Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na(2)(3-chloro­benzoate)(2)[12-MC(Mn(III)N(shi))-4](DMF)(6) and MnNa(3-chloro­benzoate)(3)[12-MC(Mn(III)N(shi))-4](DMF)(H(2)O)(4)·4DMF·0.72H(2)O

Similar synthetic schemes yield two different metallacrown (MC) complexes: bis­(μ-3-chloro­benzoato)hexa­kis­(di­methyl­formamide)­tetra­kis­(μ(4)-N,2-dioxido­benzene-1-carboximidato)tetra­manganese(III)disodium(I), [Mn(4)Na(2)(C(7)H(4)ClO(2))(2)(C(7)H(4)NO(3))(4)(C(3)H(7)NO)(6)] or Na(2)(3-chloro­benzoate)(2)[12-MC(Mn(III)N(shi))-4](DMF)(6), 1, and tetra-μ-aqua-tris­(μ-3-chloro­benzoato)(di­methyl­formamide)­tetra­kis­(μ(4)-N,2-dioxido­benzene-1-carboximidato)penta­manganese(III)sodi­um(I) di­methyl­formamide tetra­solvate 0.72-hydrate, [Mn(5)Na(C(7)H(4)ClO(2))(3)(C(7)H(4)NO(3))(4)(C(3)H(7)NO)(H(2)O)(4)]·4C(3)H(7)NO·0.718H(2)O or MnNa(3-chloro­benzo­ate)(3)[12-MC(Mn(III)N(shi))-4](DMF)(H(2)O)(4)·4DMF·0.72H(2)O, 2, where shi(3−) is salicyl­hydrox­imate and DMF is N,N-di­methyl­formamide. Both complexes have the same framework consisting of four Mn(III) ions in the MC ring and four shi(3−) ligands, resulting in an overall square-shaped mol­ecule. The Mn(III) 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 Mn(III) 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 Mn(II) ion and an Na(+) ion in the MC central cavity. The Mn(II) 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-MC(Mn(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 Mn(II) ion to three of the ring Mn(III) ions.