(2,5-Dimethylimidazole){N,N′,N′′,N′′′-[porphyrin-5,10,15,20-tetrayltetra(2,1-phenylene)]tetrakis(pyridine-3-carboxamide)}manganese(II) chlorobenzene disolvate

In the title compound, the central MnII ion is coordinated by four pyrrole N atoms of the porphyrin core in the basal sites and one N atom of the 2,5-dimethylimidazole ligand in the apical site. Two chlorobenzene solvent molecules are also present in the asymmetric unit.

In the title compound, [Mn(C 68 H 44 N 12 O 4 )(C 5 H 8 N 2 )]•2C 6 H 5 Cl, the central Mn II ion is coordinated by four pyrrole N atoms of the porphyrin core in the basal sites and one N atom of the 2,5-dimethylimidazole ligand in the apical site.Two chlorobenzene solvent molecules are also present in the asymmetric unit.Due to the apical imidazole ligand, the Mn atom is displaced out of the 24-atom porphyrin mean plane by 0.66 A ˚.The average Mn-N p (p = porphyrin) bond length is 2.143 (8) A ˚, and the axial Mn-N Im (Im = 2,5-dimethylimidazole) bond length is 2.171 (8) A ˚.The structure displays intermolecular and intramolecular N-H� � �O, N-H� � �N, C-H� � �O and C-H� � �N hydrogen bonding.The crystal studied was refined as a two-component inversion twin.
The asymmetric unit of the title compound contains one (2,5-dimethylimidazole){N,N 0 ,N 00 ,N 000 -[porphyrin-5,10,15,20tetrayltetra(2,1-phenylene)]tetrakis(pyridine-3-carboxamide)}manganese(II) molecule and two chlorobenzene solvate molecules.As illustrated in Fig. 1, the metal atom exhibits a five-coordinate structure (Table 1) with a significant metal out-of-plane displacement of 0.66 A ˚, indicative of the high-spin state of Mn II .Additional quantitative information on the structure is provided in supplementary Fig. 1, presenting the displacements of each porphyrin core atom from the 24-atom mean plane.Averaged values of the chemically unique bond lengths (A ˚) and angles ( � ) are also displayed.The hindered 2,5-dimethylimidazole ligand may also contribute to the large out-of-plane displacement for the metal atom.The dihedral angle formed by the 2,5-dimethylimidazole axial ligand plane and the closest Mn-N p vector is 37.3 � .The average N p -Mn-N p angle is 86.0 (7) � and the axial Mn-N Im bond length is 2.171 (8) A ˚.The average Mn-N p distance of 2.143 (8) A ˚is a typical value for high-spin manganese porphyrin derivatives.

Synthesis and crystallization
All experimental manipulations in this work were conducted under an argon atmosphere using a double-manifold vacuum line, Schlenkware and cannula techniques.With the exception of the solvent used in column chromatography, all solvents utilized in the experimental procedures were subjected to anhydrous and anaerobic conditions.Chlorobenzene, benzene and n-hexane were distilled over P 2 O 5 and potassium-sodium alloy, respectively.All solvents employed in the anhydrous data reports Figure 1 The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.The solvent molecules have been omitted for clarity.

Figure 2
Intra-and inter-molecular interactions in the crystal structure of the title compound.and anaerobic operations (Schlenk system) underwent the freeze-pump-thaw method three times before use.The precursors H 2 (TPyPP), [Mn(TPyPP)]Cl, and [Mn(TPyPP)] OH were prepared following literature methods (Gunter et al., 1984), with slight modifications.
[Mn(TPyPP)]OH (10 mg) was dried under vacuum for 30 minutes and dissolved in 5 ml of benzene.After adding 1 ml of ethanethiol, the solution was stirred for 1 day and then evacuated under vacuum to yield a purple powder.The resulting purple solid of [Mn(TPyPP)] (10 mg) was dried for 60 minutes, and excess 2,5-dimethylimidazole in PhCl (5 ml) was added using a cannula.The mixture was stirred for 1 h and transferred into glass tubes, which were layered with n-hexane as a non-polar solvent.Several weeks later, X-ray quality crystals of the title compound in the form of black blocks were collected.

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
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å

Figure 3 A
Figure 3A view of the packing of the title compound.H atoms have been omitted for clarity.

Table 3
Experimental details.