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 ΔC_b 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.