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-2κ(2) C-(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-1κ(6) O){μ(3)-(2α,2β)-5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]porphyrinato-1κO (5):2κ(4) N,N′,N′′,N′′′:1′κO (15)}cobalt(III)potassium] dihydrate], {[CoK(CN)(2)(C(12)H(24)O(6))(C(64)H(64)N(8)O(4)]·2H(2)O}(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.