Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chloro­benzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chloro­benzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O

Similar synthetic schemes yield two different metallacrown (MC) complexes: bis­(μ-3-chloro­benzoato)hexa­kis­(di­methyl­formamide)­tetra­kis­(μ4-N,2-dioxido­benzene-1-carboximidato)tetra­manganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chloro­benzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris­(μ-3-chloro­benzoato)(di­methyl­formamide)­tetra­kis­(μ4-N,2-dioxido­benzene-1-carboximidato)penta­manganese(III)sodi­um(I) di­methyl­formamide tetra­solvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chloro­benzo­ate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3− is salicyl­hydrox­imate and DMF is N,N-di­methyl­formamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3− ligands, resulting in an overall square-shaped mol­ecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chloro­benzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown mol­ecule, except for the central Na+ ion, exhibits whole mol­ecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na⋯Na axis. The occupancy ratio of the main disorder of the metallacrown mol­ecules and 3-chloro­benzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] mol­ecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chloro­benzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions.