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-(μ₂-3-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 [Dy^IIINa(4-OHben)₄{12-MC_{Mn(III)N(shi)}-4}(H₂O)₄]·10DMA, 1, and tetra-μ-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ₂-3-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 [Dy^IIINa(3-OHben)₄{12-MC_{Mn(III)N(shi)}-4}(H₂O)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)].

Keywords: crystal structure; heterotrimetallic; metallacrown; self-assembled coordination complex.