Crystal Structures of Hexafluoridoantimonate(V) Salts of d‐block Metals in Oxidation State +2

Abstract The crystal structures of the M(SbF6)2 salts (M=Cu, Pd) are isotypic (Type I). They crystallize in the triclinic space group , Z=1 at 150 K. M2+ cations lying in the same plane are connected via SbF6 units forming slabs. There are only van der Waals contacts of fluorine atoms between the adjacent slabs. Salts of M(SbF6)2 (M=Fe, Co, Zn) crystallize differently (Type II; space group , Z=2 at 150 K). Their crystal structures are composed of M2+ cations interconnected by [SbF6]− anions – thus forming a three‐dimensional framework. The crystal structure of Fe(SbF6)2, determined at 240 K, is currently the only representative of the Type III. The main feature of this type is also a three‐dimensional framework consisting of M2+ cations and [SbF6]− anions. However, the mode of their association differs from that observed in Type II. The crystal structures of CuFSbF6 (orthorhombic space group Imma, Z=4 at 150 K) and AgFSbF6 (orthorhombic space group Pnma, Z=4 at 150 K) are not isotypic. The crystal structures of the by‐products H3ONi(SbF6)3 (orthorhombic space group Pnma, Z=4 at 150 K) and (O2)2Ag6CuF5(SbF6)11 ⋅ 2HF (triclinic space group , Z=1 at 150 K) were determined. In the latter, HF is directly attached to an Ag(II) via a fluorine atom.