Abstract

Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides (halide = Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S 2CuX units. The Cl derivative (1) is an S-bridged dimer (C 6H 14-ClCuN 2OS 3, monoclinic, P2 1/c (No. 14), Z = 4, a = 9.525(8) Å, b = 13.022(10) Å, c = 10.835(7) Å), while the Br analogue (2) features a polymeric network of S 2CuBr units, also bridged by S atoms (C 6H 12BrCuN 2S 3, orthorhombic, P2 12 12 1 (No. 19), Z = 4, a = 7.043(2) Å, b = 9.442(3) Å, c = 17.889(4) Å). The iodo compound (3) exists as a halogen-bridged dimer (C 6H 12CuIN 2S 3, monoclinic, P2 1/m (No. 11), Z = 4, a = 9.570(1) Å, b = 10.578(1) Å, c = 12.422(1) Å). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.