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

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 m ostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and s ingle-crystal x-ray studies show a wide diversity of structural variat ions. All molecules consist of basic S(2)CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14ClCuN2OS3, monoclinic, P2(1)/c (No. 14 ), Z=4, a=9.525(8) Angstrom, b=13.022(10) Angstrom, c=10.835(7) Angstr om), while the Br analogue (2) features a polymeric network of S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P2(1)2(1) 2(1) (No.19), Z=4, a=7.043(2) Angstrom, b=9.442(3) Angstrom, c=17.889( 4) Angstrom). The iodo compound (3) exists as a halogen-bridged dimer (C6H12CuIN2S3, monoclinic, P2(1)/m (No. 11), Z=4, a=9.570(1) Angstrom, b= 10.578(1) Angstrom, c=12.422(1) Angstrom). The molecular structure s found support the assignment of the IR and Raman spectral data in al l 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 H-1-NMR for 1 is inter preted in terms of a monomer-dimer equilibrium.