Cadmium(II), bismuth(III), lead(II) and thallium(I) crown thioether chemistry: synthesis and crystal structures of [(CdI2)2([24]aneS8)], [(BiCl3)2([24]aneS8)], [Pb2([28]aneS8)][ClO4]4 and [Tl([24]aneS8)]PF6 ([24]aneS8 = 1,4,7,10,13,16,19,22-octathiacyclotetracosane; [28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclooctacosane)

Abstract

The complexes [(CdI₂)₂([24]aneS₈)], [(BiCl₃)₂([24]aneS₈)], [Pb₂([28]aneS₈)][ClO₄]₄ and [Tl([24]aneS₈)]PF₆ ([24]aneS₈ = 1,4,7,10,13,16,19,22-octathiacyclotetracosane, [28]aneS₈ = 1,4,8,11,15,18,22,25-octathiacyclooctacosane) have been prepared, characterized and their crystal structures determined. In [(CdI₂)₂([24]aneS₈)] two CdI₂ units are bound to the macrocycle forming a discrete centrosymmetric binuclear complex, Cd(1)–I(1) 2.7551(11), Cd(1)–I(2) 2.6944(8), Cd(1)–S(1) 2.817(2), Cd(1)–S(4) 2.615(2), Cd(1)–S(7) 2.927(2) Å. In [(BiCl₃)₂([24]aneS₈)] two BiCl₃ units are weakly bonded to the thioether crown, Bi–S 3.134(2)–3.313(2) Å, to give a discrete centrosymmetric binuclear complex with the two metal centres disposed on opposite sides of the mean plane of the macrocycle. In [Pb₂([28]aneS₈)][ClO₄]₄ an S₄O₄ co-ordination is realized at each Pb^II sitting in the macrocyclic cavity. The two Pb^II are bridged by two ClO₄^– ions, Pb–S 2.861(2)–2.998(2), Pb–O 2.701(7)–2.936(6) Å. In contrast, [Tl([24]aneS₈)]PF₆ adopts a polymeric structure in which each Tl^I bridges two thioether crowns to give an infinite sinusoidal chain. The [S₄ + S₄] co-ordination sphere at the metal centre is satisfied by two half ligands in a sandwich arrangement, Tl–S 3.2413(11)–3.4734(14) Å.