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RESEARCH ARTICLE
Contents Vol 73(6)

Structural Systematics of Lanthanide(iii) Picrate Solvates: Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays

Zouhair Asfari A , Eric J. Chan B , Jack M. Harrowfield B C F , Brian W. Skelton B , Alexandre N. Sobolev B , Pierre Thuéry D and Allan H. White B E
+ Author Affiliations
- Author Affiliations

A IPHC, Université de Strasbourg, 23 rue du Loess, Strasbourg, 67200, France.

B School of Molecular Sciences, M310, University of Western Australia, 35 Stirling Highway, Perth, WA 6009, Australia.

C Current address: Institut de Science et d’Ingénierie Supramoléculaires, Université de Strasbourg, 8 allée Gaspard Monge, Strasbourg, 67083, France.

D NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay, 91191 Gif-sur-Yvette, France.

E Deceased.

F Corresponding author. Email: harrowfield@unistra.fr

Australian Journal of Chemistry 73(6) 447-454 https://doi.org/10.1071/CH19169
Submitted: 13 April 2019  Accepted: 20 May 2019   Published: 17 June 2019

Abstract

Adducts of dimethylsulfoxide, dmso = Me2SO, with lanthanide(iii) picrates (picrate = 2,4,6-trinitrophenoxide, pic) of stoichiometry Ln(pic)3·3dmso have been prepared and characterised by single-crystal X-ray structure determinations as discrete, neutral, mononuclear molecular species. Such complexes have been obtained across the gamut of Ln, specifically for Ln = La, Pr, Nd, Sm, Gd, Dy, Yb, Lu, and Y, presumably also accessible for other intermediate members, the series being isomorphous (monoclinic, C2/c, Z = 8); a second triclinic PCH19169_IE1.gif form has also been identified for Ln = La, Pr. In both forms, the metal atom coordination environments are nine-coordinate, tricapped trigonal prismatic, [Ln(dmso-O)3(pic-O,O′)3], two of the three unidentate ligands lying in one of the trigonal planes and one in the other (an isomer we have termed meridional, mer). A hydrated form of Ln(pic)3·2dmso·H2O stoichiometry has also been defined for Ln = Sm, Gd, Lu, the metal atom environment again nine-coordinate, [Ln(dmso-O)2(H2O)(pic-O,O′)3], but now fac, with the three unidentate ligands occupying one triangular face of the tricapped trigonal prism and involved in a centrosymmetric H-bonding array with the three similar ligands of an adjacent complex; the three capping atoms are nitro-oxygen atoms, the phenoxy-O triad occupying the other face.


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