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

The title compound, [Ni(C48H24N8)(C5H5N)(2)].2CH(4)O, is a high-spin bis(pyridine)-Ni-II derivative of an antipodally beta-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 D-2h. The core of the tpp(CN)(4), porphyrin dianion is essentially planar. The high-spin state of the Ni-II cation leads to a lengthening of the Ni-N(pyrrole) bond distances relative to those present in the low-spin [Ni(II)tpp] derivative. Moreover, the electron-withdrawing beta-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.