Synthesis and structural characterization of bis(dimethylammonium) tetrasulfidometalates

Author： Srinivasan Bikshandarkoil Girkar Siddhali Nather Christian Bensch Wolfgang

ISSN： 0095-8972

Source： Journal of Coordination Chemistry, Vol.62, Iss.22, 2009-11, pp. : 3559-3572

Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.

Previous Menu Next

Abstract

Reaction of (NH4)2[MS4] (M = Mo, W) with aqueous dimethylamine (CH3)2NH or KOH results in the formation of bis(dimethylammonium) tetrasulfidometalates [(CH3)2NH2]2[MS4] (M = W 1; Mo 2) or dipotassium tetrasulfidotungstate K2[WS4] (3). Compounds 1-3 were characterized by elemental analysis, IR and UV-Vis spectra and their crystal structures were determined. Compounds 1 and 2 are isostructural and crystallize in the centrosymmetric monoclinic space group P21/n. The structures consist of two crystallographically independent dimethylammonium cations and a slightly distorted tetrahedral [MS4]2- anion with all atoms situated in general positions. The cations and anions are involved in several weak N-H ··· S and C-H ··· S interactions. Compound 3 crystallizes in the centrosymmetric orthorhombic space group Pnma and is isostructural with the previously reported K2[MoS4]. The structure of 3 consists of discrete slightly distorted tetrahedral [WS4]2- anions of m symmetry, separated by two crystallographically independent K+ cations located on mirror planes. A comparative description of the alkali metal, ammonium, methyl and dimethylammonium tetrasulfidometalates is presented.