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(2)-3-hy-droxy-benzoato)dys-pro-s-ium(III)-tetra-manganese(III)sodium(I) N,N-di-methyl-acetamide deca-solvate, [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--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ(2)-3-hy-droxy-benzoato)dys-pros-ium(III)tetra-manganese(III)sodium(I) N,N-di-methylformamide tetra-solvate, [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 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 [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 tetra-gonally distorted octa-hedral geometry. Both the Dy(III) and Na(+) ions are eight-coordinate. The Dy(III) 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(III) ion to the central Dy(III) ion. For 1, whole-mol-ecule disorder is observed for the main mol-ecule, excluding only the Dy(III) 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 Dy(III) 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(3-) 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)].