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, tripyridyltriazine (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