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The Crystal Structures of the Binary Mixed Valence Compound Bi(III)3Bi(V)O7 and Isotypic Bi3SbO7 as Determined by High Resolution X-Ray and Neutron Powder Diffraction

✍ Scribed by Robert E. Dinnebier; Richard M. Ibberson; Helmut Ehrenberg; Martin Jansen


Publisher
Elsevier Science
Year
2002
Tongue
English
Weight
546 KB
Volume
163
Category
Article
ISSN
0022-4596

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✦ Synopsis


The crystal structures of the mixed valence compound Bi (IIII) 3 Bi (V) O 7 (1) and isotypic Bi (III) 3 Sb (V) O 7 (2) were determined ab initio from powder di4raction data. At room temperature, both structures crystallize in space group P1 (Z ‫؍‬ 2) with a ‫؍‬ 6.7253( 2), b ‫؍‬ 6.9950(2), c ‫؍‬ 7.7961(2) A > , ‫؍‬ 72.566(2), ‫؍‬ 88.842(2), ‫؍‬ 76.925(2)3, and V ‫؍‬ 340.39(2) A > 3 for (1) and a ‫؍‬ 6.6044(3), b ‫؍‬ 7.0146(3), c ‫؍‬ 7.6048(3) A > , ‫؍‬ 73.388(2), ‫؍‬ 89.225(2), ‫؍‬ 76.190(2)3, and V ‫؍‬ 327.28(2) A > 3 for (2). Combined Rietveld re5nements based on both synchrotron and neutron powder patterns were performed (T ‫؍‬ 295 K, R-Bragg ‫؍‬ 5.4% for (1), R-Bragg ‫؍‬ 6.4% for (2)). The crystal structures contain 5ve crystallographically di4erent anion polyhedra in two di4erent coordination types and can be related to the CaF 2 -type structure with the cations forming a distorted face centered cubic lattice and the oxygen atoms 5lling positions close to seven of the eight tetrahedral cavities.