Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na(2)(3-chloro-benzoate)(2)[12-MC(Mn(III)N(shi))-4](DMF)(6) and MnNa(3-chloro-benzoate)(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-chloro-benzoato)hexa-kis-(di-methyl-formamide)-tetra-kis-(μ(4)-N,2-dioxido-benzene-1-carboximidato)tetra-manganese(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-chloro-benzoate)(2)[12-MC(Mn(III)N(shi))-4](DMF)(6), 1, and tetra-μ-aqua-tris-(μ-3-chloro-benzoato)(di-methyl-formamide)-tetra-kis-(μ(4)-N,2-dioxido-benzene-1-carboximidato)penta-manganese(III)sodi-um(I) di-methyl-formamide tetra-solvate 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-chloro-benzo-ate)(3)[12-MC(Mn(III)N(shi))-4](DMF)(H(2)O)(4)·4DMF·0.72H(2)O, 2, where shi(3-) is salicyl-hydrox-imate and DMF is N,N-di-methyl-formamide. 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 mol-ecule. 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-chloro-benzoate 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 mol-ecule, except for the central Na(+) ion, exhibits whole mol-ecule 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 mol-ecules and 3-chloro-benzoate 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] mol-ecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chloro-benzoate anions bind on the convex side of the MC and connect the Mn(II) ion to three of the ring Mn(III) ions.