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[[μ3-acetato-hexakis(μ-N,N-dimethylformamide)bis(N,N-dimethylformamide)bis[salicylhydroximato(2-)]heptakis[salicylhydroximato(3-)]hexaaluminium(III)dysprosium(III)pentasodium(I)] N,N-dimethylformamide tetrasolvate 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-μ4-acetato-nonakis(μ-N,N-dimethylformamide)octakis(N,N-dimethylformamide)tetrakis[salicylhydroximato(2-)]tetradecakis[salicylhydroximato(3-)]dodecaaluminium(III)didysprosium(III)decasodium(I)] N,N-dimethylformamide 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 salicylhydroximate and DMF is N,N-dimethylformamide, 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-nitrogen-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 enantiomers 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 octahedral aluminium ions of the metallacryptand shell.