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Crystal chemistry of basic lead carbonates. III. Crystal structures of Pb3O2(CO3) and NaPb2(OH)(CO3)(2)
Article in Mineralogical Magazine · December 2000 DOI: 10.1180/002646100549896
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Sergey V Krivovichev Peter C Burns Saint Petersburg State University University of Notre Dame
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Crystal chemistry of basiclead carbonates.
III.Crystalstructures of Pb 3O2(CO3) and NaPb2(OH)(CO3)2
, S. V. KRIVOVICHEV* { AND P. C. BURNS
Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick, University of Notre Dame, Notre Dame IN46556-0767 USA
ABSTRACT
Thecrystal structure sofsynthetic Pb 3O2(CO3) and NaPb2(OH)(CO3)2,havebeen solved by direct methodsand refined to R =0.062and 0. 024,respectiv ely.Pb 3O2(CO3)isorthorhomb ic, Pnma, a = 22.194(3), b = 9.108(1), c =5.7405(8)A Ê , V =1160.4(3)A Ê 3, Z =8.There are four symmetrica lly distinct Pb2+ cationsin irregular coordinat ionpolyhedra due to the effect of stereoacti ve s2 lone- electronpairs. The structure is based upon double [O 2Pb3]chainsof [O(1)Pb 4]and[O(2)Pb 4] oxocentredtetrahedraandCO 3 groups.The [O 2Pb3]chainsare parallel to the c axis,whereas the CO3 groupsare parallel to the (010) plane. NaPb 2(OH)(CO3)2 ishexagona l, P63mc, a = 5.276(1), c =13.474(4)A Ê , V = 324.8(1) AÊ 3, Z =2andhas been solved by direct methods. There are two symmetricallydistinct Pb 2+ cationsin asymmetric coordinat ionpolyhedra due to the effect of stereoactive s2 lone-electronpairs. The single symmetrical lyunique Na + cationis in trigonal prismaticcoordinat ion.The structure is based on hexagonalsheets of Pbatoms. Within these sheets, Pbatoms are located at vertices of a 3 6 net,such that each Pb atom has six adjacent Pb atoms that are ~5.3 AÊ away.Two sheetsare stacked in a close-packingarrangeme nt,forming layers that containthe (CO 3)groups.The layers are linked by OH groupsthat are linearly coordinat edby two Pb2+ cations. Na+ cationsare located between the layers. The structure is closely related to the structuresof other lead hydroxide carbonate s(leadhillite,macpherso nite,susannite, hydroceru ssite, ‘plumbonacrite ’).
KEY WORDS: basiclead carbonates, lone-electron pairs, oxocentred tetrahedra, hexagonal lead sublattice
Introduction (Roberts et al., 1995). Pb3O2(CO3)isalso known asan intermediateproduct of thermaldecomposi- Thephase PbCO 3 2PbO, or Pb3O2(CO3), was tionof cerussiteto leadoxide (Warne and Bayliss, identied by Roberts et al.(1995)in cerussite- 1962;Grisafe and White, 1964) . bearingmineral specimens from the Grand Reef Thesynthetic phase NaPb 2(OH)(CO3)2 was mine,Graham County, Arizona, USA, inassocia- rstreported by Bulakhova et al. (1972) as a tionwith shannonite and litharge. Although the productofreactionofhydrocerussite, phasehas a naturalorigin, its approval as a new Pb2(OH)2(CO3),with a 2:1mixture of Na 2CO3 mineralspecies awaits discovery of pure material and NaHCO3.Later,Brooker et al. (1983) reportedX -raypowder diffraction data, infrared andRaman spectra for this compound. On the basisof theirdata, Brooker et al.(1983)suggested *E-mail: [email protected] .ru thatthe carbonate groups in NaPb 2(OH)(CO3)2 *Permanent address: Department of Crystallography, arein two non- equivalentsites, and that the St. Petersburg State University, University Emb. 7/9. structurecontains a well-dened hexagonal Pb 199034 St. Petersburg Russia sublattice.
