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.