μ-Oxido-bis[(5,10,15,20-tetraphenylporphyrinato-κ4 N,N′,N′′,N′′′)manganese(III)]

The oxido-bridged dinuclear complex, [Mn(TPP)]2O, has an Mn—O distance of 1.7600 (3) Å, an Mn—O—Mn bridging angle of 176.1 (2)°, and exhibits point group symmetry 2.

l-Oxido-bis [(5,10,15,20-tetraphenylporphyrinatoj 4 (C 44 H 28 N 4 ) 2 O], the two pentacoordinate manganese(III) ions are bridged by a single oxido ligand, with an Mn-O distance of 1.7600 (3) Å and an Mn-O-Mn bridging angle of 176.1 (2) . The bridging O 2À ligand is located on a twofold rotation axis, resulting in point group 2 for the entire complex. The Mn III atom is displaced out of the 24-atom mean plane of the porphyrine entity by 0.52 Å . C-HÁ Á Á andinteractions help to stabilize the molecular packing within the crystal structure.

data reports
In the crystal structure of the title complex, the asymmetric unit contains one deprotoanted porphyrin molecule located in general position and an oxygen atom on a twofold rotation axis (Wyckoff position 4a). Figs. 1 and 2 graphically represent the molecular structure of the title -oxido complex. As can be seen, the two pentacoordinate manganese(III) ions in [Mn(TPP)] 2 O are bridged by a single oxido ligand with an Mn-O distance of 1.7600 (3) Å and an Mn-O-Mn bridging angle of 176.1 (2) . The Mn1Á Á ÁMn1 0 separation [symmetry code: (') Àx + 1, Ày + 1, z) is 3.5180 (5) Å . More quantitative numerical information is given in Fig. 3, which contains the detailed displacement of each porphyrin core atom (in units of 0.01 Å ) from the 24-atom mean plane. The average Mn III -N porphyrin bond length in the porphinato core is 2.080 (1) Å .
The manganese atom is displaced by 0.52 Å from its 24-atom mean plane toward the bridging oxido ligand. The average value for the O-Mn-N porphyrin angle is 103 (2) . The two porphyrin rings are found to be nearly parallel to each other   Edge-view of the dinuclear complex of the title compound with displacement elliposids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity.

Figure 2
Top-view of the of the dinuclear complex of the title compound with displacement elliposids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. Primed atoms are generated by symmetry operation Àx + 1, Ày + 1, z. C-HÁ Á Á andinteractions are found between the packed molecules, which is illustrated in Fig. 4. As can be seen, the interplanar distance between the relevant centroids of the rings in thestacking interactions is 4.3548 (19) Å , with a slippage of 2.139 Å . The distance between H18 and the relevant centroids of the rings in the C-HÁ Á Á interactions is 2.89 Å with an angle of 161 . The molecular packing of the title compound is shown in Fig. 5.

Synthesis and crystallization
Unless otherwise noted, all experimental manipulations were performed under argon atmosphere using double-manifold vacuum lines, Schlenk ware and cannula techniques. Except for the solvent used in column chromatography, all solvents used in the experimental process were treated under anhydrous and anaerobic conditions with the pump-freeze-thaw method three times before use. Chlorobenzene and n-hexane were distilled over P 2 O 5 and potassium-sodium alloy, respectively. H 2 TPP and [Mn(TPP)]Cl were prepared according to literature protocols (Adler et al., 1967;Fleischer et al., 1971).
The title compound was prepared following a reported procedure (He et al., 2016). Solid [Mn(TPP)]Cl was dissolved in dichloromethane and then shaken vigorously three times with 3 M KOH solution. To remove the alkali, the above system was washed with water for an additional two times. To grow single crystals, [Mn(TPP)] 2 O (10 mg) was dissolved in 4 ml of chlorobenzene and cannula-transferred into 8 mm glass tubes, then carefully layered with hexanes before sealing the tubes. X-ray quality crystals were obtained several weeks later.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 1. The crystal studied was refined as an inversion twin.

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refined as a 2-component inversion twin.