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)‐κ4O:O′;κ3O,O′:O′;κ3O:O,O′‐bis[(1,2‐dimethoxyethane‐κ2O,O′)(2,2‐diphenylacetato‐κ2O,O′)europium(III)], [Eu(C14H11O2)6(C4H10O2)2], (I), and tetrakis(μ‐2,2‐diphenylacetato)‐κ4O:O′;κ3O,O′:O′;κ3O:O,O′‐bis[(1,2‐dimethoxyethane‐κ2O,O′)(2,2‐diphenylacetato‐κ2O,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 κ2O,O′‐terminal, bidentate μ2‐κ1O:κ1O′‐bridging and tridentate μ2‐κ1O:κ2O,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)‐κ4O:O′;κO‐europium(III) methanol disolvate, [Eu(C19H15O2)3(CH3OH)4]·2CH3OH, (III)·2MeOH, with triclinic (P) 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. |