A crystallographic and spectroscopic study of mercury(II) dithiocarbamate

Abstract

CHUNG CHIEH and SING KWEN CHEUNG. Can. J. Chem. 59,2746Chem. 59, (1981. Ammonium dithiocarbamate, H,NCS2NH,, decomposes easily but the anion forms a stable mercury(I1) complex, the crystals of which are orthorhombic with a = 7.851(3), b = 17.565(7), c = 12.051(3) A, and space group Pbca. The structure was solved by the Patterson method and refined by the full-matrix least-squares method to an R of 0.038 for 781 reflections. The structure consists of layers of two-dimensional polymeric networks. The dimeric subunits in the layer containing two each of mutually connected Hg atoms and dithiocarbamates are further linked by other bridging dithiocarbamates forming a sheet-like structure. Each H atom bonds to four S atoms from four separate dithiocarbamates with Hg-S distancesof 2.499(4), 2.508(4), 2.533(4), and 2.629(4)

Spectroscopic and structural studies of some bisdithiocarbamates and cyclic thiones

“…H-N hydrogen bonds has a longer distance than the one with one strong, and one weak S ... H-N hydrogen bonds. Similar asymmetric bonding modes have also been observed in C U ( S~C N ( C H , )~)~ (20) and other dithiocarbamate complexes (21).…”

Crystal structure of N,N′-dimethyl-2-imidazolidinethione, a by-product from the reaction of Na2(CH2N(CH3)CS2)2 and HgCl2

“…These were refined as well as their positions with a total of 89 variables. Using all reflections, the final R and R,,, were 0.053 and 0.068 respectively, the (2) 2748 (1) 5.92 N (1) 6624 (2) 3393 (6) 1 189(3) 5.20 N (2) 8267 (4) 5361 (6) 1025 (3) 5.02 c (1) 7485 (4) 51 58 (7) 1621 (3) 3.63 c (2) 6769 (6) 2334 (9) 199 (5) …”

“…I I metal ions, N,N1-dimethylethylenebisdithiocarbamate was prepared (1). However, the reaction between this bisdithiocarbamate and mercury(I1) chloride led to a cyclic by-product N,N1-dimethyl-2-imidazolidinethione.…”

Bis[bis(N-2-hydroxyethyl,N-isopropyl-dithiocarbamato)mercury(II)]2: crystal structure and Hirshfeld surface analysis

“…A search of the Cambridge Structural Database [39] reveals 33 molecules of the general formula Hg(S2CNRR')2, R, R' = alkyl, aryl, plus the new structure reported in the current study and a sole example for the R, R' = H compound, Hg(S2CNH2)2, giving 37 different structures owing to the occurrence of supramolecular isomerism for two formulations [3,9,. An analysis of these structures indicates there is significant structural diversity amongst these, as summarised in Table 7 and Figure 8.…”

“…When R, R' = alkyl, these are usually zero-dimensional, being mono-or bi-or even tri-nuclear, depending on the presence of bridging ligands. By contrast, when R, R' = H, a two-dimensional framework is observed [3]; see below for further discussion on this structural diversity. By contrast to the binary mercury(II) dithiocarbamates, cadmium(II) counterparts are usually binuclear owing to the presence of two κ 2 -chelating and two µ2,κ 2 -tridentate bridging dithiocarbamate ligands leading to five-coordinate coordinate geometries; see [4] …”