INSERTION REACTION OF CS2 INTO CU-S BONDS .3. PREPARATION AND CRYSTAL-STRUCTURE OF [CU(S2CSC6H2BU3T-2, 4, 6)]4.4C2H5OH

Colorless complex [CuSC6H2Bu3t-2, 4, 6]n reacted with OS2 to give a yellow product, which was recrysterized from CS2-C2H5OH to form yellow crystals. The structure of the crystal was shown to be [Cu(S2CSC6H2Bu3t-2, 4, 6)]4.4C2H5OH by single crystal X-ray diffraction method. The crystal belongs to the tetragonal space group I42dBAR with unit cell parameters: a = b = 1.7079(3) nm, c = 3.5228(10) nm, V = 10.275(6) nm3, D(c) = 1.198 g cm-3, Z = 4. The structure was refined to R = 0.0559 for 1863 reflections. In the molecule, Cu4 cluster has a distorted tetrahedral configuration. Surrounding this tetrahedron are four thioxanthate ligands (RSCS2-) formed by insertion of CS2 into Cu-S bonds. The ligand coordinates to copper atoms through two sulfur atoms, one of which bridges two copper atoms, while the other coordinates to the third copper atom. The coordination geometry of each copper atom is planar trigonal. The trithiocarbonate CS3 group resulted from insertion of CS2 into Cu-S bond is approximately coplanar the mean C-S bond length of CS3 is 0.1712 nm. The structural characteristics and the factors influencing the insertion reaction are discussed in this paper.