bonds with it» six neighbours In a three di­ mensional array. The conformation of the glycine residue Is similar to the proposed polyglycine­II model with a torsion angle of 120*, whereas beta­ alanine is in the extended form usually found In nylons. This model was pre­ viously proposed for the polymer (gly­ cylc­beta­alanlne* /2/. figure i­ The unfct cell contains two (го 1 ecu lea ­indicated with solid black bonds­ in a head­to­tail pattern, one right handed and the other left handed. The empty bonds represent the molecules wich are around the central molecule and form hydrogen bonds with it. A sche matlc view­of the projection of a mole­ cule and its six neighbours onto the ab plane is also shown. On*y nitrogen and oxygen atoms are presented. The arrows Indicate the helix handed­ ness and the broken lines indicate the hydrogen, bonds.

/1/ Crick F.H.C., Rich A.r Na'ure (London), 176, 7780 (1955). /2/ Hufloz­Guerra >., Flta I., Aymaml J., Macromolecules, 21, 3464 (1988). ­407­ BTRUCTURE OF ADENI Г* I*lSl^S*i_Si.Qii Mitkevich V.V. ' Institute for Low Teaperatur» Physic» *» Engineering, UfcrSSR Acadeey oj­ Science», Kharkov, USSR

Aaong the nucltlc «eld baHi, only adenine forma * trlhydrate. This la conditioned by the Molecular structure pecularitles of «danin*. Studies of anhydrous adenine crystal» *r* of interest because they per«it the effect of water on the structure of crystalline hydrate» to be еиаа­ined. Adenine single crystals are prepared by cooling a weak

alkaline 10.1 M Na2C03> hydrous solution of the base fro* 90 °C et a rate of 10 degreeVday. The adenine crystal» C_H_N_ belong to mm orthorhoabic syngonia with space group F ddd and ere characterized by the following parameters! a*8.S01O> 8,

3 Ь­12.725(3> 8, c­22.337(3» 8, V­241B.4<7» 8 f ПМЗЭ. I , Z*16, d «1.4B5 g/ca , R­0.033. When refined , the adenine molecule geoawtry is fixed /l/. The crystal base occupies the position on 2rfold axis and is disordered. Each of the adenine Molecule» fore* six hydrogen bonds. As shown in the figure, the systea of hydrogen bonds Is Independent of the base disorder because of a pecular arrangement of the hydrogen bonding centers. The great nueber of hydrogen bonds in crystal result» in a high density for­ the disordered structure.

/1/ Tretyak 8.M., Hitkevlch V.V., Bukhodub L.F., Krlatallograflya, 32, 1Z6B (19671. ­408­ BTRUCTURt Of TWO B^PFfOPYL t METHYLADENINE U

Deterelnation of structure of two crystal 1 in*' hydrate* of

(C t, N ) н 8rpropyl­9:s»*thyl adenine o .3 . * ­,° ьесам a part of the subject of study into hydration of nucl HIC *L I CJ base* and their al Icy 1 der t vati ve». The pr i nc 1 pal object of the study пае estimation of geometrical parameters of hydrogen bond» to apply thaw in calculations by the atom­atom potential function method. The crystalline hydrates with the tin ratio of 4i3 and H2 мете obtained. The 4i3 crystalline hyoratea неге grown by ** vapor at lng a aqueous solution at room temperature. The crystals are unstable In air and exist solely at equilibrium with the base saturated volution. The structure мае determined at 29S and 130 K. The crystal was placed in a capillary tube to collect the room temperature data. The Ii2 single crystal* «ere prepared by evaporated slowly a *ba*e­=acetonl tri le solution. Products of the 4*3 crystal decomposition were used to prepere the solution. Total crystallography data are given bellow.

Composition m*n 4l3 4i3 li2 Temperature 293 130 293 Hoi. nelght 643.7 649.7 396.S a <8> 9.30941> 9.433(3) 7.384(1) b 13.019(2) 12.7"?9<3) 12.240(2> с 14.388(3) 14.27214) 12.442(2) I <°» I04.32<1) 103.87<2) 98.11(1) p 7*. 03 Ш 78*01 (3> 97.93 (1 > Г 1О0.32<1) 100.84(2* 108.08<1> V (Я 3) 1670.80) 1672. S49) 1038.4(3)

3 ?н (g/a* ) 1.2B4 1.322 1.269 No. ofas. reflections 3996 2*Ю 310А ft 0.074 O.093 0.097 Space group is P 1 , Z«2. fteneetries and conformation* for five independent molecule» of that ba*m mre compared. -409-

X-RAY ANAI.VSIS OF DECATRI PEPTIDE (PRO-PRO-CLY I] 0 MODKI.I. INC COLUREN ILGJumanyaj]. R.A.Abagyan. V.N.Rogulenkova. N.C.Eslpova .Institute of Molecular Biology, USSR Academy of Scien• ces. Mosco». USSR

IPro-Pro-ClyI]0 Is of Interest as a model of ho- •ologous regions of collagen. The refinement of struc• ture has been carried out using an Improved x-ray and energetical criteria on the basis of experimental Inten• sities reported In /1/. Calculation of theorejical In• tensities has been done not forasubcell IC-20A1 using an

approach ofocontIguous molecules as In /\/, but forafult cell Ic-100AI taxing Into account the Intermolecular gaps, The accurate method of molecular geometry and energy calculation has been used /?./. This method pro• vides continuous deformation of prolines. Optimization of sua of diffraction and energetic criteria leads to uneq• uivocal decision In contrast to 4--th variants from /t/. The structure Includes 640 nonhydrogen atoms; the number of independent parameters Is 17 and 4 positional molec• ular parameters. The optimized structure has minimal va• lues of R-factor (0.2241 and energy In comparison with other variant». It Is close to energetically optimal structure from /2/ that is also characterised by "donn" and *do«n* conformations of prolines, x-ray optimal structure differs from energetical one by simultaneous variations In |>, and t» ancles and by rotation of C0- troup Into enter space providing more favourable hydra• tion accompanying «eakness of Intramolecular H-bond. /1/ Okuyama K.. Okuyama K., Arnott S.. Takayanagl M..

Kakudo M.. J. Mol. Biol. 152. 427 (19811. 121 Tumanyan V.C.. Eslpova N.C., Blopolymers 21, 475 (19621.

52-1 .­410­ STUCTURE OF THE DEOXYNUCLEOTIDE d

im\ Lourdes Urpl, Ignacio Fita I Juan A.Subirana Tarn Huynh­Dinh & Jean Igolen

{*) Unitat de Qulmica Macromolecular, E.T.S.Engineer* Industri als. Diagonal 647, 0B028­Barcelona, SPAIN. (**) UnitS de Chimle Organique, Institut Pasteur, 2B Rue Docteur Roux. 75724­Parls, Cedex 15, FRANCE.

