Crystal structure of the dodecanuclear coordination compounds [RE12(DMF)24(HCOO)8(OH)16]I3·4DMF (RE = Eu, Nd)
Frank Tambornino A and Constantin Hoch
B *
A Fachbereich Chemie, Philips-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany.
B Department Chemie, LMU München, Butenandtstraße 5-13 (D), D-81377 München, Germany.
Australian Journal of Chemistry 75(9) 587-594 https://doi.org/10.1071/CH21336
Submitted: 16 December 2021 Accepted: 12 January 2022 Published: 31 March 2022
© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.
Abstract
By slow hydrolysis of solutions of [Eu(DMF)8]I3 or [Nd(DMF)8]I3 in dimethylformamide (DMF), single crystals of the coordination compounds [RE12(DMF)24 (HCOO)8(OH)16]I3·4DMF (RE = Eu, Nd) were obtained. Both compounds crystallise isotypically in a tetragonal structure with space group I422 (No. 97, Z = 2, a = 21.881(3), 21.6340(10) and c = 20.873(2), 21.0612(9) Å for Nd and Eu compounds, respectively). The crystal structure shows a [RE12O56] core unit with O atoms from formate and hydroxide anions μ3-bridging the metal centres. The dodecanuclear cationic units are arranged in a body-centred packing topology, surrounded by iodide anions in a β cage pattern. Rietveld refinement confirmed the structure model, and the presence of hydroxide anions was shown by FT-IR spectroscopy. Susceptibility measurements on the Nd compound showed paramagnetic behaviour and a temperature dependence of μeff typical for trivalent Nd cations.
Keywords: crystal structure, dodecanuclear complexes, formates, N,N-dimethylformamide, rare earth metals, single molecule magnets, susceptibility, vibrational spectroscopy.
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