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International Union of Crystallography, Acta Crystallographica Section E: Crystallographic Communications, 9(76), p. 1458-1466, 2020

DOI: 10.1107/s2056989020010725

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

Journal article published in 2020 by Rachel E. Rheam, Matthias Zeller ORCID, Curtis M. Zaleski ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

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 Ln III 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 Ln III 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 Ln III 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.