Synthesis of open-framework zinc phosphite structures of varying dimensionality

Four new organically templated zinc phosphites, [(C4N2H10)(C5NH5)][Zn2Cl2(HPO3)2], I, [(C4N2H12)(C5NH4)]4[Zn6(HPO3)8], II, [C3N2H12][Zn2(HPO3)3]⋅2H2O, III and [C3NH10]2[Zn3(HPO3)4], IV have been synthesized in the presence of 1(2-pyridyl)piperazine (Py-PIP), 1,2-diaminopropane (1,2-DAP) and propylamine (PA), under mild hydro/solvo thermal conditions. The structures were determined by single-crystal X-ray diffraction. The structure of I consists of ZnO3Cl tetrahedral and HPO3 pseudo-tetrahedral units forming four-membered rings, which are connected through their edges giving rise to a one-dimensional ladder-like structure. The structure of II consists of [Zn6P8H8O24]4− layers formed by 4- and 8-membered rings. The layers are stacked in AAAA… fashion with the organic molecules occupying the inter-lamellar space. The structure of III consists of ZnO4 and HPO3 units, forming a one-dimensional ladder-like structure, which are cross-linked through another HPO3 units forming two-dimensional layers bound by 8-T atoms (T = Zn, P). The amine and lattice water molecules occupy the inter-layer spaces. In IV, the connectivity between ZnO4 and HPO3 units gives rise to a three-dimensional structure. The three-dimensional framework is built up from one-dimensional corner-shared chains and two-dimensional layers with 4.8-membered apertures. All the structures, except II, were prepared under mild reaction conditions (typically <100 °C). The presence of 4-membered rings and one-dimensional ladder/chain structures in all the compounds show the importance of such units in the building up of structures of higher dimensionality.

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