This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. 2 Mg 2 ¨nchen I -tetrahedron in 4 ´lin 10.1524/zkri.2007.222.12.696 DOI and Philippe The V –O3) group in pectolite. . Both features are numerically A H– ... by Oldenbourg Wissenschaftsverlag, Mu # ] at 293 and 100 K , Igor Pekov (2007) 696–704 / II 9 ] is indicated by grey in order to only show its topolo- 11 O 222 O 4 3 [Si of the pectolite in comparison to Li ]. The structure projections are shown on left. The unit cells 2 11 O Mg 4 2 characterized in Tabletriclinic 1 along unit with the cell. parameters of The the unusual case of a protonated metric hydrogen bondseparated between O3 by and 2.45–2.48 O4 atoms (Fig. 1) Li gical similarity to the (O4 Fig. 1. [Si are indicated. LinesO4, 1 H, and Si1, 2 Si2,sections indicate M1, are profile M2 of represented andderlined sections in O3, crossing O4, cationic Fig. 4. H, O3, net Na A respectively. is single Both anionic these shown net on with right. the un- The Si2O )[HSi Z. Kristallogr. , Gervais Chapuis , , 0.27 IV – A A ) and (OH)], Mn 8 A ´rale de Lausanne, 1015 Lausanne, Switzerland ). This O (OH)] – 3 1.06(4) 0.97(4) 8 ´de 1.73 O ¼ ¼ ). The data 3 )[Si x [Si 178(4) 2.458(2) 2 ´ de Lausanne, 1015 Lausanne, Switzerland –O3 –O3 Mn , Nicolas Meisser x ¼ ¼ –Na interaction are 1) is related to two 2 II, III O4 –O4 O4 177(4) x ;H– ... A ... –H –H ´ochimie, Universite (OH)] (from the pegmatite at Mt. 2.473(3) 8 ;O3– , Philip Pattison ,O3– (OH)] (0 O ¼ 8 3 A A – serandite, Na(Ca O ,I,II 3 * )[Si – serandite series, NaCa –O4 ]. ´ralogie et Ge )[Si (OH)], have been investigated since the de- 11 0.27 x 8 Using synchrotron radiation, a single crystal O 1.40(4) 1.50(4) O 4 3 Mn Mn ¼ ¼ x [Si [Si 2 2 1.73 2 O4 O4 * Correspondence author (e-mail: [email protected]) Mg ...... 2 Institut de Mine Mineralogical Museum, Lausanne University, UNIL-Dorigny, 1015 Lausanne, Switzerland Geological Faculty of Moscow State University, Vorobievi Gori, Moscow, 1119992 Russia Laboratoire de Cristallographie, Ecole Polytechnique Fe Swiss-Norwegian Beamline, ESRF, BP-220, 38043 Grenoble Cedex, France specific features ofuneven their distribution structures. ofstructural The positions. Ca The first and second feature one Mn is is the on strong the the asym- M1 and M2 NaMn Received April 3, 2007; accepted September 24, 2007 Koashva, Khibiny alkalinesia). The massif, data Kolaof obtained peninsula, are the compared Rus- pectolite with other – members bond exhibitsbecomes strengthening more (O3– symmetric at 100 K (H– The crystal structuresthe (Fig. 1) pectolite of – occurring along Introduction Abstract. investigation has been performedstructural at 293 characterization andNa(Ca 100 of K for the the manganoan pectolite, Manganoan pectolite / HydrogenSingle bond crystal / structure Topology analysis / / X-ray diffraction V I II III IV Alla Arakcheeva New insight into thediffraction pectolite study – of serandite Na(Ca series: a single crystal 696 termination of the(1956) pectolite and crystal ainterest structure further by in refinementNa(Ca Buerger by the Prewitt (1967). minerals The with the general formula obtained fordency: 293 K the confirm highermetric the the the H-bond. previouslytion content The influence hinted of of ofbonded Mn, ten- the the O3 asymmetric the posi- H-bond anddiscussed. more O4 The on atoms alternative asym- topological and thebond role the is of environment H– the consideredLi close hydrogen in to comparison to the a similar structure series. The strongthe asymmetric hydrogen other bond members293 observed K in of the series has (O3– been confirmed at H H This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. 697 293 K). ¼ T 168(1) O); 178(4) 164(3) 171(1) 163.2 11; ¼ P ¼ ¼ ¼ ¼ ... 0.16(5)H2: O angle 1.413(3); O3 O4 164.0(3), 1.50(4); 1.60(3); 1.42(5), 1.54; 1.074(11), 1.078(3), (H þ O4 O4 O4 O4 ¼ 0.97(4), 0.88(3), 1.06(5), 0.97, d ... ¼ ¼ ¼ ¼ ¼ ¼ ...... ¼ ¼ ¼ ¼ ...... ) O3 1.407(11); O4 –H O4 O4 O4 O4 , –O), –H2 –H1 –O4 –O3 –H –H –H –H ...... A –O3 –O3 –O3 –O3 ...... ( (H– H2 O4– H1 O3– H2– H1– H O3– H O3– H O3– (unrefined) H O3– d the O– O4 hydrogen bond characteristics ... ], series (space group 9 –H O 3 (O3–O4) ) [HSi 2.467(2) 0.84(5)H1 x 2.473(3) H– 2.464(1) H– 2.473(2) H– 2.470(3) No data 2.473(3) No data 2.482(4) H– The O3– d Mn x i 2 –O M– ) h A Mn, 98.3; 2.234 Ca, 73.0; Mn, 27.0; 2.327 Mn, 98.9; 2.236 Ca, 94.3; Mn, 5.7; 2.352 Mn, 100; 2.235 Ca, 36; Mn, 64; 2.263 Ca, 100; 2.360; distance ( – serandite, Na(Ca (OH)] 8 O 3 positions (M,%); Mn, 94.1; 2.262 Ca, 99.9; Mn, 0.1; 2.371 Mn, 94.4; 2.261 Ca, 99.8; Mn, 0.2; 2.365 Ca, 34; Mn, 66; 2.286 Ca, 87; Mn, 13; 2.376 Ca, 100; 2.368 M1 M2 Occupation of M1 and M2 )[Si 0.77 ), Mn A ( 1.23 c , b , a ) ( g , b 7.7163(7) 6.9116(7) 6.7368(5) 7.9572(12) 7.0200(10) 7.0006(11) 7.7185(4) 6.9064(5) 6.7624(5) 7.980(1) 7.023(1) 7.018(1) 7.740(9) 6.913(9) 6.789(4) 7.868(4) 6.978(8) 6.920(6) 7.9882(1) 7.0400(1) 7.0247(1) , 90.465(7) 94.037(7) 90.562(12) 94.962(13) 90.492(5) 94.085(5) 90.54(1) 95.14(1) 90.51(6) 94.26(6) 90.72(6) 94.53(6) 90.520 95.181 102.844(7) 102.722(13) 102.775(6) 102.55(1) 103.05(6) 102.92(6) parameters: 102.469 a . 2000) . 2000) , 0.77 a (reference) Unit cell et al et al Specific structural characteristics of minerals in the pectolite – x ´uchi and Kudoh 1977) a: Old name of the pectolite with composition Na(Ca «» neutron study Serandite, 2 (Jacobsen Manganoan pectolite, 0.27 (present publication) Mn-bearing pectolite, 0.057 (Take X-ray study Serandite, 2 (Jacobsen Ca-rich serandite, 1.67 (Ohashi and Finger 1978) , (Ohashi and Finger 1978) Pectolite, 0 (Prewitt 1967) Table 1. Manganoan pectolite at 293 and 100 K This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. ¼ ek ˇ ı )] ´c et al. ˇ 0.057 F (OH)] closed ( 8 , lomo- ], and s 4 3 ¼ x O 3 x CO >3 2 ][PO )[Si 7 0.38 mm was x 0.015 (293 K) (2002) in con- F O [ 2 ¼ Mn R x [Si eq 2 2 et al. U O 2 0.12 mm larger than 0.77 (0.77, 1.67 and x (Ti,Nb,Fe,Mn) A. Arakcheeva, P. Pattison, N. Meisser 4 – serandite Na(Ca ]. The detailed description of the oc- 6 O 2 . A combination of sagitally focusing mono- A 0.77. Since the strong hydrogen bond appears to 0.026 at 293 K and 0.028 at 100 K). ¼ 0.27) allows us to cover the gap between ¼ x ., 2000). The atomic parameters obtained for Ca1, The investigated sample of pectolite was recently found in As can be seen from the Table 1, the previous structural ¼ int R x 0.0462 (293 K) and 0.0414 (100 K). and be largely independentcomprehensively of investigated the composition, atwe performed and room a hastigation synchrotron temperature been at single only, both crystal 293tion structure and inves- about 100 K theunusual in type order temperature of to hydrogen obtain dependent bond. informa- behaviour ofa pegmatite this at Mt.peninsula, Koashva, Russia) in Khibiny association alkaline with natrite, massif Na (Kola et al Ca2, Na andreported for for 9 O pectolitemodel atom (Prewitt, sites including 1967). weremeters Refinement anisotropic close of (ADPs) to atomic this the was values displacement performed para- up to chromator crystal andline vertically bent provide mirrormain a experimental in focused characteristics the areOxford beam- beam shown in Diffraction of Table 2. KM6165 0.5 An mm mm diffractometer diameter diameter. equippedthe CCD The with diffraction area a images. detectorusing Temperature was a control used cooled wasford to nitrogen Cryosystems achieved record gas Ltd.merged The cryostream intensities supplied with were by2002). the integrated Ox- and Lorentz CrysAlis andand program polarization absorption (Oxford corrections( were Diffraction effects applied were corrected using SADABS study of the pectolite – and 0.007 (100 K) appeared essentially higher for the nosovite, (Na,Ca)Na aegirine, NaFe[Si series has beento performed 0 for (0 the2). and minerals 0.057) The with and present( investigation of the manganoan pectolite currence has been given by Zubkova A fragmentshape of of the dimensions pectolite 0.12 mm crystal with a needle-like Structure determination and results A starting structure97 model (Sheldrick, was 1997). All obtainedformed other using with calculations the SHELXL- have JANA2000 been system per- of programs (Petr Experimental selected and mounteddata on collection a wasSwiss-Norwegian glass beamline performed fiber. BM01A at X-raychrotron of 293 the diffraction Radiation European and FacilitySi(111) Syn- 100 (ESRF, monochromator K Grenoble, was atof France). used the 0.7218 A to select a wavelength nection with theWell average formed, structure colourless investigationwith of and maximal natrite. transparent size pectoliteted 0.1–0.02 in crystals mm a bulk were sample randomly of distribu- coarse-grained natrite. -axis `uchi ) and b 1.42– A ¼ O4 hydro- (serandite) -axis. 1 a –O4 ... -axis was asso- –H b –O4 distance be- 2.46–2.48 ] wollastonite chain. ¼ 9 while H– O 3 A –O4 -proton position obtained by þ . (2000) using neutron diffraction . (1976) and Ohashi and Finger 0.94–1.06 et al (pectolite) and 1386 cm et al ¼ and parallel to the 1 1 direction was linked to the low probabil- -axis. The absence of the bending motion –O3 c a . (1998). According to the data obtained ´uchi ] pectolite chain was considered as a pyroxe- `uchi and Kudoh 1977). 