Abstract: | The crystal structures of rare‐earth diaryl‐ or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]chloridotetrakis(methanol‐κO )neodymium methanol disolvate, [Nd(C24H34O4P)Cl(CH4O)4]·2CH3OH, (1), and of the lutetium, [Lu(C24H34O4P)Cl(CH4O)4]·2CH3OH, (2), and yttrium, [Y(C24H34O4P)Cl(CH4O)4]·2CH3OH, (3), analogues have been obtained by reactions between lithium bis(2,6‐diisopropylphenyl)phosphate and LnCl3(H2O)6 (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C 2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6‐diisopropylphenyl)phosphate ligands all display a κ1O‐monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O2P(O‐2,6‐iPr2C6H3)2}2Cl(CH3OH)4] molecular unit exhibits two intramolecular O—H…O hydrogen bonds, forming six‐membered rings, and two intramolecular O—H…Cl interactions, forming four‐membered rings. Intermolecular O—H…O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two‐dimensional hydrogen‐bond network. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]tetrakis(methanol‐κO )(nitrato‐κ2O ,O ′)neodymium methanol disolvate, [Nd(C24H34O4P)(NO3)(CH4O)4]·2CH3OH, (4), have been obtained in an analogous manner from NdCl3(H2O)6. Compound (4) also crystalizes in the C 2/c space group. Its crystal structure is similar to those of (1)–(3). The κ2O ,O ′‐bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CNNd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO3− ligand. The structure of (4) displays intra‐ and intermolecular O—H…O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare‐earth complexes. |