μ3-Acetato-μ2-acetato-(dimethylformamide)pentakis(μ-N,2-dioxidobenzene-1-carboximidato)pentakis(1-methyl-1H-imidazole)pentamanganese(III)manganese(II)–diethyl ether–dimethylformamide–methanol–water (1/1/1/1/0.49)

The title compound, [Mn6(C7H4NO3)5(CH3CO2)2(C4H6N2)4.62(C3H7NO)1.38]·(C2H5)2O·C3H7NO·CH3OH·0.49H2O or MnII(OAc)2[15-MCMn(III)N(shi)-5](Me—Im)4.62(DMF)1.38·diethyl ether·DMF·MeOH·0.49H2O (where MC is metallacrown, −OAc is acetate, shi3− is salicylhydroximate, Me—Im is 1-methylimidazole, DMF is N,N-dimethylformamide, and MeOH is methanol), is comprised of five MnIII ions in the metallacrown ring and an MnII ion which is encapsulated in the central cavity. Four of the ring MnIII ions are six-coordinate with distorted octahedral geometries. Two of these MnIII ions have a planar configuration, while the other two MnIII have Λ absolute stereoconfiguration. The fifth MnIII is five-coordinated with distorted square-pyramidal geometry. Four of the ring MnIII ions each bind one 1-methylimidazole, while the final ring MnIII ion binds a DMF solvent molecule in an axial position and located in a trans position is either a Me—Im or a DMF molecule. The occupancy ratio of Me—Im to DMF is 0.62 (2) to 0.38 (2). The central MnII is seven-coordinate with a geometry best described as distorted face-capped trigonal–prismatic. DMF, diethyl ether, MeOH, and water molecules are located in the interstitial voids between the metallacrown molecules. The methanol molecule is positionally disordered [0.51 (1):0.49 (1)] and associated with a partially occupied water molecule [0.49 (1)]. This disorder is also associated with the positional disorder of the diethyl ether molecule [0.51 (1):0.49 (1)].

The title compound, [Mn 6 (C 7 H 4 NO 3 ) 5 (CH 3 CO 2 ) 2 -(C 4 H 6 N 2 ) 4.62 (C 3 H 7 NO) 1.38 ]Á(C 2 H 5 ) 2 OÁC 3 H 7 NOÁCH 3 OHÁ-0.49H 2 O or Mn II (OAc) 2 [15-MC Mn(III)N(shi) -5](Me-Im) 4.62 -(DMF) 1.38 Ádiethyl etherÁDMFÁMeOHÁ0.49H 2 O (where MC is metallacrown, À OAc is acetate, shi 3À is salicylhydroximate, Me-Im is 1-methylimidazole, DMF is N,N-dimethylformamide, and MeOH is methanol), is comprised of five Mn III ions in the metallacrown ring and an Mn II ion which is encapsulated in the central cavity. Four of the ring Mn III ions are six-coordinate with distorted octahedral geometries. Two of these Mn III ions have a planar configuration, while the other two Mn III have Ã absolute stereoconfiguration. The fifth Mn III is five-coordinated with distorted square-pyramidal geometry. Four of the ring Mn III ions each bind one 1methylimidazole, while the final ring Mn III ion binds a DMF solvent molecule in an axial position and located in a trans position is either a Me-Im or a DMF molecule. The occupancy ratio of Me-Im to DMF is 0.62 (2) to 0.38 (2). The central Mn II is seven-coordinate with a geometry best described as distorted face-capped trigonal-prismatic. DMF, diethyl ether, MeOH, and water molecules are located in the interstitial voids between the metallacrown molecules. The methanol molecule is positionally disordered [0.51 (1)
However, recently it has been shown that imidazole and its derivatives can also be readily used to produce a manganese 15-MC-5 compound (Emerich et al., 2010;Tigyer et al. 2011Tigyer et al. , 2012. Herein we report the synthesis, IR data, and single-crystal X-ray structure of the title compound Mn1 is located in the central cavity and is seven-coordinate with distorted face-capped trigonal prismatic geometry (Fig.   2). The geometry assignment is supported by both the calculated azimuthal angle (Φ) and the s/h ratio (Stiefel & Brown, 1972). These parameters can be used to distinguish an ideal trigonal prism and octahedron. In an ideal trigonal prism the angle between the atoms on opposite triangular faces is Φ = 0°, and the s/h ratio is 1.00. In an ideal octahedron the azimuthal angle equals 60°, and the s/h ratio is  et al., 1984). For an ideal square pyramidal geometry τ = 0, while for an ideal trigonal bipyramidal geometry τ = 1. For Mn2 τ is 0.21. Mn3 -Mn 6 are six-coordinate with distorted octahedral geometry. In addition, the coordination about these Mn can be described by their configurations. Mn3 (Fig. 4 b) and Mn6 (Fig. 4 e) have a propeller configuration of two chelate rings of different shi 3ligands with Λ absolute stereochemistry. Mn4 (Fig. 4c) and Mn5 (Fig. 4 d)

Refinement
The crystals under investigation were heavily intergrown and fragile and no single piece sufficiently large for XRD analysis could be obtained. Attempts to obtain single pieces from larger fragments through careful cutting were not successful due to the dark colour and fragility of the crystallites. Instead a sufficiently large fragment with three larger and a number of smaller moieties was chosen for analysis. The orientation matrices for the three largest moieties were identified using the program CELL_NOW (Sheldrick, 2008b) with the three components being not related by any obvious twin operations. The three components were integrated using SAINT (Bruker, 2012) resulting in the following statistics: The exact twin matrices identified by the integration program were found to be: The total number of reflections given (_diffrn_reflns_number) is before the cutoff at 0.8 Å. The R int value (_diffrn_reflns_av_R_equivalents) given is for these reflections and is based on agreement between observed single and composite intensities and those calculated from refined unique intensities and twin fractions before the cutoff at 0.8 Å (TWINABS).
One of the coordinated 1-methylimidazole ligands is partially replaced by a DMF molecule. Overlapping atoms were constrained to have identical ADPs and to be close to isotropic. The DMF molecule was restrained to have a geometry similar to that of another not disordered DMF molecule. The occupancy ratio refined to 0.61983 (2000) to 0.38017 (2000) in favor of the 1-methylimidazole molecule.
A methanol molecule is positional disordered with one of the molecules associated with a partially occupied water molecule. The disorder is associated with disorder of a diethyl ether molecule. Occupancy ratios of all three solvent molecules refined to essentially 1:1 (0.50926 (1100) to 0.49074 (1100)). The oxygen and carbon atoms of the methanol and water molecules were restrained to have similar ADPs (SIMU restraint in Shexltl).
Reflections 0 0 1 and 1 -1 1 were obstructed by the beam stop and were omitted from the refinement.  (2)). Hydrogen atoms and the lattice solvent molecules have been omitted for clarity.

Computing details
Color scheme for all figures: green -Mn II and Mn III , red -oxygen, blue -nitrogen, and gray -carbon.

Figure 2
Side (   The thermal ellipsoid plots are at a 50% probability level. Hydrogen atoms have been omitted for clarity.