Oxoanion influences on the self-assembly of cationic co-ordination complex polymers of the nickel(II)-di-4-pyridylamine family

摘要

Hydrothermal reactions of Ni~(II), di-4-pyridylamine (dpa) and the appropriate oxide yield materials of the Ni~(II)-organoddiamine-EO_4~(2-) family. Specifically, reaction of NiCl_2.6H_2O, dpa, and MoO_3 in water at 120degC yield [Ni(dpa)_2(MoO_4)] 1, while the reaction of NiSO_4.6H_2O and dpa in water at 120degC gave [Ni(dpa)(SO_4)(H_2O)].2H_2O 2. The structures reveal the dramatic influence of the anion identity and ligation modes in the {Ni(dpa)_n}_n~(2n+) substructure. The structure of 1 is constructed from two motifs, two-dimensional {Ni(dpa)}_n~(2n+) sheets and one-dimensional {NiMoO_4}_n chains, to produce a three-dimensional covalently linked framework. In contrast, the {Ni(dpa)}_n~(2n+) substructure of 2 is three-dimensional, with co-ordinated SO_4~(2-) and aqua ligands projecting into channels formed by the {Ni(dpa)}_n~(2n+) framework. The void is reduced through the common characteristic of interpenetration. such that the structure of 2 exhibits two independent three-dimensional fraweworks.