Synthesis and Structural Characterization of [2,3-Naphtho-12- nitro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato]nickel(II)

The title compound was obtained by complexation of the corresponding nitro-chlorin with Ni(OAc)2×4H2O. During this process at 100°C the spontaneous oxidation of chlorin to porphyrin was observed. The product, Ni(II)C52H11F20N5O2·H2O·CH2Cl2, crystallizes in the triclinic system, space group P1, with cell constants a = 7.5855(2) Å, b = 15.5580(4) Å, c = 21.1029(5) Å, α = 91.675(2)°, ß = 96.294(2)°, . = 96.212(2)°, γ = 2458.79(11) Å3, and Z = 2. The nickel(II) atom is coordinated by four N-atoms from porphyrin core and the NiN4 unit adopts a square-planar geometry. The Ni–N bond lengths are within the range 1.887(4)–1.931(4) Å, while the average N–Ni–N angles are 178.83 and 90.01°. The porphyrin core 20-membered ring adopts non-planar saddle conformation and the four pentafluorophenyl substituents are oriented nearly perpendicular to the macrocyclic porphyrin system. The molecular packing in the crystal is influenced by p···p interactions of the naphthalene rings and weak intermolecular C–H···F dipole–dipole attractions linking the Ni(II)-porphyrin complex and dichloromethane molecules.