Two molecular-type complexes of the octahedral rhenium(III) cyanocluster anion [Re6Se8(CN)6]4- with M2+ (Mn2+, Ni2+)

Two novel octahedral rhenium(III) selenocyanide cluster complexes [(nBu)(4)N](2)Ni(H2O)(5)[Re6Se8(CN)(6)].2H(2)O (1) and [(nBU)(4)N](2)Mn(H2O)(4)[Re6Se8(CN)(6)].2H(2)O (2) have been prepared by the reaction of K-4[Re6Se8(CN)(6)].3.5H(2)O, (nBu)(4)NBr kand Ni(OAC)(2) (or MnSO4) in aqueous solution. The complexes have been structurally solved in the orthorhombic unit cell Pbca with parameters: a = 19.393(2), b = 17.292(2), c = 37.255(4) Angstrom for 1, and a = 19.518(41), b = 17.488(3), c = 37.997(5) Angstrom for 2. The cluster anions and M2+ form ionic pairs (M(H2O)(n)[Re6Se8(CN)(6)])(2-) that are packed in the solid state with n-tetrabutylammonium cations. Coordinated and solvate water molecules as well as the nitrogen atoms of the anions form a network of hydrogen bonds in the structures. These compounds are isomorphous, although the coordination environments of the metal cations differ