Organic-inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O_(17)(H2O)(O3PCH2NH2CH2PO3)2] · H2O, a bimetallic oxide constructed from novel {Mo6O_(17)(H2O)(O3PCH2NH2CH2PO3)2}~(4-) clusters

摘要

The hydrothermal reaction of MoO3, CuSO4 · 5H2O, 2,2':6':2"-terpyridine (terpy) and bis-N,N-(methyl-phosphonic acid) amine (H2O3PCH2NHCH2PO3H2) provided blue crystals of the bimetallic oxide [{Cu(ter-py)}2Mo6O_(17)(H2O)(O3PCH2NH2CH2PO3)2] · H2O (1 · H2O). The three-dimensional structure of 1 is constructed from {Mo6O_(17)(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 {P=O) 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 {P=O) unit. Crystal data: C_(35)H_(45)Cu2Mo6N8O_(35)P4: monodinic, P2_1, a = 11.9431(7) A, b = 17.382(1) A, c = 27.524(2) A, β = 90.429(1)°, V= 5713.7(6) A~3, Z = 4, D_(calc) = 2.270 g cm~(-3), R1= 0.0466.