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Response to Heterocyclic tautomerism: reassignment of two crystal structures of 2-amino-1,3-thiazolidin-4-one derivatives by Gzella et al. (2014)

aInstitute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Republic, and bDepartment of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Republic
*Correspondence e-mail: jiri.hanusek@upce.cz

(Received 8 July 2014; accepted 21 July 2014; online 31 July 2014)

Prototropy tautomerism and E/Z-stereoisomerism of 2-im­ino­thia­zolidin-4-ones was extensively studied in the literature during the past several decades. This tautomerism was studied for both alk­yl/ar­yl–amino/imino-substituted thia­zolidinones/thia­zolinones by several authors (Comrie, 1964[Comrie, A. (1964). J. Chem. Soc. p. 3478.]; Åkerblom, 1967[Åkerblom, E. (1967). Acta Chem. Scand. 21, 1437-1442.]; Chowdry et al., 2000[Chowdry, M. M., Mingos, D. M. P., White, A. J. P. & Williams, D. J. (2000). J. Chem. Soc. Perkin Trans. 2, pp. 2265-2268.]; Mornon & Raveau, 1971[Mornon, J.-P. & Raveau, B. (1971). Acta Cryst. B27, 95-108.]; Ramsh et al., 1978[Ramsh, S. M., Ginak, A. I., Sochilin, E. G. & Skachko, T. G. (1978). Zh. Org. Khim. 14, 1070.]) in the solid state, as well as in solution, and the results can be generalized as follows. Exo-N-unsubstituted and N-alkyl-substituted compounds exist in solution preferentially as 2-(alk­yl)amino­thia­zolin-4-ones, whereas N-aryl-substituted com­pounds prefer the 2-(aryl­imino)­thia­zolidin-4-one arrange­ment, although some exceptions to this rule were also reported (Sedlák et al., 2002[Sedlák, M., Hejtmánková, L., Hanusek, J. & Macháček, V. (2002). J. Heterocycl. Chem. 39, 1105-1107.]; Kammel & Hanusek, 2014[Kammel, R. & Hanusek, R. J. (2014). J. Heterocycles, 89, 1183-1194.]). For example, in a recent article (Kammel & Hanusek, 2014[Kammel, R. & Hanusek, R. J. (2014). J. Heterocycles, 89, 1183-1194.]) we have found that base-catalyzed cyclization of N-isopropyl-S-(2-oxo-2,3-di­hydro-1-benzo­furan-3-yl)iso­thio­uronium bro­mide gives 5-(2-hy­droxy­phen­yl)-2-iso­propyl­imino-1,3-thia­zoli­din-4-one, which during crystallization or simple heating undergoes the above-mentioned prototropy tautomerism to give 5-(2-hy­droxy­phen­yl)-2-iso­propyl­amino-1,3-thia­zolin-4-one. From this observation it is evident that the solvent, purification method, temperature and other parameters can influence the position of tautomeric equilibrium and also the crystal packing. In our article from 2009 (Váňa et al., 2009[Váňa, J., Hanusek, J., Růžička, A. & Sedlák, M. (2009). J. Heterocycl. Chem. 46, 635-639.]), the single crystal of 5-(2-hy­droxy­eth­yl)-2-[(pyridin-2-yl)imino]-1,3-thia­zolidin-4-one was grown from di­methyl sulfoxide (DMSO), whereas the single crystal studied by Gzella et al. (2014[Gzella, A. K., Kowiel, M., Suseł, A., Wojtyra, M. N. & Lesyk, R. (2014). Acta Cryst. C70, 812-816.]) was grown from methanol from a sample previously prepared in refluxing ethanol. In order to support our refinement (Váňa et al., 2009[Váňa, J., Hanusek, J., Růžička, A. & Sedlák, M. (2009). J. Heterocycl. Chem. 46, 635-639.]), the following arguments are given: three peaks assignable to the `amino or imine' H atoms were located on our Fourier difference map under the given measurement conditions (150 K). Both tautomers were refined but based on the known NMR assignment, literature data and higher electron density we decided to refine the structure as the imine tautomer.

To conclude, we are surprised how Gzella et al. (2014[Gzella, A. K., Kowiel, M., Suseł, A., Wojtyra, M. N. & Lesyk, R. (2014). Acta Cryst. C70, 812-816.]) could suggest that our structure had an incorrectly-positioned H atom based on the measurement under different conditions on crystals grown from a different solvent, and last, but not least, from a disordered structure, when tautomerism is always a chemical equilibrium.

References

First citationÅkerblom, E. (1967). Acta Chem. Scand. 21, 1437–1442.  Google Scholar
First citationChowdry, M. M., Mingos, D. M. P., White, A. J. P. & Williams, D. J. (2000). J. Chem. Soc. Perkin Trans. 2, pp. 2265–2268.  Google Scholar
First citationComrie, A. (1964). J. Chem. Soc. p. 3478.  Google Scholar
First citationGzella, A. K., Kowiel, M., Suseł, A., Wojtyra, M. N. & Lesyk, R. (2014). Acta Cryst. C70, 812–816.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKammel, R. & Hanusek, R. J. (2014). J. Heterocycles, 89, 1183–1194.  CAS Google Scholar
First citationMornon, J.-P. & Raveau, B. (1971). Acta Cryst. B27, 95–108.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationRamsh, S. M., Ginak, A. I., Sochilin, E. G. & Skachko, T. G. (1978). Zh. Org. Khim. 14, 1070.  Google Scholar
First citationSedlák, M., Hejtmánková, L., Hanusek, J. & Macháček, V. (2002). J. Heterocycl. Chem. 39, 1105–1107.  Google Scholar
First citationVáňa, J., Hanusek, J., Růžička, A. & Sedlák, M. (2009). J. Heterocycl. Chem. 46, 635–639.  Google Scholar

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