Crystals of the self­complementary DNA hexamer d(GGCGCC) were grown by the vapour diffusion technique. X­ray diffraction analy

sis showed cell diroensionat а­4б.15<1), b­36.90(2), c­110.03<3) A, space group C222.. For a crystal obtained in the presence of

Ac(Arg)4NHEtr pH 7, the resolution attained was 2.3 A. Recently a whole data set to 2.0 A resolution has also been collected for an isomorphous. crystal that waa, however, obtained at pH 8 and in the presence of Arglnlne and that may, therefore, clarify the kind of interactions between oligonucleotide» and peptides. The с axis is unt Jally long for an hexanucleotlde crystal. This fact means that tie volume of the asymmetric unit la bigger than in normal cases and the structure resolution la more difficult. To solve the structure without the use of heavy derivatives it la necessary to construct a model making hypothesis about the pa eking of the helices and the conformation of the DNA. The long с axle observed la in agreement with the packing of the three hexa mere contained in trie asymmetric unit, along the с *xis, in a conformation close to the В form. He know by Raman spectroscopy that this oligonucleotide has а В conformation in the crystals. (Measurements made in collaboration with E.Talllandier and J. Liquier).

It is unusual for a sequence that only contains С and G bases to have а В form in crystals. Until now only an hexanucleotlde with these bases and cc Gaining phophotionate units has been found in the В conformation in crystals/1/.

/1/ Cruse,И.В.Т., Salisbury,S.A., Brown,Т., Cosstick,R., Ecks_

teln,F. 4 Kenr.3rdfp. И986) . J.Hol.Biol. ,1S£, 891­905. ­411­

(FO­ElWlBatLtUrV «MF TIME tPIR«>C{ESTI[EO?«XNE SfclOUEItfXN. X­RUN7

It appeares that at I the molecules fit one another very veil and the only differences appear in the orientation of the A ring relative to the rest of steroid skeleton and the aide chain conformation. This research was supported by RP.II.10 project from the Polish Ministry of National Education (to PG. ZW fi. ZG) and by NIAAMDD Grant No. DK26546 (formerly AM­26546) and DDR Grant No. RR­05716 (to WLD).

•>•&-* ­412­ STHUCTURB OP CATALASE FROM MICROCOCCUS LYS0DEIKTICU8 E.P.Yusifov, A.I.Grebenko, V.V.Barynin, G.M.Uurshudov, A.A.Vagin, W.H.Melllc­Adaayan. Institute of Crystallography, USSR Academy of Sciences,. Hoaco», USSR

Catalaae (HgOgiHpO, ­ oxidoreductaae, SO 1,11.1,6} la an enzyae responsible for decomposition of hydrogen peroxide to molecular oxygen and water. Crystals of catalaae from Mlcro­ coccua lyaodclktlcus (MM) (MW 4xJ>e kDa) were grown by the hanging drop vapor diffusion technique, Crystals have space group 14,2­2 with a=b=106.7, 0=106.3 i and 1/* molecule par assynnstric unit. The MXC crystals diffract to 2.0 i re­ solution and are stable in the X­ray beau for about 100 houra, Heavyraton derivatives have been prepared by soaking the nati­ ve oryatale In solution» of heavy^atoa reagents KgPtCl^, 1ША ,

U02(H0,)a and met­salyl. X­ray dlffraotlon intensity data for the native orya ­ tale and derivatives have been collected using KARDJ* arrea deteotor dlffraotometer* Sleotron density maps have been calculated at 3,0 X resolution with phases obtained from four lsoaorpboua derivatives. Phases had an average figure of merit 0,62. Analysis of ULO seoondary structure and its ooaparleon with that of beef liver oatalase (BLC) and Fenlollllua vltale catalase (PVO) revealed that 13 °<­helloee and 8 fl­ strands consisting of about 450 amino acid residues have been found In the subunlt of ULO in the same spatial positions as in BLO and PVO, but In BLO there la an additional H­torminal t* ­helix (of about 25 anlno aoid realduss) and in PVC there la an additional domain (of about 150 amino aoid residuea). The high degree of aiailarity of the three oatalaa* structure» makes .it aost probable that they diverged froa ooaaon ancestor «or» than on* billion years ago, when aain structure feature» of oatalaea» already have bean exlated. ­413­ CHLOROACETATES ­ NEW MEMBERS OF THE PROTONATED ADENINE CRYSTALS J.ZACHOVA, J.MAIXNER, K.HUML

Institute of Physics of the Charles University, Inetitute of Chen 1 с ill Technology, Institute of Macromol. Chemistry, CEechosl. Academy of Science, Prague, Czechoslovakia

Adenine crystals were grown as modsla for studying the electron structure, H­bondв and interactions between the NA bases by means of spectroscopic jnethods. Crystals were grown by « method of the solution cooling» Mostly f roe seeds in special crystal11zers. Grown crystals are optically homogeneous and weight up to 10 g. We have prepared and Mostly solved the structure of the crystals of double ­ protonated adenine (sulphate), .single­protonated, (here i sulphate heel hydrate, bra* ids and chloride /1/ heal hydrates, phosphate) and non­protonated (complex with Ыs­N­methyIpyrroll done, trlhydrate /2/ ). More recently we have also determined the crystal and molecular structure of the newly prepared crystals: adenine bis­chloroacetate ­ orthbrhomblc, Pccn, a * 24.138(40), b > 15.526(20), с ­ 7.136(1) X adenine Ые­trichloroacetate, monocllnic, P2,, a ­ 6.629(3), b * 26.168(4), с • 11.4.00(3) A, f? « *6.66<3)*.

An important change in the geometry of purine skeleton (e.g. change to N1 is 7') as a function of the protonatlon degree was observed.

/1/ Klatenmacher T.J., Shlgeaat.su т.. Acta Crystallogr. B30.1fle (1»74) /2/ Tretiak S.N. et al.,KriatalloTtrafiya 92, 1268 (1987). ­414­ ТИЕ STRUCTURE OF HUMAN CERULOPLASMIN AND THE EVOLUTION OF THE COPPER­BINDING ACTIVE SITES V,W. Zaltaev, A.A. Vagln, IC.A. Moshkov Institute of Crystallography, USSR Academy of Sciences, Moscow; Institute of Experleental Hediclne, USSR Academy of Medical Sciences, Leningrad

SOJSB results of the structural studies or, copper­cental nlng glycoprotein of human plasma blood, ceruloplasmin (CP), will be presented.

