Crystal structures of two heterotrimetallic dysprosium-manganese-sodium 12-metallacrown-4 complexes with the bridging ligands 3-hy-droxy-benzoate and 4-hy-droxy-benzoate.

The syntheses and crystal structures for the compounds tetra-μ-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ-3-hy-droxy-benzoato)dys-pro-s-ium(III)-tetra-manganese(III)sodium(I) ,-di-methyl-acetamide deca-solvate, [DyMnNa(CHO)(CHNO)(HO)]·10CHNO or [DyNa(4-OHben){12-MC-4}(HO)]·10DMA, , and tetra-μ-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ-3-hy-droxy-benzoato)dys-pros-ium(III)tetra-manganese(III)sodium(I) ,-di-methylformamide tetra-solvate, [DyMnNa(CHO)(CHNO)(HO)]·4CHNO or [DyNa(3-OHben){12-MC-4}(HO)]·4DMF, , and where MC is metallacrown, shi is salicyl-hydroximate, 3-OHben is 3-hy-droxy-benzoate, DMA is ,-di-methyl-acetamide, 4-OHben is 4-hy-droxy-benzoate, and DMF is ,-di-methyl-formamide, are reported. For both and , the macrocyclic metallacrown consists of an [Mn-N-O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a Dy ion on the convex side of the metallacrown and an Na ion the concave side. The Mn ions are six-coordinate with an elongated tetra-gonally distorted octa-hedral geometry. Both the Dy and Na ions are eight-coordinate. The Dy ions possess a square-anti-prismatic geometry, while the Na ions have a distorted biaugmented trigonal-prismatic geometry. Four 3-hy-droxy-benzoate or 4-hy-droxy-benzoate ligands bridge each Mn ion to the central Dy ion. For , whole-mol-ecule disorder is observed for the main mol-ecule, excluding only the Dy and Na ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14). Three DMA mol-ecules were refined as disordered with two in general positions by an approximate 180° rotation and the third disordered twice by general disorder as well as by an exact 180° rotation about a twofold axis that bis-ects it. The occupancy ratios refined to 0.496 (8):0.504 (8), 0.608 (9):0.392 (9), and 2×0.275 (7):2×0.225 (7), respectively. For , segments of the metallacrown are disordered including the Dy ion, one of the Mn ions, two of the Mn-bound 4-hy-droxy-benzoate ligands, the Mn-bridging salicyl-hydroximate ligand, and portions of the remaining three shi ligands. The occupancy ratio for the metallacrown disorder refined to 0.849 (9):0.151 (9). Two DMF solvent mol-ecules are also disordered, each over two orientations. The disorder ratios refined to 0.64 (3):0.36 (3) and to 0.51 (2):0.49 (2), respectively. For , the crystal under investigation was refined as a non-merohedric twin by a 90° rotation around the real axis [twin ratio 0.9182 (8):0.0818 (8)].