# 2000The Mineralogical Society S.V.KRIVOVICHEVAND P.C.BURNS
Asa partof our ongoing study of the crystal Two suitablecrystals of the compounds were chemistryof basic Pb carbonates (Krivovichev mountedon a Brukerthree-circle CCD- based andBurns, 2000 a,b),we have determined the X-raydiffractome teroperated at 50 kV and structuresofsyntheticPb 3O 2(CO 3 ) and 40mA. Morethan a hemisphereof three- NaPb2(OH)(CO3)2,andreport the results herein. dimensionaldata was collected using monochro- matic Mo-Ka X-radiationfor each crystal, with framewidths of 0. 3 8 in o,andwith 10 s spent Experimental countingfor each frame. The unit-cell parameters Singlecrystals of synthetic Pb 3O2(CO3) were (Table1) were re ned using least- squarestech- obtainedusingthe procedu redescrib edby niqueswith 1572 and 1510 re ections for Krivovichevand Burns (2000 a).Thecrystals Pb3O2(CO3) and NaPb2(OH)(CO3)2,respectively. occuras colourless needles up to 2. 0mm in Theintensity data were reduced and corrected for lengthand 0.03 mm across. Lorentz,polarization, and background effects Singlecrystals of synthetic NaPb 2(OH)(CO3)2 usingthe Bruker program SAINT. Asemi- wereobtained by hydrothermal methods from a empiricalabsorption-correcti onfor Pb 3O2(CO3) mixtureof 0. 05g ofPbO, 0. 05g ofPbCl 2, and wasperformed based upon 696 intense re ec- 0.05g ofPbCO 3 with5 mlof ultrapureH 2O. The tions.The crystal was modelled as an ellipsoid, pHof the solution was adjusted using aqueous whichlowered the Razimuthal from23.1 to 10. 7 %. NaOH to~10. The reactants were placed in a Asemi-empiricala bsorption-correctionfor Teon-lined Parr bomb and were heated to 230 8C NaPb2(OH)(CO3)2 wasperformed on the basis for~24 h. The products were lteredand washed of1340 intense re ections. The crystal was withultrapure water. Several single crystals of modelledas a (001)plate; re ections with a NaPb2(OH)(CO3)2 wereobtained. The crystals plate-glancingangle of <3 8 werediscarded from occuras colourlesshexagonal plates up to 0.7mm thedata set, which lowered the Razimuthal from indiameter and 0.05 mm thick. 27.4 to 4.8%.
TABLE 1.Crystallographic data for Pb 3O2(CO3) and NaPb2(OH)(CO3)2.
Parameter Pb3O2(CO3) NaPb2(OH)(CO3)2
a (AÊ ) 22.194(3) 5.276(1) b (AÊ ) 9.108(1) c (AÊ ) 5.7405(8) 13.474(4) V (AÊ 3) 1160.4(3) 324.8(1) Space group Pnma P63mc F000 2336 486 m (cm 1) 867.78 518.24 3 Dcalc (g/cm ) 8.17 5.86 Crystal size (mm) 0.2060.0360.04 0.5860.2460.04 Radiation Mo-Ka Mo-Ka Total Ref. 6601 1605 Unique Ref. 1472 342 Unique |Fo| = 4sF 1047 331 R 0.062 0.024 wR 0.170* 0.059** S 1.058 1.058
2 Ý Note: R = S(|Fo| |Fc|)/S|Fo|; S = [Sw(|Fo| |Fc|) /(m n)] , for m observations and n parameters 2 2 2 2 2 * w = 1/[s (Fo) + (0.0987P) ] where P = (Fo + 2Fc)/3 2 2 2 2 2 ** w = 1/[s (Fo) + (0.1170P) + 3.6042P] where P = (Fo + 2Fc)/3
1078 CRYSTAL STRUCTURE OFP B3O2(CO3) AND NAPB2(OH)(CO3)2
Structuresolution and refinement Results Cationcoordina tion TheBruker SHELXTL Version5 systemof Pb3 O2 (CO3) programswas used for the determination and renement of the crystal structures. The structures Thereare four symmetrically independent Pb 2+ weresolved by direct methods and were success - cationsin the structure of Pb 3O2(CO3) (Fig. 1). fullyre ned on the basis of F2 forall unique data in ThePb(1) and Pb(3) cations are coordinated by thespace groups Pnma and P63mc for Pb3O2(CO3) sixO atoms,whereas the Pb(2) and Pb(4) cations and NaPb2(OH)(CO3)2,respectively.The choice of arecoordinated by four and seven O atoms, space group P63mc for NaPb2(OH)(CO3)2 is in a respectively.The coordinati onpolyhedra are goodagreement with the results of spectroscopic stronglydistorted due to the effect of s2 lone studiesby Brooker et al.(1983).The nal electronpairs on the Pb 2+ cations.In both Pb renement converged to an agreement index ( R1) coordinationpolyhedra the location of the lone of0. 062for Pb 3O2(CO3),calculated for 1047 electronpair is apparent from the asymmetry of uniqueobserved ( |Fo|5 4sF)reections, and to thepolyhedra (Fig. 1) .Thetwo symmetrically anagreementindex( R 1)of0.024for independentcarbonate triangles show typical NaPb2(OH)(CO3)2,calculatedfor 331 unique bond-lengths,with a
4 2 TABLE 2.Atomic coordinates and displacement parameters ( 610 AÊ ) for Pb3O2(CO3).
