COPPER THIOETHER CHEMISTRY - THE SYNTHESIS AND SINGLE-CRYSTAL X-RAY STRUCTURES OF [CU2([18]ANES6)(NCME)2](CLO4)2 AND [CU([9]ANES3)(ASPPH3)](CLO4)

Reaction of [18]aneS6 with two molar equivalents of [Cu(NCMe)4](ClO4) in CH2Cl-2-MeCN affords the binuclear copper(I) complex [Cu2([18]aneS6)(NCMe)2](ClO4)2. The single crystal X-ray structure of the complex shows a centrosymmetric cation with two tetrahedral copper(I) centres each coordinated to three thioether S-donors of [18]aneS6, Cu-S(1) = 2.3200(15), Cu-S(4) = 2.3415(16), Cu-S(7) = 2.3250(15) angstrom, and to one MeCN molecule, Cu-N(1) = 1.939(5) angstrom, to give an overall Ns3-donation at the metal centres. Additionally, S(7') shows a long-range interaction, Cu...S(7') = 3.318(2) angstrom thus distorting the coordination geometry of the metal ion towards trigonal bipyramidal. The metal-metal separation of 4.428(2) angstrom suggests that there is no significant interaction between the copper centres of the dimer. Reaction of [9]aneS3 with one molar equivalent of [Cu(NCMe)4](ClO4) in refluxing MeCN in the presence of ligands, L, affords the adducts [Cu([9]aneS3)L]+ (L = PPh3, AsPh3). The single crystal X-ray structure of the complex [Cu([9]aneS3)(AsPh3)](ClO4) shows tetrahedral AsS3 coordination at copper(I) with [9]aneS3 bound facially to the metal centre, Cu-S = 2.303(6), Cu-As = 2.322(4) angstrom.