Solid-state 1D → 3D transformation of polynitrile-based coordination polymers by dehydration reaction

In crystal structures of two chain coordination polymers [M(tcnopr3OH)(2)(H2O)(2)] (M = Ni-II and Co-II; tcnopr3OH(-) = [(NC)(2)CC(O(CH2)(3)OH)C(CN)(2)](-)) based on a N,O or N,N'-bridge polynitrile ligand, the parallel chains are connected via, respectively, C N center dot center dot center dot H-O and O-H center dot center dot center dot O hydrogen bonds between uncoordinated functional groups of the ligand and coordinated water molecules. Upon heating, both solids undergo dehydration accompanied by degradation of their single crystals. Powder X-ray diffraction showed that non-isostructural triclinic single crystals transformed to isostructural monoclinic compounds. The solid-state reaction yielded 3D coordination polymers [M(tcnopr3OH)(2)] (M = Ni-II and Co-II) based on a N,N',O-connected tcnopr3OH(-). Although previously tens of complexes based on tcnopr3OH and similar anions were synthesized and X-ray characterized, none of these contain a tridentate polynitrile ligand. Thus, this study provides evidence that solid-state reactions allow obtaining novel coordination modes of polynitrile ligands. The possible pathways for the transformation of H-bonded networks to 3D coordination polymers are discussed on the basis of the topological approach. Applicability of the topological approach to predict possible networks of solid-state reaction products based on the crystal structures of initial compounds is demonstrated.