(2,3,5,6-Tetrafluorophenolato-κO)(5,10,15,20-tetraphenylporphyrinato)iron(III)

The title compound, [Fe(C44H28N4)(C6HF4O)], is a porphyrin complex with iron(III) in fivefold coordination with a tetrafluorophenolate group as the axial ligand. The Fe atom and the phenolate ligand are disordered across the porphyrin ring with the two phenolates appearing to be roughly related by a center of symmetry. The occupancies of the two phenolate groups refined to 0.788 (3) for the major component and 0.212 (3) for the minor component. The structure shows extraordinary Fe displacements of 0.488 (4) (major) and 0.673 (4) Å (minor) from the 24-atom mean plane of the porphyrin. The Fe—Np distances range from 2.063 (4) to 2.187 (6) Å and the Fe—O distances are 1.903 (5) Å for major component and 1.87 (2) Å for minor component. The four phenyl groups attached to the porphyrin ring form dihedral angles of 63.4 (4), 49.6 (4), 62.4 (4), and 63.3 (4)° (in increasing numerical order) with the three nearest C atoms of the porphyrin ring. The major and minor component phenolate groups form dihedral angles of 24.9 (4)° and 24.8 (4)°, respectively, with the four porphyrin N atoms. The Fe⋯Fe distance between the two iron(III) atoms of adjacent porphyrin molecules is 6.677 (3) Å. No close intermolecular interaction was observed. The crystal studied was twinned by inversion, with a major–minor component ratio of 0.53 (3):0.47 (3).

The title compound, [Fe(C 44 H 28 N 4 )(C 6 HF 4 O)], is a porphyrin complex with iron(III) in fivefold coordination with a tetrafluorophenolate group as the axial ligand. The Fe atom and the phenolate ligand are disordered across the porphyrin ring with the two phenolates appearing to be roughly related by a center of symmetry. The occupancies of the two phenolate groups refined to 0.788 (3) for the major component and 0.212 (3) for the minor component. The structure shows extraordinary Fe displacements of 0.488 (4) (major) and 0.673 (4) Å (minor) from the 24-atom mean plane of the porphyrin. The Fe-N p distances range from 2.063 (4) to 2.187 (6) Å and the Fe-O distances are 1.903 (5) Å for major component and 1.87 (2) Å for minor component. The four phenyl groups attached to the porphyrin ring form dihedral angles of 63.4 (4), 49.6 (4), 62.4 (4), and 63.3 (4) (in increasing numerical order) with the three nearest C atoms of the porphyrin ring. The major and minor component phenolate groups form dihedral angles of 24.9 (4) and 24.8 (4) , respectively, with the four porphyrin N atoms. The FeÁ Á ÁFe distance between the two iron(III) atoms of adjacent porphyrin molecules is 6.677 (3) Å . No close intermolecular interaction was observed. The crystal studied was twinned by inversion, with a major-minor component ratio of 0.53 (3):0.47 (3).

Experimental
Crystal data [Fe(C 44

Experimental
To a CH 2 Cl 2 solution (20 ml) of [(TPP)Fe] 2 O (Helms et al., 1986) (0.025 g, 0.018 mmol) was added 2,3,5,6-tetrafluorophenol (0.045 g, 0.271 mmol) (purchased from Aldrich Chemical Company and used as received) under N 2 . After stirring for 1 h, the color of the solution changed from green brown to red. The solution was reduced to 2 ml and 10 ml hexane was added. The resulting dark brown precipitate was collected by filtration and dried under vacuum. A suitable rodshaped crystal was grown by slow evaporation of a CH 2 Cl 2 -hexane (1:2) solution of the complex at room temperature under N 2 .

Refinement
The iron and the phenolate ligand were disordered across the porphyrin ring. The occupancies of the metal and axial ligand refined to 0.787 (3) and 0.213 (3) for the primed and unprimed atoms. Rigid-body restraints were applied to the displacement parameters of both phenolate disorder components. The hydrogens were located by geometry assuming C-H distances of 0.95 Å, and were refined with a riding model. The hydrogen displacement parameters were set to 1.

Figure 1
The molecular structure of (TPP)Fe(OC 6 HF 4 ) with displacement ellipsoids drawn at the 35% probability level. H atoms and the minor disorder component are omitted for clarity.