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Keywords:

  • Dithiocarbamates;
  • Copper;
  • Preparation;
  • X-ray diffraction;
  • Thermal decomposition

Abstract

Abstract. The title compounds NH4[Cu(S2CNH2)2]·H2O (A) and CuS2CNH2 (B) were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with copper sulfate in presence of excess cyanide as reductive. (A) crystallizes in the orthorhombic space group C2221 (No. 20) with a = 8.9518(6), b = 9.6414(6) and c = 10.6176(8) Å, Z = 4. (B) crystallizes in the orthorhombic space group P212121 (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = 9.4834(5) Å, Z = 4. In the crystal structure of (A) copper has a tetrahedral surrounding of four monodentate dithiocarbamate ligands. These structural units form 2D nets stacked along [001]. Staggered chains consisting of H2O and NH4+ penetrate the crystal structure along [001] yielding additional coherence via hydrogen bonds. The crystal structure of (B) comprises a three-dimensional tetrahedral framework of CuS4 units exclusively linked by vertices. The arrangement is reminiscent of a filled β-cristobalite structure with the dithiocarbamate ligands extending into the hollow spaces. Thermal decomposition precedes stepwise finally giving Cu2S in each case.