Bis(dimethylformamide)pentakis(μ-N,2-dioxidobenzene-1-carboximidato)tetrakis(1-methylimidazole)di-μ-propionato-pentamanganese(III)manganese(II)–dimethylformamide–methanol (1/0.24/1.36)

The title compound [Mn6(C7H4NO3)5(C3H5O2)2(C4H6N2)4.17(C3H7NO)1.83]·0.24C3H7NO·1.36CH3OH or Mn(II)(C3H5O2)2[15-MCMn(III)N(shi)-5](Me—Im)4.17(DMF)1.83·0.24DMF·1.36MeOH (where MC is metallacrown, shi3− is salicylhydroximate, Me—Im is 1-methylimidazole, DMF is N,N-dimethylformamide, and MeOH is methanol), contains an MnII ion in the central cavity and five MnIII ions in the MC ring. The central MnII ion is seven coordinate and has a geometry best described as distorted face-capped trigonal prismatic with Φ angles of 6.13, 10.36, and 11.73° and an estimated average s/h ratio of 1.03±0.11. Four of the ring MnIII ions are six coordinate with distorted octahedral geometries. Two of the MnIII ions have Λ absolute stereoconfiguration, while the other two MnIII ions have a planar configuration. The fifth MnIII ion is five coordinate and has a distorted square pyramidal geometry with τ = 0.20. Three of the MnIII ions bind one 1-methylimidazole ligand. Two of the ring MnIII ions have a 1-methylimidazole and a DMF disordered over a coordination site. For one of the ring MnIII ions, the occupancy ratio of the ligands refines to 0.51 (1):0.49 (1) in favor of the DMF. For the other ring MnIII ion, the occupancy ratio of the ligands refines to 0.68 (1):0.32 (1) in favor of the 1-methylimidazole. Two propionate anions serve to bridge the central MnII ion between two different MnIII ions. The methyl groups of the bridging propionate anions are disordered over two positions. The methyl group disorder also induces disorder in the H atoms of the adjacent methylene C atom to the same degree. For one of the propionate anions, the occupancy ratio refines to 0.752 (8):0.248 (8) and for the second, the occupancy ratio refines to 0.604 (6):0.396 (6). In addition, the disorder of the methyl group of the latter propionate anion is correlated with a partially occupied [0.604 (6)] methanol molecule. Furthermore, a methanol molecule and a DMF molecule are positionally disordered in the lattice. The occupancy refines to 0.757 (7):0.243 (7) in favor of the methanol molecule. Correlated to the occupancy of the methanol and DMF molecules is a disordered benzene ring of one salicylhydroximate ligand. The benzene ring is disordered over two positions with an occupancy ratio of 0.757 (7):0.243 (7). Lastly, the two lattice methanol molecules are hydrogen bonded to the 15-MC-5 molecule. For the partially occupied methanol molecule associated with the disordered propionate anion, the hydroxyl group of the methanol is hydrogen bonded to a carboxylate O atom of the propionate anion. For the partially occupied methanol molecule associated with the partially occupied lattice DMF molecule, the hydroxyl group of the methanol is hydrogen bonded to the phenolate O atom of a salicylhydroximate ligand and to the carbonyl O atom of a coordinated DMF molecule.

