Inorganic Fluorides and Related Compounds
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Abstract
Abstract
The structure determination of Hf 2 OF 6 and of isostructural Zr 2 OF 6 by Rietveld refinement on powder samples has surprisingly shown that these compounds have in fact a more complex formula. The Hf 5 O 2 F 16 and Zr 5 O 2 F 16 compositions are slightly richer in anions than those already published: M(O,F) 3.6 instead of M(O,F) 3.5 .Their stoichiometries and crystal structures are completely new. Furthermore, the structural characterization on single crystal of Zr 3 O 2 F 8 and of isostructural Hf 3 O 2 F 8 are described. All these structures are based on different associations of M 6 (O,F) 32 clusters. These clusters are built from octahedral arrangements of cation-centered M(O,F) 8 square antiprisms (SA) sharing corners around a threefold axis to enclose an anionic distorted cube: O 4 F 4 for Zr 3 O 2 F 8 and O 2 F 6 for Hf 5 O 2 F 16 . The complex O/F partial ordering in these structures is discussed.
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@article{Laval2026Structural,
title = {Structural characterization and O/F order/disorder of Hf and Zr oxyfluorides Hf5O2F16 and Zr3O2F8},
author = {Jean-Paul Laval},
journal = {Journal of Fluorine Chemistry},
year = {2026},
doi = {10.1016/j.jfluchem.2026.110615},
url = {https://doi.org/10.1016/j.jfluchem.2026.110615}
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