Crystal structures of two heterotrimetallic dysprosium-manganese-sodium 12-metallacrown-4 complexes with the bridging ligands 3-hydroxybenzoate and 4-hydroxybenzoate

The syntheses and crystal structures for the compounds tetra-mu-aqua-tetrakis{2[azanidylene (oxido) methyl] phenolatoltetrakis (mu(2)-3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) N,N-dimethylacetamide decasolvate, [DyMn4Na(C7H5O3)(4)(C7H4NO2)(4)(H2O)(4)]center dot 10C(4)H(9)NO or [(DyNa)-Na-III(4-OHben)(4)-{12-MCMn(III)N(shi)-4} (H2O)(4)]center dot 10DMA, 1, and tetra--aqua-tetrakis{2-[azanidylene(oxido)methyl] phenolatoltetrakis(mu 2-3-hydroxybenzoato)dysprosium(III)tetramanganese(M)sodium(I) N,N-dimethylformamide tetrasolvate, [DyMn4Na(C7H(5)O(3))(4)(C7H4NO2)(4) (H2O)(4)]center dot-4C(3)H(7)NO or [(DyNa)-Na-III(3-OHben)(4)-Mn(III)N(shi)-4} (H2O)(4)]12-MC-4DMF, 2, and where MC is metallacrown, shi3is salicylhydroximate, 3-OHben is 3-hydroxybenzoate, DMA is N,N-dimethylacetamide, 4-OHben is 4-hydroxybenzoate, and DMF is N,N-dimethylformamide, are reported. For both 1 and 2, the macrocyclic metallacrown consists of an [Mee N-0] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a Dy-III ion on the convex side of the metallacrown and an Na+ ion the concave side. The Mn-III ions are six-coordinate with an elongated tetragonally distorted octahedral geometry. Both the Dy(III)and Na+ ions are eight-coordinate. The Dy-III ions possess a square-antiprismatic geometry, while the Na+ ions have a distorted biaugmented trigonal-prismatic geometry. Four 3-hydroxybenzoate or 4-hydroxybenzoate ligands bridge each Mn-III ion to the central Dy-III ion. For 1, whole-molecule disorder is observed for the main molecule, excluding only the Dy-III and Na+ ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14). Three DMA molecules 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 bisects it. The occupancy ratios refined to 0.496 (8):0.504 (8), 0.608 (9):0.392 (9), and 2x0.275 (7):2 x 0.225 (7), respectively. For 2, segments of the metallacrown are disordered including the Dy-III ion, one of the Mn ions, two of the Mn-bound 4-hydroxybenzoate ligands, the Mn-bridging salicylhydroximate ligand, and portions of the remaining three shi(3-) ligands. The occupancy ratio for the metallacrown disorder refined to 0.849 (9):0.151 (9). Two DMF solvent molecules 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 degrees rotation around the real a axis [twin ratio 0.9182 (8):0.0818 (8)].