Crystal structures of three anionic lanthanide–aluminium [3.3.1] metallacryptate complexes

Acta Crystallographica Section E: Crystallographic Communications

Rachel E. Rheam¹  Curtis M. Zaleski¹  Matthias Zeller² 

[1] Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA;Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA;

关键词: metallacrown;    metallacryptate;    aluminium complex;    crystal structure;   

DOI  :  10.1107/S2056989020010725

来源: DOAJ

【 摘 要 】

The three isomorphous [3.3.1] metallacryptate complexes bis(pyridinium) diaquadipyridinehexakis[μ3-salicylhydroximato(3−)]bis[μ2-salicylhydroximato(1−)]hexaaluminiumgadolinium–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) diaquadipyridinehexakis[μ3-salicylhydroximato(3−)]bis[μ2-salicylhydroximato(1−)]hexaaluminiumdysprosium–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(pyridinium) diaquadipyridinehexakis[μ3-salicylhydroximato(3−)]bis[μ2-salicylhydroximato(1−)]hexaaluminiumytterbium–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 salicylhydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an LnIII 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 LnIII ions are nine-coordinate with a spherical capped-square-antiprism geometry, while the six AlIII ions are all octahedral. 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 molecule 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 LnIII 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.

【 授权许可】

Unknown