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.Reaction 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.