Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bondsстатья
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Аннотация:The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are
poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-O]chloridotetrakis(
methanol-O)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 C2/c space group. Their crystal structures are isomorphous. The
molecule possesses C2 symmetry with a twofold crystallographic axis passing
through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands
all display a 1O-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-O]tetrakis(methanol-O)(nitrato-2O,O0)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 C2/c space group. Its crystal structure is similar to those of
(1)–(3). The 2O,O0-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.