Synthesis, crystal structure and thermal properties of a new polymorphic modification of diiso-thio-cyanato-tetra-kis-(4-methyl-pyridine)cobalt(II).

ABSTRACT

The title compound, [Co(NCS)2(C6H7N)4] or Co(NCS)2(4-methyl-pyridine)4, was prepared by the reaction of Co(NCS)2 with 4-methyl-pyridine in water and is isotypic to one of the polymorphs of Ni(NCS)2(4-methyl-pyridine)4 [Kerr & Williams (1977 ▸). Acta Cryst. B33, 3589-3592 and Soldatov et al. (2004 ▸). Cryst. Growth Des. 4, 1185-1194]. Comparison of the experimental X-ray powder pattern with that calculated from the single-crystal data proves that a pure phase has been obtained. The asymmetric unit consists of one CoII cation, two crystallographically independent thio-cyanate anions and four independent 4-meth-yl-pyridine ligands, all located in general positions. The CoII cations are sixfold coordinated to two terminally N-bonded thio-cyanate anions and four 4-methyl-pyridine coligands within slightly distorted octa-hedra. Between the complexes, a number of weak C-H⋯N and C-H⋯S contacts are found. This structure represent a polymorphic modification of Co(NCS)2(4-methyl-pyridine)4 already reported in the CCD [Harris et al. (2003 ▸). NASA Technical Reports, 211890]. In contrast to this form, the crystal structure of the new polymorph shows a denser packing, indicating that it is thermodynamically stable at least at low temperatures. Thermogravimetric and differential thermoanalysis reveal that the title compound starts to decomposes at about 100°C and that the coligands are removed in separate steps without any sign of a polymorphic transition before decomposition.