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 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)].