Solid state coordination chemistry in the design of molybdenum oxides: The hydrothermal synthesis and structure of a layered copper-molybdenum oxide, [Cu(tpytrz)₂Mo₄O₁₃] (tpytrz = tripyridyltriazine)

The hydrothermal reaction of CuSO₄·5H₂O, tripyridyl-triazine (tpytrz), MoO₃, and H₂O in the mole ratio 2.1:1.0:1.9:3470 for 84 h at 160 °C yields green needles of [Cu(tpytrz)₂Mo₄O₁₃] (MOXI-37). The structure of MOXI-37 consists of bimetallic {CuMo₄O₁₃} layers buttressed by tpytrz ligands occupying the interlamellar region. The overall structure adopts the motif of alternating inorganic and organic subunits characteristic of many organic-inorganic composite materials. The inorganic network is constructed from {Mo₄O₁₃} chains of corner-sharing octahedra and tetrahedra, linked by octahedral {CuN₂O} units into a two-dimensional structure. The structure of MOXI-37 may be compared to other examples of copper-molybdate networks sandwiching bridging organonitrogen ligands, namely, [Cu(dpe)MoO₄] (MOXI-1) and [Cu(bpa)_0.5MoO₄] (MOXI-24). In contrast to the network connectivity of MOXI-37, the layer structure of [Cu(dpe)MoO₄] consists of corner-sharing {MoO₄} tetrahedra and {CuN₂O₅} trigonal bipyramids, while the two-dimensional oxide substructure [Cu(bpa)_0.5MoO₄] is constructed from tetranuclear copper clusters linked through corner-sharing {MoO₄} tetrahedra. (C) 2000 Academic Press.