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Crystal chemistry of basic lead carbonates. III. Crystal structures of Pb3O2(CO3) and NaPb2(OH)(CO3)2

Published online by Cambridge University Press:  05 July 2018

S. V. Krivovichev  and
P. C. Burns
S. V. Krivovichev*
Affiliation:
Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick, University of Notre Dame, Notre Dame IN 46556-0767, USA
P. C. Burns
Affiliation:
Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick, University of Notre Dame, Notre Dame IN 46556-0767, USA
*
*E-mail: [email protected]
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Abstract

The crystal structures of synthetic Pb3O2(CO3) and NaPb2(OH)(CO3)2, have been solved by direct methods and refined to R = 0.062 and 0.024, respectively. Pb3O2(CO3) is orthorhombic, Pnma, a = 22.194(3), b = 9.108(1), c = 5.7405(8) Å, V = 1160.4(3) Å3, Z = 8. There are four symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone electron pairs. The structure is based upon double [O2Pb3] chains of [O(1)Pb4] and [O(2)Pb4] oxocentred tetrahedra and CO3 groups. The [O2Pb3] chains are parallel to the c axis, whereas the CO3 groups are parallel to the (010) plane. NaPb2(OH)(CO3)2 is hexagonal, P63mc, a = 5.276(1), c = 13.474(4)Å, V = 324.8(1) Å3, Z = 2 and has been solved by direct methods. There are two symmetrically distinct Pb2+ cations in asymmetric coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The single symmetrically unique Na+ cation is in trigonal prismatic coordination. The structure is based on hexagonal sheets of Pb atoms. Within these sheets, Pb atoms are located at vertices of a 36 net, such that each Pb atom has six adjacent Pb atoms that are ~5.3 Å away. Two sheets are stacked in a close-packing arrangement, forming layers that contain the (CO3) groups. The layers are linked by OH groups that are linearly coordinated by two Pb2+ cations. Na+ cations are located between the layers. The structure is closely related to the structures of other lead hydroxide carbonates (leadhillite, macphersonite, susannite, hydrocerussite, ‘plumbonacrite’).

Keywords

basic lead carbonateslone-electron pairsoxocentred tetrahedrahexagonal lead sublattice
Type
Research Article
Information
Mineralogical Magazine , Volume 64 , Issue 6 , December 2000 , pp. 1077 - 1087
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

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Footnotes

†

Permanent address: Department of Crystallography, St. Petersburg State University, University Emb. 7/9. 199034 St. Petersburg Russia

References

Brese, N.E. and O’Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallogr., B47, 192–7.CrossRefGoogle Scholar
Brooker, M.H., Sunder, S., Taylor, P. and Lopata, V.J. (1983) Infrared and Raman spectra and X-ray diffraction studies of solid lead(II) carbonates. Canad. J. Chem., 61, 494-502.CrossRefGoogle Scholar
Brown, I.D. (1981) The bond-valence method: an empirical approach to chemical structure and bonding. Pp. 1-30 in: Structure and Bonding in Crystals, Vol. 2 (O’Keeffe, M. and Navrotsky, A., editors). Academic Press, New York.Google Scholar
Bulakhova, V.I., Ben’yash, E.Ya., Shokarev, M.M. and Vershinina, F.I. (1972) Lead and sodium hydroxocarbonate. Zh. Neorg. Khim., 17, 23–8 (in Russian).Google Scholar
Gaines, R.V., Skinner, H.C.W., Foord, E.E., Mason, B., Rosenzweig, A., King, V.T. and Dowty, E. (1997) Dana’s New Mineralogy. 8th edition. Wiley, New York.Google Scholar
Giuseppetti, G., Mazzi, F. and Tadini, C. (1990) The crystal structure of leadhillite: Pb4(SO4) (CO3)2(OH)2 . Neues Jahrb. Mineral. Mh., 255–68.Google Scholar
Grisafe, D.A. and White, W.B. (1964) Phase relations in the system PbO-CO2 and the decomposition of cerussite. Amer. Mineral., 49, 1184–98.Google Scholar
Krivovichev, S.V. (1997) On the using of Schlegel diagrams for description and classification of minerals’ crystal structures. Zap. Vses. Mineral. Obshchest., 126(2), 37-46.Google Scholar
Krivovichev, S.V. (1999) Encapsulation effect and its influence on bond-valence parameters. Zeits. Kristallogr., 214, 371–2.Google Scholar
Krivovichev, S.V. and Burns, P.C. (2000 a) Crystal chemistry of basic lead carbonates. I. Crystal structure of shannonite, Pb2O(CO3). Mineral. Mag., 64, 1063–8.CrossRefGoogle Scholar
Krivovichev, S.V. and Burns, P.C. (2000 b) Crystal chemistry of basic lead carbonates. II. Crystal structure of ‘plumbonacrite’, Pb5O(OH)2(CO3)3 . Mineral. Mag., 64, 1069–75.CrossRefGoogle Scholar
Krivovichev, S.V. and Filatov, S.K. (1999) Metal arrays in structural units based on anion-centered tetrahedra. Acta Crystallogr., B55, 664–76.CrossRefGoogle Scholar
Krivovichev, S.V., Filatov, S.K. and Semenova, T.F. (1997) On the systematics and description of polyions of linked polyhedra. Zeits. Kristallogr., 212, 411–7.Google Scholar
Krivovichev, S.V., Filatov, S.K. and Semenova, T.F. (1998) Types of cationic complexes based on oxocentered tetrahedra [OM4] in the crystal structures of inorganic compounds. Russ. Chem. Rev., 67, 137–55.CrossRefGoogle Scholar
Roberts, A.C., Stirling, J.A.R., Carpenter, G.J.C., Criddle, A.J., Jones, G.C., Birkett, T.C. and Birch, W.D. (1995) Shannonite, Pb2OCO3, a new mineral from the Grand Reef mine, Graham County, Arizona, USA. Mineral. Mag., 59, 305–10.CrossRefGoogle Scholar
Steele, I.M., Pluth, J.J. and Livingstone, A. (1998) Crystal structure of macphersonite (Pb4SO4(CO3)2(OH)2): comparison with leadhillite. Mineral. Mag., 62, 451–9.CrossRefGoogle Scholar
Steele, I.M., Pluth, J.J. and Livingstone, A. (1999) Crystal structure of susannite, Pb4SO4(CO3)2(OH)2): a trimorph with macphersonite and leadhillite. Eur. J. Mineral., 11, 493–9.CrossRefGoogle Scholar
Warne, S.S.J. and Bayliss, P. (1962) The differential thermal analysis of cerussite. Amer. Mineral., 47, 1011–23.Google Scholar