metal-organic compounds
Open access
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-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 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—HO and O—HN hydrogen bonds, as well as weak C—HO, O—Hπ and C—Hπ interactions into a three-dimensional supramolecular architecture.
data reports
Open access
The reaction of [CoIII(TPP)Cl] (TPP is the dianion of 5,10,15,20-tetraphenylporphyrin) with an excess of 4-nitroaniline in dichloromethane leads to the title compound, [CoIII(C44H28N4)(C6H6N2O2)2]Cl·CH2Cl2. The CoIII ion lies on an inversion centre and is octahedrally coordinated by two N atoms of the NH2 groups of the two 4-nitroaniline trans-axial ligands and four pyrrole N atoms of the porphyrin. The asymmetric unit contains one half of the [CoIII(TPP)(4-nitroaniline)2]+ ion complex, one chloride counter-ion (lying on a twofold rotation axis) and one half dichloromethane solvent molecule, where the C atom lies on a twofold rotation axis. The average equatorial Co—N(pyrrole) distance (Co—Np) is 1.982 (2) Å and the axial Co—N(4-nitroaniline) bond length is 2.006 (2) Å. The crystal packing is stabilized by an N—HCl hydrogen bond between the N atom of the amino group of the 4-nitroaniline axial ligand and the chloride counter-ion. The supramolecular architecture is further stabilized by weak C—Hπ interactions.