Solid state coordination chemistry of polyoxomolybdate clusters: Hydrothermal synthesis and structures of image and image (Hpt = 5(4′-pyridyl)tetrazole)

The hydrothermal reactions of MoO3, Cu(CH3CO2)2·H2O and 5(4′-pyridyl)tetrazole (4-Hpt) yielded a low temperature Cu(II) phase [{Cu3(4-pt)2(4-Hpt)2(H2O)2}{Mo8O26}]·2H2O (1·2H2O) and a high temperature Cu(I) material [{Cu10(4-pt)6(4-Hpt)2}{Mo8O26}]·2H2O (2·2H2O). The two-dimensional structure of 1 is constructed from β-octamolybdate clusters embedded in a image network. The copper(II)-pyridyltetrazolate layer consists of trinuclear clusters of corner-sharing copper ‘4 + 2’ octahedra linked through the dipodal 4-pt ligands. In contrast, the three-dimensional structure of 2 contains the {β-Mo8O26}4− building block embedded in a three-dimensional image framework. The copper(I)-pyridyltetrazolate substructure consists of chains of Cu tetrahedra and trigonal planes bridged by tetrazolate groups and connected through exo-catenate {CuN2O} trigonal planar units bonding to the pyridyl nitrogens of the dipodal ligand.