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

The title compound, [Ni(C₄₈H₂₄N₈)(C₅H₅N)₂].2CH₄O, 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_2 h. 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^IItpp] 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.

-1