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-octathiacyclotetracosane; [28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclooctacosane)

The complexes [(HgBr2)2([24]aneS8)], [{Ag2([24]aneS8)(CF3SO3)2(MeCN)2}∞] ([24]aneS8 = 1,4,7,10,13,16,19,22-octathiacyclotetracosane), [Au2([28]aneS8)][PF6]2 and [Ag2([28]aneS8)][NO3]2 ([28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclooctacosane) have been synthesized, characterised and their crystal structures determined. In [(HgBr2)2([24]aneS8)] two HgBr2 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(1)–S(7) 2.581(4) A. In [{Ag2([24]aneS8)(CF3SO3)2(MeCN)2}∞] infinite polymeric chains of [24]aneS8 molecules and silver(I) ions are observed, Ag(1)–S(1) 2.5400(14), Ag(1)–S(4) 2.627(2), Ag(1)–S(7i) 2.556(2), Ag(1)–S(10i) = 2.5984(14) A (i x, y + 1, z), with the large-ring crown acting as a bidentate ligand to two tetrahedral silver(I) centres. In contrast, [Ag2([28]aneS8)][NO3]2 is a binuclear complex with each AgI co-ordinated to four S-donors of the macrocyclic ligand, Ag(1)–S(1) 2.5257(12), Ag(1)–S(4) 2.6314(11), Ag(1)–S(8) 2.8932(12), Ag(1)–S(11) 2.4921(11) A, and one NO3– completing a very distorted trigonal bipyramidal co-ordination sphere, Ag(1)–O(2) 2.759(3) A. In [Au2([28]aneS8)][PF6]2 two gold(I) centres are complexed tetrahedrally within the octathiamacrocycle in a [2 + 2] manner, Au(1)–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) A. The redox properties of the complexes are described.