Structural Systematics of Lanthanide(iii) Picrate Solvates: Hexamethylphosphoramide and Octamethylpyrophosphoramide Adducts
Eric J. Chan A , Jack M. Harrowfield A B D , Brian W. Skelton A , Alexandre N. Sobolev A and Allan H. White A CA School of Molecular Sciences, M310, University of Western Australia, 35 Stirling Hwy, Perth, WA 6009, Australia.
B Current address: Institut de Science et d’Ingénierie Supramoléculaires, Université de Strasbourg, 8, allée Gaspard Monge, Strasbourg, 67083, France.
C Deceased.
D Corresponding author. Email: harrowfield@unistra.fr
Australian Journal of Chemistry 73(6) 477-487 https://doi.org/10.1071/CH19251
Submitted: 2 June 2019 Accepted: 27 August 2019 Published: 9 October 2019
Abstract
Crystalline products of the reactions of lanthanide picrates, Ln(pic)3 (pic = 2,4,6-trinitrophenoxide), with hexamethylphosphoramide (hmpa) and octamethylpyrophosphoramide (ompa) have been characterised by single-crystal X-ray diffraction studies. With hmpa and lighter lanthanides (La, Sm, Eu), isomorphous species (monoclinic, P21/c, Z 4) of stoichiometry [Ln(pic)3(hmpa)3]·0.5H2O, have been defined where the molecular units in the lattice contain 9-coordinate Ln with tricapped trigonal-prismatic coordination geometry. The picrate ligands are bidentate through phenoxide-O and 2-nitro-O, with the latter occupying the capping positions, while the hmpa ligands are singly O-bound to one trigonal face. Heavier lanthanides (Gd, Lu) and Y have been found to give isomorphous (monoclinic, P21/n, Z 4) species of stoichiometry [Ln(pic)3(hmpa)2], with 8-coordinate Ln of an irregular geometry best considered as close to that of a bicapped trigonal-prism. The picrate ligands chelate in the same manner as in the lighter Ln complexes but with one spanning a trigonal edge, and the hmpa-O donors occuping two apices of the other trigonal face. The ligand ompa has been found to act as a bidentate chelate in all isolated species, displacing one picrate from the metal ion coordination sphere to give ionic complexes. For La, Nd, and Gd, isomorphous (monoclinic, P21/n, Z 4) complexes of stoichiometry [Ln(pic)2(ompa)2(OH2)](pic)·0.5H2O containing 9-coordinate, tricapped trigonal-prismatic Ln with a single aqua ligand have been defined, while for Er, Yb, Lu, and Y, both the coordinated and lattice water molecules are lost in isomorphous (monoclininc, P21/c, Z 8) 8-coordinate, square-antiprismatic species of stoichiometry [Ln(pic)2(ompa)2](pic). For Er, further polymorphs, one monoclinic, P21/c, and the other triclinic, 
, have also been characterised.
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