The [ReF] ( = K, Rb and Cs) salts are isotypic and crystallize in the trigonal space group type [Formula: see text] 1, adopting the K[GeF] structure type. Common to all [ReF] structures are slightly distorted octa-hedral [ReF] anions with an average Re-F bond length of 1.951 (8) Å. In those salts, symmetry lowering on the local [ReF] anions from (free anion) to (solid-state structure) occur. The distortions of the [ReF] anions, as observed in their Raman spectra, are correlated to the size of the counter-cations.
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