Mercury(II), silver(I) and gold(I) thioether crown chemistry:: Synthesis, electrochemistry and structures of [(HgBr2)2([24]aneS8)], [{Ag2([24]aneS8)(CF3SO3)2(MeCN)2}∞], [Ag2([28]aneS8)][NO3]2 and [Au2([28]aneS8)][PF6]2 ([24]aneS8 = 1,4,7,10,13,16,19,22-octathia-cyclotetracosane;: [28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclo-octacosane)

The complexes [(HgBr(2))(2)([24]aneS(8))], [{Ag(2)([24]aneS(8))(CF(3)SO(3))(2)(MeCN)(2)}(infinity)] ([24]aneS(8) = 1,4,7,10,13,16,19,22-octathiacyclotetracosane), [Au(2)([28]aneS(8))][PF(6)](2) and [Ag(2)([28]aneS(8))][NO(3)](2) ([28]aneS(8) = 1,4,8,11,15, 18,22,25-octathiacyclooctacosane) have been synthesized, characterised and their crystal structures determined. In [(HgBr(2))(2)([24]aneS(8))] two HgBr(2) units are bound to the macrocycle forming a discrete binuclear complex, Hg(1)-Br(1) 2.511(2), Hg(1)-Br(2) 2.588(2), Hg(1)-S(4) 2.835(4), Hg(l)-5(7) 2.581(4) Angstrom. In [{Ag(2)([24]aneS(8))-(CF(3)SO(3))(2)(MeCN)(2)}(infinity)] infinite polymeric chains of [24]aneS(8) molecules and silver(I) ions are observed, Ag(l)-S(1) 2.5400(14), Ag(1)-S(4) 2.627(2), Ag(1)-S(7(i)) 2.556(2), Ag(1)-S(10(i)) = 2.5984(14) Angstrom (i x, y + 1, z), with the largering crown acting as a bidentate ligand to two tetrahedral silver(I) centres. In contrast, [Ag(2)([28]aneS(8))][NO(3)](2) is a binuclear complex with each Ag(1) co-ordinated to four S-donors of the macrocyclic ligand, Ag(l)-S(1) 2.5257(12), Ag(1)-S(4) 2.6314(11), Ag(1)-S(8) 2.8932(12), Ag(l)-S(11) 2.4921(11) A, and one NO,- completing a very distorted trigonal bipyramidal co-ordination sphere, Ag(l)-O(2) 2.759(3) Angstrom. In [Au(2)([28]aneS(8))][PF(6)](2) two gold(I) centres are complexed tetrahedrally within the octathiamacrocycle in a [2 + 2] manner, Au(l)-S(1) 2.330(2), Au(1)-S(4) 2.789(2), Au(1)-S(8) 2.763(2), Au(1)-S(11) 2.338(2) Angstrom. The redox properties of the complexes are described.