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.