Atom x y z Ueq
Pb(1) 0.42738(5) 1/4 0.7828(2) 82(4) Pb(2) 0.18557(5) 1/4 0.7855(2) 96(4) Pb(3) 0.32522(4) 0.0487(1) 0.7845(2) 132(3) Pb(4) 0.06986(4) 0.0226(1) 0.7821(2) 140(3) C(1) 0.036(2) 1/4 0.741(6) 120(70) C(2) 0.207(2) 1/4 0.799(6) 180(80) O(1) 0.1279(6) 0.097(2) 0.532(3) 80(30) O(2) 0.1288(5) 0.098(2) 0.034(2) 60(30) O(3) 0.146(1) 1/4 0.785(4) 150(50) O(4) 0.023(1) 1/4 0.787(4) 120(50) O(5) 0.0612(8) 0.125(2) 0.710(3) 220(40) O(6) 0.236(1) 0.127(3) 0.786(4) 410(60)
Atom U11 U22 U33 U23 U13 U12
Pb(1) 59(6) 89(6) 97(7) 0 10(4) 0 Pb(2) 47(5) 122(7) 120(7) 0 14(4) 0 Pb(3) 188(5) 83(5) 124(6) 1(3) 7(4) 77(4) Pb(4) 168(5) 150(5) 103(6) 4(3) 10(3) 99(4)
1079 2 TABLE 3. Atomic coordinates and displacement parameters (AÊ ) for synthetic NaPb2(OH)(CO3)2. S.V . K
Atom x y z Ueq U11 U22 U33 U23 U13 U12 RIV OVICHEV
Pb(1) 2/3 1/3 0.8195(1) 0.018(1) 0.019(1) 0.019(1) 0.018(1) . . 0.010(1)
Pb(2) 1/3 2/3 0.9883(1) 0.019(1) 0.023(1) 0.023(1) 0.011(1) . . 0.012(1) 1
. . 080 Na 1/3 1/3 0.6503(15) 0.021(2) 0.031(2) 0.031(2) 0.000(3) 0.016(1)
C(1) 0 0 0.785(2) 0.015(5) 0.020(8) 0.020(8) 0.006(10) . . 0.010(4) AND
C(2) 0 0 0.028(2) 0.016(5) 0.019(8) 0.019(8) 0.011(10) . . 0.010(4) P
O(1) 0.718(3) 0.141(2) 0.7856(9) 0.020(3) 0.007(6) 0.018(5) 0.033(6) 0.001(2) 0.002(4) 0.004(3) . O(2) 0.277(4) 0.138(2) 0.0264(9) 0.025(3) 0.018(7) 0.023(5) 0.031(6) 0.002(2) 0.005(5) 0.009(4) C. BURNS O(3) 2/3 1/3 0.654(3) 0.046(4) 0.065(6) 0.065(6) 0.010(5) . . 0.032(3) CRYSTAL STRUCTURE OFP B3O2(CO3) AND NAPB2(OH)(CO3)2
TABLE 4.Selected interatomic distances (A Ê )inthe structure of Pb 3O2(CO3).
