SYNTHESIS, CHARACTERIZATION AND CRYSTAL-STRUCTURE OF COPPER(I) THIOLATES - [(C6H5)4P+]2[CU4(C2H5S-)6].0.5C2H6O2 AND [(C6H5)4P+][CU7(C2H5S-)8]

The reaction of the monodentate ligand thioethane with (C6H5)4PBr and Cu2O in organic solvents results in the crystallization of two new homoleptic polynuclear copper(I) thiolates: [(C6H5)4P+]2[Cu4(C2H5S-)6]·0.5C2H6O2 (1) and [(C6H5)4P+][Cu7(C2H5S-)8] (2). Both compounds have been characterized by X-ray crystallography, thermal analysis, luminescence spectroscopy and IR spectroscopy. Compound 1 is triclinic, space group P1- with a = 12.066(5), b = 13.824(5), c = 19.112(3) Å, α = 90.82(2), β = 101.85(2), γ = 93.53(3)° and Z = 2. Compound 2 is monoclinic, space group P21/c with a = 19.208(3), b = 16.975(4), c = 16.394(6) Å, β = 108.68(2)° and Z = 4. The structure of 1 is built up by [(Cu4(RS-)6)2-] adamantane-type cluster units, separated by [(C6H5)4P+] cations. Compound 2 consists of copper(I) thiolate chains, also separated by [(C6H5)4P+] cations. In 2, structural units of the stoichiometry Cu7(C2H5S-)10 are connected by common sharing of four sulphur atoms, leading to a chain of the stoichiometry Cu7(C2H5S-)8. The shortest CuCu distance is 2.692(1) Å in 1 and 2.736(2) Å in 2. Excitation at 450 nm of 1 in the solid state results in a weak emission at 665 nm, compound 2 exhibits in the solid state an intense luminescence at 591 nm upon excitation at 365 nm. © 1990.