CP is a single chain protein with a molecular weight of about 1Э0ОО0, which has at least five peptide bords highly sensitive to a proteolysis. X­*ray crystalloaraphlc studies о on the tetragonal crystal form (sp. group I 4,a • 268,2 A, о ° с ­ 129,1 A) at the resolution of 6,5 A shows the presence of six domains in the CP molecule. The identification of possible Uganda in the copper*blndlng centers of three types ("blue", "nonsblue" and blnuclaar) is carried out by computer similarity analysis' for the sequences of CP and several other copper­containing proteins; asurln, plaatocyanin» superoxide dlenutase, laccase­ tyrosinase and nemocyanln. A scheme of possible evolutionary pathways of CP from a more simple ances­ tor protein is suggested. 415­ XJIAY STRUCTURE INVESTIGATIONS OF THE COMPOUNDS ACTING ON ТИС CENTRAL NERVOUS SYSTEM N.E.Zhukhlistova. V.I.Smirnovi. 6.N.Tishchenko [nilltut* of Crystallography, USSR Acad«my of Sciences. Moscow, USSR

Oy th* method of X­ray structure analysis the ' crystal structures of four compound» different in chemical origin. but related to the group of, substancea acting on the central ntrvoui ay•tarn, have been investigated. Pharmacological action spectrum of onn of them, ketamine. used mainly in anesthesiology, la partially similar to that of meso trine synthesized on th* basis of phenamino (amphetamine') displacing pronounced antiarhythmic action. Two other compounds, N­b*naoyl­ and N­phenylacety1­L­aspartic acids, зге inhibitors of specific binding of glutamic acid. The ketamine molecule hat substituted cyclohexane and benzene rings it well as N­methyl group tied up in the common tetrahedral "knot" , Amphetamine fragment• of th* mesotrine molecule connected by the chain of four methyl one groups , have the same conformation, almo'st Identical with that of the amphetamine Itself. Comparison of the conformations of ketamine, amphetamine and morphine molncuiet enables one to reveal stereochemical feature* common fa. these molecules, chemically different,but having some common features in spectra of pharmacological action. in the N­Bzl­Atp and H Phe­AcAup mnleculos the conformations of the aspartic acid residues almost practically coincide being different from their conformations in crystals of l­ and L.O­aipartic acid. At the same time the orientation of the phenyl ring relative to the mea­n plane of the backbone C­atoms in these molecules is different. By the compar ison of the Phe­Ac­Asp molecule conformation with that of phenobarbital and diphenlne molecules displaying antiepileptic activity it wcs shown that presence of a functional group with, carbonyl 0 atom in th* molecule is necessary for such «n activity. *11 structures w*r* solved by direct me'thod with SHELX­*6 crys t*ilographi с programs. The *hydrogen atoms were located from difference Fourier map and refined. Full­^natrix l*ast=squares refinements Converged at R=0.0ЭЗ­ 0.06*. ­416­ Author Index

Abagyan R,A. 411 Averbuch­Pouchot M.T. 281 Abaflhev G,G. 304 Aymaml J. 406 Abdullayev R,A> 215 Babel 0. 63,18< Acharya R. 344 Bachechl F. 353,354 Adam» H. 190,Adam G. 386 Baqlei,­Beucher H. 261 Aflr A. 26 Bakhtiyarov I.B. 112 Ahlgren M. 303 Balarew chr, 35 Ahmed Farag 1,8. 223 Balcazar J.L» 225 Albano V.O. 191, 192 Bankovsky Yu.A. 289 Alejnlkova K.B. 27,28,29 Barandika G. 32 Aleonard S. 30,64 Bartczak T.J. 199,334 Aleshln A.E. 356,387 Bartela K. 345 Allev z.s. 193 Bartolucci C. 355 Amellnckx S. 101 Baryckl J. 309 Amthauer G. 6 Barynln V.V. 412 Anderaen N.H. 288 Basto M.J. 60 Andreetti O.D. 272 Bataanov л,С 18,333 Andraeva N.S. 39f, 401 BattadUa L.P. 299 Andrusyak R.I. 67 Baukov Yu.I. 275 Angelova 0. 194 Baumalater U. 200,243 Anshlta A.G. 93* Baydlna I.A. 197,198,317 Antlpln H.Yu. 214.292 Becker J.Y. 17 Antson 0. 42 Behruzl H. 71 Anulewlcz R. 198 Beljaev A.V, 239 And T. 380 Bellver с 201 Arakcheeva A.V. 31 Belokoneva E.L. 117 Argary Gy. 300,382 Belaky V.K. 20,153,213,276 Arlon V.B. 233 Belyakov V.A. 8 Armbruster T. 6 Bennett j.с 136 Arrlortua M.I. 32 Bennett IT. 345 Arroyo P. 395 Bente X. 36 Artioll G, 33 Berkovltch­Vellln t. 345 Arzotaaanlan H. 291 Berraejo H.R. 212 Aslaplan s. 34,118 Bernath G. ЗОО Aslanov b.A. 171,172 Bernatein J. 17 Aatankoy A.V. 340 Bertaut e.P. 64 Atanaaor B, 367 Bertolaal V. 237 Atovayan P.O. 109,193,342 Berzlna I.R.. 289 Attxnaalo 0. 19* Beahkenadze I.A. 314 -417- Bespalova S.V. 357 Bourosch P.N. 233, 299 Bevon D.J.M. 120 Bovio B. 206, 207 Be2rukova I.N. 349 Braga D. 191 .Blali S.B. 256 Brandenburg H, 265 Blanchl A. 249 Branzburg H.Z. 240 Bibby H. 363 Brazhnikov E.V. 362 Blchurtn R.Ch. 132 Brezina F. 258 Biellmann J.-F. 359 Brigattl M.F. 33 Blkbau M.Ja. 77,78 Brito I. 301 Blttervolf Т.Е. 202 Brizzl V. 355 Bittner S. 17 Brown F. 344 Biyuahkin V.N. 277,279,307 Brown 1.0. 56 BUznjuk N.A. 11 Brufani M. 355 Blomberg И.К. 37 • Bruno G. 284 Boche G. 24 2 Bruvo M. 257 Boohkova R.I. 338, 339 Brzezinaka E. 324 Bodak 0,1. 28,29,123,126,127 Buckleton J.S. 358 Boeyena J.C.A. 203 Budarin L.I. 19 Bogdanova A.V. 356 Budkowski A. 100, 136 Bohl И. 400 Budaychuk N.T. 90 Boklj G.B. 40 Bukow3ka-Strzyzewaka M. 208 Bolei И.О. 41 Bullenkov N.A. 45 Bollmann U. 99 • Bulkin A.P. 42 Bologa O.A. 210 Bulychev B^B. 20 Bolotoveky R.L. 42 Sundule M.F. 209 Bonaccorsl E. 14 Bulger V. 35 9 Bonamartinl C.A. 299 Burlni A. 206 Bonamico K. 196,204 Burshtein I.F, 210 Bonatl P. 206 Busettl V. 207 Bond D.R. 254 Busetto L. 191 Bonder V.I. 297 Buslaev Yu.A. 313 Bond&renko Ye.I. 46 Butaahin A.V. 117 Bordoni S. 191 Butikova I.K. 152 Boriaov S.V. 11,197,196,317 Calcagnl A. 370, 371 Boriaova Ye.A. 62 Borowlak T. 270, 33 5 Campbell J.H. '386 Borutaky B.E. 43 Capitani 0. 211 BoatrOm D, 20S Capobianco M.L. 353 Boawell F.w. 100, 136 Carrell H.L. 359 Bouas-Laurent H. 280 Caatedo L. 247 Boudjada A. 44 Castineiras A. 212 247 5Л-- Cataldo F. 397 -418- Catti M. 7 Demartln F. 192 Ceccon A. 202 Dement"ev V.V. 251 Cellai L. 355 Demyanets L.N. 66 Cernlk M. 3 37 Denny W.A. 358 Cerny R. 169 Derewenda U. 323 Cerrinl S. 355, 36^ Derevenda Z. 366 Chaban N.F. 102 Dergunova N.V. 52,53 Chapurina L.F. 217 Desvergne J.F. 280