The title compound [Mn 6 (C 7 H 4 NO 3 ) 5 (C 3 H 5 O 2 ) 2 (C 4 H 6 N 2 ) 4.17 -(C 3 H 7 NO) 1.83 ]Á0.24C 3 H 7 NOÁ1.36CH 3 OH or Mn(II)(C 3 H 5 -O 2 ) 2 [15-MC Mn(III)N(shi) -5](Me-Im) 4.17 (DMF) 1.83 Á0.24DMFÁ-1.36MeOH (where MC is metallacrown, shi 3À is salicylhydroximate, Me-Im is 1-methylimidazole, DMF is N,Ndimethylformamide, and MeOH is methanol), contains an Mn II ion in the central cavity and five Mn III ions in the MC ring. The central Mn II ion is seven coordinate and has a geometry best described as distorted face-capped trigonal prismatic with È angles of 6.13, 10.36, and 11.73 and an estimated average s/h ratio of 1.03AE0.11. Four of the ring Mn III ions are six coordinate with distorted octahedral geometries. Two of the Mn III ions have Ã absolute stereoconfiguration, while the other two Mn III ions have a planar configuration. The fifth Mn III ion is five coordinate and has a distorted square pyramidal geometry with = 0.20. Three of the Mn III ions bind one 1-methylimidazole ligand. Two of the ring Mn III ions have a 1-methylimidazole and a DMF disordered over a coordination site. For one of the ring Mn III ions, the occupancy ratio of the ligands refines to 0.51 (1):0.49 (1) in favor of the DMF. For the other ring Mn III ion, the occupancy ratio of the ligands refines to 0.68 (1):0.32 (1) in favor of the 1-methylimidazole. Two propionate anions serve to bridge the central Mn II ion between two different Mn III ions. The methyl groups of the bridging propionate anions are disordered over two positions. The methyl group disorder also induces disorder in the H atoms of the adjacent methylene C atom to the same degree. For one of the propionate anions, the occupancy ratio refines to 0.752 (8):0.248 (8) and for the second, the occupancy ratio refines to 0.604 (6):0.396 (6). In addition, the disorder of the methyl group of the latter propionate anion is correlated with a partially occupied [0.604 (6)] methanol molecule. Furthermore, a methanol molecule and a DMF molecule are positionally disordered in the lattice. The occupancy refines to 0.757 (7):0.243 (7) in favor of the methanol molecule. Correlated to the occupancy of the methanol and DMF molecules is a disordered benzene ring of one salicylhydroximate ligand. The benzene ring is disordered over two positions with an occupancy ratio of 0.757 (7):0.243 (7). Lastly, the two lattice methanol molecules are hydrogen bonded to the 15-MC-5 molecule. For the partially occupied methanol molecule associated with the disordered propionate anion, the hydroxyl group of the methanol is hydrogen bonded to a carboxylate O atom of the propionate anion. For the partially occupied methanol molecule associated with the partially occupied lattice DMF molecule, the hydroxyl group of the methanol is hydrogen bonded to the phenolate O atom of a salicylhydroximate ligand and to the carbonyl O atom of a coordinated DMF molecule.
The MC framework is built from five shi 3ligands and five Mn III ions which form a -[Mn III -N-O]-repeat unit. Located in the central cavity of the MC is a Mn II ion. This Mn II is bound to five oxime O atoms of the shi 3and is also connected to the MC framework via two bridging propionate anions. Charge neutrality is maintained for the MC by the five Mn III cations, one Mn II cation, and the five shi 3and two propionate anions.
The central manganese ion (Mn1) is seven coordinate with a geometry best described as distorted face-capped trigonal prismatic (Fig. 2). The coordination of Mn1 is completed by five oxime oxygen atoms of the shi 3ligands and two carboxylate oxygen atoms of two different propionate anions. The two propionate anions bridge the central Mn1 to Mn3 and Mn5 of the MC ring. The geometry assignment is supported by both the azimuthal angle, Φ, and the calculated s/h ratio (Stiefel & Brown, 1972). These parameters are used to distinguish between octahedral and trigonal prismatic geometry. In an ideal octahedron, the angle between the atoms on opposite triganular faces is Φ = 60°, and the s/h ratio is 1.22. In an ideal trigonal prism, the azimuthal angle is 0°, and the s/h ratio is 1.00. To calculate these parameters the centroids of opposite triangular faces made by the donor oxygen atoms (O6, O9, and O16; O12, O15, and O18) were defined using the program Mercury ( Fig. 3; Macrae et al., 2006). The azimuthal angles were measured between atoms on opposite faces through the centroids. To calculate the s/h ratio, the distance between the centroids was defined as h, and supplementary materials sup-2 . E69, m483-m484 the distances between atoms on the same triangular face were defined as s. For Mn1 the Φ angles are 6.13°, 10.36°, and 11.73°, and the estimated average s/h ratio is 1.03±0.11. Thus, both the Φ angle and s/h ratio support a distorted facedcapped trigonal prismatic geometry. Mn1 is assigned a 2+ oxidation state, which is supported by a Bond Valence Sum (BVS) value of 1.93 (Liu & Thorp, 1993) and an average Mn-O bond distance of 2.24 Å.