9 O et al 3 (Table 1); (iii) the angles and distances related to the – serandite series was precisely described and ana- H] tetrahedron (silanol group) is another interesting A 4 From this short review on the strong asymmetric hydro- The ordered Ca and Mn cation distribution in the pec- The very strong, but asymmetric, hydrogen bond in pec- The hydrogen bond was also confirmed for both pecto- direction. Another and sharperserved OH at bending 1396 cm mode was ob- ciated with the hydrogen bond elongated along the noid chain by analogy to the [Si neutron diffraction study fortrical serandite than is the position still of more the symme- electron density maximum. asymmetric, H– gen bond investigation infollowing the conclusions pectolite-serandite can series,density be the maximum drawn: associated with (i) the a O3– single electron ity of H moving closer to Na atom along the parallel to the activity in the gen bond appears atstandard a deviations position, for which allbond is compositions; identical is (ii) within this 3 extremely hydrogen strong (O3– hydrogen bond, areexcept also of independent a on the slight composition, difference in the O3– 1.54 tween two terminal members ofnonequivalent the splitting series (Table of 1); H (iv) the [SiO 698 tolite – lyzed by Take aspect of pectolite structure. tolite was the object oflong many structural period investigations from overpresence a of 1956, an when H atom2000, Buerger between when O3 first Jacobsen and O4 proposed atoms, and the up to lite and seranditeHammer from single-crystalfrom IR polarized spectroscopy FTIR by serandite at absorption 298 spectraon and of 83 the K, pectolite therecompositions. hydrogen and is The no bond essentialaround very characteristics difference 1000 broad cm between absorption the band two centred The experimental basislocalization of for Ca theiratoms atoms in discussion, mainly M2 namelyquality in position, the crystal M1 was structure position obtainedviously refinements and from (Take published their Mn in own part high pre- experiment with serandite revealed twoand proton H2, positions, with H1 0.84 andtowards 0.16 occupations, O3 which were andtechniques, shifted O4 the same respectively authorssity (Table found maximum, 1). only one Using Htowards electron O3. X-ray (0.179(4), den- This electron 0.621(4),published density by 0.533(4)), position Prewitt is (1967) shifted for closed(0.162, pectolite, to 0.625, where that the 0.530) Hresidual coordinates atom were electron extractedstructure from density investigation the map ofand Kudoh without Mn-bearing 1977) pectolite refinement. alsoimum (Take revealed between The one O3 electronO3; and density O4 max- the asymmetrically0.527(6)). shifted reported toward coordinates are (0.178(5), 0.645(5), (1978) in theirThe crystal [HSi chemical analyses of pyroxenoids. This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. þ ) 2 699 F 9 ! l at 100 K is ) + 0.0001 ! 0.732(8)Ca F A 9 ( 2 ¼ ] tetrahedra are s 4 (100 K), is closer 3 1/( 9; ) cationic composi- ¼ ! 0.27 A w k (100 K) in M2. In the Mn 0.38 mm ! 3 of this maximum were in- 9 1.73 z A , y , 10 ; x 0.12 mm ! 11 . The resulting occupations of 3 P 0.001(8)Mn and M2 at 293 K and 2.458(2) h ) 0.66 I have been refined ( þ A ! A s z (293 K) and 0.35 e , y 0.0376. The residual electron density map 3 ) section containing the O3 and O4 atoms 0.0009 10 >3 , x < I xy ¼ A (293 K), 0.12 e iso ) Based on measured s.u.’s 3 2 U (OH)] at 293 and 100 K. F 8 A O 0.999(8)Ca 9 3 ¼ ! The hydrogen bond between O3 and O4 atoms sepa- 0.0001 )[Si 0.1 to 0.1 e l þ 0.27 illustrated in Fig.lysed 3. in The the residual(Fig. ( electron 3). density One isand maximum ana- O4 is atomsmum, clearly 0.37 at observed e both between temperatures O3 (Fig. 3). This maxi- 0.21 e tion of thetional parameters investigated for pectolite alltomic atoms crystal. are cation- The listedGeometrical in final distances Table posi- 3. characteristics Intera- are of shown the in [SiO Table 4. presented in Fig.good 4, approximation right of formum the of both hydrogen electron temperatures density. bond The shows by refined a one coordinates of maxi- H are to O3. Thecluded coordinates into refinementfixed as as H while the isotropic ADP was M1 0.268(8)Mn lead to the Na(Ca vicinity of Si and Na, we observe values varying from listed in Table 5. rated by 2.473(3) ) ! F ( Mn 9 2 s 1.73 3 1/( 9; A ¼ ! w k , corre- 0.38 mm 0.12 mm 3 1] which ! A 9 ¼ 10 ; 0.12 mm ! 