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Zeitschrift für Kristallographie - Crystalline Materials

Editor-in-Chief: Pöttgen, Rainer

Ed. by Antipov, Evgeny / Bismayer, Ulrich / Boldyreva, Elena V. / Huppertz, Hubert / Tiekink, E. R. T.

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Crystal chemistry of the mendipite-type system Pb3O2Cl2—Pb3O2Br2

Oleg I. Siidra / Sergey V. Krivovichev / Thomas Armbruster / Wulf Depmeier
Published Online: 2009-09-25 | DOI: https://doi.org/10.1524/zkri.2008.0018

Abstract

The crystal structures of the mendipite series Pb3O2Cl2—Pb3O2Br2 have been solved by direct methods. The structures are based upon [O2Pb3]2+ double chains of edge-sharing OPb4 tetrahedra. There are three symmetrically independent Pb2+ cations. The number of nonequivalent halogen sites is two (X1, X2). Short Pb—O bonds are located on one side of the Pb2+ cations and weak Pb-X bonds are located on the other side of the Pb2+ coordination sphere. The evident strong distortion of the Pb2+ coordination polyhedra is due to the stereoactivity of the 6s2 lone electron pairs of the Pb2+ cations. Pb1-X2 and Pb2-X2 bonds are the most sensitive to the X site occupancy, which is in agreement with the non-linear behavior of the a and c parameters. Determination of unit-cell parameters by single crystal studies showed strong deviation from Vegard's rule. Nonlinearity of the lattice parameters is caused by selective ordering of the halide anions over X1 and X2 sites. Br atoms prefer the X2 position, whereas Cl prefers the X1 site. The angle between two adjacent OPb4 tetrahedra was determined to analyze the influence of halogen atoms on the structure of the [O2Pb3]2+ chain. Different occupancy of the X1 site by Cl and Br atoms leads to most pronounced angular changes. These observations may be interpreted as adaptation of the [O2Pb3]2+ double chains to the large halide ions in the crystal structures of the mendipite series compounds.

Keywords: Lead oxyhalides; Mendipite; Oxocentered tetrahedra; Conformation; Single crystal structure analysis; X-ray diffraction

About the article

Received: 2007-09-10

Accepted: 2007-12-18

Published Online: 2009-09-25

Published in Print: 2008-03-01


Citation Information: Zeitschrift für Kristallographie, Volume 223, Issue 3/2008, Pages 204–211, ISSN (Print) 0044-2968, DOI: https://doi.org/10.1524/zkri.2008.0018.

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