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Identification of robust synthon in the molecular salts of 2-aminothiazole with substituted benzoic acids: A case study

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Abstract

Six new salts of an API intermediate 2-aminothiazole with different carboxylic acid coformers were synthesized and characterized by IR (Infrared spectroscopy), 1H-NMR, DSC (Differential scanning calorimetry), XRPD (X-ray powder diffraction) and single crystal XRD. The crystal structure of the salts with benzoic acid, 2,3-, 2,4-, 2,5-, 2,6- dihydroxybenzoic acids and 2,4-dinitrobenzoic acid were determined. The thiazole moiety exhibited solvent (polarity) assisted tautomerism in all reported salts and proton transfer was noticed to the ring N of thiazole due to which two point supramolecular synthon N+−H(thiazole)⋯O−(acid), N−H(amine)⋯O−(acid) was observed. The crystal structures were studied with respect to the positional effect of the competing functional groups like hydroxyl (−OH) and nitro (−NO2) as well as their donor and acceptor abilities for hydrogen bonding. The presence of the non-conventional hydrogen bond (C−H⋯O) has been found to play a critical role in the formation of secondary supramolecular architectures.

A series of new salts of 2-aminothiazole with substituted benzoic acids were reported and the robustness of the two point supramolecular synthon is explored.

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References

  1. Huang K, Britton D, Etter M C and Byrn S R 1997 J. Mater. Chem. 7 713

  2. (a) Gao X, Friscic T and MacGillivray L R 2004 Ange. Chem. Int. Ed. 43 232; (b) Xiao J, Yang M, Laugher J W and Fowler F W 2000 Angew. Chem. Int. Ed. 39 2132

  3. (a) Ma B Q, Zhang M and Coppens P 2002 Cryst. Growth Des. 2 7; (b) MacGillivray L R, Diamente P R, Reid J L and Ripmeester J A 2001 Chem. Commun. 1034; (c) MacGillivray L R, Diamente P R, Reid J L, Ripmeester J A 2000 Chem. Commun. 359

  4. Taylor L D and Warner J C Process and composition for use in photographic materials containing hydroquinones. U.S. patent 5338644 A August 16, 1994. Cont. of U.S. 5, 177, 262

  5. Dastidar P 2008 Chem. Soc. Rev. 37 2699

  6. Desiraju G R 1995 Angew. Chem. Int. Ed. Engl. 34 2311

  7. Brody T 1999 In Nutritional Biochemistry (2nd ed.) (San Diego: Academic Press)

  8. Martin P R, Singleton C K and Hiller-Sturmhofel S 2003 Alcohol Research and Health 27 134

  9. Metzger J V In Thiazole and its Derivatives (II) 1979 (New York: John Wiley & Sons)

  10. Décor A, Grand-Maître C, Hucke O, O’Meara J, Kuhn C, Constantineau-Forget L, Brochu C, Malenfant E, Bertrand-Laperle M, Bordeleau J, Ghiro E, Pesant M, Fazal, G, Gorys V, Little M, Boucher C, Bordeleau S, Turcotte P, Guo T, Garneau M, Spickler C and Gauthier A 2013 Bioorg. Med. Chem. Lett. 13 3481

