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

Jordan R Travis; Gerard P Van Trieste Iii; Matthias Zeller; Curtis M Zaleski

doi:10.1107/S2056989020010130

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

Acta Crystallogr E Crystallogr Commun. 2020 Jul 31;76(Pt 8):1378-1390. doi: 10.1107/S2056989020010130. eCollection 2020 Aug 1.

Authors

Jordan R Travis¹, Gerard P Van Trieste Iii¹, Matthias Zeller², Curtis M Zaleski¹

Affiliations

¹ Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA.
² Department of Chemistry, Purdue University, West Lafayette, IN 47907, 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} _n , 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} _n , 2, where shi^3- 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.

Keywords: aluminium complex; crystal structure; metallacrown; metallacryptate.

Grants and funding

This work was funded by Shippensburg University Foundation Undergraduate Research Fund grant . Faculty Professional Development Council, Pennsylvania State System of Higher Education grant . National Science Foundation grants DMR 1337296 and CHE 0087210. Ohio Board of Regents grant CAP-491 to M. Zeller. Youngstown State University grant .