Octahedral niobium chloride clusters as building blocks of templated prussian blue framework analogues.

The preparation, structure, and magnetic properties of the first three-dimensional framework containing octahedral niobium cyanochloride clusters as building units are reported. Reactions of aqueous solutions of (Me(4)N)(2)K(2)[Nb(6)Cl(12)(CN)(6)] (2) with aqueous solutions of MnCl(2) result in the precipitation of the compound (Me(4)N)(2)[MnNb(6)Cl(12)(CN)(6)] (3). The structure of 3 was determined from single-crystal X-ray diffraction study (crystal data: cubic, Fm3macrom(No. 225), a = 15.513(4) A, V = 3733.2(12) A(3), Z = 4). Its 3D framework is based on edge-bridged Nb(6)Cl(12) clusters and Mn(2+) ions bridged by cyanide ligands to form a cfc lattice MnNb(6)Cl(12)(CN)(6)(-) in which all tetrahedral sites are occupied by the cations (Me(4)N)(+) which act as charge compensating template. The structure of 3 can be considered as an expansion of the Prussian blue framework in which Fe(CN)(6)(-) is replaced by the cluster Nb(6)Cl(12)(CN)(6)(-). Magnetic susceptibility measurements indicate that Mn(2+) is present in a high spin d(5) configuration. No magnetic ordering is observed.