Journal of Chemical Crystallography

, Volume 47, Issue 1–2, pp 30–39 | Cite as

Synthesis and X-ray Crystal Structure of 2 and 4-Trifluoromethyl Substituted Phenyl Semicarbazone and Thiosemicarbazone

  • T. K. Venkatachalam
  • Paul V. Bernhardt
  • Gregory K. Pierens
  • David C. Reutens
Original Paper

Abstract

NMR and single crystal X-ray structure data for four structurally similar semicarbazones and thiosemicarbazones were compared. In solution, proton NMR showed considerable variation in their chemical shift values especially for the NH2 protons. In the case of the semicarbazones this peak appeared as a broad singlet with an integration ratio of two while for the thiosemicarbazones the amino group showed two distinct singlets with marked chemical shift differences. This is attributed to the differences in the canonical forms of the thiosemicarbazone amino group and the semicarbazone analogue. Additionally, we provide evidence that the 2-trifluoromethyl phenyl substituted semicarbazone (2) formed an intermolecular hydrogen bond with one of the hydrogens of the NH2 group while this was totally absent in the thiosemicarbazone. We explain this by the restricted rotation of the CN bond in the thiosemicarbazone due to its double bond character compared to the less restricted rotation in semicarbazone compound.

Graphical Abstract

NMR and single crystal X-ray structure data for four structurally similar semicarbazones and thiosemicarbazones were compared for their hydrogen bonding characteristics.

Keywords

Semicarbazones NMR X-ray crystal structure Hydrogen bond 

Notes

Acknowledgements

This research work is partially supported by a Linkage Grant (LP130100703 for DCR) from Australian Research Council Australia.

Supplementary material

10870_2017_677_MOESM1_ESM.pdf (350 kb)
Supplementary material 1 (PDF 349 KB)

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Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • T. K. Venkatachalam
    • 1
  • Paul V. Bernhardt
    • 2
  • Gregory K. Pierens
    • 1
  • David C. Reutens
    • 1
  1. 1.Centre for Advanced ImagingThe University of QueenslandBrisbaneAustralia
  2. 2.School of Chemistry and Molecular BiosciencesThe University of QueenslandBrisbaneAustralia

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