Pb(1) O(2)a,b 2.34(1) 26 C(1) O(5),f 1.28(2) 26 O(1)a,b 2.34(1) 26 O(4) 1.34(4) O(4)c 3.05(2)
a: x + Ý, y, z + Ý; b: x + Ý, y + Ý, z + Ý; c: x + Ý, y, z Ý; d: x, y, z + 1; e: x, y Ý, z + 1; f: x, y Ý, z; g: x + Ý, y, z + 3/2; h: x, y, z + 1; i: x, y, z + 2; j: x, y + Ý, z
atoms,with Pb Odistancesof ~2.7A Ê , and six O structure.The Pb fn coordinationpolyhedra are atomswith Pb Odistances~3.2 3.3 AÊ . The stronglydistorted due to the effect of s2 lone- Pb OHbondsare relatively short [Pb(1) OH = electronpairs on the Pb 2+ cations.The s2 lone- 2.23 AÊ ; Pb(2) OH = 2.24 AÊ ] and are the electronpairs probably project opposite to the strongestPb f bonds (f =O,OH)inthe Pb OHbond(Fig. 1 ).The Na c ationis
TABLE 5.Selected interatomic distances (A Ê )inthe structure of synthetic NaPb2(OH)(CO3)2.
Pb(1) OH(3) 2.23(4) Pb(2) OH(3) 2.24(4) O(1) 2.688(2) 66 O(2) 2.700(3) 66 O(2) 3.31(1) 36 O(1) 3.25(1) 36
C(1) O(1) 1.29(2) 36 Na O(2) 2.44(2) 36 C(2) O(2) 1.27(2) 36 O(1) 2.53(2) 36
1081 S.V.KRIVOVICHEVAND P.C.BURNS
Amorestraightfo rwarddescripti oninvolves Pb O (CO ) 6+ 3 2 3 oxocentred(OPb 4) tetrahedraand CO 3 groups. TheO(1) and O(2) atoms do not participate in 2+ CO3 trianglesand are bonded to Pb cations only.The O(1) and O(2) atoms are tetrahedrally coordinatedby four Pb atoms with O Pb bonds inthe range 2. 2 2.4 AÊ ,andthus are centres of oxocentred(OPb 4)tetrahedra.The [O(1)Pb 4] and Pb1 Pb2 [O(2)Pb4]tetrahedraare linked by sharing edges toform double [O 2Pb3]chainsthat extend along the c-axis(Fig. 2). The arrangement of thedouble [O2Pb3]chainsand CO 3 groupsin thestructure is shownin Fig. 3. The CO 3 groupsare parallel to the(010) plane.
NaPb2 (OH)(CO3)2 Inaccord with the interpretation of IR spectra by Brooker et al.(1983),the structur eof Pb3 Pb4 NaPb2(OH)(CO3)2 containsa hexagonalsublat- ticeof Pbatoms. As is thecase in thestructures of otherPb hydroxide carbonates, the sublattice may bedescribed as based on the hexagonal sheet of Pbatoms shown in Fig. 4 a.Withinthis sheet, Pb atomsare located at the vertices of 3 6 net and NaPb2(OH)(CO 3 ) 2 eachPb atom has six nearest Pb atom neighbours ~5.3 AÊ away.Two suchsheets are stacked togetherinaclose-packedarrangement (Fig. 4b).Theshortest distance between any two Pbatoms in adjacen tsheetsis ~3. 8A Ê . In NaPb2(OH)(CO3)2,twosuch sheets form a layer thatcontains (CO 3)groups.These layers are in turnlinked by OHgroups(Fig. 5) .Na + cations are locatedbetween the layers. As noted previously, the Pb OHbondsare stronger than the Pb O bondsin NaPb 2(OH)(CO3)2.Thus,it is ofinterest Na toconsider the coordination of the OH groupin Pb1, Pb2 thestructure. In the structures of Pb hydroxide oxysalts,OH groupstypically have either a FIG.1. Metal atom coordination polyhedra in the threefoldcoordination or twofold coordination structures of Pb 3O2(CO3) and NaPb2(OH)(CO3)2. with a Pb (OH) Pbangle in the range 90 1408. Incontrast, in NaPb 2(OH)(CO3)2, the (OH)Pb2 dimeris linear (Fig. 5) . coordinatedby six O atomsin atrigonalprismatic arrangement,with a
1082 CRYSTAL STRUCTURE OFP B3O2(CO3) AND NAPB2(OH)(CO3)2
Pb1 Pb4 Pb4 O2 O2
Pb3 Pb3 Pb2 O1 O1
Pb4 Pb1 Pb4
FIG. 2. The [O2Pb3]double chain of (OPb 4)oxocentred tetrahedra shown in polyhedral (left) and ball-and-stick (right) representations. The connectivity diagram for the (OPb 4)tetrahedra of the chain is given (see text for details).
