On ammonium-tetrakis(dithiocarbamato)-bismuth(III)-monohydrate and tris(dithiocarbamato)-bismuth(III)

摘要

The title compounds were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with bismuth trichloride. NH _4Bi(S_2CNH_2)_4·H_2O crystallises in the monoclinic space group P2_1/c (No. 14) with a = 8.4109(17), b = 13.198(3) and c = 16.678(3) ?, β = 97.17(3)°and Bi(S_2CNH_2)_3 crystallises in the triclinic space group P$ar{1}$ (No. 2) with a = 5.8951(5), b = 8.3026(7), c = 12.5030(10) ?, α = 103.460(10), β = 95.080(10) and γ = 91.330(10) °. The crystal structure of NH_4Bi(S _2CNH_2)_4·H_2O comprises isolated polyhedrons around bismuth (eightfold coordination) linked by hydrogen bonds originating from ammonium, the co-crystallised water and the dithiocarbamate. In the crystal structure of Bi(S_2CNH _2)_3 exist dimeric aggregates comprising two distorted square antiprisms around bismuth, which are linked together by a common edge. They form infinite double chains with composition [Bi_2(S _2CNH2)_6]_∞, which are bridged by N-H···S hydrogen bonds. Evaluation of differential thermal analysis data shows that Bi_2S_3 develops in the temperature range between 125 and 150 °C, whereas mainly gaseous NH _3 and CS_2 are emitted during the decomposition reaction.