11 triclinic, (100 K) in M1, and P h ) 3 0.59 0.77, I have been refined ( ! s z A ek, M.; Palatinus, L. (2000). Jana2000. , ˇ y 0.0004 10 >3 , occupation(Ca) 0.0355, 0.0451, 2.05x 0.0314, 0.0448, 2.21 FF < 0.026 0.028 22 3069, 1620, 1344I 12897, 1836, 1675 þ ek, V.; Dus ˇ c at 100 K, was also observed in the ı ´ ˇ 3 A S (293 K), 0.20 e ) synchrotron, 0.7218 synchrotron, 0.7218 ), 3 ) 0.50, A F ( –3 ( R A A l l w ) 2.941 2.971 (e , 3 M2 position. For both 293 and 100 K experi- k a )], , min ¼ F h ) 7.9572(12), 7.0200(10), 7.0006(11) 7.9220(9), 7.0090(9), 6.9770(9) ) 90.562(12), 94.962(13), 102.722(13) 90.596(10), 95.037(11), 102.715(12) ( r Experimental characteristics for manganoan pectolite, Na(Ca ) 2.51 2.52 M2 position; a weaker maximum, about 1.0 e M1 (Fig. 2a). Refinement of the Ca1 and Ca2 occu- M1 position in comparison to the much lower s ( A 0.003 (293 K) and 0.001 (100 K) characteristic of D ( ) 30.03 30.03 –1 , ) 379.85(10) 376.26(8) g parameters of M1 and M2 positions converged to ¼ ¼ ¼ max c ( 3 ¼ ) >3 , , (Mg mm s max A b / b and observed reflections ( F (mm eq eq r x [ int , max D Weighting scheme Based on measured s.u.’s No. of relectionsNo. of parametersH-atom treatment 1620 141 1836 141 Radiation type, m ( sponded to theCa2 strong and well defined maximum in the V a: Computer programs: Petr pations lead toM1 1.001(3)Ca and and M2to 1.100(3)Ca positions the values respectively. in presence Thesesite. the of results Thus significant pointed Mnrestriction amount was [occupation(Mn) of included Mn in in the the refinement M2 using the Ca1 improved essentially thelated different Fourier for syntheses bothU calcu- 293 and 100 K experiments (Fig. 2b). The U at 293 K and 0.4 e Ca1 Refinement on R Table 2. Manganoan pectolite at 293 and 100 K D q D Z Range of Crystal data Cell setting, space groupTemperature (K)a, triclinic, 293 100 0.011 and 0.0067 fortion 293 factors and were 110 Kever also respectively. their refined Occupa- values forstandard did Na deviations not and and deviate were Sisponding further from residual atoms, fixed 1 electron how- to density byima 1. (Fig. of less The 2b) 0.21 corre- than indicates e 0.5 max- mental temperatures, theFourier maximal synthesis value of of the electron different density, 1.6 e the Ca2 R Crystal form, colorCrystal size (mm) irregular, colorless 0.12 mm irregular, colorless a Data collection DiffractometerData collection methodAbsorption correctionNo. of measured, independent Criterion for CCD observed area reflections detector Oxford Diffraction SADABS KM6 Oxford Diffraction KM6 CCD area detector SADABS Refinement This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. . – cov- et al. et al . Scale A 3 A from the se- ´uchi A ] tetrahedra are slightly re- 4 ] group; the decrease of the 4 . In the bottom, the corresponding A A. Arakcheeva, P. Pattison, N. Meisser Mn) from neutron diffraction experiment by O4 hydrogen bond (Table 6). The ¼ ... M2 ¼ . (2000). The dashed contoured circle labeled as H1 –H –O distances in the M1, M2 and Na octahedra –O distances in [SiO et al Illustration of the influence of the asymmetric position of H- The comparison of the non-hydrogen atom characteris- The most interesting observation in the lower tempera- (1976) and Ohashimeters and measured Finger at (1978).fined 293 The K composition unit are cell sincewith also para- they in data accord are obtainedserandite with in (Fig. previously the 5). a for re- proper the agreement seriestics pectolite obtained at – twobe different summarized temperatures in (Table the 3–5)corresponding following way. can The atomic coordinates positions ofstandard all deviations are (Table 3). identicalaverage In Si– within comparison to 1–3 293 K, the and distances are indicated in Fig. 4. bond on thedifference environment around Fourier the sectionsand bonded cross H1 O3 O3, (right). and Si1 Summation O4 and normal atoms. H1 to The the (left) sections and within O3, 0.5 Na ers others shown atoms deviating with less than 0.1 indicates position of thewith electron 84% density occupancy maximum.is Only is missing. H1 shown, position