Highly nonplanar macrocyclic ring conformation in the crystal structures of Ni(II) and Cu(II) octaphenylporphyrins

Abstract

Crystal structures of solvated highly nonplanar nickel(II) and copper(II) complexes of 2,3,5,10,12,13,15,20-octaphenylporphyrin are determined by single crystal XRD analysis. The macrocycles in these systems exhibit mainly ruffled and saddled conformations. The average displacement of the pyrrole carbon atom ΔCb from the mean plane of the porphyrin ring is as high as ±0.70 Å. The Hirshfeld surface analysis of both structures reveals mainly H…H (57—59 %) intermolecular short contacts with a smaller contribution from C…H (16—22 %) and H…Cl (11—19 %) interactions. The present work suggests that the nonplanarity of the macrocycle in NiTPP(Ph)4 is largely due to the core Ni(II) ion and less influenced by intermolecular interactions/crystal packing forces, whereas the opposite is true in the case of the nonplanar CuTPP(Ph)4 structure.