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Crystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets.

ABSTRACT: The two [3.3.1] metallacryptate complexes, namely, poly[[?3-acetato-hexa-kis-(?-N,N-di-methyl-formamide)-bis-(N,N-di-methyl-formamide)bis-[salicyl-hydroxi-mato(2-)]hepta-kis-[salicyl-hydrox-im-ato(3-)]hexa-aluminium(III)dysprosium(III)penta-sodium(I)] N,N-di-methyl-formamide tetra-solvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·4DMF·H2O or {[DyAl6Na5(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]·4C3H7NO·H2O} n , 1, and poly[[di-?4-acetato-nona-kis-(?-N,N-di-methyl-form-amide)-octa-kis-(N,N-di-methyl-formamide)tetra-kis-[sali-cyl-hydroximato(2-)]tetra-deca-kis-[salicyl-hydroximato(3-)]dodeca-aluminium(III)didysprosium(III)deca-sodium(I)] N,N-di-methyl-form-amide 6.335-solvate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2·6.335DMF or {[Dy2Al12Na10(C7H5NO3)4(C7H4NO3)14(C2H3O2)2(C3H7NO)17]·6.335C3H7NO} n , 2, where shi3- is salicyl-hydroximate and DMF is N,N-di-methyl-formamide, both consist of an aluminium-based metallacryptand. In 1 and 2, the metallacryptand encapsulates a dysprosium(III) ion in the central cavity, and the resulting metallacryptates are connected to each other via sodium-DMF linkages to generate a two-dimensional sheet. The metallacryptates of 1 and 2 are the three-dimensional analogues of metallacrowns as the metallacryptates contain a metal-nitro-gen-oxygen cyclic repeat unit throughout the complexes. For 1 the building block of the two-dimensional sheet is comprised of only one type of metallacryptate, which is connected to four neighboring metallacryptates via four sodium-DMF linkages. In 2, the building block is a dimeric unit of two metallacryptates. Each dimeric metallacryptate unit is connected to four other dimeric units via six sodium-DMF linkages. The two metallacryptates of each dimeric unit can be considered enanti-omers of each other. In both 1 and 2, chirality is imparted to the metallacryptate due to the ? and ? propeller configurations of the four octa-hedral aluminium ions of the metallacryptand shell.

SUBMITTER: Travis JR

PROVIDER: S-EPMC7405589 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Crystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets.

Travis Jordan R JR Van Trieste Iii Gerard P GP Zeller Matthias M Zaleski Curtis M CM

Acta crystallographica. Section E, Crystallographic communications 20200731 Pt 8

The two [3.3.1] metallacryptate complexes, namely, poly[[μ3-acetato-hexa-kis-(μ-N,N-di-methyl-formamide)-bis-(N,N-di-methyl-formamide)bis-[salicyl-hydroxi-mato(2-)]hepta-kis-[salicyl-hydrox-im-ato(3-)]hexa-aluminium(III)dysprosium(III)penta-sodium(I)] N,N-di-methyl-formamide tetra-solvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·4DMF·H2O or {[DyAl6Na5</su ...[more]

PMID: 32844034

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Project description:The three isomorphous [3.3.1] metallacryptate complexes bis-(pyridinium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydroxim-ato(1-)]hexa-aluminiumgadolinium-pyridine-water (1/7.396/1), (C5H6N)2[GdAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.396C5H5N·H2O or [Hpy]2[GdAl6(H2shi)2(shi)7(py)1.855(H2O)2]·7.396py·H2O, 1, bis-(pyridinium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydroxim-ato(1-)]hexa-aluminiumdysprosium-pyridine-water (1/7.429/1), (C5H6N)2[DyAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[DyAl6(H2shi)2(shi)7(py)1.891(H2O)2]·7.429py·H2O, 2, and bis-(pyrid-in-ium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydrox-imato(1-)]hexa-aluminiumytterbium-pyridine-water (1/7.386/1), (C5H6N)2[YbAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[YbAl6(H2shi)2(shi)7(py)1.818(H2O)2]·7.386py·H2O, 3, where Hpy+ is pyridinium, shi3- is salicyl-hydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an Ln III ion in the central cavity. The metallacryptand portions are comprised of an Al-N-O repeat unit; thus, they can be considered three-dimensional metallacrowns. The encapsulated Ln III ions are nine-coordinate with a spherical capped-square-anti-prism geometry, while the six AlIII ions are all octa-hedral. Four of the AlIII ions are chiral centers with 2 Δ and 2 Λ stereoconfigurations. The remaining two AlIII ions have trans chelate rings from two different shi3- ligands. For 1-3, a section of the main mol-ecule is disordered induced by the presence or absence of a pyridine ligand coordinated to one of the AlIII ions. In the absence of the pyridine moiety, an H2shi- ligand moves into the space otherwise occupied by the pyridine and the phenol oxygen atom coordinates to the AlIII ion. The movement of the H2shi- ligand induces movement for the Ln III ion, for another AlIII ion that also binds the same H2shi- ligand, and for one of the shi3- ligands coordinated to the latter AlIII ion. For 1-3 the occupancy ratio of the metallacryptand portions refined to 0.8550 (13):0.1450 (13), to 0.8909 (13):0.1091 (13), and to 0.8181 (14):0.1819 (14), respectively.

Project description: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)].

Dataset Information

Crystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets.

Publications

Crystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets.

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