TRANSITION-METAL COMPLEXES OF OLIGOTHIOETHER QUINOLYLOXY TERMINATED PODANDS .2. CRYSTAL AND MOLECULAR-STRUCTURE OF (1,8-BIS(QUINOLYLOXY)-3,6-DITHIAOCTANE)-COPPER(II) DIPERCHLORATE TRIHYDRATE

The synthesis of the new ligand 1,8-bis(quinolyloxy)-3,6-dithiaoctane (1) and the corresponding Cu(II), Cu(I) and Co(II) complexes is report ed. The crystal and molecular structure of the copper(II) complex, [Cu (1)](ClO4)2.3H2O, has been determined by X-ray diffraction methods. Th e complex crystallizes in the orthorhombic space group Fddd, with cell data Z = 16, a = 20.326(2), b = 20.879(3) and c = 28.308(4)angstrom. The structure consists of discrete [Cu(1)]2+ cations separated by (str ucturally disordered) perchlorate anions and three lattice water molec ules per cation. The coordination geometry about the copper atom is ps eudo-octahedral with the quinoline nitrogen and thioether sulfur atoms at the equatorial positions and the ether oxygen atoms at the axial p ositions. H-1 NMR line-broadening experiments indicate that electron-t ransfer self-exchange reactions between the copper(I) and copper(II) c omplexes of (1) is immeasurably slow on the NMR time-scale. The coordi nation chemistry of (1) is compared with its oxygen analogue, 1,8-bis( quinolyloxy)-3,6-dioxaoctane.