circlelinksthetetrahedrontoanother goodagreement with the average value 3.74 A Ê (Krivovichev,1997; Krivovichev et al. 1997, givenby Krivovichev and Filatov (1999) . 1998).Therefore,each (OPb 4)tetrahedronin this typeof chain is linked via sharing edges to three Bond-valenceanalysi s othertetrahedra, and to two additional tetrahedra Pb O (CO ) viasharing two corners. Evidently, each tetra- 3 2 3 hedronhas two topologically distinct Pb corners: Thebond- valencesums for cations calculated twoPb are shared between two (OPb 4)tetrahedra, usingth eparametersgiven by Brese and whereasthe other two Pb are shared between four O’Keeffe(1 991)are2. 31,2. 04,2. 16and (OPb4)tetrahedra.The O Pbdistances from the 2.11v.u. for Pb(1), Pb(2), Pb(3) and Pb(4), centralO atomsto the Pb atoms in the (OPb 4) respectively,and 3. 88and 3. 72v. u.for C(1) and tetrahedraare shown in Fig. 6 a,b.Itis clear that C(2),respectively. The bond-valence sums for O anincrease in the number of tetrahedrasharing a atomsbelonging to CO 3 groupsare 1.68, 1.78, cornercorrelates with an increase of the O Pb 1.87and 1.63 v.u. for O(3), O(4), O(5) and O(6), bondlength. This observation holds in generalfor respectively.The bond- valencesums for the O(1) structuralunitsbased on oxocentr ed(OM 4) andO(2) atoms that are at the centres of Pb 4 tetrahedra(Krivovichev et al.,1998).Figure6 c tetrahedraare 2. 55and 2.53 v.u., respectively. It givesthe usual values for the O Pbdistances for hasbeen demonstrated recently (Krivovichev, thesetypes of coordination scalculatedfrom 1999)that the O atomscontained in (OPb 4) previouslyknown structures by Krivovichev et oxocentredtetrahedraof Pb compounds are al.(1998).Themean Pb _Pbdistance for (OPb 4) signicantly overbonded [when using the bond- tetrahedrain Pb 3O2(CO3) is 3.73 AÊ for both valenceparameter ssuggestedby Brese and [O(1)Pb4]and[O(2)Pb 4]tetrahedra,which is in O’Keeffe(1991)] in comparison with O atoms
1083 S.V.KRIVOVICHEVAND P.C.BURNS y y
x x
a b
FIG.3.Projection of the crystal structure of Pb 3O2(CO3) along the c-axis.
participatingin polyhedra of cations of high conclusionby Krivovichev (1999) that using valenceand low coordina tionnumber [e. g. Brown’sparameters(1981) also results in an 2 2 2 3 (CO3) , (NO3) , (SO4) , (MoO4) , (PO4) , overbondingof O atomsin (OPb 4)tetrahedra, etc.].Applicationof thebond- valenceparameters althoughnot to the same effect as for the for Pb Obondsprovided by Brown(1981) gives parametersestablished by Brese and O ’Keeffe 2.13,1. 76,2.04, 1.99 and 2.24 and 2. 15v.u. for (1991).Therefore,the observed overbonding may Pb(1),Pb(2), Pb(3), Pb(4) and O(1) and O(2), beexplained by incorrectnessof the bond-valence respectively.This is in agreement with the parametersfor short Pb O bonds.
a b ~ 3.8 Å
~ 5. 2 Å Å .1 9 ~
FIG.4. The hexagonal sheet of Pb atoms in the structure of NaPb 2(OH)(CO3)2 (a)and the arrangement of two adjacent sheets ( b)(Pb atoms from adjacent sheets are shown as white and dark circles).
