Synthesis and Crystal Structure and Characterization of Copper(I) Thiocyanato–Thiuram Disulfide, CuSCN[(SCNH 2 ) 2 S 2 Christoph L. Teske, Sebastian Mangelsen, Huayna Terraschke, Tobias A. Engesser
The copper(I) thiocyanate adduct CuSCN[(SCNH 2 ) 2 S 2 ], with thiuram disulfide, was synthesized via mechanochemical grinding of equimolar CuSCN and (SCNH 2 ) 2 S 2 with minimal amounts of acetone, yielding a yellow microcrystalline powder. The compound crystallizes in the monoclinic space group P2 1 /c (No. 14) with a = 7.0249(8) Å, b = 12.93384(14) Å, c = 11.25067(12) Å, β = 108.5270(7)°, and Z = 4. Structural analysis by PXRD reveals infinite zigzag chains of distorted, tetrahedrally coordinated Cu atoms along [001], which are interconnected into two‐dimensional wavy networks via thiuram disulfide ligands along [010] and stabilized by hydrogen bonding along [100]. The S─S bond within the thiuram disulfide ligand is elongated to 2.093(3) Å. Optical measurements indicate a bandgap of 2.65 eV and orange luminescence upon UV excitation ( λ max = 601 nm; CIE 1931 coordinates: 0.4566, 0.4605). Infrared (IR) and Raman spectroscopic studies characterize the vibrational properties of the compound and show the characteristic bands of both ligands, thiocyanate and thiuram disulfide. Thermal analysis (DTA/TG) of CuSCN[(SCNH 2 ) 2 S 2 ] reveals its decomposition to Cu 2 S with minor amounts of metallic copper.