Crystal structures of unsymmetrically mixed β-pyrrole substituted nickel(II)-meso-tetraphenylporphyrins

Crystal structures of solvated unsymmetrically substituted meso-tetraphenylporphyrins, 2,3,12,13,17-pentachloro-5,7,8,10,15,18,20-hepta-phenylporphyrin, H2TPP(Ph)(3)(Cl)(5), 1 and its nickel(II), NiTPP(Ph)(3)(Cl)(5), 2 were determined by single crystal XRD analysis. In addition, a new unsymmetrically substituted porphyrin, 2,3,12,13,17-pentacyano-5,7,8,10,15,18,20-heptaphenyl-porphinato nickel(II) complex, NiTPP(Ph)(3)(CN)(5), 3 complex was synthesized and its solvated structure was examined by crystallography. These porphyrins exhibited dramatic nonplanar conformation of the macrocycle as evidenced from the average displacement of the beta-pyrrole carbon (+/-Delta C-beta) from the mean plane of the porphyrin ring and the trend in nonplanarity varies in the order: 2 (1.189(5) angstrom) > 1 (1.036(6) angstrom) > 3 (0.895(6) angstrom). The normal-coordinate structural decomposition analysis of these structures revealed mainly saddle distortion of the macrocycle combined with small degree of ruffled or domed distortions. The Hirshfeld surface analysis of structures 1-3 revealed solvate dependent intermolecular contacts with varying degree of H center dot center dot center dot H (43-49%), C center dot center dot center dot H (17-19%), H center dot center dot center dot Cl (25-30%) and N center dot center dot center dot H (similar to 19%) contact contributions.