1084 CRYSTAL STRUCTURE OFP B3O2(CO3) AND NAPB2(OH)(CO3)2
OH(3) OH(3)
Pb
z Na O C {110} Pb
FIG.5.The structure of NaPb 2(OH)(CO3)2 viewed along [110] (left) and the linear (OH)Pb 2 group (right).
NaPb (OH)(CO ) 2 3 2 atoms.From this viewpoint, the structure can be Thebond-valence sums incident at the atoms, relatedto the known structures of Pb hydroxide calculatedusing the bond- valenceparameters carbonates.The crystallographic information for givenby Brese and O ’Keeffe(1991), are equal thesecompounds is listed in Table 6. The relation to2. 11,2.07, 3.93, 4.15, 1.92, 1.97 and 1. 43v. u. ofthe Pb sublattices can be derived easily by forPb(1), Pb(2), C(1), C(2), O(1), O(2) and comparisonof unit-cell parameters. Figure 4 a OH(3),respectively. The bond-valence sums for showstwo major Pb Pbvectors within the cationsare in agreemen twiththeir formal hexagonalsheet of Pb atoms. The lengths of valencesexpected from the chemical formula. thesevectorsare~ 5.2 and~9.1A Ê . The Thebond- valencesum for OH(3) (1.43 v.u. )isin compoundslisted in Table 6 haveeither hexa- agreementwith its assignment as ahydroxyl. gonal(trigonal) or orthorhombic symmetry. The hexagonallattice can be constructed on the basis of the 5.2 AÊ vectors[hydrocerussite (I.M. Steele, Relationshipsof NaPb (OH)(CO ) to leadhydro xide 2 3 2 pers.comm. ),NaPb (OH)(CO ) ] or 9.1 AÊ carbonatem inerals 2 3 2 vectors(susannite, plumbonacrite) .Theorthor- Themajor feature of the crystal structure of hombiccell of leadhillite is based on one 9.1 A Ê NaPb2(OH)(CO3)2 isa hexagonalsublattice of Pb vectorand four 5.2 A Ê vectors[5.2 64 & 20.8 AÊ
2.21(1) 2.22(1) 2.27
O1 2 . 34(1) O2 2 . 34(1) T 2.40
2.38(1) 2.22(1) 2.35(1) 2.24(1) 2.40 2.27 a b c
FIG.6. Connectivity diagrams for (OPb 4)oxocentred tetrahedra in Pb 3O2(CO3) with O Pb distances near the corners (a, b)and average O Pbdistances for such atetrahedra in Pb oxide salts ( c).
1085 S.V.KRIVOVICHEVAND P.C.BURNS
TABLE 6.Crystallographic information for lead hydroxide oxysalts based on hexagonal Pb sublattice.
Mineral Formula Sp. gr. a (AÊ ) b (AÊ ) c (AÊ )Sheet*Ref.