Charelishvili L.Sh. f314 Devedjiev Ya. 367 Chekhlov A.N. 193 Diakon I.A. 217 Cherednikova T.V. 356 Dianez M.J. 274 Cherkezova V.R. 26^ Diaz c, 301 Chernaya N.G. 48 Dietz E. 23 Chernega A.N. 214 Divjakovlc V. 218 Cherner Ya.E. 46 Djafrl F. 291 Chernichkov V.A. 46, 47 Djuneva K. 83 Chernyshev V.V. 49 Dmitrienko V.E, 8 Chetklna L.A. 213 Dmitrieva M.T. 54 Chikhrlj S.I. 102 Doblaeova L. 169 Chiragov M.I. 50,51 Dodony I. 55, 157 Chiroadze N. 361 Dodson E.J. 366 Chlrgadze Yu.N. 362, 363 Domashevskaya O.A. 283 Chmielova M. 159 Domnln I.M. 230 Chromov Г.Уи. 84 Donkova B. 118 Chyragov F.M. 215 Donu S.V, 217 Chyragov M.I. 215 Dorta L. 395 Ciechanowicz-Rutkowska M, 21 Drabent K. 199 Cirilli M. 353 Dragalln I.P. 278 Clark G.R. 358 Duax H.L. 379,411 Colacio E.. 384 Dubkov A.A. 93 Colonns P.P. 353 Dubkova S.A. 93 Corbett J.M. 136- Dubler E. 219 Cota Л.В. 365 Dubovsklj A.B. 129 Cotrait M. 374 Duburs S,J. 209 Couriellle c. 374 Dudklna S.I. 52 CsOregh I, 388 Duhlev R; 56 Cueva* J. 301 Durant F. 375 Cynober L.I. 45 Durif A. 281 Dantaiger A.Ya.. 52,53,142 Durovld '•. 12. 174 Dc Munno G. 284 Dvorkln A.A. 19,220,283,327- :;claerolx H. ; 13 Dvortsova N.V. 295 «9­ Dyrbusch M, 221 FlBrke U. 226 Dzyabchenko A.V, 57 Foklna Z.A. 171 Edenharter A. 36 Fomenkova N.P. 362 Efremov V.A. 48 Fomlnenkov A.M. 187 Egert E. 221 Fanar M.S. 327 Egorov TB.A. 356, 387 Fonseca I. 225, 227 Egorov­Tiemenko Yu.K. ifl Font­Altata M. 228 Elck H.A. 75 Fox G. 344 E)­Rahman Abd A.M. 59 Frangis N. 101 El­Sayed K. 59 Frank­Kamenetskaya O.V. 177 Sl­Shora A. 223 Frank­Kamenetsky V.A. 68,177 El­zahraa El­Feky 59 Frederick C.A. 37 3 Emelyanov S.M. 178 Fredlani F. 249 Ermrlch M. 73 Frenzen G. 63 Erokhin V.V. 368 Frltsky 1.0. 220 Eslpova N.G. 409 Frolova N.A. 229 Eepenbetov A.A. 222 Frolov F. 345 Estrada M.D. 274 Frommel С 404 Evans D.G. 203 Evarard G. 375 Fry E. 344 Evdoklmov E.P. 87 Falap F. зоо Evers U. 345 Fandamensky V.S. 61,230 Fages F, 280 Furmanova N.S. 42,231 Fares V. 196, 204 Galdeckl Z. 369,379,411 Faille R. 21B Galltsky H.M. 376,377 Fedorchuk A.A. 85 Galll E. 65 Fedorov A.A. 403 Garabarov D.G. 215 Felgln L.A. 368 Ganin Ed.v. 327 Farg E. 104 GanlB P. 202 Ferrettl V. 237 Garbarczyk J, 232 t'esenko E.G. 53 Garber M.S. 401 Fetlsjv G.V. 49 Garsla J.A. 212 Figas E. 224,315 Gasanov T.Kh. 402 Flgueiredo M.O. 60 Gavuzzo E. 360,370,371,372 Filat.v S,K, 61,Flnko V;62,1 Gawron N. 270 Fita I. 406, 410 Gdanlec 234, 250 g Flamini A. 204 Gelger C.A. 6 FlorFr>clo F. 225 Genklna E.A. 66 Geoffre S. 374, 382

