Crystal structure of mercury(II) bromide dithiocarbamate, [HgBr₂(S₂CNEt₂)Hg(S₂CNEt₂)]_n, an inorganic polymer

Abstract

A pale yellow crystal obtained from reaction of HgBr2 and tetraethylthiuram disulfide (TETD) has the composition of HgBr2•Hg[S2CN(C2H5)2]2. TETD was reduced to dithiocarbamate. The molecules are polymeric chains with HgBr2 and Hg2+ alternately bridging to dithiocarbamate ions and vice versa. The crystal is monoclinic: a = 10.421(7), b = 15.244(13), c = 14.649(8) Å, β = 113.3(1)°; space group P21/c. The final R factor for 2085 observed reflections is 0.083. There are two types of coordination geometries for the mercury(II) ions in the crystal: the coordination for one is digonal with two short Hg—S distances of 2.385(11) and 2.365(10) Å. The coordination for the other is tetrahedral with two Hg—S, 2.552(10) and 2.569(10) Å, and two Hg—Br, 2.640(4) and 2.552(7) Å, bonds. The average C=S distance is 1.72(4) Å.

Heterodi- [MAg, MAu (M = Pd, Pt)], Tri- [PdAg2, PtAg2, PtAu2, Pt2M (M = Ni, Pt, Cd, Hg)], and Tetranuclear (Pt2Ag2, Pt2Au2) 1,1-Ethylenedithiolato Complexes

“…It is reasonable to assume that, in 8 , the geometry around the central platinum atom is square planar. However, the geometry around the mercury atom in complex 9 could be tetrahedral or square planar because both geometries are found in some related diorganodithiocarbamate complexes. − …”

A crystallographic and spectroscopic study of mercury(II) dithiocarbamate

“…In our study of interaction between mercury(I1) ion and tetraethylthiuram disulfide (I), we encountered and reported many crystal structures of dithiocarbamate complexes (2)(3)(4)(5). Results from these structures indicate that mercury(I1) and dithiocarbamates bond in various ways and the complexes formed depend not only on the solvent used, but also on the concentration of halide ions which are often incorporated into the complex.…”

Xanthate and dithiocarbamate complexes of group IIb elements, and an interesting relationship between two mercury(II) ethylxanthate phases

“…We have reported several crystal structures of Hg u complexes of diethyldithiocarbamate (dtc) in our studies of interactions between N,N,N',N'-tetraethyl-thiuram disulfide (TETD) and mercurials (Chieh, 1978;Chieh & Leung, 1976). In these structures, the -C(--S)S-group was found to be a unidentate, bridging or chelating ligand.…”