Crystal structures of mixed oxonium–cadmium(II) salts with [SbF6]−/[Sb2F11]− anions: From complex chains to layers and three-dimensional frameworks

Pure H3OCd(SbF6)(Sb2F11)2 is prepared by the reaction of CdO with nSbF5 (n ⩾ 5) or by reaction of H3OSbF6, Cd(SbF6)2 and nSbF5 (n ⩾ 2) in anhydrous hydrogen fluoride. H3OCd(SbF6)(Sb2F11)2 crystallizes in the monoclinic space group P21/a (No. 14) with a = 986.1(4) pm, b = 1257.3(5) pm, c = 1826.8.4(8) pm, β = 98.062(4)° and Z = 4. on of CdO with SbF5 (n ⩽ 3) in anhydrous HF yields only a mixture of H3OSbF6 and Cd(SbF6)2. No reactions were observed also when different ratios of H3OSbF6 and Cd(SbF6)2 were used as starting materials. However, the re-crystallization of these mixtures yielded single crystals of new phases: (H3O)2Cd(SbF6)3(Sb2F11) and (H3O)2Cd2F(SbF6)5. The former crystallizes in the orthorhombic Pcca space group (No. 54) with a = 2189(2) pm, b = 1121.2(8) pm, c = 1894(1) pm and Z = 8 and the latter in the monoclinic P21/a space group a = 1019(4) pm, b = 1112(1) pm, c = 1147(1) pm, β = 107.81(1)° and Z = 2. The attempt to prepare single crystals of Cd(SbF6)2 resulted in the preparation of few single crystals of (H3O)[Cd(HF)]4(SbF6)9, which crystallizes in the monoclinic space group C2/c (No. 15) with a = 2087(3) pm, b = 1021(5) pm, c = 2112(2) pm, β = 99.36(2)° and Z = 4.