The double cluster compound [Nb₆Cl₁₄(MeCN)₄][Nb₆Cl₁₄(pyz)₄]·6MeCN (Me: methyl, pyz: pyrazine) with a layered structure resulting from weak intermolecular interactions

Abstract The synthesis and the crystal structure of the double cluster compound [Nb6Cl14(MeCN)4][Nb6Cl14(pyz)4]·6CH3CN are described. The synthesis is based on a partial ligand exchange reaction, which proceeds upon dissolving [Nb6Cl14(pyz)4]·2CH2Cl2 in acetonitrile. The compound is built up of two discrete neutral cluster units, which consist of octahedra of Nb6 atoms coordinated by 12 edge-bridging chlorido and two terminal chlorido ligands, and four acetonitrile ligands on one and four pyrazine ligands on the other cluster unit. Co-crystallized acetonitrile molecules are also present. The single-crystal structure determination has revealed a cluster arrangement in which the [Nb6Cl14(pyz)4] units are connected by (halogen) lone-pair–(pyrazine) π interactions. These lead to chains of [Nb6Cl14(pyz)4] clusters. These chains are further connected to cluster layers by (nitrile-halogen) dipole–dipole interactions, in which the [Nb6Cl14(MeCN)4] and co-crystallized MeCN molecules are also involved. These cluster layers are arranged parallel to the crystallographic {011} plane.