Abstract
The A2[ReF6] (A = K, Rb and Cs) salts are isotypic and crystallize in the trigonal space group type P [Formula: see text] m1, adopting the K2[GeF6] structure type. Common to all A2[ReF6] structures are slightly distorted octa-hedral [ReF6]2- anions with an average Re-F bond length of 1.951 (8) Å. In those salts, symmetry lowering on the local [ReF6]2- anions from Oh (free anion) to D3d (solid-state structure) occur. The distortions of the [ReF6]2- anions, as observed in their Raman spectra, are correlated to the size of the counter-cations.