Trinuclear cyanido-bridged MII-WV complexes (M = Mn, Co): Crystal structures and magnetic properties

Two new trinuclear heterometallic complexes, [{MnII(L)(CH3OH)}2{WV(CN)8}](NO3)·CH3OH·H2O (2) and [{CoII(L)(CH3OH)}2{WV(CN)8}](NO3)·CH3OH·H2O (3), have been assembled from mononuclear cationic modules, [M(L)(H2O)2]2+, and [W(CN)8]3– as a metalloligand (M = MnII; CoII, L is the pentadentate ligand resulting from the condensation reaction between 2,6-diacetylpyridine and semicarbazide). The crystal structure of the manganese(II) precursor, [MnII(L)(H2O)2](NO3)2·H2O 1, and of the trinuclear compounds 2 and 3 have been solved. Within the three compounds the 3d metal ions show a pentagonal bipyramidal coordination geometry. The magnetic properties of compounds 2 and 3 have been investigated. Compound 2 shows an irregular spin state structure with S = 9/2 arising from MnII-WV antiferromagnetic interactions (J = −8.00 cm−1, H = -2JS1S2). In compound 3, the CoII-WV exchange interaction was found ferromagnetic (J = +12.3 cm−1).