A one-dimensional polymeric cobalt(III)–potassium complex with 18-crown-6, cyanide and porphyrinate ligands

The reaction of Co^II(TpivPP) {TpivPP is the dianion of 5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]por­ph­yrin} with an excess of KCN salts and an excess of the 18-crown-6 in chloro­benzene leads to the polymeric title compound catena-poly[[dicyanido-2κ²C-(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-1κ⁶O){μ₃-(2α,2β)-5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]porphyrinato-1κO⁵:2κ⁴N,N′,N′′,N′′′:1′κO¹⁵}cobalt(III)potassium] dihydrate], {[CoK(CN)₂(C₁₂H₂₄O₆)(C₆₄H₆₄N₈O₄]·2H₂O}_n. The Co^III ion lies on an inversion center, and the asymmetric unit contains one half of a [Co^III(2α,2β-TpivPP)(CN)₂]⁻ ion complex and one half of a [K(18-C-6]⁺ counter-ion (18-C-6 is 1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne), where the K^I ion lies on an inversion center. The Co^III ion is hexa­coordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The K^I ion is chelated by the six O atoms of the 18-crown-6 mol­ecule and is further coordinated by two O atoms of pivalamido groups of the porphyrin ligands, leading to the formation of polymeric chains running along [011]. In the crystal, the polymeric chains and the lattice water mol­ecules are linked by N—H...O and O—H...N hydrogen bonds, as well as weak C—H...O, O—H...π and C—H...π inter­actions into a three-dimensional supra­molecular architecture.