Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O, a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO3, CuSO4 · 5H2O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H2O3PCH2NHCH2PO3H2) provided blue crystals of the bimetallic oxide [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O (1 · H2O). The three-dimensional structure of 1 is constructed from {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters linked through {Cu(terpy)}2+ subunits. The cluster consists of three pairs of edge-sharing {MoO6} octahedra linked through corner-sharing interactions into a {Mo6O6} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO3} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO3} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C34H45Cu2Mo6N8O35P4: monoclinic, P21/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å3, Z = 4, Dcalc = 2.270 g cm−3, R1 = 0.0466.

The hydrothermal reaction of MoO3, CuSO4 · 5H2O, terpyridine and bis-N,N-(methylphosphonic acid) gave crystals of a three-dimensional bimetallic oxide [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O, constructed from the unusual {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters linked through {Cu(terpy)}2+ subunits.Figure optionsDownload as PowerPoint slide