Study of metal dithiocarbamate complexes, Part V. Metal complexes of [S2CN(CH2CH(OMe)2]: A standard dimeric zinc dithiocarbamate structural motive, a rare cadmium dithiocarbamate coordination polymer, and a hydrated sodium dithiocarbarmate complex, with a[Na2O2] core and chain

Abstract

The synthesis and crystal structures of three metal salts of the dithiolato ligand, [S2CNMeCH2CH(OMe)2]−, namely {[NaS2CNMeCH2CH(OMe)2]·(H2O)2}, [1·(H2O)2], [Zn(S2CNMeCH2CH(OMe)2)2] (2) and [Cd(S2CNMeCH2CH(OMe)2)2] (3), are reported. Compound 2, which crystallizes in the monoclinic space group, P21/n with Z=2, as a centrosymmetric dimer, in which one dithiocarbamato ligand is chelating and the other is bridging. Present in the dimer is an eight-membered [Zn2C2S4] ring, which adopts a chair conformation. The coordination geometry for the zinc atom is a highly distorted tetrahedron with SZnS bond angles ranging from 75.41(4) to 125.73(5)°. Compound 3 crystallizes in the triclinic space group P1¯, with Z=2. Structure of 3 is a 1-D coordination polymer, with a distorted octahedral CdS6 unit. Each dithiocarbamate ligand in 2 is μ2,κ2-tridentate, bridging two Cd centres and chelating one Cd centre. The ranges of SCdS angles and CdS bond lengths vary from 67° to 167° and 2.5918(17) to 2.8358(18)Å, respectively. Hydrated complex, [1·(H2O)2] crystallizes in the monoclinic space group P21/a, with Z=4. The dithiocarbarmate ligand in [1·(H2O)2] acts as a monodentate bridging ligand. Sheets of molecules in [S2CNR1R2] are composed of chains of [Na2O2] rings, linked by S to provide Na centres with O4S2 distorted octahedral geometries. The alkoxy groups are not involved in the coordination to the metal centres, and are only involved in the supramolecular arrays in 3.