A range of divalent metal complexes (1–10) of 1,10-dithia-18-crown-6 (L) were synthesised in benzonitrile and structurally characterised. In particular cases (Cd, Hg and Pb), the anion effect on the resulting structures was investigated. The calcium(II) complex [Ca(L)(ClO4)2] (1) for L, adopting an ‘egg-in-nest’ conformation was isolated. The calcium centre is six-coordinate with a distorted trigonal prismatic geometry, being bound to four oxygens of L and two perchlorato ligands. When Co(ClO4)2·6H2O was employed, the purple complex [Co(L)(H2O)3]2(ClO4)4 (2a) with a distorted octahedral geometry was obtained as a kinetic product, which then transformed to the solvato-complex [Co(C6H5CN)4(H2O)2](ClO4)2 (2b, yellow) as a thermodynamic product. In contrast to 2a, the reaction with Cu(ClO4)2·6H2O afforded an anion-coordinated complex [Cu(L)(ClO4)2]·2C6H5CN (3). In 3, the copper centre is also six-coordinate, being bound to two oxygens and two sulfurs from L, in which the distorted octahedral geometry is completed by two perchlorato ligands. Reaction of L with Zn(ClO4)2·6H2O yielded the mononuclear species [Zn(L)(H2O)3]2(ClO4)4 (4), in which the octahedral geometry of the zinc(II) is almost same as that of 2a. L reacts with CdX2 (X = ClO4 and NO3) to yield [Cd(L)(ClO4)2] (5) and [Cd(L)(NO3)]2[Cd(NO3)4] (6), respectively. In perchlorato-complex 5, all six donors in L participate in the coordination sphere, in which the eight-coordinated ‘tight and bent’ conformation is completed by two perchlorate ions, adopting a dicapped trigonal prismatic geometry. Interestingly, the nitrato-complex 6 features three separated units of formula [Cd(L)(NO3)]2[Cd(NO3)4]: two macrocyclic complex cation units and one cadmium quadru-nitrato complex anion unit. In the reaction with HgX2 (X = ClO4 and NO3), L afforded an unusual triple-decker type dinuclear complex [Hg2(L)3](ClO4)4 (7) with 3 : 2 (L : M) stoichiometry and a 1 : 1 complex [Hg(L)(NO3)2]·2H2O (8) with an eight-coordinate mercury centre, adopting a distorted hexagonal bipyramidal geometry. L reacts with PbX2 (X = ClO4 and NO3) to yield [Pb(L)(ClO4)2] (9) and [Pb(L)(NO3)2] (10). In 9, the lead(II) is six-coordinate, being bound to four oxygens, in which the distorted octahedral geometry is completed by two perchlorato ligands. In 10, the lead(II) coordinates to four oxygens together with two bidentate nitrato-ligands to yield an overall metal coordination geometry of eight, adopting the ‘egg-in-nest’ conformation again.