Acta Crystallographica Section C

Crystal Structure Communications

Volume 59, Part 4 (April 2003)

metal-organic compounds

Acta Cryst. (2003). C59, m132-m135 [ doi:10.1107/S0108270103004384 ]

The first phosphite complex of a metalloporphyrin

O. Q. Munro and G. L. Camp

Abstract: (Diphenyl phosphite- [kappa] O)(5,10,15,20-tetraphenylporphyrinato- [kappa] ⁴N)manganese(III) hexafluoroantimonate(V), [Mn(C₄₄H₂₈N₄)(C₁₂H₁₁O₃P)](SbF₆), is the first example of a structurally characterized diaryl or dialkyl phosphite complex of a metal-porphyrin ion. The axial phosphite ligand binds to the Mn^III ion via the P=O O atom, affording a nominally five-coordinate complex with an Mn-O distance of 2.120 (4) Å. The mean porphyrin Mn-N distance is 2.000 (4) Å and the Mn^III ion is displaced from the 24-atom porphyrin mean plane by 0.1548 (13) Å towards the axial O atom. The porphyrin adopts a marked saddle conformation, with a small domed component. The saddle distortion of the porphyrin ligand reflects the tight back-to-back dimers formed in the lattice by pairs of neighboring cations. The `non-covalent' dimers in the lattice exhibit an unusual (weak) [eta] ²-type coordination of a pyrrole C=C bond from a neighboring molecule, with Mn^IIIC distances of 3.697 (5) and 3.537 (5) Å.

Formula: [Mn(C₄₄H₂₈N₄)(C₁₂H₁₁O₃P)](SbF₆)