A series of soluble, discrete homo and heteroleptic Ca(II) complexes of hexanuclear sulfidochloride rhenium clusters, [Ca(X)n(Y)m][Re6S6Cl8], (n=6, m=0, X=DMF, THF, DMSO; n=4, m=3, X=MeCN, Y=THF, dioxane) and the 1D co-ordination polymer [Ca(MeCN)3(OH2)2(

Six homo- and heteroleptic calcium complexes involving different ligands such as dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofurane, dioxane or water and the hexanuclear sulfidochloride rhenium cluster [Re6S6Cl8]2− as counter-ion have been synthesised and structurally characterised by X-ray diffraction on single crystals. The coordination geometry around the calcium centre is of octahedral type within the three homoleptic complexes Ca(DMF)6 (1), Ca(THF)6 (2) and Ca(DMSO)6 (3), while in the heteroleptic complexes Ca2+ is seven-coordinated either in a monocapped trigonal prism (4 and 5) geometry or in a pentagonal bipyramid (6) one. The compound 6 is a 1D co-ordination polymer formed via Odiox⋯HOH hydrogen bonds.