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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 …