THALLIUM THIOETHER CHEMISTRY - SYNTHESIS AND CRYSTAL-STRUCTURE OF [TL([9]ANES3)]PF6([9]ANES3 = 1,4,7-TRITHIACYCLONONANE), SHOWING INFINITE HELICES OF [TL([9]ANES3)]+ FRAGMENTS

Treatment of TINO3 with an excess of 1,4,7-trithiacyclononane ([9]aneS3) in MeCN followed by addition of NH4PF6 affords the 1:1 complex [Tl([9]aneS3)]PF6, which crystallises in the orthorhombic space group P2(1)2(1)2(1) with a = 7.7655(11), b = 8.3767(18), c = 20.838(4) angstrom and Z = 4 as determined by X-ray crystallography. The structure shows the trithia ligand bound facially to the Tl(l) centre, Tl-S(1) 3.114(3), Tl-S(4) 3.092(3) and Tl-S(7) 3.110(3) angstrom. A secondary interaction between the thallium and S(7') {in a neighbouring [Tl([9]aneS3)]+ unit at (1/2 + x, 1/2 - y, 1/2 - z)}, Tl-S(7') 3.431(3) angstrom, gives overall [3 + 1] thioether co-ordination at Tl(l). These contacts between cations related by the 2(1) screw axis parallel to a link [Tl([9]aneS3)]+ fragments to form infinite helices running in that direction. Further secondary interactions occur between the Tl(l) centre and the fluorines of three different PF6- counter ions, Tl...F(2) 3.228(8), Tl...F(4) 3.389(8), Tl...F(3) 3.246(8) and Tl...F(5) 3.272(9) angstrom, to give formally an eight-co-ordinate metal complex.