The effect of the rcation/ranion ratio on the structural and chemical properties of N-chloroarenesulfonamidates

Isabella Lois, Eszter Holló-Sitkei, László Párkányi, Gábor Keresztury, István Sajó, Gábor Besenyei

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Abstract

A comparative structural study on sodium and potassium N-chloroarenesulfonamidates has been carried out using X-ray diffraction and IR spectroscopy as experimental techniques. As shown by crystallographic studies, the sodium ions tend to incorporate more water oxygen atoms in their coordination spheres than the potassium ions, while the potassium congeners prefer the interaction with sulfonamidate moieties. The marked dissimilarity between the compositions of the coordination spheres as well as the different tendency of the sodium and potassium salts to absorb moisture from the air have been attributed to the different sizes of the sodium and potassium ions. The opposite shifts of the νas(SO2) and ν(SN) bands upon dehydration have been ascribed to an increased polarization of the sulfonyl group by the metal centers. Based on IR spectroscopic observations, a weakening of the N-Cl bonds is suspected in the water-free compounds, which may contribute to the known thermal instability of the dehydrated salts of N-chloroarenesulfonamides. Various sections of IR spectra as well as X-ray powder diffraction patterns have proved to be suitable to identify the water-free and hydrated samples.

Original languageEnglish
Pages (from-to)2686-2696
Number of pages11
JournalInorganica Chimica Acta
Volume360
Issue number8
DOIs
Publication statusPublished - May 30 2007

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Keywords

  • Anhydrous chloramine-T
  • Dehydration/rehydration
  • N-Cl bond
  • Radius ratio rule
  • X-ray structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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