Crystal Structure and Magnetic Interactions in Nickel(II) Dibridged Complexes Formed by Two Azide Groups or by Both Phenolate Oxygen−Azide, −Thiocyanate, −Carboxylate, or −Cyanate Groups

Tridentate/tetradentate Schiff base ligands L1 and L2, derived from the condensation of o-vanillin or pyridine-2-aldehyde with N,N-dimethylethylenediammine, react with nickel acetate or perchlorate salt and azide, cyanate, or
thiocyanate to give rise to a series of dinuclear complexes of formulas [Ni(L1)(μ1,1-N3)Ni(L1)(N3)(OH2)]·H2O (1),
{[Ni(L1)(μ1,1-NCS)Ni(L1)(NCS)(OH2)][Ni(L1)(μ-CH3COO)Ni(L1)( NCS) (OH2)]} (2) {[2A][2B]}, [Ni(L1)(μ1,1-NCO)Ni(L1)(NCO)(OH2)]·H2O (3), and [Ni(L2-OMe)(μ1,1-N3)(N3)]2 (4), where L1 = Me2N(CH2)2NCHC6H3(O-)(OCH3) and L2
= Me2N(CH2)2NCHC6H3N. We have characterized these complexes by analytical, spectroscopic, and variable-temperature magnetic susceptibility measurements. The coordination geometry around all of the Ni(II) centers is a
distorted octahedron with bridging azide, thiocyanate/acetate, or cyanate in a μ1,1 mode and μ2-phenolate oxygen
ion for 1−3, respectively, or with a double-bridging azide for 4. The magnetic properties of the complexes were
studied by magnetic susceptibility (χM) versus temperature measurements. The χM νs T plot reveals that compounds
1 and 4 are strongly ferromagnetically coupled, 3 shows a weak ferromagnetic behavior, and 2 is very weakly
antiferromagnetically coupled.