Susannite Pb4(SO4)(CO3)2(OH)2 P3 9.0718 . 11.570 (001) 1 Leadhillite Pb4(SO4)(CO3)2(OH)2 P21/a 9.110 20.820 11.590 (001) 2 Macphersonite Pb 4(SO4)(CO3)2(OH)2 Pcab 9.242 23.050 10.383 (010) 3 ‘Plumbonacrite ’ Pb5O(OH)2(CO3)3 P63cm 9.092 . 24.923 (001) 4 Hydrocerussite Pb 3(CO3)2(OH)2 trigonal 5.24 . 23.74 (001) 5 NaPb2(OH)(CO3)2 P63mc 5.276 . 13.474 (001) 6
*Orientation of the hexagonal sheet of Pbatoms. References: 1 Steele et al. (1999); 2 Giuseppetti et al. (1990); 3 Steele et al. (1998); 4 Krivovichev and Burns (2000b); 5 Gaines et al. (1997); 6 this work
Ê (20.820 A inthe actual structure)] .Theunit cell the system PbO-CO 2 and the decomposition of ofmacphersonite is based on one 9.1 A Ê vector cerussite. Amer.Mineral ., 49, 1184 98. and two 5.2 AÊ vectors[5.2 62 & 10.4 AÊ Krivovichev, S.V.(1997) On the using of Schlegel (10.383 AÊ inthe actual structure)] . diagrams for description and classication of minerals’ crystal structures. Zap. Vses.Mineral. Obshchest., 126(2), 37 46. Acknowledgements Krivovichev, S.V.(1999) Encapsulation effect and its Thiswork was supported by an NSF-NATO inuence on bond-valence parameters. Zeits. Fellowshipin Science and Engineering (DGE- Kristallogr ., 214, 371 2. 9903354)to SVK. Krivovichev, S.V.and Burns, P.C.(2000 a) Crystal chemistry of basic lead carbonates. I. Crystal structure of shannonite, Pb 2O(CO3). Mineral. Mag ., References 64, 1063 8. Krivovichev, S.V.and Burns, P.C.(2000 b) Crystal Brese, N.E.and O ’Keeffe, M. (1991) Bond-valence chemistry of basic lead carbonates. II. Crystal parameters for solids. Acta Crystallogr ., B47, structure of ‘plumbonacrite ’, Pb5O(OH)2(CO3)3. 192 7. Mineral.Mag ., 64, 1069 75. Brooker, M.H., Sunder, S., Taylor, P.and Lopata, V.J. Krivovichev, S.V.and Filatov, S.K.(1999) Metal arrays (1983) Infrared and Raman spectra and X-ray in structural units based on anion-centered tetra- diffraction studies of solid lead(II) carbonates. hedra. Acta Crystallogr ., B55, 664 76. Canad.J. Chem ., 61, 494 502. Krivovichev, S.V., Filatov, S.K.and Semenova, T.F. Brown, I.D. (1981) The bond-valence method: an (1997) On the systematics and description of empirical approach to chemical structure and polyions of linked polyhedra. Zeits. Kristallogr ., bonding. Pp. 1 30 in: Structure and Bonding in 212, 411 7. Crystals, Vol. 2 (M. O’Keeffe and A.Navrotsky, Krivovichev, S.V., Filatov, S.K.and Semenova, T.F. editors).Academic Press, NewYork. (1998) Types of cationic complexes based on Bulakhova, V.I.,Ben ’yash, E.Ya., Shokarev, M.M. and oxocentered tetrahedra [OM 4]in the crystal struc- Vershinina, F.I. (1972) Lead and sodium hydro- tures of inorganic compounds. Russ.Chem. Rev ., 67, xocarbonate. Zh. Neorg. Khim ., 17, 23 8 (in 137 55. Russian). Roberts, A.C.,Stirling, J.A.R., Carpenter, G.J.C., Gaines, R.V., Skinner, H.C.W., Foord, E.E.,Mason, B., Criddle, A.J., Jones, G.C., Birkett, T.C.and Birch,
Rosenzweig, A., King, V.T.and Dowty, E.(1997) W.D. (1995) Shannonite, Pb 2OCO3,anew mineral Dana’sNewMineralogy .8th edition. Wiley, New from the Grand Reef mine, Graham County, York. Arizona, USA. Mineral. Mag ., 59, 305 10. Giuseppetti, G., Mazzi, F.and Tadini, C.(1990) The Steele, I.M., Pluth, J.J. and Livingstone, A. (1998)
crystal structureofleadhillite:Pb 4(SO4 ) Crystalstructureofmacphersonite (CO3)2(OH)2. Neues Jahrb. Mineral. Mh ., 255 68. (Pb4SO4(CO3)2(OH)2): comparison with leadhillite. Grisafe, D.A.and White, W.B. (1964) Phase relations in Mineral.Mag ., 62, 451 9.
1086 CRYSTAL STRUCTURE OFP B3O2(CO3) AND NAPB2(OH)(CO3)2
Steele, I.M., Pluth, J.J.and Livingstone, A.(1999) thermal analysis of cerussite. Amer.Mineral ., 47, Crystal structure of susannite, Pb 4SO4(CO3)2(OH)2): 1011 23. atrimorph with macphersonite and leadhillite. Eur. J. Mineral., 11, 493 9. [Manuscript received 9May 2000: Warne, S.S.J.and Bayliss, P.(1962) The differential revised 21 September 2000 ]
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