~>rw Georges G. 375 Gurln V.N. 37 Gerasimchuk N.N, 283 Gurskaya G.V. 380 Gerbeleu N.V. 18,210,333,299 Gustchina A.E. 391 Gessner R.V. 373 Gutlerrez-Zorrilla J.M. 241 Gill P. 305 Gyepeaova D. 159 Gilli G. 237,397 Gyr E. 219 Giordano F. 238 Hahn Th. 71- Gladyshevaky E.I. 68,86,126 Halill M.H. 127 Glinka H. 323 Hamalainen R. 330 Glinskaja L.A. 95,96,97 HSnggi G. 219 Glovyak T. 102 Hansen H. 345 Glowiak T. 269,309,337 Harlev E. 17 Glowka M,L. 235,253. Harms K. 242 Glusker J.P. 359 • Hartung H. 243 Gluzlnskl P. 236 Harutyunyan E.G. 349,356,361, Glyakin V.P. 72 367,387,399,404 GDIIO E.A, 68 Haupt H.-J. 226 Golubev A. ft 69 Hausdorl G. 361 Goncharov G.N. 70 Hecht H.J. 381 Gonzalez A.G. 301 Helllwell J.R. 36', Gorelenko Yu.K. 154 Herman 4iV. 179 Gorius M.F. 64 Rellner E.E. lo Gorshkov A.I. 54 Hennig Н.-Г. 162 Gorskaya M.G. 61 Henager K.E. 121 Gotz D. 71 HerbsteIn F.H. 244, 24S Govorova A.A. 376, 377 Hermann H. 73 Grabownki M.J. 323, 324 Hiismakl P. 42 Grebenko A.I." 412 Hllber* M. 246 Gribanov A.V. 39 Hillebrecht H. 74 Grin Y.N. 85 Hlller W. 76,212,247 Griteuk V.I. '378 Minechberger J. 280 Grochuleki P. 37 9, 411 Hodorowlcz E, 75 Gromilov S.A. .197,239 Hodorowicz S.A. 75,108 Grzeszczuk И. 199 Hohne W. 361,404 GubJch I.S. 102 Horner M. 76 Guilhem 16 Hosklns B.F. 120 Gukalova A.G. 72 Hospital H. 382 Gulea Л.Р. 313 Howard J.'A.K. 21,248 Gurevlch M.S. 240 Howie R.A. 175 -421- Hudo)arov А,в. 310 Xaftory H. 256 Hural к. 413 Kalryak L.N. 217 Huekoweka E. 388 Kal'ohav V.F. 84 Huynh-Dinh T. 410 Kalb (Gilboa) A.J. 366 lanelll S. 249 Kall£aes 0. 252 Ibragimov B,T. 234,250 Kalman A. 300,352 Igolen J. 410 Kaluekl 2. 224,315,393 Igcmln V.A. 251 Kalychak Ya.M. 86 Igumenov I.K. 198 Kamenar B. 257 Ikraml J,J. 124 Kamenicek J. 25B IXali J. 30 Kaplunnlk L.N. 129 Ilineta A.M. 77,76 Kapon И. 244,245 Iljuhin A.B. 312 Karanianeva T.A. 87 Iljuehin G.D. 79 Xarayev z.sh. 261 Imperatori F. 196,204 Kargin Yu.p. 138 Irngartiner H. 252 Karolak-Wojclechowska J.259,348 Irodova A.V. 80 Karor Z.G. 109 Iehchenko V.N. 9.6 Karpenko G.A. 124' IBkhakova L.D. 81 Karpinskly O.G. 31 Ivan'ov V.S, 82 Karpova L.Ya. 57 Ivanova S. 83 Kartenko N.F. 304 Ivanova L.S. 142 Xaahaev A.A. 88,341 Ivanovskaya T.A, 168 Kataev V.E. 260 Iwanicka I. 235, 249 Kataeva O.N. 260,273 Izotov V.G. 84 Xatzke H. )25 Jabloftaki J.M. 89 KayuBhina R.L. 368 Jahn R. 252 Kazumov M.G. 187 Janes M.N.G. 403 Keller- P.A. 21 Jancke X. 1S2 Kelia E. 333 Jedamzik J. 162 Kemne A.A. 209, 236 Je2ovmka-Tr2ebiatou9ka B. 269 Kepifiskl b. 89 Jo>maon L. 254 Keseler V.G. -336 Johnaon 0. 21 Khaenko B.V. 90 Jorgenaen J.-E. 255 Khalabuda Yu.E. 91 Jorjoliani N.B. 314 Khalllov A.D. 91 Jost K.H. 149,175 KS\arohenko L.Vu. 134 Judin A.N. 129 Khasabova G.I. 47 Julve M. 284 Khialna N.R. 116 Junuskodjaev A.N. -398 Khranertko S.P. 239 Kachalova G.s. 383 Kierkegaard P-. 388 ­422­ Kiriazla L, 246 Krech F. 24 3 Ktrlk S.D. »3,м,262 Xretachmar M. 76 Klrin V.P.' 332 Kretzechraar U. 99,162 Klrkova Б. 95 Kroh A. 23 Klvekaa R. 288,329,384 Krol I.A. 268 Klenent U. 218 Krollkowaka M, 232 Klevteov P.V . 96,97,98 Kruglik A.I. 93,262 Klevteova R .F. 96,97,98 Krutov S.A. 42 Knox S.A.R. 248 Krygowskl T.M. 195 Xochkina V.H. 385 Kubiak M. 269 Koetzle Th.F. 263 Kubloki M. 270 Kokunov 5fu.V. 313 Kucharczyk D. 100 Ко1ава A, 216 Kudrjaahev V.A. 42 Koleanlchenko V.L. 171 Kuduk­JaworBka J. 269 X641 p. 265 Kukina G.A. 294 Koman H. 264 Kuppers H. 263 Xooarovaka.L.P. 154 Kuranova I.P. 361,399,404 Konecny V. 333 Kurbanov T.Kh. 402 XOnlg H. 247 Kurtanidze R.Eb. 328 Konovallkhln S.V. 342 Kusneteov M.V. 151 Kopf J. 265 Kutschabaky L. 386 Kopf J. 266 Kutvltakly V.A. 94 Koretaka O.E. 154 Xuypera S. 101 Xoroteev M.P. 276 Kuz'ma Yu.B. 10a,Kuz'mlna L.295 Xorpar­Collg B. 257 Ku&el R. 169 Korsukova M.H. 37 Xvitaahvlll A.I, 328 Koryagina T.I. 94 Kwlatkowskl H, 259,348 Xoaturklevlcz z. 200 Laban G. Э94 Kotlyar S.A. 327 LabUshkln v.G. 167 Kotov A.I. 286 Lager G.A, 6 Kotov H.A. 298 Lai R. 291 Kotov N.V. 68 Laltalalnen T°. 288, 3 25 Kotur B.Ya. 67 Lajslc S. 218 Kozlol A.E. 267 Lamba D. 355 Kozlova N.I. 336 Lanpeka R.D. 220 Xraaenov K.V. 319 Larazln V.s. 349,356,3B7 Krajevakl J.H. 236 Lasocha A. 103 Kraptvko A.A. 262 Laaocha K. 103 Kraanobaev A.A. 173 Kxavtsov V.Ch. 229,279 Latos­Grazynaki L. 199 Le Pur У. 10,64 -423- Leban I. 271 Lygina Т.г, 107 Lecocg S- 324 Maeharashvlll A.A. 275 Legendziewi.cz J. 388 Machmudova N.K. ЗЮ Legrofl J.