Cation-anion pairs of niobium clusters of the type [Nb6Cl12(RCN)6][Nb6Cl18] (R= Et, nPr, iPr) with nitrite ligands RCN forming stabilizing inter-ionic contacts

Three new niobium cluster compounds with edge bridged, octahedral hexanuclear metal cores have been synthesised. They consist of cluster pairs with [Nb6Cl12(RCN)(6)](2+) cations, [Nb6Cl18](2-) anions, and co-crystallised nitrile molecules, with R=C2H5 (propionitrile), (C3H7)-C-n (butyronitrile), (C3H7)-C-i, (isobutyronitrile). The synthesis is based on the dehydration of [Nb6Cl14(H2O)(4)] center dot 4(H2O) with carboxylic acid anhydrides in the presences of an excess of the respective nitrile. An interesting aspect of these compounds is that the metal atoms of the cluster cation have an average oxidation state different from that of the cluster anion, the former being oxidized losing two electrons. In crystals of all three compounds layers of cluster cations are separated by layers of cluster anions. Perpendicular to these layers of the same cluster types, every cation is surrounded by four anions and vice versa. Between the cations and anions short distances are found between the halogenido ligands and the positively charged C atoms of the nitrile ligands (N-C center dot center dot center dot Cl angles of similar to 90 degrees). These contacts indicate relatively strong dipole-dipole interactions, which presumably contribute to the arrangement of the cluster ions in the crystals.