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.

Elizabeth C Manickas,Matthias Zeller,Curtis M Zaleski

doi:10.1107/s2056989020008853

Abstract

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 [DyIIINa(4-OHben)4{12-MCMn(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 [DyIIINa(3-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·4DMF, 2, and where MC is metallacrown, shi3- 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 [MnIII-N-O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a DyIII ion on the convex side of the metallacrown and an Na+ ion the concave side. The MnIII ions are six-coordinate with an elongated tetra-gonally distorted octa-hedral geometry. Both the DyIII and Na+ ions are eight-coordinate. The DyIII 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 MnIII ion to the central DyIII ion. For 1, whole-mol-ecule disorder is observed for the main mol-ecule, excluding only the DyIII 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 DyIII 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 shi3- 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)].

Highlights

[azanidylene(oxido)methyl]phenolato}tetrakis(2-3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) N,N-dimethylacetamide decasolvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]Á10C4H9NO or [DyIIINa(4-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]Á10DMA, 1, and tetra--aqua-tetrakis{2-[azanidylene(oxido)methyl]phenolato}tetrakis(2-3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) N,N-dimethylformamide tetrasolvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]Á4C3H7NO or [DyIIINa(3-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]Á4DMF, 2, and where MC is metallacrown, shi3À 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 1, whole-molecule disorder is observed for the main molecule, excluding only the DyIII and Na+ ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14)
In 2014 we reported a series of LnIIINa(OAc)4[12MCMn(III)N(shi)-4](H2O)4 complexes, where LnIII is PrIII to YbIII and YIII, ÀOAc is acetate, and shi3À is salicylhydroximate, that were the first heterotrimetallic MCs and the first 12-MC-4 complexes to bind a lanthanide ion in the central cavity (Azar et al, 2014)

Summary

Supramolecular features

For both 1 and 2 the solvent molecules form hydrogen bonds with the MC complexes. For 1, the MC complex forms. The hydroxyl group (O6) of each 3-hydroxybenzoate forms a hydrogen bond to the carbonyl oxygen atom (O9i) of a DMA molecule [Fig. 3; symmetry code: (i) x, y, z À 1]. The water molecule (O7) coordinated to the central Na+ ion hydrogen bonds to the carbonyl oxygen atoms (O8 and O8ii) of two DMA molecules [Fig. 4; symmetry code: (ii) Àx + 32, y, z]. The hydroxyl group (O15) of a 4-hydroxybenzoate anion forms a hydrogen bond to O3i (a phenolate oxygen atom of a shi3À ligand) of a neighboring MC through two hydrogen bonds: O15—H15OÁ Á ÁO3i and C32—H32Á Á ÁO3i [symmetry. The hydroxyl group (O24) of a 4-hydroxybenzoate anion forms a hydrogen bond to a third MC via the hydrogen bond O24— H24OÁ Á ÁO6iii [a phenolate oxygen atom of a shi3À ligand; symmetry code: (iii) x À 12, Ày + 2, z + 12].

Database survey

Synthesis and crystallization

Findings

Refinement