Crystal structures of mixed oxonium-cadmium(II) salts with [SbF _6]-/[Sb_2F_(11)]- anions: From complex chains to layers and three-dimensional frameworks

摘要

Pure H_3OCd(SbF_6)(Sb_2F_(11)) _2 is prepared by the reaction of CdO with nSbF_5 (n ≥ 5) or by reaction of H_3OSbF_6, Cd(SbF_6) _2 and nSbF_5 (n ≥ 2) in anhydrous hydrogen fluoride. H_3OCd(SbF_6)(Sb_2F_(11))_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 H _3OSbF_6 and Cd(SbF_6)_2 were used as starting materials. However, the re-crystallization of these mixtures yielded single crystals of new phases: (H_3O)_2Cd(SbF _6)_3(Sb_2F_(11)) and (H _3O)_2Cd_2F(SbF_6)_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 P2_1/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(SbF_6)_2 resulted in the preparation of few single crystals of (H_3O)[Cd(HF)]_4(SbF_6) _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.