Crystal structure of a TbIII-CuIIglycinehydroxamate 15-metallacrown-5 sulfate complex

Abstract

The core of the title complex, bis[hexaaquahemiaquapentakis(μ3-glycinehydroxamato) sulfatopentacopper(II)terbium(III)] sulfate hexahydrate, [TbCu5(SO4)(GlyHA)5(H2O)6.5]2(SO4)μ6H2O (1), which belongs to the 15-metallacrown-5family, consists of five glycinehydroxamate 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 octacoordination level by oxygen atoms of a bidentate sulfate and an apically coordinated water molecule, while the copper(II) atoms are square-planar, penta- or hexacoordinate due to the apical coordination of water molecules. Continuous shape calculations indicate that the coordination polyhedron of the Tb3+ion in 1 is best described as square antiprismatic. The positive charge of each pair of [TbCu5(GlyHA)5- (H2O)6.5(SO4)]22+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 LnIII = Pr, Nd, Sm, Eu, Gd, Dy and Ho.