[TRIS(PYRAZOLYL)BORATO]VANADIUM(III) PHOSPHATES - STRUCTURAL MOTIFS FROM THE EXTENDED SOLID AND MODELS FOR THE INTERACTION WITH DNA

The syntheses of five mixed ligand vanadium(III) phosphate/phosphonate complexes are described: dinuclear I, [LVCl{mu-(Pho)(2)Po-2}]2; II, [ LVCl{mu-Ph(2)PO(2)}](2); and III, [LVCl{mu-PhP(H)O-2}](2); along with mononuclear IV, [LV{(PhO)(2)POS}(2)DMF]; and V, [LV{(PhO)(2)PO2}](2) . H2O where L = hydrotris(pyrazolyl)borate. X-ray crystal structure ana lysis of I, II, IV, and V gave the following parameters: I, C12H10B2Cl 2N12O8P2V2, P1, a = 9.949(4)Angstrom, b=11.732(4) Angstrom, c=12.729(3 ) Angstrom, alpha=110.37(1)degrees, beta=106.78(1)gamma, gamma=104.36( 1)degrees, Z=1, V=1228.8(7) Angstrom(3); II, C16H98B2Cl10N12O4P2V2, P1 , a=11.801(2) Angstrom, b=12.086(1) Angstrom, c=12.955(2) Angstrom, al pha=81.99(1)degrees, beta=65.51(1)degrees, gamma=62.60(1)degrees, Z=1, V=1491.1(5) Angstrom(3); IV, C36H37BN7O7P2S2V, P1, a=11.003(2) Angstr om, b=11.816(2) Angstrom, c=17.167(5) Angstrom, alpha=98.68(2)degrees, beta=101.81(2)degrees gamma=102.59(2)degrees, Z=2, V=2087.0(6) Angstr om(3); V, C69.5H65B2N15O8P4V2, C2/C, a=12.360(2) Angstrom, b=26.362(4) Angstrom, c=23.254(2) Angstrom, beta=91.24(8)degrees, Z=4, V=7575(2) Angstrom(3). Magnetic measurements indicate little or no interaction b etween the V(III) ions in II but a modest antiferromagnetic coupling i n I. These complexes should be good models for the possible modes of b onding between V(III) and biological phosphates such as DMA as well as provide insight into one of the common structural motifs present in v anadium(III) phosphate solid state materials.