while H2 position (16% occupancy) average M– (Table 4) are slightlyrepresent higher the (about changes 0.4%).decrease responsible These in distances for the lower the temperature structure unit (Table 2). cell volume ture structurestrong concerns O3– the atoms participating in the and Mn distribution onence M1 of Mn and atoms M2the in positions. crystal the The chemical M2 prefer- position analysis is published in by agreement Take with Jacobsen atomic planes areserandite drawn (M1 on the basis of structural data obtained for duced at 100 K bycal about 0.1% rigid (Table behaviour 5) confirming of the the typi- [SiO lected sections. Contours are drawn at intervals of 0.1 e b a –O3 within H– Ca and Ca and z –O and ... ¼ ¼ ) crosses the A . The section has 3 A within 0.5 z . -factors and the low residual section (summation along A R xy (OH)] (Table 1). The refined occu- 8 ) the refinement with the M1 O a 3 0.732(8)Ca. Contours are drawn at intervals of þ ) from the refinement yielding M1 )[Si b section (summation along 0.27 xy Mn ; the zero contours are broken, the negative contours are 3 Difference Fourier 1.73 Illustration of the H position determination in the O4 0.268(8)Mn Ca and ( ) crossing the M1 and M2 positions. The section is shown for A –O distances (Table 1 and 4; Fig. 5) justifies the Ca ¼ ¼ A M2– pations along withand identical M2 ADP positions (Table parameters 3), of and the the M1 average M1– been obtained from refinements without H atom. strong hydrogen bondence at Fourier 293 K (left) and 100 K (right). The differ- Fig. 3. The low values of the Discussion included in Tablecharacteristics 3, of while the thetemperatures hydrogen corresponding are bond listed geometrical at in Table the 6. two measured Fig. 2. 700 0.1 dashed. Scales are indicated in O4 and O3however, atoms. contours are Contours drawn and at intervals scale of drawing 0.1 is e similar to Fig. 2, the 293 Kbeen (left) obtained and 100 from K (right) ( measurements. The section has electron densityNa(Ca (Table 2) justify the composition M2 0.2 e M2 This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. . A 701 , while –O dis- 0.647 at A ¼ a a (2005). The eq 0.762 character- et al. ¼ 0.757 at 100 K (Fig. 5d); the last ¼ –O4) is about 0.2%. A similar obser- O4) is equal to 0.97 : 1.50 ... (H , (2000). d O4 distance decrease from 1.50(4) to 1.40(4) ), while the average decrease of the O– et al. 0.1019(3) 0.1762(3) 0.0132(8) 0.1016(2)0.0920(3) 0.1762(2) 0.0093(5) 0.2800(3) 0.0142(8) 0.0916(2) 0.2813(2) 0.0102(5) ... A –H) : –H distance increase from 0.97(4) to 1.06(4) –O4 distance is shorter by 0.6% (from 2.473 to (OH)], at 293 K (upper lines) and 100 K (lower lines). 8 (O3– O 3 electron density maximumshifted from associated O3 withO3– toward H O4 is (Table 3, slightly Figs. 3 and 4): the tances (including O3– vation has been mentioned by Jacobsen the H O3– 2.458 These results indicatestronger and that more themore symmetric hydrogen symmetric at bond H-bondlinked 100 K. to at becomes the The lowerthe shift reason temperature of of proton the might a temperature H-bond position, be electron density (Fig. which 4).d towards has In been the found present at study room the ratio 293 K and 1.06 : 1.40 value being very close to 1.078 : 1.413 istic of thecobsen H1 (main) proton position as reported by Ja- )[Si 0.27 i Mn 1.73 2.320 xyzU 0.181(5) 0.650(5) 0.537(5) 0.0376 0.84894(6)0.21919(9) 0.08458(5)0.21262(9) 0.40374(8) 0.13864(5)0.45141(9) 0.95553(8) 0.33767(8) 0.00666(15) 0.73893(8) 0.34697(8) 0.0063(2) 0.14468(8) 0.0068(2) 0.0070(2) 0.0596(2) 0.55351(13)0.6547(2) 0.25457(12)0.6713(2) 0.34426(13) 0.7933(2)0.1876(2) 0.2897(2) 0.0112(3) 0.1704(2) 0.1246(2) 0.5011(2)0.0630(2) 0.0546(2) 0.0100(5) 0.8470(2) 0.5407(2) 0.0104(5) 0.3869(2) 0.5449(2) 0.0086(5) 0.1733(2) 0.0097(5) 0.0083(5) 0.85336(6) 0.59378(5) 0.14446(6) 0.00672(16) 0.3954(2) 0.4016(2) 0.5340(2) 0.2685(2) 0.0094(5) 0.2647(2) 0.19314(19) 0.3892(2) 0.0076(5) ih 2.327 293 K 100 K h ) ) in manganon pectolite, 0.27 A Mn ¼ 0.73 –O1–O2–O4–O5 2.268(2)–O6 2.265(1) 2.275(3)–O6 2.270(2) 2.291(2) 2.280(1) 2.408(2) 2.400(1) 2.345(3) 2.333(2) 2.379(2) 2.369(2) Average (Ca 0.268(8) Mn 0.84816(8) 0.08421(7) 0.13873(8) 0.0109(2) –O distances ( i i þ (OH)] at 293 and 100 K. 2.426 2.362 8 O 3 –O and Na– ih ih )[Si 0.27 2.437 2.371 h h The M– Mn Positional parameters for manganoan pectolite, Na(Ca Ca 293 K 100 K M2 1.73 ¼ –O2 2.303(3) 2.293(2) –O3–O4 2.441(2)–O7 2.433(2) 