-P, 160 Macicek J. 110 Leimkuhler H. 246 Macichek I. 134 Lenatra A.Т.Н. 331 Magazina L.O. 148 Leonov S.B. 229 Magneli A. 4 Lesln A.V. 231 Magomedova N.S. 276 Lesovoj M.V. 28 Malxner J. 413 Levendie D.C. 104 Makltova O.D. 109 Lezama L. 32 . Maksakov V.A. 332 Liroa-de-Faria J. 105 Malakhova L.F. 137 Llncke G. 23 Maleev A.V. 298 Llndeman S.V. 329 Mallna M. 121 Lindley P. 363 Malinina L.V. 346 Liopo V.A. 106 Malinovskly Yu.A. 111 Malinoveky S.T. 19, 278 Lipkowaki J. 272 Malinoveky T.I. 210,220,277,279, Llpkowsky Ya. 32.7 Lltvinenko G.S. 222 283,307,327 Litvinov Г.А. 260,273,399 Majnedotr Kh.S. 112 Lobsanov Yu.D. 389 Marain B.F. 66 Logan D. 344 Manfre F. 359 Lokaj J. 333 Maniukiewlcz H. 208 Longonl G. 192 Manoll F. 202 Lopez-Castro A. 201, 274 Manrlquez v. 301 Lopuai&skl-Ai 267 Manyako N.B. 180 Loshmanov A.A. 42 Mariani P; 113 Loskutov I,Yu. 156 Mariaasy M. 264 Loub J. 266 MarlnJcovic V. 10O, 136 Lubnin H.Yu. 389 MarJin A.A. 129 LUC V. 375 Marsau P. 280 Lucente G. 360^370,371,372 Marsch M. 242' Martin J.o. 396 Luczak L. 267,mkin P.M> 342 Martinez-Carrera S, 227 Lumtie P. 288 Martinez-Ripoll 'м. 241 Lumne P. 330 Martynova T.N. 131 - Lunin V.Yu. 362 Maruein E.p. 127 Luque A. 24-1 Maecarenhas Y.P. 365 Lutoslawska-Rogoz J.А. Ю8 Maslenikov A.V. 114 Luzzati V. 113 Mason S.A. 2T Lvov Yu.H. 368 Massa W. 63 Lyakhovltskaya 0.1. 80 Masse R. 281 Lyatifov I.R. 402 -424- Majtln-Zarza P. 305 Musayev F.N. 261,285 Mattes R. 246 Mutlkalnen I. 3 30 Matuazewki J. 282 Myaehln E.T. 383 Maxlmov B.A. об, 115 Mye'klv M.G. 119 Mayer H. 34 Nadezhlna T.N. 5 Mazus M.D. 28 , 313 Nahapetyan S.S. 286 Mazza F. 370, 71,372 Nardelll M. 249 Mednlkov E.B. 316 Narlmanidze A.P. 328 Mel'nlkov O.K. 176 Nasakin O.E. 342 Melik-Adarayan i .R, 412 Naumov V.A. 273 Merelter K. 9 Nazlmova N.v. 390 Merisalo M.J. 37 Nedel'kln V.I. 340 Merlirio 8. 14 Nejelekaya L.A. 277,279 Meaa J.L. 32 Nesambenl L.R. 254 Keahalkin s.s. 4f Nevakaya N.A. 362,363 Michalak! J. 767 Nlfant'ev E.E. 276 Mlkenda W. 9 Nlklahova L.V. 144 Miljkovlc D. 218 Nlkonov S.V. 362 . Mill B.V. 117 . Nlkullna L.D. 131 Mlminoahvill E.B. 314 Noren B. 205 Minacheva L.Kh. 318 Norte M. 395,397 Minkova N. IV Novgorodova M.I, 54 Mlronova M.K. 33 Novosel-Padovlfc Vj. 121 Mlrzoev R.S. •19 Novotny J. 122 Mishnev A.F. .'59 Nozlk Yu.Z. 80 .Mitkevlch V.V. 407,408 Oblomova G.V, 39 9 Mitrofanov B.V. 151 Obodovakaya A.E. 287 Mohyla J. 120 Oeser T. 252 Mokra I.B. 12: Oksanen A. 288 Mokulskil М.Л. ЭВ9 Olcftaweka A. 108 Morozov V.N. 63 Olekhnovioh L.P. 231 Morozova T.Ya. 383 Olekeyn O.Ya. 123 Moshkov K.A. 14 Olkhovaya L.A. 124 Mosyak L.E. 2' 7 Ondrejovic G. 264 Mura P. 211 Orlahchin S.V. 102 Muradyan L.A, 137,138 Oskareson A. 205 Murashova E.V. 170 Ovchinnikov Yu.E. 251 Murshudov G.N. 412 Ovohlnnikova E.N. 167 ­425­ Pinnen F. 360,370 Ovrutaky V.M. 277 PlBarenko L.M. 193 Ozolina S.V. 153 Plsaarenko V.F. 48 Pagllalunga Paradlal M. 372 Platnev V.2. 389 Раккапвп т.А. 303 Plotkin V.N. 230 Palacloa.M.S. 305 Plyusnlna I.I. 128 Palenlk G.J. 267 Pobedlmekaja E.A. 129 Paraiatnlkh A. 83 Poohettl G. 370,371,372 Pannetler J. 141 Podberezakaya N.V. 302,332 PapK M.Z. 366 Poll N. 204 Parkhomov L.8. 298 Pollehchuk A.P. 292 Parthe E. 182 Poltav V,I. 347 Paacard C. 16 Polyakova I.N. 293 Paaero И. 14 Polyanskaya T.M. 130,131 Paatorek R. 2S8 Popolltov V.I. 132 PauluaE.F. 23 Popov 0. 349 Paulua И. 125 Popov A.N. 399 Pavlov A.N. 46 Popov M.S. 307 Pavlova 8.V. 19 Popov V.O. 349 Pavlyuk V.V. 123 Popov V.O. 356, 387 Paaraon И.В. 10 Popova E.B. 213 Pech L.J. 28» Poppi L. 65 Pacharakaya A.O. 127 Poray­Koehltz M.A. 294,295,296, Pecharaky V.X, 38,39,123,126 318 Pachlk I.V. 391 Posfal И. 55 Pedroao A.G. 76 Potapova O.G. 131,133,134 Pakhnyo V.I. 172 Poyry H. 42 Pelocl G. 299 Poznlyak A.L, 316 Peralea A. 290 Precigoux G. 374,382 Perepelltaa A.P. 96 Prelalnger A, 9,34 Perm Yu.N. 28 Praut H. 15, 135 Perroux M. 30,64 Prlev S.Ya. 304 Pervukhlna N.v. 302 Prouan A. 100,136 Peatunovlch V.A. 275 Prokhorov A.I. 342 Petrooaha I.A. 49 Prokaohy F. 23 Petropavlov N.N, 392 Protaaova V.'I. 134 Petrov K. 185 Pucalov K.G. 91 en c° Petrova I.V. 129 Pugashova N.M. 276 Phesenko E.V. 20 Puiggall J. 406 Piacenti F. 249 Pulkklnen E.­L. 288 Pierrot M. 291 Pursiainen J. 303 Pietronl B.B. 205 Pushcharovsky D.Yu. 5, 13 9 -4B6- Quinoa E. 247 Rowlands D. 344

