Di-μ-acetato-bis(dimethylformamide)pentakis(μ-N,2-dioxidobenzene-1-carboximidato)tetrakis(1-ethylimidazole)pentamanganese(III)manganese(II)–diethyl ether–dimethylforamide–methanol–water (1/1/1/1/0.12)

The title compound [Mn6(C7H4NO3)5(CH3CO2)2(C5H8N2)4(C3H7NO)2]·(C2H5)2O·C3H7NO·CH3OH·0.12H2O, abbreviated as MnII(OAc)2[15-MCMnIII(N)shi-5](EtIm)4(DMF)2·diethyl ether·DMF·MeOH·0.12H2O (where −OAc is acetate, MC is metallacrown, shi3− is salicylhydroximate, EtIM is n-ethylimidazole, DMF is N,N-dimethylformamide, and MeOH is methanol) contains five MnIII ions as members of the metallacrown ring and an MnII ion bound in the central cavity. The central MnII ion is seven-coordinate with a distorted face-capped trigonal–prismatic geometry. The five MnIII ions of the metallacrown ring are six-coordinate with distorted octahedral geometries. The configuration of the MnIII ions about the metallacrown ring follow a ΔΛΔPP pattern, with P representing planar. The four 1-ethylimidazole ligands are bound to four different MnIII ions. A diethyl ether solvent molecule was found to be disordered over two mutually exclusive sites with an occupancy ratio of 0.568 (7):0.432 (7). A methanol solvent molecule was found to be disordered over two mutually exclusive sites by being hydrogen bonded either to a dimethylformamide solvent molecule (major occupancy component) or to an O atom of the main molecule (minor occupancy component). The occupancy ratio refined to 0.678 (11):0.322 (11). Associated with the minor component is a partially occupied water molecule [total occupancy 0.124 (15)].


S2. Experimental
Manganese(II) acetate tetrahydrate (99+%) and N,N-dimethylformamide (ACS grade) were purchased from Acros Organics, salicylhydroxamic acid (H 3 shi, 99%) was purchased from Alfa Aesar, n-ethylimidazole (98%) was purchased from TCI America, methanol (HPLC grade) was purchased from Fisher Scientific, and absolute diethyl ether was purchased from EMD Chemicals. All reagents were used as received and without further purification.

S3. Refinement
A solvent diethyl ether molecule was found to be disordered over two mutually exclusive sites. The molecules were restrained to have similar geometries and equivalent atoms were constrained to have identical ADPs. The occupancy ratio refined to 0.568 (7) to 0.432 (7). A solvent methanol molecule was found to be disordered over two mutually exclusive sites by being hydrogen bonded either to a solvent DMF molecule (major moiety) or to an oxygen atom of the main molecule (minor moiety). The two molecules were restrained to have similar C-O distances. The occupancy ratio refined to 0.678 (11) to 0.322 (11). Associated with the minor moiety is a partially occupied water molecule (total occupancy: 0.124 (15). This position of the water oxygen atom and of its H atoms was restrained based on hydrogen bonding considerations. It was also restrained to be approximately isotropic. The carbon atoms of one ethyl group (C48, C49) showed signs of unresolved disorder and were restrained to be approximately isotropic.
Hydrogen atoms were placed in calculated positions with C-H = 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methylene) and were refined with Uĩso~(H) = 1.5 U eq (C) for methyl H atoms and 1.2 U eq (C) for methylene and aromatic moieties.  Single-crystal X-ray structure of Mn II (OAc) 2 [15-MC Mn III N(shi) -5](EtIm) 4 (DMF) 2 .Diethyl ether.DMF.MeOH.0.14H 2 O (1). The thermal ellipsoid plot of 1 is at a 50% probability level. All atoms composing the MC ring are labeled. Hydrogen atoms and the lattice solvent molecules have been omitted for clarity. Color scheme for all figures: purple -Mn II and Mn III , red -oxygen, blue -nitrogen, and gray -carbon.

Figure 2
Side (left) and top (right) views of the first coordination sphere about Mn1 (2+ oxidation state) of 1 with face-capped trigonal prismatic geometry. The thermal ellipsoid plots are at a 50% probability level.     Packing diagram of 1 along the a axis. The thermal ellipsoid plot is at a 50% probability level. Hydrogen atoms have been omitted for clarity.

ethylimidazole)pentamanganese(III)manganese(II)-diethyl ether-dimethylforamide-methanol-water
(  Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.