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)

The complexes [(CdI2)(2)([24]aneS(8))], [(BiCl3)(2)([24]aneS(8))], [Pb-2([28]aneS(8))][ClO4](4) and [T1([24]aneS(8))]PF6 ([24]aneS(8) = 1,4,7,10,13,16,19,22-octathiacyclotetracosane [28]aneS(8) = 1,4,8,11,15,18,22,25-octathiacyclooctacosane) have been prepared, characterized and their crystal structures determined. In [(CdI2)(2)([24]aneS(8))] two CdI2 units are bound to the macrocycle forming a discrete centrosymmetric binuclear complex, Cd(1)-I(I) 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) Angstrom. In [(BiCl3)(2)([24]aneS(8))] two BiCl3 units are weakly bonded to the thioether crown, Bi-S 3.134(2)-3.313(2) Angstrom, to give a discrete centrosymmetric binuclear complex with the two metal centres disposed on opposite sides of the mean plane of the macrocycle. In [Pb-2([28]aneS(8))][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) Angstrom. In contrast, [TI([24]aneS(8))]PF6 adopts a polymeric structure in which each TP bridges two thioether crowns to give an infinite sinusoidal chain. The [S-4 + S-4] co-ordination sphere at the metal centre is satisfied by two half ligands in a sandwich arrangement, TI-S 3.2413(11)-3.4734(14) Angstrom.