Rabotkina N.S. 29 Rozhdestvenskaya I.V. 61,144,145, Radaev S.F. 137,138 177, 304 Ragimov K.G. 50,51 Rubinsky S.V. 399 Ruiz J. 384 Rappoport Zvi. 256 Ruiz-Parez C. 301,305,395,397 Rastsvetaeva R.K. 43,139 Rupnik A. 271• Ratajczak-Sitarz M. J93 Rusakov A.A. 399 Rau Т.Е. 297 Rusanovsky M.E. 308 Rau V.G. 297,296 Russkikh V.S. 304 Raveau В. 141 Ryabov E.V. 151 Razumovskaya I.V. 340 Ryazanteev S,N. 401 Razumovskaya O.N. 52,142 Rybakov V.B. 49,171,172,223 Keai J. A. 284 Sabirov W.lth. 398 Rebbah A. 140,26 Sabirsiyanov N.A. 85 Rebbah H. 141 Sacerdoti M. 146 Rebrova O.N. 277 Saf'yanov Yu.N. 338,339 Reck G. 394 Safonof A.A. 147 Rego J. 365 Safonova T. 367 Reisner G.H. 244, 245 Safonova T.N. 399 Revenko M.D. 299 Sakharov B.A. 168 Reznlchenko b.A. 46,47,142 Sakhnenko V.P. 142 Ribar В. ЗОО, 352 Salamaha P.S. 38 Rich A. 373 Salvini A. 249 Richardson J.F. 6 Samotoin N.D. 62,148 Ridouane P. 291 SamuB N.H. 306,307,308 Riquera R. 247 Samus I.D. 306,308 Rodrlquez J.G, 227 Sanusikov V.P. 145 Rodrlquez M.L. 301,305,395,397 Sandulenko V.A. 124 Rodriguez-Ronero F.V. 305 Sarin V.A. 138 Rogova T.v. 336 Sarroa J.A.R.P. 17 Rogulenkova V.N. 409 Sawka-OobrowolBka W. 309 Rojo T. 32 Scharfenberg D. 400 Roman P. 241 Scheludyakova L.A. 320 Romanenko G.V. 302 Schlerhom E. 99 Romanoff E.G. 143 Schmalle H. .219 Rossi D. 371, $70 Schmidt R.E. 63 Rossi S. 303 Schneider h. 149 Rotter H. 74 SchUllhorn 125 Roux M.T. 30,64 •427­ Schomburg 0. 3B1 Skolozdra R.V. 154 Schwarz R. 10 Skopenko V.V. 220,283 Scordari Г. 150 Slovokhotov Vu.L. 316 .Beelhor.t W. 265 Slyudkln O.P. 317,318 Segre A.. 211,355 Srairnov E.V. 167 Semenova T.F. 61 Smirnova V.I. 415 Semkin V.N. 304 Smith A.J. 190 Serda P. 216 Smolln Yu.I. 152 Sergeev Yu.V. 362,401 Smollar B.B. 168 Sergeyev V.A. 340 Smolyaninova N.N. 62 Sergienko V.S. 296 Smrcok L. 159 Seropegln Yu.D. 39 Sobolev A.N. 213,276,289 Shalk S.S. 17 Sobolev B.P. 31 Shalaeva E.V. 151 Soboiev E.V. 319,320 Sharipov H.T. 310 SobOluya S.V. 155 Sharonov* O.N. 93 Sokolova E.V. 5B Shepelav Vu.r. 152 Solana X. S13 Shllklna L.A. 47,142 . Solodovnlkov S.F. 97,98 Shllnlkov V.I. 402 Sologub O.L. 38,39 Shlrokov V.A. 401 Solotchlna E.P. 1S6 Shlahova T.G. 231 Solpzhenko V.L. 49 Shklover V.E. 251,275,286,340 Somenkov V.A. 80 Shkol'nikova L.M. 311,312 • Soo« H. 157 Shnulin A.N. 402 Soroklna N.I. 147 Shova S.S. 313 Soanovaky V.A. 158 Shpyrka Z.N. 123 Sotofte I. 321 Shumilin I.A. 356,387 Spencer J.L. 21 Shvelaahvlli A.E. 314 Stabnlkov P.A. 198 Slchevich O.N. 85 Stadler U. 354 Sldorov V.S, 124 Stjdnlk Yu.V. 1S4 Sieleckl A.R. 403 Stahl K. 160 SIlino E.J. 153 Sllva G.D.F 365 Staklc г. 35 2 Slrainakl J. 31S Stalhandake C. 161 Simon K. 400 Starlkova Z.A. 240,268,287,293 Simonen T. 325 Starova G.L. 61,230 Лтопоу V.I. 137,138 Starynowicz P. 322 Simonov Vu.A. 19,220,233,283, Staal F. 150 Steen J.R. 120 299, 327 Stegen K. 345 Slrota M.I. 115 Steinike U. 99,162 VI­ г Stepanov S.V. 2 97 Thozet A. 323 Stepien A. 323,324 Tiltta A. 42 Strahle J. 212 Tlmko G.A. 18 Strandberg R. 205 Timofeeva T.V. 251.292,329,340 Streltsova N.R. 20 Tlmoshchenko N.I. 171 Stringer A. 21 Tiahenko G.N. 390,405,415 Strokopytov B.V. 361,383 Tiahenko S.V. 401 Strong P. 379 Tkachev V.v. 109 Struchkov Yu.T. 18,214,222,251, Toda F. 254 275,286,'292,297, Todorov T, 110 316,329,333,336, Todorovakl D. 118 336, 339 340 Tolpekln I.G. 167 Stuart D. 344 TolpygeK.B. 357 Sturis A.F. 289' • Torino J. 406 Suber L. 1 96 Torrlnl I. 372 Sublrana J.A. 406,410 Toaik A. 208 Sublrats J.B. . 227 Trakhanov 8.D. 401 Sundberg H.H. 384,12Г Traub W. 350 Surov E.V. 151 Tretyak 9.M. 407,408 Suwlneka K. 272,326,327 Trltach D. 359 Suyarov K.D. 312 TroJlmov V,B. 114 Svenaaon C. 161 Trubkln N.V. 168 Sysoeva T.F. 240 Trunov V.A. 42 Szurgot H. 164 Trunov V.K. 48,81 Tagiev D.S. 285 Tsapkina E.N. 380 Talanov V.M. 165 Taapkov V.i. 306,307 . Talipov S.fi. 234,250 Talntaadza G.V. 285,328 Taran G.G. 306 Tsipuraky 8.1. 168 Tarasov W.I. 176 Talvtilvadra T.I. 328 Tchumakov Vu.M. 307 Taurgan L.s. 94 Talnurov G.S. 166 Tunanyan V.G. 409 Telegenov A.A. 13;2 Turdybekov X.H. 329 Tapavitaharova S. 35 Turevskaya E.P. 336 Taplukhin 347 Turiaahvlli T.N. 328 Teplyakov A.v. 399,404 Turik A.v. 47 Tarentjeva L.B. 129 Turova N.Ya. 336 Taraahko V.A. 346 Turpelnen U. 330 Terrill H.i. 248 UghettoG. 353 Thlele G. 74 Ukhin L.Yu. 286 429- Ul'yanov V.A. 42 Volkov V.V. 319 Urpi L. 410 Voronkov M.G. 341 Urueov V.S. 116 Votyakov 8.L. 173 Urzhumtaev A.G. 362,363 Voyna V.V. 106 Ueov O.A. 304 Vrabel V. 333 Uatlnnikova T.B. 3B7 Vrublevakaja Z.V. 40 Vagln A.A. 383,412,414 Vtyurln N.N. 389 Valle G. 202 Wajaman 324 Valvoda V. 169 Wan T. 366 Van Landuyt J. 101 Wang A.H.-J. 373 Van Hoey P. 396 Wawriak I. 379,411 Vanhouteghem F. 331 Weber G. 345 Varakaina T.V. 61 Welner S. 350 VardosanWie Т.О. 314 Heinatein 8. 345 Vaaillev V.D. -401 Weil* Z. 174 Vaailjeva S.G. 319 Williami L.D. 373 Vaakln A.N. 178 Wlttnann H.G. 345 Velikodny Yu.A. ,170 Wolrcyri H. 89 VeK.nakiy V.V. 156 Wolf W.M. 334 Vena'nil L.M. 354 Wonka 1. 335 Vanio A. 202 Morula И. 175 Vercauteren D.P. 375 Hyalouch A, 199 Verdaguer M. 284 Yagubaky E.B. 286 Verejan A.V. 210 Yakinov 1.8. 262 Vereihchaglna T.A. 93 Yekubovlch 0,V. 176 Vergaaova L.P. 61 Yamnova N.A. 5 Verin I.A. 147 Vanovaky A.I. 336,339 Vernoalova E.A. 362,363 Yanaon T.I. 179,180 Via J. 32 Yanulova L.A. 177 Vickovlc I. 257 Yarlv J. 366 Vldmar T. 136 Yate* M.J. 248 VigdorchlX A,G. 111 Yaraenko S.P. 85 Viroveta A.V. 332 Yonath A. 345 Vivian И. 41 Yatru A.B. '158 Vlad P.Ph. 278 Yu£it O.S. 230 Vladimlrov S. 352 Yua^fov E.F. 412 Vlaaova R.M. 304 Yuaupov M.M. 401 Volgt B. 386 Zachova J. 413 VoXkmann N. 345 Zadorozhhaya L.A. 278 Volkov S.V. 171,172 Zagoruiko V.A. • 178 ­430­ глк г, ззт Zedelaohvill E.N. 314 Zelbet E.A. 340 Zakharov L.N. 338,339 Zevtn L.8. 181 Zaaaav Т.Л. 340 Zhao J.Т.. 182 Zanottt V. 191 Zhukhllatov A.P. 107,183,187 Zarachnyuk 0.8. 179,180 Zhukhllatova N.E. 415 Zaraaba V.t. «« Zi.glar B. 184 Zarraga И. 395 Zolotov Л.В. 342 Zavallaltln C.I. 29 Zotov N. 185 Zavodnlk V.I. 153,213 Zuav И.8. 273 zayaklna N.V. 145 Zukerman E.A. 82 Zaytaav 8.И. 17» ZvXedra I.I. 186 Zaytaav V.N. 414 Zvyagln B.B. 13,187 Zdanova L.I. 277 Zacohlnl Q.r, 372 ­431­ LIST OF CONTENTS

