Bis(pyridine-N)(7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrinato)nickel(II) Dimethanol Solvate

Abstract

The title compound, [Ni(C48H24N8)(C5H5N)2].2CH4O, is a high-spin bis(pyridine)-NiII derivative of an antipodally β-pyrrole-tetracyano-substituted meso-tetraphenylporphyrin. The [Ni(py)2{tpp(CN)4}] molecule [py is pyridine and tpp(CN)4 is 7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrinato] lies on a crystallographic centre of symmetry, but its non-crystallographic symmetry is close to D2 h. The core of the tpp(CN)4 porphyrin dianion is essentially planar. The high-spin state of the NiII cation leads to a lengthening of the Ni—N(pyrrole) bond distances relative to those present in the low-spin [NiIItpp] derivative. Moreover, the electron-withdrawing β-pyrrole cyano substituents, which lie in the antipodal pyrrolic rings, cause an increase in the C7—C8 and the antipodal C7′—C8′ bond distances as well as an opening of the C6—N2—C9 and the antipodal C6′—N2′—C9′ bond angles.