Synthesis and characterization of dicopper(II) and one-dimensional nickel(II) complexes with MO4 (M = Mo, W) as bridging ligands

The reaction of [M(L)]Cl-2. H2O (M = Cu2+, Ni2+ , and L = 3,14-dimethyl-2,6 , 13,17-tetraazatricyclo[14,4,0(1.18),0(7.12)]docosane) with [MO2](2-) (M = Mo and W) in water-methanol solution yields dinuclear copper(II) and one-d imensional nickel(II) complexes, [{Cu-II(L)}(2)(mu-MoO4)][MoO4]. 11H(2)O (1 ), [{Cu-II(L)}(2)(mu-WO4)][WO4]. 11H(2)O (2), and catena-(mu-MoO4-O,O')[Ni- 11(L)]. 5H(2)O (3). The crystal structures and the magnetic properties have been studied. Complexes 1 and 2 are isomorphous and the structures are mad e up of discrete dimers in which two copper(II) ions are bridged by the [MO 4](2-) anion. The cationic units of 3 are bridged by the [MoO4](2-) anions to give a chain structure in the lattice. The coordination geometry about t he copper(II) ions is a distorted square pyramid with the secondary amines of the macrocycle and an oxygen atom of [MO4](2-). However, each nickel(II) ion is coordinated by one macrocycle and two molybdate ligands in an octah edral trans arrangement elongated in the direction of the chain. Magnetic s usceptibilities for 1 and 2 revealed that a ferromagnetic interaction betwe en copper(II) ions is propagated through the [MO4](2-) bridge and the coupl ing constants (2J) were calculated to be + 2.5(1) cm(-1) for [MoO4](2-) and + 5.9(1) cm(-1) for [WO4](2-) (H= - 2J Sigma S1S2), respectively. In 3, tw o nickel(II) ions bridged by the [MoO4](2-) anion are antiferromagnetically coupled with the J value of - 1.24(2) cm(-1) (H = - J Sigma SiSi + 1). Cry stal data: 1, monoclinic, space group P2(1), a = 9.651(1), b = 20.561(3), c = 14.794(5) Angstrom, beta = 99.03(2)degrees, V = 2899.4(11) Angstrom(3) Z = 2; 2, monoclinic; space group P2(1), a = 9.683(1), b = 20.602(2), c = 14 .882(6) Angstrom, beta = 99.03(2)degrees, V = 2932.1(13) Angstrom(3), Z = 2 ; 3, triclinic, space group P (1) over bar, a = 10.089(1), b = 11.622(1), c = 13.433(2) Angstrom, alpha = 113.46(1), beta = 100.01(1), gamma = 92.22(1 )degrees, V = 1412.8(3) Angstrom(3), Z = 2. (C) 2000 Elsevier Science S.A. All rights reserved.