ABSTRACT: The syntheses and crystal structures for the compounds tetra-?-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(?2-3-hy-droxy-benzoato)dys-pro-s-ium(III)-tetra-manganese(III)sodium(I) N,N-di-methyl-acetamide deca-solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·10C4H9NO or [DyIIINa(4-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·10DMA, 1, and tetra-?-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(?2-3-hy-droxy-benzoato)dys-pros-ium(III)tetra-manganese(III)sodium(I) N,N-di-methylformamide tetra-solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·4C3H7NO or [DyIIINa(3-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·4DMF, 2, and where MC is metallacrown, shi3- is salicyl-hydroximate, 3-OHben is 3-hy-droxy-benzoate, DMA is N,N-di-methyl-acetamide, 4-OHben is 4-hy-droxy-benzoate, and DMF is N,N-di-methyl-formamide, are reported. For both 1 and 2, the macrocyclic metallacrown consists of an [MnIII-N-O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a DyIII ion on the convex side of the metallacrown and an Na+ ion the concave side. The MnIII ions are six-coordinate with an elongated tetra-gonally distorted octa-hedral geometry. Both the DyIII and Na+ ions are eight-coordinate. The DyIII 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 MnIII ion to the central DyIII ion. For 1, whole-mol-ecule disorder is observed for the main mol-ecule, excluding only the DyIII 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 2, segments of the metallacrown are disordered including the DyIII 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 shi3- 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 2, the crystal under investigation was refined as a non-merohedric twin by a 90° rotation around the real a axis [twin ratio 0.9182?(8):0.0818?(8)].
