New topology of CN-bridged clusters: dodecanuclear face-sharing defective cubes based on octacyanometallates(iv) and nickel(ii) with diimine ligands.

New dodecanuclear bimetallic Ni8M4 clusters were obtained in the reaction between octacyanometallates(IV), nickel(II) cations and diimine ligands. {[Ni(LL)(H2O)]2[Ni(LL)(H2O)2]6[M(CN)8]4} assemblies, where LL = 1,10-phenanthroline M = Mo, (1) or LL = 2,2'-bipyridine M = W (2) or Mo (3), are among the largest octacyanometallate-based clusters. They show the same compact topology of the cluster core, which can be described as defective face-sharing cubes with corners defined by alternating metal centres. The structures are stabilised by π­π interactions between aromatic rings of diimine ligands and hydrogen bonds connecting terminal CN groups and coordinated H2O molecules through a crystallisation solvent. Different decorating ligands cause different arrangements of clusters in the crystal structure. 1 crystallises in the triclinic system space group P, while 2 and 3 crystallise in the monoclinic system space group P21/n. The clusters show paramagnetic behaviour with weak antiferromagnetic interactions between the NiII centres through diamagnetic NC-MIV-CN linkages.