The five ring Mn ions possess various coordination numbers and configuration modes ( Fig. 4 and 5). Mn2 has a coordination number of five and possesses a distorted square pyramidal geometry (Fig. 4a). To evaluate the geometry about Mn2 the τ parameter was calculated (Addison et al., 1984). For an ideal square pyramidal geometry τ = 0, while for an ideal trigonal bipyramidal geometry τ = 1. For Mn2 the τ parameter is 0.20. Mn3 -Mn6 are six-coordinate with distorted octahedral geometry, but the configuration of the coordination about each Mn is different. Mn3 has a propeller configuration of two chelate rings of different shi 3ligands with Λ absolute stereochemistry (Fig. 4b). In addition, Mn3 binds one 1-methylimidazole ligand. Mn4 has a planar configuration, where two chelate rings of different shi 3ligands are located trans to each other ( Fig. 4c and 4d). Along the axial axis Mn4 also binds a DMF molecule, and located in a trans position is either a 1-methylimidazole or a DMF. For the ligands bound to Mn4, the occupancy ratio refines to 0.51 (1) to 0.49 (1) in favor of the DMF molecule. Mn5 also has a planar configuration of two trans chelate rings of different shi 3ligands ( Fig. 5a and 5b). Along the axial axis is an carboxylate oxygen atom of a propionate ligand and located in a trans position is either a 1-methylimidazole or a DMF. For the ligands bound Mn5, the occupancy ratio refines to 0.68 (1) to 0.32 (1) in favor of the 1-methylimidazole molecule. Mn6 has a propeller configuration of two chelate rings of different shi 3ligands with Λ absolute stereochemistry (Fig. 5c). In addition, Mn6  Lastly, several more instances of disorder exist in the structure. The methyl groups of the bridging propionate anions are disordered over two positions. The methyl group disorder also induces disorder in the hydrogen atoms of the adjacent methylene carbon atom to the same degree. For the propionate anion that bridges Mn1 to Mn3, the occupancy ratio refines to 0.752 (8) to 0.248 (8). For the propionate anion that bridges Mn1 to Mn5, the occupancy ratio refines to 0.604 (6) to 0.396 (6). In addition, the disorder of the methyl group of the latter propionate anion is correlated with a partially occupied methanol molecule. The occupancy of the methanol molecule is 0.604 (6). Furthermore, a methanol molecule and a DMF molecule are positionally disordered in the lattice with an occupancy ratio of 0.757 (7) to 0.243 (7) in favor of the methanol molecule. Correlated to the occupancy of the methanol and DMF molecules is a disordered benzene ring (C15 to C20 and C15B to C20B) of one salicylhydroximate ligand. The benzene ring is disordered over two positions with an occupancy ratio of 0.757 (7) to 0.243 (7).
Manganese(II) chloride tetrahydrate (0.75 mmol) was dissolved in 12.5 ml of methanol resulting in a light pink solution.
Initially the solution turned a yellow color, but after stirring for 1 h the solution became dark brown. After 1 h of stirring, neat 1-methylimidazole (2.5 mmol) and a mixture of sodium propionate (0.75 mmol) in 12.5 ml of DMF were added to

Refinement
For Mn4 and Mn5, a 1-methylimidazole molecule and a N,N-dimethylformamide (DMF) molecule are disordered over a coordination site. Overlapping atoms were constrained to have identical anisotropic displacement parameters (ADPs).
