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Face-sharing octahedra in Cs3Al2F9 and Cs2AlF5

Published online by Cambridge University Press:  11 March 2015

A. Le Bail Open the ORCID record for A. Le Bail [Opens in a new window]  and
L'. Smrčok
A. Le Bail*
Affiliation:
Institut des Molécules et des Matériaux du Mans, UMR CNRS 6283, Université du Maine, avenue O. Messiaen, 72085 Le Mans Cedex 9, France
L'. Smrčok
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 36 Bratislava, Slovak Republic
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]
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Abstract

The structure of Cs2AlF5 obtained by thermal dehydration of Cs2AlF5•H2O is determined ab initio from powder diffraction data, space group Pmn21, a = 6.36216 (17) Å, b = 12.7523 (4) Å, c = 11.4102 (3) Å, and Z = 6. Contrarily to most A2MF5 compounds presenting MF5cis or trans-chains of corner-sharing MF6 octahedra, Cs2AlF5 is characterized by the rare occurrence of the face-sharing anion Al2F93− combined with an isolated AlF63− octahedron, the sum leading to Al3F156−. The structure of Cs3Al2F9 [space group P63/mmc, a = 6.2535 (2) Å, c = 14.7193 (6) Å, Z = 2] is confirmed to be isostructural with Cs3Fe2F9, built up from the same M2F93− dimers (M = Fe, Al). Both crystal structures are optimized by energy minimization density funtional theory (DFT) in the solid state using a hybrid PBE0 functional, and their relations with the hexagonal perovskites and elpasolites are discussed.

Keywords

cesium aluminium fluoridepowder diffractioncrystal structureab initioDFT
Type
Technical Articles
Information
Powder Diffraction , Volume 30 , Issue 2 , June 2015 , pp. 130 - 138
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Copyright
Copyright © International Centre for Diffraction Data 2015 

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