Two New Antiferromagnetic Nickel(II) Complexes Bridged by Azido Ligands in the Cis Position. Effect of the Counteranion on the Crystal Structure and Magnetic Properties

Two new nickel(II) end-to-end azido-bridged compounds, cis-catena-[NiL(2)(-N(3))](n)()(ClO(4))(n)().nH(2)O (1) and [Ni(2)L(4)(-N(3))(2)](PF(6))(2) (2), were synthesized and characterized; L is 2-(aminoethyl)pyridine. The crystal structures of 1 and 2 were solved. Complex 1: monoclinic system, space group P2(1)/a, a = 8.637(2) Å, b = 18.9995(7) Å, c = 12.3093(7) Å, beta = 105.92(2) degrees, Z = 4. Complex 2: triclinic system, space group P, a = 9.139(7) Å, b = 10.124(3) Å, c = 12.024(2) Å, alpha = 70.407(14) degrees, beta = 84.19(2) degrees, gamma = 67.67(4) degrees, Z = 1. In the two complexes the nickel atom is situated in a similarly distorted octahedral environment. The two complexes are different; 1 is a one-dimensional helicoidal complex with the two L ligands and the two end-to-end azido bridges in a cis arrangement while complex 2 is a dinuclear system with two end-to-end azido bridges, indicating the extreme importance of the counteranion present (ClO(4)(-) for 1 and PF(6)(-) for 2). The magnetic properties of the two compounds were studied by susceptibility measurements vs temperature. The chi(M) vs T plot for 1 shows the shape for a weakly antiferromagnetically coupled nickel(II) one-dimensional complex without a maximum until 4 K. In contrast, for complex 2 the shape of the chi(M) vs T curve shows a maximum near 40 K, indicating medium antiferromagnetic coupling. From the spin Hamiltonian -J(ij)()S(i)()S(j)(), J values for 1 and 2 were less than -1 and -29.1 cm(-)(1), respectively. The magnetic behavior for 1 and 2 may be explained in terms of the overlap between magnetic orbitals, taking into account the torsion of the Ni(II) atoms and azido-bridging ligands in the two structures.