Effect of Synthesis and Crystallization Conditions on the Composition and Structure of Europium(III) Mixed-Carboxylate Benzoate–Pentafluorobenzoate Complexes

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Abstract

In the present work, the influence of the nature of the solvate molecules and N-donor ligands on the structures of the benzoate–pentafluorobenzoate europium complexes was investigated. It was established that the reaction of europium benzoate (bz) and pentafluorobenzoate (pfb) with 1,10-phenanthroline (phen) in acetonitrile in the presence of toluene, o-xylene, or dichloromethane leads to the formation of compounds [Eu2(phen)2(pfb)4(bz)2]·4C6H5CH3 (I), [Eu2(phen)2(pfb)4(bz)2]·4C6H4(CH3)2 (II), and [Eu2(phen)2(pfb)4 (bz)2]·2.898CH2Cl2 (III), respectively, which possess similar structures. Using quinoline (quin) as the N-donor ligand, mixed-carboxylate coordination polymer crystals [Eu(H₂O)(pfb)2(bz)]n·2n(quin) (IV) were obtained in good yield. The synthesized compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, and CHN elemental analysis. Non-covalent interactions were analyzed by Hirshfeld surface analysis.

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About the authors

M. A. Shmelev

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: shmelevma@yandex.ru
Russian Federation, Moscow

D. S. Lebedev

Faculty of Chemistry, HSE University

Email: shmelevma@yandex.ru
Russian Federation, Moscow

A. S. Chistyakov

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: shmelevma@yandex.ru
Russian Federation, Moscow

J. K. Voronina

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: shmelevma@yandex.ru
Russian Federation, Moscow

L. M. Efromeev

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences; Faculty of Chemistry, HSE University

Email: shmelevma@yandex.ru
Russian Federation, Moscow; Moscow

A. V. Rogachev

MIREA — Russian technological university

Email: shmelevma@yandex.ru
Russian Federation, Moscow

A. A. Sidorov

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: shmelevma@yandex.ru
Russian Federation, Moscow

I. L. Eremenkoa

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: shmelevma@yandex.ru
Russian Federation, Moscow

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Supplementary files

Supplementary Files
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1. JATS XML
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2. Fig. 1. Structure of complexes I (a), II (b), III (c). Hydrogen atoms are not shown. The dotted lines indicate π···π- and C‒F···π-interactions.

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3. Fig. 2. Fragment of the crystal packing of complexes I (a) and III (b). The dotted lines show π···π- and C‒F···π-interactions.

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4. Fig. 3. Fragment of the crystal packing of compound IV. The dotted lines show π···π-interactions and hydrogen bonds.

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5. Fig. 4. Hirschfeld surface for complexes I (a), II (b), III (c) and IV (d).

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6. Fig. 5. Two-dimensional fingerprint plots corresponding to the C···F (a), H···F (b), O···H (c), C···H (d), C···C (e), and H···H (e) interactions in structure I.

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7. Fig. 6. Two-dimensional fingerprint plots corresponding to the C···F (a), H···F (b), O···H (c), C···H (d), C···C (e), and H···H (e) interactions in structure II.

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8. Fig. 7. Two-dimensional fingerprint plots corresponding to the interactions C F (a), H F (b), O H (c), C H (d), C C (e), H H (f), C Cl (g), and H Cl (h) in structure III.

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9. Fig. 8. Two-dimensional fingerprint plots corresponding to the C···F (a), H···F (b), O···H (c), C···H (d), C···C (e), and H···H (e) interactions in structure IV.

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10. Scheme 1. Synthesis of compounds I‒IV.

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