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In the crystal structure of the title compound, [Co(H(2)O)(6)](2)(C(24)H(12)O(16)S(8))·H(2)O, the thia-calix[4]arenetetra-sulfonate (= TCAS(4-)) anions adopt a cone-type conformation with an additional water mol-ecule as a guest mol-ecule in the hydro-phobic cavity. The TCAS(4-) anions are arranged in layers in an up-down fashion. These anionic layers alternate with cationic layers consisting of rather regular octahedral cations (symmetry m). Several medium O-H⋯O hydrogen-bond inter-actions exist between the aqua ligands of the [Co(H(2)O)(6)](2+) cations and the O atoms of the sulfonate groups. In addition to the two crystallographically different Co atoms, two S and four O atoms are situated on mirror planes.

Bis[hexaaquacobalt(II)] 25,26,27,28-tetrahydroxy-2,8,14,19-tetrathiacalix[4]arene-5,11,17,23-tetrasulfonate monohydrate