Di- and triphenylacetate complexes of yttrium and europium

Mikhail E Minyaev; Alexandr A Vinogradov; Dmitrii M Roitershtein; Konstantin A Lyssenko; Ivan V Ananyev; Ilya E Nifant'ev

doi:10.1107/S2053229616009748

Di- and triphenylacetate complexes of yttrium and europium

Acta Crystallogr C Struct Chem. 2016 Jul 1;72(Pt 7):578-84. doi: 10.1107/S2053229616009748. Epub 2016 Jun 23.

Authors

Mikhail E Minyaev¹, Alexandr A Vinogradov¹, Dmitrii M Roitershtein¹, Konstantin A Lyssenko², Ivan V Ananyev², Ilya E Nifant'ev¹

Affiliations

¹ A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prospect, Moscow 119991, Russian Federation.
² A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Str., Moscow 117813, Russian Federation.

PMID: 27377281
DOI: 10.1107/S2053229616009748

Abstract

The significant variety in the crystal structures of rare-earth carboxylate complexes is due to both the large coordination numbers of the rare-earth cations and the ability of the carboxylate anions to form several types of bridges between rare-earth metal atoms. Therefore, these complexes are represented by mono-, di- and polynuclear complexes, and by coordination polymers. The interaction of LnCl3(thf)x (Ln = Eu or Y; thf is tetrahydrofuran) with sodium or diethylammonium diphenylacetate in methanol followed by recrystallization from a DME/THF/hexane solvent mixture (DME is 1,2-dimethoxyethane) leads to crystals of the non-isomorphic dinuclear complexes tetrakis(μ-2,2-diphenylacetato)-κ(4)O:O';κ(3)O,O':O';κ(3)O:O,O'-bis[(1,2-dimethoxyethane-κ(2)O,O')(2,2-diphenylacetato-κ(2)O,O')europium(III)], [Eu(C14H11O2)6(C4H10O2)2], (I), and tetrakis(μ-2,2-diphenylacetato)-κ(4)O:O';κ(3)O,O':O';κ(3)O:O,O'-bis[(1,2-dimethoxyethane-κ(2)O,O')(2,2-diphenylacetato-κ(2)O,O')yttrium(III)], [Y(C14H11O2)6(C4H10O2)2], (II), possessing monoclinic (P21/c) symmetry. The [Ln(Ph2CHCOO)3(dme)]2 molecule (Ln = Eu or Y) lies on an inversion centre and exhibits three different coordination modes of the diphenylacetate ligands, namely bidentate κ(2)O,O'-terminal, bidentate μ2-κ(1)O:κ(1)O'-bridging and tridentate μ2-κ(1)O:κ(2)O,O'-semibridging. The terminal and bridging ligands in (I) are disordered over two positions, with an occupancy ratio of 0.806 (2):0.194 (2). The interaction of EuCl3(thf)2 with Na[Ph3CCOO] in methanol followed by crystallization from hot methanol produces crystals of tetrakis(methanol-κO)tris(2,2,2-triphenylacetato)-κ(4)O:O';κO-europium(III) methanol disolvate, [Eu(C19H15O2)3(CH3OH)4]·2CH3OH, (III)·2MeOH, with triclinic (P-1) symmetry. The molecule of (III) contains two O,O'-bidentate and one O-monodentate terminal triphenylacetate ligand. (III)·2MeOH possesses one intramolecular and four intermolecular hydrogen bonds, forming a [(III)·2MeOH]2 dimer with two bridging methanol molecules.

Keywords: crystal structure; diphenylacetate; europium; hydrogen bonding; molecular complex; rare-earth carboxylates; triphenylacetate; yttrium.