Abstract
Reaction of Co(NCS)2 or Ni(NCS)2 with pyridine-4-thio-amide in different solvents led to the formation of two compounds with composition [Co(NCS)2(C2H3N)(C6H6N2S)3]·2CH3CN (1) and [Ni(NCS)2(C6H6N2S)4]·5CH3OH (2), respectively. The asymmetric unit of compound 1 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 2 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 1, 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 via inter-molecular hydrogen bonding into a three-dimensional framework. In compound 2, 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.
Highlights
Reaction of Co(NCS)2 or Ni(NCS)2 with pyridine-4-thioamide in different solvents led to the formation of two compounds with composition [Co(NCS)2(C2H3N)(C6H6N2S)3]Á2CH3CN (1) and [Ni(NCS)2(C6H6N2S)4]Á5CH3OH (2), respectively
The asymmetric unit of compound 1 consists of one cobalt(II) cation, two thiocyanate anions, three pyridine-4-thioamide ligands, one coordinating and two solvate acetonitrile molecules
In compound 1, the cobalt(II) cations are octahedrally coordinated into discrete complexes by two terminal N-bonding thiocyanate anions, the N atoms of three pyridine-4-thioamide ligands and one acetonitrile molecule
Summary
For several years we have been interested in the structural, thermal and magnetic properties of coordination compounds and polymers based on transition metal thio- and selenocyanates (Wohlert et al, 2013a, 2014a). In the majority of cases, these cations are octahedrally coordinated by two anionic ligands and four monodentate N-donor co-ligands If such complexes are heated, they frequently decompose in discrete steps, forming new compounds as intermediates in which the metal cations are linked into one- or two-dimensional network structures. In the course of our project we became interested in the monodentate ligand pyridine-4-thioamide, which might be able to link M(NCS) chains (M = Co, Ni) into layers by intermolecular N—HÁ Á ÁS hydrogen bonding. This motif is observed in the crystal structure of the pure ligand (Colleter & Gadret, 1967; Eccles et al, 2014). To check if our assumption can be verified, we have performed single-crystal structure determinations of 1 and 2 and report the results in this communication
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