Mercury complexes with thiacrowns: The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate

Monte Helm, Donald G. Vanderveer, Gregory J. Grant

Research output: Contribution to journal › Article

13 Citations (Scopus)

Abstract

We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3), bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg-S distances (2.623(2), 2.708(2), 2.784(2) Å) with a tetragonal elongation. The 199Hg{1H} NMR spectrum exhibits a single resonance with a chemical shift at -596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, β = 123.358(2)°, V = 2777.9(6) Å3, Z = 4.

Original languageEnglish
Pages (from-to)625-630
Number of pages6
JournalJournal of Chemical Crystallography
Volume33
Issue number8
DOIs
Publication statusPublished - Aug 2003

Fingerprint

Mercury
Crystal structure
crystal structure
Sulfides
Salts
Ligands
salts
nuclear magnetic resonance
ligands
Stereoisomerism
Coordination Complexes
Chemical shift
perchlorates
Crowns
Nuclear magnetic resonance spectroscopy
elongation
chemical equilibrium
Cations
Elongation
Magnetic Resonance Spectroscopy

Keywords

  • 1,4,7-trithiacyclodecane
  • Crown thioethers
  • Mercury complexes
  • Mercury NMR

ASJC Scopus subject areas

  • Spectroscopy
  • Condensed Matter Physics
  • Structural Biology

Cite this

Mercury complexes with thiacrowns : The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate. / Helm, Monte; Vanderveer, Donald G.; Grant, Gregory J.

In: Journal of Chemical Crystallography, Vol. 33, No. 8, 08.2003, p. 625-630.

Research output: Contribution to journal › Article

Helm, M, Vanderveer, DG & Grant, GJ 2003, 'Mercury complexes with thiacrowns: The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate', Journal of Chemical Crystallography, vol. 33, no. 8, pp. 625-630. https://doi.org/10.1023/A:1024954028516
Helm M, Vanderveer DG, Grant GJ. Mercury complexes with thiacrowns: The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate. Journal of Chemical Crystallography. 2003 Aug;33(8):625-630. https://doi.org/10.1023/A:1024954028516
Helm, Monte ; Vanderveer, Donald G. ; Grant, Gregory J. / Mercury complexes with thiacrowns : The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate. In: Journal of Chemical Crystallography. 2003 ; Vol. 33, No. 8. pp. 625-630.
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abstract = "We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3), bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg-S distances (2.623(2), 2.708(2), 2.784(2) {\AA}) with a tetragonal elongation. The 199Hg{1H} NMR spectrum exhibits a single resonance with a chemical shift at -596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) {\AA}, b = 15.235(2) {\AA}, c = 11.3791(15) {\AA}, β = 123.358(2)°, V = 2777.9(6) {\AA}3, Z = 4.",
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AB - We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3), bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg-S distances (2.623(2), 2.708(2), 2.784(2) Å) with a tetragonal elongation. The 199Hg{1H} NMR spectrum exhibits a single resonance with a chemical shift at -596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, β = 123.358(2)°, V = 2777.9(6) Å3, Z = 4.

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