The 1-methylimidazole molecules were restrained to have geometries similar to that of another non-disordered 1-methylimidazole. The DMF molecules were also restrained to have a geometry similar to that of another non-disordered DMF molecule. Carbon and nitrogen atoms of the 1-methylimidazole molecules and carbon, nitrogen, and oxygen atoms of the DMF molecules were restrained to have similar U ij components of the ADPs (e.s.d. = 0.01 Å 2 ; SIMU restraint in Shexltl).
For the ligands bound to Mn4, the occupancy ratio refined to 0.506 (12) to 0.494 (12) in favor of the DMF molecule. For the ligands bound Mn5, the occupancy ratio refined to 0.680 (12) to 0.320 (12) in favor of the 1-methylimidazole molecule.
The methyl groups of the bridging propionate ligands are disordered over two positions. The methyl group disorder also induces disorder in the hydrogen atoms of the adjacent methylene carbon atom to the same degree. The ADPs for each pair of methyl groups were constrained to be identical. For the propionate that bridges Mn1 to Mn3 the occupancy ratio refined to 0.752 (8) to 0.248 (8). For the propionate that bridges Mn1 to Mn5 the occupancy ratio refined to 0.604 (6) to 0.396 (6). In addition, the disorder of the methyl group of the latter propionate anion is correlated with a partially occupied methanol molecule. The occupancy of the methanol molecule is also 0.604 (6).
A methanol molecule and a DMF molecule are positional disordered in the lattice. Carbon, nitrogen, and oxygen atoms of the DMF molecule were restrained to have similar U ij components of the ADPs (e.s.d. = 0.01 Å 2 ; SIMU restraint in Shexltl). The occupancy refined to 0.757 (7) to 0.243 (7) in favor of the methanol molecule.
Correlated to the occupancy of the methanol and DMF molecules is a disordered benzene ring (C15 to C20 and C15B to C20B) of one salicylhydroximate ligand. The benzene ring is disordered over two positions with an occupancy ratio of 0.757 (7) to 0.243 (7). Equivalent atoms of the benzene ring have nearly the same atom positions leading to highly correlated thermal parameters. To avoid correlation, the ADPs of every pair of overlapping atoms were constrained to be identical. For the disordered benzene ring carbon atoms that connect to the non-disordered portion of the salicylhydroximate ligand, carbon-carbon (C20-C21 and C20B-C21) and carbon-oxygen (C15-O7 and C15B-O7) bond distances were restrained to be similar (e.s.d. = 0.02 Å). To maintain the planarity of each disordered benzene ring, the chiral volumes of the carbon atoms (C15, C15B, C20, and C20B) that connect to the non-disordered portion of the salicylhydroximate ligand were restrained to zero (e.s.d. = 0.1 Å 3 ).
All hydrogen atoms were placed in calculated positions and refined as riding on their carrier atoms with O-H distances of 0.84 Å for methanol oxygen atoms and C-H distances of 0.95 Å for sp 2 carbon atoms, 0.99 Å for methylene carbon atoms, and 0.98 Å for methyl carbon atoms. The U iso values for hydrogen atoms were set to a multiple of the value of the carrying carbon atom (1.2 times for sp 2 hybridized carbon atoms and methylene carbon atoms or 1.5 times for methyl carbon atoms and methanol oxygen atoms).
One low angle reflection (0 1 0) was affected by the beam stop and omitted from the refinement.

Figure 1
Single-crystal X-ray structure of Mn(II)( The thermal ellipsoid plot of 1 is at a 50% probability level. For Mn4 only the DMF is shown bound to the Mn III , since the DMF possesses a higher occupancy rate compared to the coordinated 1-methylimidazole (0.51 (1):0.49 (1)). For Mn5 only the 1-methylimidazole is shown bound to the Mn III , since the 1-methylimidazole possesses a higher occupancy rate compared to the coordinated DMF (0.68 (1):0.32 (1)). The disordered benzene ring is only shown at the higher occupancy factor. Hydrogen atoms and the lattice solvent molecules have been omitted for clarity. Color scheme for all figures: green -Mn II and Mn III , red -oxygen, blue -nitrogen, and gray -carbon.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 )
x y z U iso */U eq Occ.  (2)