Vol. 2

А. Cryntal Chemistry Oral presentations 3 8.1. Inorganic Materials and Mineral* PoUtPTS 2B 8.2. Organic Crystals OrjranomelaJllo and Coordination C£hv* pounds Posters , 189 4. Biologically Active Small Molecules aad Biological Macro— molnculee Or*) presentation* ,...*,..*.,.., 343 Pouter в , 361 Author Index », ,,,..,..,. 418

Vol, 1

Plenary Lectures 1. Fundamentals of Structural Cryatalloarapay S. Atomic Structure and Physics of Ciyeiala

VoK, 5

6. Diffraction from Ideal and Real Crystals. Tbeory and Experiment 0, Apparatus and Technique» for Structural 8tad4es of Crystal! Г. Compotttf onaj Methods of Sin»ct*raJ CryaUllojraphy» Crystallofa­aphiс Data Banks Postsymposia 1. Protein Crystallography 9. Synchrotron Radiation In Crystallography 8. Structure оГ Ptrtially Ordered Systems 4: Chemical Bonding and Lattice Dynamics by Diffraction Methods Лигммгг Варопавсяаа Кртзтшллогрлф/нтошлт Конференция. Мосааа, СССР. 20­20 август* 1969 г. Т«а*сы ащщашт. Том 2 (англ.)

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