Solvatomorphs of dimeric transition metal complexes based on the V4O12 cyclic anion as building block: Crystalline packing and magnetic properties

Dinuclear [{M(phen)2}2V4O12] · C6H12O · H2O (M = CoII 1, MnII 2, NiII 3 and CuII 4) and [{Cu(phen)2}2V4O12] · 3.5H2O 5 has been prepared by biphasic and hydrothermal syntheses, respectively. All five structures exhibit the {V4O12}4− cluster in a chair-like configuration, covalently bonded to two [M(phen)2]2+ fragments, producing a super-exchange magnetic phenomenon. The magnetic study of complexes 1–5 shows that they are very weak antiferromagnetically coupled systems, with J values of −0.14, 2; −0.64, 3 and −0.23, 4 cm−1. Complexes 1 to 3 correspond to isostructural compounds in which the cyclovanadate group acts as a bidentate bridged ligand. In the copper complexes (4 and 5) the {V4O12}4− anion presents the novel monodentate bridging mode, and therefore a more significant distortion from the chair-like configuration. The mentioned complexes, together with that reported in the literature, permit to conclude that it is quite common for a single molecular species to exist in more than one crystalline arrangement. A detailed analysis of the structures of 1–4 shows that the crystal symmetry cannot be strictly centrosymmetric, due to the presence of the cyclohexanol molecule with a single –OH group in the lattice.