2.526(3)–O8 2.508(2) 2.558(3)–O9 2.552(2) 2.505(3) 2.488(2) 2.291(3) 2.283(2) –O1 2.331(3) 2.321(2) – –O2–O3 2.343(2)–O5 2.340(1) 2.339(2)–O5 2.331(1) – 2.443(3)–O6 2.431(2) – 2.379(2) 2.366(2) – 2.389(2) 2.381(1) – – – – – – – – – – – – – Average Na– Average Position Occupation Table 4. Si1Si2 1Si3 1H 1 1 0.21830(13) 0.21198(13) 0.40373(11) 0.45050(12) 0.95569(11) 0.33730(12) 0.181(5) 0.73888(11) 0.34603(12) 0.0101(3) 0.14434(12) 0.0104(3) 0.637(6) 0.0109(3) 0.544(6)Na(Ca 0.0376 Na 1 0.55319(18) 0.25546(19) 0.3454(2) 0.0217(5) O1O2 1O3 1O4 1O5 1O6 1 1 0.6538(3) 0.6712(3) 0.7937(3) 0.1880(3) 0.2897(3) 0.1704(3) 0.1252(3) 0.5004(3) 0.0627(3) 0.0553(3) 0.0144(8) 0.8477(3) 0.0595(3) 0.5399(3) 0.0145(8) 0.3866(3) 0.5441(3) 0.0142(8) 0.1733(3) 0.0151(8) 0.0117(8) M1 1 Ca 0.85251(9) 0.59369(8) 0.14474(9) 0.0112(2) Table 3. M2 0.732(8) Ca Manganoan pectolite at 293 and 100 K M1 O7O8 1 1 0.4008(3) 0.3942(3) 0.5341(3) 0.2676(3) 0.0142(8) O9a: Unrefined parameters 1 0.2641(3) 0.1929(3) 0.3879(3) 0.0128(8) This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. et al. –Si2 et al. et al. (about A –Na dis- (polarized i a 1.628 ion. The proton þ –Na in comparison distance decreases by i –Si2 with 0.25% elonga- further away from Na –O –Na interaction. ih axis direction, hence the ab- /4 Na– a- 2 A ) (Fig. 4, bottom-right). The h ) –M1) in comparison to O4– 1.629 A (OH)] at 273 and 100 K. avr h 8 1.000805 0.999561 14.256 14.600 /l i O l 3 A. Arakcheeva, P. Pattison, N. Meisser 2.12 22( ) than the maximum of H-electron )[Si ¼ A 0.27 i¼ –Si1 (O3– l h Mn –Na 2.29 1.73 a ¼ a –Na (Fig. 4, right) are the results of the H-bond –O6–O8–O9–O8–O9 114.31(12)–O9 108.21(13) 109.07(11) 114.24(9) 110.69(13) 108.29(9) 110.10(12) 109.22(8) 102.82(12) 110.76(9) 110.92(9) 102.76(9) –Na – –M2) (Fig. 4, left) and shorter O3– ] 293 K 100 K þ 4 –H line is close to the The short distance between Na and the maximum of –O4–O6–O8–O9 1.611(2) 1.605(2) 1.660(3) 1.642(2) 1.609(2) 1.604(2) 1.655(2) 1.642(1) –Si2– –Si2– –Si2– –Si2– –Si2– –Si2– density (H1– Na– FTIR absorption(1998)) might spectra be due to reported the H– by Hammer sence of the H-bond vibration parallel to (O4– (2000) for seranditeatom, hints which to has a a small component toward dipole Na splitting of H 1.75%) more elongatedtion. than Longer O4– O3– position is(H1 about 0.17 to O4– asymmetry. The shift ofimum the towards H-bond the electrontance, O4 density which affects max- decreases essentially from0.7%), 2.526(3) the while to O4– 2.508(2) the0.45%. average H-bond electronright) density is another (Fig. interesting 4,lite. detail This of top-right specific the featuredite manganoan and is pecto- also structure middle- characteristictween of (Fig. the 4, the seran- electron bottom-right).atom density A and (Fig. 4, the comparison proton bottom-right) be- positions reported of H by Jacobsen Average . 1971); quadratic elongation –Si and et al i i (OH)], at 8 O 1.625 1.636 3 – serandite series )[Si ] tetrahedra in manganoan pectolite, Na(Ca /5 (Robinson 4 2 (OH)], and pure ser- 0.27 ) 8 O 3 Mn –Si1 is essentially (about [Si ih ih 1.73 ) in [SiO – 109.47 – 0.057 i O4) ratio characteristic of the 1.628 1.639 q h 1.000757 1.001140 13.927 15.003 1.004211 1.000128 Elongation 19.077 17.763 Angle variance h Mn 22( ... ¼ (H (OH)] (Table 1). The manganoan pec- 1.943 q 8 d 2 s ) and angles ( –Si2 can be estimated in relation to O ) –Si2 respectively, where O5 and O6 are 3 A 2 [Si –H) : 2 a a (O3– a a d Distances ( –O5–O7–O9–O7–O9 114.94(14)–O9 107.05(11) 106.20(12) 114.52(10) 111.30(12) 107.12(8) 112.89(11) 106.22(8) 103.65(13) O4– 111.30(8) 113.04(8) O4– 103.89(9) O4– O6– O6– O8– –O2–O7–O8–O7–O8 115.61(13)–O8 109.52(13) 110.16(12) 115.59(9) 108.39(11) 109.63(9) 108.46(13) 110.26(8) 104.06(12) 108.34(8) 108.44(9) 103.93(8) –M distances–Na (Fig. 4, distances left) and (Fig. 4, a right). decrease The of the elongation of ] 293 K 100 K ] 293 K 100 K [Si2O 4 4 –Si1 and O6– –O4 constriction is an elongation of the O3(4)– –Si1 and O4– –O3–O5–O7–O9 1.625(3) 1.597(2) 1.653(2) 1.635(2) 1.629(2) 1.595(2) 1.645(2) 1.631(2) Si2– Si2– Si2– Si2– –O1–O2–O7–O8 1.596(3) 1.614(2) 1.674(2) 1.673(3) 1.590(2) 1.609(2) 1.674(2) 1.673(2) The The influence of the asymmetric position of the H-bond –Si1– –Si1– –Si1– –Si1– –Si1– –Si1– –Si3– –Si3– –Si3– –Si3– –Si3– –Si3– Elongation Elongation manganoan pectolite, Na(Ca O3– O3– O3– O5– O5– O7– Angle variance [Si3O [Si1O andite, NaMn Si1– Si1– Si1– Si1– Average Table 5. 