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-μ-aqua-tetrakis{2-[azanidylene(oxido)methyl]phenolato}tetrakis(μ 2 -3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) N , N -dimethylacetamide decasolvate, [DyMn 4 Na(C 7 H 5 O 3 ) 4 (C 7 H 4 NO 2 ) 4 (H 2 O) 4 ]·10C 4 H 9 NO or [Dy III Na(4-OHben) 4 {12-MC Mn(III)N(shi) -4}(H 2 O) 4 ]·10DMA, 1 , and tetra-μ-aqua-tetrakis{2-[azanidylene(oxido)methyl]phenolato}tetrakis(μ 2 -3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) N , N -dimethylformamide tetrasolvate, [DyMn 4 Na(C 7 H 5 O 3 ) 4 (C 7 H 4 NO 2 ) 4 (H 2 O) 4 ]·4C 3 H 7 NO or [Dy III Na(3-OHben) 4 {12-MC Mn(III)N(shi) -4}(H 2 O) 4 ]·4DMF, 2 , and where MC is metallacrown, shi 3− is 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 [Mn III —N—O] 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 2×0.275 (7):2×0.225 (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 t