On Ammonium‐tetrakis(dithiocarbamato)‐bismuth(III)‐monohydrate and Tris(dithiocarbamato)‐bismuth(III)

The title compounds were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with bismuth trichloride. NH 4 Bi(S 2 CNH 2 ) 4 ·H 2 O crystallises in the monoclinic space group P 2 1 / c (No. 14) with a = 8.4109(17), b = 13.198(3) and c = 16.678(3) Å, β = 97.17(3)°and Bi(S 2 CNH 2 ) 3 crystallises in the triclinic space group P $\bar{1}$ (No. 2) with a = 5.8951(5), b = 8.3026(7), c = 12.5030(10) Å, α = 103.460(10), β = 95.080(10) and γ = 91.330(10) °. The crystal structure of NH 4 Bi(S 2 CNH 2 ) 4 ·H 2 O 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 2 CNH 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 2 CNH 2 ) 6 ] ∞ , which are bridged by N–H···S hydrogen bonds. Evaluation of differential thermal analysis data shows that Bi 2 S 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.