Crystal structure of bis­{μ2-22′-(410-dimethyl-14710-tetra­aza­cyclo­dodecane-17-di­yl)bis(meth­yl­ene)bis­(4-oxo-4H-pyran-3-olato)}dicobalt­calcium bis­(perchlorate) 1.36-hydrate

摘要

The title compound, [CaCo2(C22H30N4O6)2](ClO4)2·1.36H2O or {Ca[Co(H–2 >L1)]2}·2ClO4·1.36H2O {where >L1 is 4,10-bis­[(3-hy­droxy-4-pyron-2-yl)meth­yl]-1,7-dimethyl-1,4,7,10-tetra­aza­cyclo­dodecane}, is a trinuclear complex whose asymmetric unit comprises a quarter of the {Ca[Co(H–2 >L1)]2}²⁺ trinuclear complex, half of a perchlorate ion and 0.34-water mol­ecules. In the neutral [Co(H–2 >L1)] moiety, the cobalt ion is hexa­coordinated in a trigonal–prismatic fashion by the surrounding N₄O₂ donor set. A Ca²⁺ cation holds together two neutral [Co(H_–2 >L1)] moieties and is octa­coordinated in a distorted trigonal–dodeca­hedral fashion by the surrounding O atoms belonging to the deprotonated oxide and carbonyl groups of two [Co(H_–2 >L1)] units. The coordination of the Co^II cation preorganizes >L1 and an electron-rich area forms, which is able to host hard metal ions. The comparison between the present structure and the previously published ones suggests a high versatility of this ligand; indeed, hard metal ions with different nature and dimensions lead to complexes having different stoichiometry (mono- and dinuclear monomers and trinuclear dimers) or even a polymeric structure. The heterotrinuclear Co^II–Ca^II–Co^II complexes are connected in three dimensions via weak C—H⋯O hydrogen bonds, which are also responsible for the inter­actions with the perchlorate anions and the lattice water mol­ecules. The perchlorate anion is disordered about a twofold rotation axis and was refined giving the two positions a fixed occupancy factor of 0.5. The crystal studied was refined as a two-component inversion twin [BASF parameter = 0.14 (4)].