Reaction of Bis(N,N-dimethylthiocarbamoyl) Sulfide with Copper(II) Halides and the Crystal and Molecular Structures of Halogeno(bis(N,N-dimethylthiocarbamoyl) sulfido)copper(I) Complexes

• Published in: Inorganic chemistry 1997-02, Vol.36 (4), p.688-693
• Main Authors: Victoriano, Luis I, Garland, María Teresa, Vega, Andrés
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic960625r

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 S2CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14ClCuN2OS3, monoclinic, P21/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 S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P212121 (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 (C6H12CuIN2S3, monoclinic, P21/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.