Coordination polymers and polygons using di-pyridyl-thiadiazole spacers and substituted phosphorodithioato Ni-II complexes: potential and limitations for inorganic crystal engineering

Coordinatively unsaturated P-substituted dithiophosphonato, dithiophosphato, and dithiophosphito complexes {[Ni((MeO)(2)PS2)(2)] (1), [Ni((EtO)(2)PS2)(2)] (2), [Ni(MeOdtp)(2)] (3), and [Ni((Ph)(2)PS2)(2)] (4)} were reacted with the bis-functional ligands 3,5-di-(4-pyridyl)-1,2,4-thiadiazole (L1) and 3,5-di-(3-pyridyl)-1,2,4-thiadiazole (L2) to give the coordination polymers (1-4 center dot L1)(infinity), (3 center dot L2)(infinity), and (4 center dot L2 center dot 2C(7)H(8))(infinity) and the discrete dimers (1-2N center dot L2)(2), all characterised by single crystal X-ray diffraction. A comparison of the structures shows that L1 can be exploited for the predictable assembly of undulating chains independent of the nature of the Ni-II complex, while L2 allows for the existence of different supramolecular constructs ensuing from different ligand conformations deriving from the rotation of the pyridyl rings.