Molecular and crystal structure of dichloro(5,10,15,20-tetraphenylporphinato)phosphorus(V) chloride dichloromethane solvate

Abstract

The crystal structure of dichloro(5,10,15,20-tetraphenylporphinato)phosphorus(V) chloride dichloromethane solvate has been determined by X-ray diffraction at ambient temperature. A saddle shape of the meso-tetraphenylporphinate disc is attributed to marked S 4 deviation from planarity. The mode of the torsion of four phenyl rings around the CC bonds connecting these rings to the respective meso carbon atoms are also of S 4 character. The phosphorus atom lies just in the mean plane of the porphinate nitrogen atoms. The PN bond distances range from 1.804(3) to 1.821(3) Å, which are shorter than those observed in [P(OH) 2(tpp)] + (1.870–1.916 Å), while the axial PCl bond distances [2.149(1) and 2.153(1) Å] are significantly longer than the distance expected for the normal covalent PCl bond (2.10 Å). This phosphorus porphyrin reveals characteristic features peculiar to the structure of metalloporphyrins with the smallest-sized central cations.