Novel Layered Structures Formed by Iodocuprate Clusters Stabilized by Dialkylsulphide Ligands

From solutions of copper iodide and dodecyldimethylsulphonium iodide in acetonitrile, single crystals of [Cu 4 I 4 (DodecylMeS) 4 ] ( 1 ) and [Cu 3 I 4 (DodecylMeS) 3 ](DodecylMe 2 S) ( 2 ) could be obtained. Both compounds crystallize in the triclinic crystal system, space group P 1¯ ( 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 Cu 4 clusters, which are capped by four iodide ions over the tetrahedral faces. 2 contains trigonal Cu 3 clusters, which are coordinated by four iodide ions, one centered over the plane, three bridging over the edges of the Cu 3 triangle. In both compounds, the S atoms of (DodecylMeS) ligands coordinate to the Cu atoms. In 2 , a (DodecylMe 2 S) cation is also present.