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Dimers of oxocentred [OCu4]6+ tetrahedra in two novel copper selenite chlorides, K[Cu3O](SeO3)2Cl and Na2[Cu7O2] (SeO3)4Cl4, and related minerals and inorganic compounds

Published online by Cambridge University Press:  02 January 2018

Vadim M. Kovrugin ,
Marie Colmont ,
Olivier Mentré ,
Oleg I. Siidra  and
Sergey V. Krivovichev
Vadim M. Kovrugin
Affiliation:
Department of Crystallography, St Petersburg State University, Universitetskaya nab. 7/9, 199034 St Petersburg, Russia UCCS, ENSCL, Université Lille 1, CNRS, UMR 8181, 59652 Villeneuve d’Ascq, France
Marie Colmont
Affiliation:
UCCS, ENSCL, Université Lille 1, CNRS, UMR 8181, 59652 Villeneuve d’Ascq, France
Olivier Mentré
Affiliation:
UCCS, ENSCL, Université Lille 1, CNRS, UMR 8181, 59652 Villeneuve d’Ascq, France
Oleg I. Siidra
Affiliation:
Department of Crystallography, St Petersburg State University, Universitetskaya nab. 7/9, 199034 St Petersburg, Russia
Sergey V. Krivovichev*
Affiliation:
Department of Crystallography, St Petersburg State University, Universitetskaya nab. 7/9, 199034 St Petersburg, Russia
*
*E-mail: s.krivovichev@spbu.ru
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Abstract

Two novel copper selenite chlorides, K[Cu3O](SeO3)2Cl (I) and Na2[Cu7O2](SeO3)4Cl4 (II), have been synthesized by the CVT method. Their crystal structures have been solved by direct methods and refined by least-squares techniques. I is triclinic, space group P1̄, a = 7.6821(5), b = 8.1179(5), c = 8.7836(6) Å, α = 113.193(3), β = 108.735(4), γ = 98.245(4)°, V = 453.32(5) Å3, R1 = 0.0481 for 1210 unique reflections with F≥4σ(F); II is triclinic, space group P1̄,a = 7.4362(6), b = 8.3361(7), c = 9.1343(11) Å,α = 110.277(6), β = 106.212(6), γ = 105.158(4)°, V = 467.94(8) Å3, R1 = 0.0265 for 2498 unique reflections with F≥4σ(F). The structures of I and II can be described in terms of dimers of copper oxocentred tetrahedra. In I, two (OCu4)6+ tetrahedra share a common Cu···Cu edge to form the [O2Cu6]8+ dimer, whereas the structure of II is based upon two (OCu4)6+ tetrahedra linked together by one common Cu atom resulting in the formation of the [O2Cu7]10+ dimer. A comparison with related minerals and inorganic compounds is given.

Keywords

Crystal StructureOxocentred TetrahedraLone Electron PairStereoactivityEuchlorineFedotovitePrewittiteBurnsite
Type
Research Article
Information
Mineralogical Magazine , Volume 80 , Issue 2 , April 2016 , pp. 227 - 238
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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References

Becker, R., Berger, H. and Johnsson, M. (2007) Monoclinic Cu3(SeO3)2Cl2: an oxohalide with an unusual CuO4Cl trigonal-bipyramidal coordination. Acta Crystallographica, C63, i4–i6.Google Scholar
Berdonosov, P.S., Olenev, A.V. and Dolgikh, V.A. (2009) Strontium—copper selenite—chlorides: synthesis and structural investigation. Journal of Solid State Chemistry, 182,2368–2373 CrossRefGoogle Scholar
Berdonosov, P.S., Janson, O., Olenev, A.V., Krivovichev, S.V., Rosner, H., Dolgikh, V.A. and Tsirlin, A.A. (2013) Crystal structures and variable magnetism of PbCu2(XO3)2Cl2 with X = Se, Te. Journal of the Chemical Society, Dalton transactions, 42,9547–9554 CrossRefGoogle Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197. CrossRefGoogle Scholar
Burns, P.C. and Hawthorne, F.C. (1995a) Coordination-geometry pathways in Cu + oxysalt minerals. The Canadian Mineralogist, 33,889–905 Google Scholar
Burns, P.C. and Hawthorne, F.C. (1995b) Mixed-ligand Cu2+Φ6 octahedra in minerals: observed stereoche¬mistries and HartreFock calculations. The Canadian Mineralogist, 33, 1177–1188. Google Scholar
Burns, P.C., Krivovichev, S.V. and Filatov, S.K. (2002) New Cu2+ coordination polyhedra in the crystal structure of burnsite, KCdCu7O2(SeO3)2Cl9 . The Canadian Mineralogist, 40, 1587–1595. CrossRefGoogle Scholar
Burrows, A.D., Mahon, M.F., Sebestyen, V.M., Lan, Y. and Powell, A.K. (2012) Synthesis, structures, and magnetic behavior of new anionic copper(II) sulfate aggregates and chains. Inorganic Chemistry, 51, 10983–10989. CrossRefGoogle ScholarPubMed
Christy, A.G. and Mills, S.J. (2013) Effect of lone-pair stereoactivity on polyhedral volume and structural flexibility: application to TeIVO6 octahedra. Acta Crystallographica, B69, 446–56.Google Scholar
Effenberger, H. and Pertlik, F. (1986) Die Kristallstrukturen der Kupfer(II)-oxo-selenite Cu2O(SeO3) (kubisch und monoklin) und Cu4O(SeO3)3 (monoklin und triklin). Monatsheftefür Chemie, 117,887–896 CrossRefGoogle Scholar
Filatov, S.K., Semenova, T.F. and Vergasova, L.P. (1992) Types of polymerization of [OCu4]6+ in inorganic compounds with ‘additional’ oxygen atoms. Doklady Akademii Nauk SSSR, 322, 539-539.Google Scholar
Kampf, A.R., Mills, S.J., Housley, R.M., Marty, J. and Thorne, B. (2010) Lead-tellurium oxysalts from Otto Mountain near Baker, California: VI. Telluroperite, Pb3Te4+O4Cl2, the Te analogue of perite and nadorite. American Mineralogist, 95, 1569—1573 CrossRefGoogle Scholar
Krivovichev, S.V. and Filatov, S.K. (1999) Structural principles for minerals and inorganic compounds containing anion-centered tetrahedra. American Mineralogist, 84, 1099–1106. CrossRefGoogle Scholar
Krivovichev, S.V., Shuvalov, R.R., Semenova, T.F. and Filatov, S.K. (1999a) Crystal chemistry of inorganic compounds based on chains of oxocentered tetrahedra. III. Crystal structure of georgbokiite, Cu5O2(SeO3)2Cl2 . Zeitschriftfür Kristallographie, 214,135–138 Google Scholar
Krivovichev, S.V., Starova, G.L. andFilatov, S.K. (1999b) ‘Face-to-face’ relationships between oxocentred tetra¬hedra and cation-centred tetrahedral oxyanions in crystal structures of minerals and inorganic com¬pounds. Mineralogical Magazine, 63,263—266 CrossRefGoogle Scholar
Krivovichev, S.V., Vergasova, L.P., Starova, G.L., Filatov, S.K., Britvin, S.N., Roberts, A.C. and Steele, I.M. (2002) Burnsite, KCdCu7O2(SeO3)2Cl9, a new mineral species from the Tolbachik Volcano, Kamchatka Peninsula, Russia. The Canadian Mineralogist, 40, 1171–1175. CrossRefGoogle Scholar
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