SYNTHESIS OF COPPER AND SILVER COMPLEXES WITH PENTADENTATE N,S AND HEXADENTATE N,O CHELATE LIGANDS - CHARACTERIZATION AND CRYSTAL-STRUCTURES OF (CU-2[C6H4(SO2)NC(O)](2)(C5H5N)4), (CU-2[C5H3N(CHNC6H4SCH3)(2)](2))(PF6)2, AND (AG[C5H3N(CHNC6H4SCH3)(2)])PO2F2

In the course of the reaction of copper(II)-acetate monohydrate with 2 ,2'-bisbenzo[d][1,3]thiazolidyl in methanol the organic component is t ransformed to N,N'-bis-(2-thiophenyl)ethanediimine and subsequently ox idized to the N,N'-bis-(2-benzenesulfonyl)ethanediacid H4BBSED, which coordinates in its deprotonated form two Cu2+ ions. Crystallisation fr om pyridine/n-hexane yields [Cu-2(BBSED)(py)(4)].MeOH. It forms tricli nic crystals with the space group P1 and a = 995.5(2) pm, b = 1076.1(3 ) pm, c = 1120.7(2) pm, alpha = 104.17(1)degrees, beta = 105.28(1)degr ees, gamma = 113.10(1)degrees and Z=1. In the centrosymmetrical dinucl ear complex the copper ions are coordinated in a square-pyramidal arra ngement by three nitrogen and two oxygen atoms. The Jahn-Teller effect causes an elongation of the axial bond by approximately 30 pm. The re actions' of the pentadentate ligand ,6-Bis-[(2-methylthiophenyl)-2-aza ethenyl]pyridine BMTEP with salts of copper(I), copper(II) and silver( I) yield the complexes [Cu-2(BMTEP)(2)](PF6)(2), [Cu(BMTEP)]X-2 (X=BF4 -, ClO4- and [Ag(BMTEP)IX (X = PO2F2-, ClO4-). [Cu-2(BMTEP)(2)](PF6)(2 ) crystallizes from acetone/diisopropyl-ether in form of monoclinic cr ystals with the space group C2/c, and a = 1833.2(3) pm, b = 2267.30(14 ) pm, c = 1323.5(2) pm, beta = 118.286(5)9 and Z = 4. In the dinuclear complex cation with the symmetry C-2 the copper ions are tetrahedrall y coordinated by two bridging BMTEP ligands. The Cu-Cu distance of 278 .3 pm can be interpreted with weak Cu-Cu interactions which also manif est itself in a temperature independent paramagnetism of 0.45 B.M.. Th e monomeric silver complex [Ag(BMTEP)]PO2F2 crystallizes from acetone/ thf in the triclinic space group P (1) over bar with a = 768.7(3)pm, b = 1074.0(5)pm, c = 1356.8(5)pm, alpha = 99.52(2)degrees, beta = 96.83 (2)degrees, gamma = 99.83(2)degrees and Z = 2. The central silver ion is coordinated by one sulfur and three nitrogen atoms of the ligand in a planar, semicircular arrangement. The bond lengths Ag-N = 240.4-261 .7 and Ag-S = 257.2 pm are significantly elongated in comparison with single bonds.