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

Abstract

The double crown hexakis[(di-µ-benzylthio) nickel] cluster, [Ni6(SCH2C6H5)12]·C2H5OH, was obtained by reacting C6H5CH2SNa with [(CH3)2CHOCS2]2Ni in EtOH. The results of electrochemical studies show that [Ni6(SCH2C6H5)12] is a quasi-reversible process. The crystal structure of [Ni6(SCH2C6H5)12]·C2H5OH is composed of discrete [Ni6(SCH2C6H5)12] and C2H5OH solvent molecules. Each Ni atom is surrounded by four S atoms of the µ2-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 π-π and C–H···π 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.