A Double Crown Hexakis[(Di-mu-benzylthio) Nickel] Cluster: Synthesis, Structure and Properties

The double crown hexakis[(di-mu-benzylthio) nickel] cluster, [N(i)6(SCH2C6H5)(12)] center dot C2H5OH, was obtained by reacting C6H5CH2SNa with [(CH3)(2)CHOCS2](2)Ni in EtOH. The results of electrochemical studies show that [Ni-6(SCH2C6H5)(12)] is a quasi-reversible process. The crystal structure of [Ni-6(SCH2C6H5)(12)]center dot C2H5OH is composed of discrete [Ni-6(SCH2C6H5)(12)] and C2H5OH solvent molecules. Each Ni atom is surrounded by four S atoms of the mu(2)-SCH2C6H5 ligands in a distorted square-planar structure. The C6H5CH2S - side chains are arranged in the axial and equatorial positions, alternately, concerning the pseudo-hexagonal axis of the molecule. Strong pi-pi and C-H center dot center dot center dot pi effects form the supramolecular nano-channel along the a-axis in the crystal, which wraps the solvent ethanol molecules in it. In addition, a wall is formed along the b- and c-axes, so that the ethanol molecules can freely enter and leave along the a-axis. These effects result in the ability of the title compound to adsorb and desorb ethanol molecules. Thermogravimetric analysis and powder X-ray diffraction at different temperature are provided to demonstrate this point.