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The crystal structures of { Ln Cu 5} 3+ ( Ln = Gd, Dy and Ho) 15-metallacrown-5 complexes and a reevaluation of the isotypic Eu III analogue

The crystal structures of { Ln Cu 5} 3+ ( Ln = Gd, Dy and Ho) 15-metallacrown-5 complexes and a reevaluation of the isotypic Eu III analogue

Anna Pavlishchuk, Dina Naumova, Matthias Zeller, Sebastian Calderon Cazorla, Anthony W Addison

Acta Crystallogr E Crystallogr Commun. 2019 Jul 19;75(Pt 8):1215-1223.

PMID: 31417795

Abstract:

Three new isotypic heteropolynuclear complexes, namely penta-aqua-carbonato-penta-kis-(glycinehydroxamato)nitrato-penta-copper(II)lanthanide(III) x-hydrate, [LnCu5(GlyHA)5(CO3)(NO3)(H2O)5]·xH2O (GlyHA2- is glycine-hydrox-amate, N-hy-droxy-glycinamidate or amino-aceto-hydroxamate, C2H4N2O2 2-), with lanthanide(III) (Ln III) = gadolinium (Gd, 1, x = 3.5), dysprosium (Dy, 2, x = 3.28) and holmium (Ho, 3, x = 3.445), within a 15-metallacrown-5 class were obtained on reaction of lanthanide(III) nitrate, copper(II) acetate and sodium glycinehydroxamate. Complexes 1-3 contain five copper(II) ions and five bridging GlyHA2- anions, forming a [CuGlyHA]5 metallamacrocyclic core. The Ln III ions are coordinated to the metallamacrocycle through five O-donor hydroxamates. The electroneutrality of complexes 1-3 is achieved by a bidentate carbonate anion coordinated to the Ln III ion and a monodentate nitrate anion coordinated apically to one of the copper(II) ions of the metallamacrocycle. The lattice parameters of complexes 1-3 are similar to those previously reported for an EuIII-CuII 15-metallacrown-5 complex with glycine-hydroxamate of proposed composition [EuCu5(GlyHA)5(OH)(NO3)2(H2O)4]·3.5H2O [Stemmler et al. (1999 ▸). Inorg. Chem. 38, 2807-2817]. High-quality X-ray data obtained for 1-3 have allowed a re-evaluation of the X-ray data solution proposed earlier for the EuCu5 complex and suggest that the formula is actually [EuCu5(GlyHA)5(CO3)(NO3)(H2O)5]·3.5H2O.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP304675498	Dysprosium(III) acetate hydrate		304675-49-8	Price

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