Crystal structure of bis-(N,N'-di-methyl-thio-urea-κS)bis-(thio-cyanato-κN)cobalt(II)

During systematic investigations on the synthesis of coordination polymers with Co(NCS)₂ involving different thio-urea derivatives as coligands, crystals of the title compound Co(NCS)₂(N,N'-di-methyl-thio-urea)₂, or [Co(C₃H₈N₂S)₂(NCS)₂], were obtained. These crystals were non-merohedric twins and therefore, a twin refinement using data in HKLF-5 format was performed. In the crystal structure of this compound, the Co^II cations are coordinated by two N-terminally bonded thio-cyanate anions as well as two S-bonding N,N'-di-methyl-thio-urea mol-ecules, forming two crystallographically independent discrete complexes each with a strongly distorted tetra-hedral geometry. An intricate network of inter-molecular N-H⋯S and C-H⋯S hydrogen bonds can be found between the complexes. The thermogravimetric curve of the title compound shows two discrete steps in which all coligand mol-ecules have been emitted, which is also accompanied by partial decomposition of the cobalt thio-cyanate. If the measurement is stopped after the first mass loss, only broad reflections of CoS can be found in the XRPD pattern of the residue, which proves that this compound decomposes completely upon heating. However, at lower temperatures an endothermic signal can be found in the DTA and DSC curve, which corresponds to melting, as proven by thermomicroscopy.