The asymmetric unit of the title compound, [Cd2Na2(N3)2(C44H28N4)2(C12H24O6)2], consists of one half of the dimeric complex; the tetra­nuclear mol­ecule lies about an inversion centre. The CdII atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetra­phenyl­porphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the NaI atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (∼40%) and the crystal structure is stabilized by weak C—H⋯π inter­actions. The mol­ecular structure features weak intra­molecular hydrogen bonds: two O—H⋯O inter­actions within the 18-crown-6 mol­ecule and one C—H(18-crown-6)⋯N(azido) contact.

The title compound, [Cd(C44H28N4)(H2O)]·(C12H24O6), was made by the reaction of the [Cd(TPP)] with an excess of 18-crown-6 in chloro­benzene (where TPP is tetra­phenyl­porphyrinate). The CdII cation is chelated by a TPP anion and coordinated by a water mol­ecule in a distorted N4O square-pyramidal geometry, the CdII cation being displaced by 0.7533 (9) Å from the mean plane of four N atoms of TPP anion. The porphyrin core presents a significant distortion, the maximum atomic deviation from the 24-atom mean plane is 0.1517 (2) Å. The 18-crown-6 mol­ecule is linked with the CdII complex via classical O—H⋯O hydrogen bonds. In the crystal, weak C—H⋯π inter­actions link the complex and 18-crown-6 mol­ecules into a three-dimensional supra­molecular architecture.

The reaction of CoII(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-2κ2 C-(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-1κ6 O){μ3-(2α,2β)-5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]porphyrinato-1κO 5:2κ4 N,N′,N′′,N′′′:1′κO 15}cobalt(III)potassium] dihydrate], {[CoK(CN)2(C12H24O6)(C64H64N8O4]·2H2O}n. The CoIII ion lies on an inversion center, and the asymmetric unit contains one half of a [CoIII(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 KI ion lies on an inversion center. The CoIII ion is hexa­coordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The KI 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.