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Published on: December 4, 2014
Crystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets
Jordan R Travis1, Gerard P Van Trieste Iii1, Matthias Zeller2
1Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA.
Abstract:
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(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]·4C3H7NO·H2O} , 1, and poly[[di-μ4-acetato-nona-kis-(μ-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} , 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 Λ and Δ propeller configurations of the four octa-hedral aluminium ions of the metallacryptand shell.
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