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The first phosphite complex of a metalloporphyrin.

(Diphenyl phosphite-kappaO)(5,10,15,20-tetraphenylporphyrinato-kappa(4)N)manganese(III) hexafluoroantimonate(V), [Mn(C(44)H(28)N(4))(C(12)H(11)O(3)P)](SbF(6)), 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) A. The mean porphyrin Mn-N distance is 2.000 (4) A and the Mn(III) ion is displaced from the 24-atom porphyrin mean plane by 0.1548 (13) A 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(III).C distances of 3.697 (5) and 3.537 (5) A.