Novel Layered Structures Formed by Iodocuprate Clusters Stabilized by Dialkylsulphide Ligands

From solutions of copper iodide and dodecyldimethylsulphonium iodide in acetonitrile, single crystals of [Cu4I4(DodecylMeS)4] (1) and [Cu3I4(DodecylMeS)3](DodecylMe2S) (2) could be obtained. Both compounds crystallize in the triclinic crystal system, space group P1¯ (1: a = 957.23(1), b = 967.25(2), c = 3818.38(6) pm, α = 90.3837(6)°, β = 86.4687(7)°, γ = 75.0996(7)°, 2: a = 874.23(1), b = 979.29(1), c = 4388.75(4) pm, α = 90.4472(3)°, ß = 94.7088(3)°, γ = 116.1162(3)°). 1 consists of tetrahedral Cu4 clusters, which are capped by four iodide ions over the tetrahedral faces. 2 contains trigonal Cu3 clusters, which are coordinated by four iodide ions, one centered over the plane, three bridging over the edges of the Cu3 triangle. In both compounds, the S atoms of (DodecylMeS) ligands coordinate to the Cu atoms. In 2, a (DodecylMe2S) cation is also present.