702 293 K adds athe third H-bond dot in asymmetry the(Fig. in 5d). compositional the dependence Two pectolite of otherbasis values – of of the thispure refined ratio pectolite, H calculated NaCa position on are the associated with almost O1– a: Angle variance ( O1– O1– O2– O2– O7– Angle variance Si3– Si3– Si3– Si3– Average O5– non-bridged O atoms (similartion to shows O3 that and the O4). distance The O3– estima- on the environment closecan to be the bonded analysedatoms O3 in is and bonded the O4Na with atoms following one atom way. Si (Figs. Eachand atom, 1 O4 of one and atoms, M thesebecause 4). atom, the O and O3 The of one atom H-bondO3– the being constricts more the H-bond hitched O3 than asymmetry. O4 The result of the tolite reinforce thethe tendency basis of the ofMn, dependence the these more hinted two asymmetric on values: the H-bond. the higher the content of O3(4)– O3(4)– O3– This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. 2 in 4 ] 204 ), a 703 4 Mg 11 et al. 2 A O 4 (Si 2 (OH)]. Am. in Li (OH)], has 8 8 Mg O 2 3 O 3 A [Si 2 H] (silanol) entity )[Si 4 6.88 0.27 –O3) group per 4-fold ¼ c H– Mn (1956) 248–261. observed by Hammer –O3) group in pectolite-ser- ... 1.73 a ] differing by replacement of H– 108 ] tetrahedron in the 4-fold ring –O3) group plays the same to- 11 ] and by about 2.47 4 in pectolite, reinforce this ana- ... O 11 H– 4 –Si distances and a shortening of O A 4 ... is consequently followed by the loss [Si 2 3 7.01 ]; hence, pectolite cannot be considered This research was supported by the Swiss Na- M 11 2 ¼ O . Z. Kristallogr. b 9 4 (OH)], and serandite, NaMn (1998) 569–576. –O3) 8 ] (pectolite). The similar translation vectors ion in the cationic net, while the arrangement O 9 ions is identical in both structure (Fig. 1). This 2 O atomic position resulting in a rearrangement of [Si H– 3 83 O4 strong hydrogen bond becomes stronger and –H interaction can explain the absence of the O in A þ ] tetrahedron by (O4 þ 3 2 þ 4 2 [Si 2 ... –O distances. At room temperature, the manganoan ] and ... ] tetrahedron in the 4-fold ring of the (Si,O)-ribbon A NaHSi Mg 4 11 2 2 [HSi 2 O –H loop-branched dreier(1993) single 129–142. chain silicate. Z.spectroscopy Kristallogr. ofNaCa very strong hydrogen bonds in pectolite, Ca Mineral. 4 pological role as an [Si2O logy. Hence, the (O4 andite structures[Si2O plays the same topological role as an AM of the (Si,O)-ribbon (Fig. 1). The replacement of [SiO topological analysis shows thatered pectolite as cannot a be pyroxenoid consid- and that the [SiO the rest A in Li Hammer, V. M. F.; Libowitzky, E.; Rossman, G. R.: Single-crystal IR Czank, M.; Bissert, G.: The crystal structure of Li should not be considered in pectolite. of one A logical analogues of [Si Buerger, M. J.: The determination of the crystal structure of pectolite, Acknowledgements. tional Sciencegrateful Foundation, to grant thesion Swiss-Norwegian no. of beamline synchrotron 2000021–109470/1. radiation consortiumPresident facilities. of for We IP Russian the is Federation,sian are grateful grant provi- Science no. to Support MD-7230.2006.5, Foundation Foundation. and of Rus- References [Si by (O4 Summary The crystal structurehigh of content the of manganoan pectolite Mn, with Na(Ca a one [SiO of the M been characterised atO3– 293 and 100 K. It is shown that the (1998). An alternativebeen topological considered: role the of (O4 the H-bond has as a pyroxenoid. along the ribbon elongation, ring (Fig. 1).2.538 The two connected O atoms are distant by more symmetric attron 100 density K. towards The theble shift proton reason of position of might a theture. more be H-bond symmetric a The elec- H-bond possi- environment at close influence lower tempera- tobeen of the considered: bonded theasymmetric the O3 H-bond constriction and gives hydrogen of riseof O4 to O3 the atoms an bond asymmetric corresponding and has the elongation O– O4 on Na– bypectolite the the justifiesand the degree of dependence asymmetrycontent previously between of hinted: the Mn, composition posed higher the Na– the more asymmetric H-bond. The pro- H-bond vibration parallel to ] 2 b d ¼ þ 11 ] A 9 O ) and 4 .As a O 7.401, ¼ 3 ] pecto- ] ¼ 9 11 ) ); O b 3 O [HSi A 99.41 4 2 (OH)]: ( 8 ¼ [Si O 3 O4) ( g O4 distances in the 2 8.645, ... )[Si ... x O4 angle ( interatomic distances in ¼ Mg (H i 2 d ... Mn a x ], the anionic (Si,O,H)- –O 2 9 –H 101.08, M– O h 3 –O3), ¼ –H and H ) c ) at 