Crystal structures of (aceto-nitrile-κ)tris-(pyridine-4-thio-amide-κ)bis-(thio-cyanate-κ)cobalt(II) aceto-nitrile disolvate and tetra-kis-(pyridine-4-thio-amide-κ)bis-(thio-cyanate-κ)nickel(II) methanol penta-solvate.

Reaction of Co(NCS) or Ni(NCS) with pyridine-4-thio-amide in different solvents led to the formation of two compounds with composition [Co(NCS)(CHN)(CHNS)]·2CHCN () and [Ni(NCS)(CHNS)]·5CHOH (), respectively. The asymmetric unit of compound consists of one cobalt(II) cation, two thio-cyanate anions, three pyridine-4-thio-amide ligands, one coordinating and two solvate aceto-nitrile mol-ecules. One of the two aceto-nitrile solvate mol-ecules is disordered over two sets of sites in a 0.62:0.38 ratio. The asymmetric unit of compound comprises of one nickel(II) cation, two thio-cyanate anions, four N-bonding pyridine-4-thio-amide ligands and five methanol solvate mol-ecules. In compound , the cobalt(II) cations are octa-hedrally coordinated into discrete complexes by two terminal N-bonding thio-cyanate anions, the N atoms of three pyridine-4-thio-amide ligands and one aceto-nitrile mol-ecule. Additional aceto-nitrile solvate mol-ecules are located between the complexes,. The complexes and solvate mol-ecules are linked inter-molecular hydrogen bonding into a three-dimensional framework. In compound , the nickel(II) cations are likewise octa-hedrally coordinated by two terminal N-bonded thio-cyanate anions and four N-bonding pyridine-4-thio-amide ligands into discrete complexes. From their arrangement cavities are formed, in which the methanol solvate mol-ecules are located. Again, the complexes and solvate mol-ecules are linked into a three-dimensional framework by inter-molecular hydrogen bonding.