Crystal structure of a TbIII-CuII glycine-hydroxamate 15-metallacrown-5 sulfate complex
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Updated: Oct 9, 2025
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Anna V Pavlishchuk1,2, Inna V Vasylenko2, Matthias Zeller3
1Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 62, Kyiv, 01601, Ukraine.
Abstract:
The core of the title complex, bis-[hexa-aqua-hemi-aqua-penta-kis-(μ3-glycine-hydroxamato)sulfato-penta-copper(II)terbium(III)] sulfate hexa-hydrate, [TbCu5(SO4)(GlyHA)5(H2O)6.5]2(SO4)·6H2O (1), which belongs to the 15-metalla-crown-5 family, consists of five glycine-hydroxamate dianions (GlyHA2-; C2H4N2O2) and five copper(II) ions linked together forming a metallamacrocyclic moiety. The terbium(III) ion is connected to the centre of the metallamacrocycle through five hydroxamate oxygen atoms. The coordination environment of the Tb3+ ion is completed to an octa-coordination level by oxygen atoms of a bidentate sulfate and an apically coordinated water mol-ecule, while the copper(II) atoms are square-planar, penta- or hexa-coordinate due to the apical coordination of water mol-ecules. Continuous shape calculations indicate that the coordination polyhedron of the Tb3+ ion in 1 is best described as square anti-prismatic. The positive charge of each pair of [TbCu5(GlyHA)5(H2O)6.5(SO4)]2 2+ fragments is compensated by a non-coordinated sulfate anion, which is located on an inversion center with 1:1 disordered oxygen atoms. Complex 1 is isomorphous with the previously reported compounds [LnCu5(GlyHA)5(SO4)(H2O)6.5]2(SO4), where Ln III = Pr, Nd, Sm, Eu, Gd, Dy and Ho.
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