Crystal and molecular structure of dihydroxo(5,10,15,20-tetraphenylporphinato)phosphorus(V) hydroxide dihydrate

Abstract

The structure of dihydroxo(5,10,15,20-tetraphenylporphinato)phosphorus(V) hydroxide dihydrate, (C4H3,,02P+)(OH-).2H20,
\nhas been determined from three-dimensional diffractometer data. It crystallizes in the monoclinic space group P2,/c with
\na = 14.636 (4) A, b = 13.953 (3) A, c = 17.592 (4) A, /3 = 90.21 (2)", and Z = 4. The structure was solved by heavy-atom
\nmethods and refined by full-matrix least-squares methods to yield a final R factor of 0.090. This is the first reported structural
\nanalysis of a "metalloporphyrin" where the central ion is a nonmetal. The coordination geometry is distorted octahedral
\nwith the phosphorus atom displaced 0.09 8, from the mean plane of the pyrrole nitrogen atoms. The P-N bond lengths
\nrange from 1.87 (1) to 1.92 (1) 8,. The two P-O distances are 1.644 (8) and 1.545 (8) 8,. The porphyrin ring shows marked
\nS4 deviations from planarity. There is extensive hydrogen bonding between the axial hydroxyl groups, the hydroxide counterion
\nand the waters of hydration forming quasi-linear hydrogen-bonded polymers.