Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na(3-chloro-benzoate)[12-MC-4](DMF) and MnNa(3-chloro-benzoate)[12-MC-4](DMF)(HO)·4DMF·0.72HO.

Similar synthetic schemes yield two different metallacrown (MC) complexes: bis-(μ-3-chloro-benzoato)hexa-kis-(di-methyl-formamide)-tetra-kis-(μ-,2-dioxido-benzene-1-carboximidato)tetra-manganese(III)disodium(I), [MnNa(CHClO)(CHNO)(CHNO)] or Na(3-chloro-benzoate)12-MC-4, , and tetra-μ-aqua-tris-(μ-3-chloro-benzoato)(di-methyl-formamide)-tetra-kis-(μ-,2-dioxido-benzene-1-carboximidato)penta-manganese(III)sodi-um(I) di-methyl-formamide tetra-solvate 0.72-hydrate, [MnNa(CHClO)(CHNO)(CHNO)(HO)]·4CHNO·0.718HO or MnNa(3-chloro-benzo-ate)12-MC-4(HO)·4DMF·0.72HO, , where shi is salicyl-hydrox-imate and DMF is ,-di-methyl-formamide. Both complexes have the same framework consisting of four Mn ions in the MC ring and four shi ligands, resulting in an overall square-shaped mol-ecule. The Mn ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 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 ions. For 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 is slightly domed, and the MC binds both an Mn ion and an Na ion in the MC central cavity. The Mn ion is located on the convex side of the MC, while the Na ion binds to the concave side. Complex represents the first instance of a [12-MC-4] mol-ecule binding both 3 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 ion to three of the ring Mn ions.