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

Zouhair Asfari, Eric J. Chan, Jack M. Harrowfield, Brian W. Skelton, Alexandre N. Sobolev, Pierre Thuéry, Allan H. White

Research output: Contribution to journalArticle

3 Citations (Scopus)

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.

Original languageEnglish
JournalAustralian Journal of Chemistry
DOIs
Publication statusE-pub ahead of print - 17 Jun 2019

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Lanthanoid Series Elements
Dimethyl Sulfoxide
Atoms
Ligands
Stoichiometry
Picrates
Metals
Prisms
Isomers
Single crystals
Oxygen
X rays
picric acid

Cite this

@article{0d0a265cee5645bdb01c1e70af7faa68,
title = "Structural Systematics of Lanthanide(iii) Picrate Solvates: Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays",
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.",
author = "Zouhair Asfari and Chan, {Eric J.} and Harrowfield, {Jack M.} and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and Pierre Thu{\'e}ry and White, {Allan H.}",
year = "2019",
month = "6",
day = "17",
doi = "10.1071/CH19169",
language = "English",
journal = "Australian Journal of Chemistry:an international journal for chemical science",
issn = "0004-9425",
publisher = "CSIRO Publishing",

}

Structural Systematics of Lanthanide(iii) Picrate Solvates : Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays. / Asfari, Zouhair; Chan, Eric J.; Harrowfield, Jack M.; Skelton, Brian W.; Sobolev, Alexandre N.; Thuéry, Pierre; White, Allan H.

In: Australian Journal of Chemistry, 17.06.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural Systematics of Lanthanide(iii) Picrate Solvates

T2 - Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays

AU - Asfari, Zouhair

AU - Chan, Eric J.

AU - Harrowfield, Jack M.

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - Thuéry, Pierre

AU - White, Allan H.

PY - 2019/6/17

Y1 - 2019/6/17

N2 - 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.

AB - 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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