293 and 100 K. The dark signs b c a (H– d d the O3– ;( [HSi x 2 (OH)] at 293 and 120 K. 8 ] ribbons, each of them being topo- 9 O (refined data obtained with only X-ray ex- 3 ) O x 3 A 104.71, )[Si ¼ 0.27 ]) can be interpreted in comparison to 9 a ), at 293 K; in ( –O4) ( c O Mn ], the anionic (Si,O)-net consists of [Si 3 ) the ratio of the O3– ] (Czank and Bissert, 1993), which is also tri- , – serandite series, Na(Ca d 11 1.73 11 A (O3– O d O 4 4 [HSi ) and ( The strong hydrogen bond characteristics in manganoan pec- 2 b Some compositionally dependent structural characteristics of [Si ] tetrahedra. In AM 2+ [Si 2 4 2 6.884 ), ( As mentioned in the introduction, the pectolite struc- M þ a M 2 (K) ) unit cell parameters versus 2 þ ¼ b c M1 and M2M octahedra position; versus ( hydrogen the bond composition versus of the corresponding periments). The open signsin refer ( to data obtained in the present work: correspond to previously publishedmental data points listed are in connected for Table 1. a The better experi- visualization only. net consists of [HSi ribbons, which are[SiO formed by connected 4-fold rings of 293100 2.473(3) 2.458(2) 0.97(4), 1.50(4); 178(4) 1.06(4), 1.40(4); 177(4) clinic with unit cell parameters Table 6. tolite, Na(Ca M Fig. 5. the pectolite – Manganoan pectolite at 293 and 100 K ture was studied inlysis the of frame pyroxenoids (Ohashi ofthe presence the and of crystal Finger, 1978). the chemical However, hydrogen ana- bond in the [HSi the very similar structure of Li A T ( shown in Fig.as 1, both alternatingA these structures anionic can (Si,O) be presented and cationic nets. In lite chain wastopological ignored role in of thiscrystal the discussion. chemical H-bond Considering analysis in can the role be pectolite, of proposed. an The the alternative topological H-bond in pectolite (Na(Ca,Mg) This article is protected by German copyright law. You may copy and distribute this article for your personal use only. Other use is only allowed with written permission by the copyright holder. 146 et al. (1977) 281–292. (2002) 85–96. 146 2 A. Arakcheeva, P. Pattison, N. Meisser ¨ttingen 1997. (1971) 567–570. . Neues JB. Miner. Monat. 3 172 CO 2 -Na ´uchi, Y.; Kudoh, Y.; Yamanaka, T.: Crystal chemistry of the ser- ´uchi, Y.; Kudoh, Y.: Hydrogen bonding and cation ordering in (1976) 229–237. kov, I.g V.; Chukanov, N. V.: Crystal structure of natrite, quantitative measureScience of distortion inment. coordination Universitat Go polyhedra. andite-pectolite series and related minerals. Z. Kristallogr. Magnet Cove pectolite. Z. Kristallogr. Zubkova, N. V.; Pushcharovsky, D. Yu.; Ivaldi, G.; Ferraris, G.; Pe- Robinson, K.; Gibbs, G. V.; Ribb,Sheldrick, P.H.: G. Quadratic M.: elongation: SHELXL-97 Program A for Crystal Structure Refine- Take Take . 9 90 O 3 t from: t NaHSi 2 peer review process peer review progress tracking progress up- and download facilities comfortable shorter time turn-around information status current easy, step-by-step submission step-by-step easy, You benefi You • • • • • Online • (1978) 274–288.

63 Oldenbourg (2000) 745–752. 85 10/2007 et al. (1967) 298–316. Volume 222 Volume by E.Edited J. Mittemeijer, U. and R. Welzel Kuz ˇel Letter T. L. Kuhl International journal for structural, physical, and chemical aspects of crystalline materials ZEITSCHRIFT FÜR KRISTALLOGRAPHIE now with Editorial Manager now with Editorial Zeitschrift für Kristallographie Zeitschrift See more at www.zkristallogr.de / Author Submission / Author at www.zkristallogr.de See more 125 (OH)]. Am. Mineral. ek, M.; Palatinus L.: Jana2000. Structure Determina-

8 ˇ

O

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Oldenbour [Si g 2 ek, V.; Dus ˇ c ı ´ Z. Kristallogr. proton positions inNaMn the very strong hydrogen bond of serandite, A systematic studyFTIR of spectroscopy OH and insites hydrous single-crystal for wadsleyite X-ray hydrogen from diffraction: storage polarized Oxygen in Earth’s interior. Am. Mineral. tion Software Programs. Institutelic of 2000. Physics Praha, Czech Repub- (2005) 61–70. noid crystal chemistry.lite-schizolite-serandite I. series. Bustamite, Am. Mineral. wollastonite, and the pecto- ˇ Jacobsen, S. D.; Smyth, J. R.; Swope, R. J.; Sheldon, R. I.: Two 704 Jacobsen, S. D.; Demouchy, S.; Frost, D. J.; Ballaran, T. B.; Kung, J.: Prewitt, C. T.: Refinement of the structure of pectolite, Ca Ohashi, Y.; Finger, L. W.: The role of octahedroal cations in pyroxe- Petr