  11. Yadapalli R K, Chourastra O P, Jogi, M P, Podile A R and Perali R S 2013 Med. Chem. Res. 22 2785

  12. Samadhiya P, Sharma R, Srivastava S K and Srivastava S D 2012 J. Serb. Chem. Soc. 77 5995

  13. Li M, Sim Y and Ham S W 2010 Bull. Korean Chem. Soc. 31 1463

  14. Nardelli M, Pellizi G, Vitali F, Bordi, F, Plazzi, P V and Vitali T 1987 Acta Crystallogr. C 43 507

  15. Jin S, Yan P, Wang D, Xu, Y, Jiang, Y, Hu L 2012 J. Mol. Struc. 1016 55

  16. Lynch D E, Smith G, Byriel K A and Kenard C H L 1998 Aust. J. Chem. 51 587

  17. Kuz’mina L G and Struchkov Y T 1984 Zh. Struckt. Khim 25 88

  18. Mohamed H A, EI-Medani S M and Ramadan R M 2005 J. Indian Chem. Soc. 82 799

  19. Lynch D E, Nicholis L J, Smith G, Byriel K A and Kennard C H L Acta Cryst. B 55 758

  20. Kelleher J M, Lawrence S E, Moynihan H A 2006 Cryst. Eng. Comm. 6 327

  21. Cheney M L, Weyna D R, Shan N, Hanna M, Wojtas L and Zaworotko M 2010 Cryst. Growth Des. 10 4401

  22. (a) Childs S L, chyall L J, Dunlap J T, Smolenskaya, V N, Stahly B C and Stahly G P 2004 J. Am. Chem. Soc. 56 241; (b) Tao Q, Chen J, Ma L and Lu T 2012 Cryst. Growth Des. 12 3144; (c) Nishiguchi N, Kinuta T, Sato T, Nakano Y, Harada T, Tajima N, Fujiki M, Kuroda R, Matsubara Y and Imai Y 2012 Cryst. Growth Des. 12 1859; (d) Okuno T, Sakoda Y, Kinuta T, Sato T, Tokutome H, Tajima N, Nakano Y, Fujiki M, Kuroda R and Imai Y 2012 Cryst. Eng. Comm. 14 4819; (e) Smith G, Wermuth U D and Healy P C 2006 Acta Cryst. Sect. E: Struct. Rep. Online 62 o1863; (f) Imai Y, Murata K, Asano N, Nakano Y, Kawaguchi K, Harada T, Sato T, Fujiki M, Kuroda R and Matsubara Y 2008 Cryst. Growth Des. 8 3376; (g) Lemmerer A 2011 Cryst. Growth Des. 11 583; (h) Ivanova B and Spiteller M 2011 Spectrochim. Acta Part A 77 849; (i) Chen S, Patrick B O, Scheffer J R 2004 J. Org. Chem. 69 2711; (j) Smith G and Wermuth U D 2011 Acta Crystallogr. Sect. E: Struct. Rep. Online 67 O2461; (k) Tani T, Sada K, Ayabe M, Iwashita Y, Kishida T, Shirakawa M, Fujita N and Shinkai S 2004 Collect. Czech. Chem. Commun. 69 1292; (l) Nishiguchi N, Kinuta T, Sato T, Nakano Y,Tokutome H, Tajima N, Fujiki M, Kuroda R, Matsubara Y and Imai Y 2012 Chem. Asian J. 7 360; (m) Lemmerer A 2012 J. Chem. Cryst. 42 498; (n) Lemmerer A 2011 Acta Cryst. Sect. C: Cryst. Struct. Commun. 67 o92; (o) Koshima H, Nagano M and Asahi T 2005 J. Am. Chem. Soc. 127 2455; (p) Das U K, Trivedi D R, Adarsh N N and Dastidar P 2009 J. Org. Chem. 74 7111

  23. (a) Ji B, Deng D, Ma N, Miao S, Ji L, Liu P and Li X 2011 Cryst. Growth Des. 11 4090; (b) Li J, Tao Y, Yu Q and Bu X 2006 Cryst. Growth Des. 11 2493; (c) Mac Donald J C, Dorrestein P C and Pilley M M 2001 Cryst. Growth Des. 1 29; (d) Aakeroy, C B, Desper J, Leonard B and Urbina J F 2005 Cryst. Growth Des. 5865; (e) Lemmerer A, Bourne S A and Fernendes M A 2008 Cryst. Growth Des. 8 1106

  24. (a) Ermer O and Eling A 1994 J. Chem. Soc. Perkin Trans. 2 925; (b) Hannesian S, Simard M and Roelens S 1995 J. Am. Chem. Soc. 117 7360; (c) Allen F H, Hoy V J, Howard J A K, Thalladi V R, Desiraju G R, Wilson C C and McIntyre G J 1997 J. Am. Chem. Soc. 119 3477; (d) Vangala V R Bhogala B R, Dey A, Desiraju G R, Broder C K, Smith P S, Mondal R, Howard, J A K Wilson C C 2003 J. Am. Chem. Soc. 14495; (e) Hannesian S, Saladino R, Margarita R and Simard M 1999 Chem. Eur. J. 5 2169; (f) Dey A, Desiraju G R, Mondal R and Howard J A K 2004 Chem. Commun. 2528

  25. (a) Aakeroy C B and Salmon D J 2005 Cryst EngComm. 7 439; (b) Grossel C M, Dwyer A N, Hursthouse M B and Orton J B 2006 Cryst. Eng. Commun. 8 123; (c) Varughese S and Pedireddi V R 2006 Chem. Eur. J. 12 1597; (d) Du M, Zhang Z H, Zhao X J, Cai H 2006 Cryst. Growth Des. 6 114; (e) Bond A D 2003 Chem Commun. 250; (f) Bhogala B R and Nangia A 2008 New J. Chem. 32 800; (g) Sarma B, Nath, N K, Bhogala B and Nangia A 2009 Cryst. Growth Des. 9 1546; (h) Bis, J A and Zaworotko M J 2005 Cryst. Growth Des. 5 1169

  26. Oxford Diffraction, CrysAlis PRO, Oxford Diffraction Ltd., Yarnton, England 2009

  27. Bruker SMART V5.630, SAINT-PLUS V6.45 and SADABS Bruker Analytical X-ray Systems Inc., Madison, Wisconsin, USA, 2003

  28. Sheldrick G M 2008 Acta Crystallogr. A 64 112

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Acknowledgements

D R T and M O would like to acknowledge the Director and HOD (Chemistry Department), NITK Surathkal for providing the research infrastructure. M O is grateful to NITK Surathkal for the fellowship. D R T and M O are also thankful to the Metallurgy Department for the PXRD facility. D R T and M O are indebted to the CSMCRI for extending NMR facility.

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Authors and Affiliations

  1. Supramolecular Chemistry Laboratory, Department of Chemistry, National Institute of Technology Karnataka (NITK), Surathkal, Mangalore, 575 025, India

    MADHAVI ORUGANTI & DARSHAK R TRIVEDI

  2. National Single Crystal Diffractometer Facility, University of Hyderabad, Hyderabad, 500 046, India

    RAGHAVAIAH PALLEPOGU

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  1. MADHAVI ORUGANTI
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Correspondence to DARSHAK R TRIVEDI.

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Supplementary Information

IR spectral data of the salts;1H NMR spectra of the salts; DSC of the salts; XRPD of the bulk salt samples. Crystallographic information files (CIF’s) have been deposited at the Cambridge Crystallographic Data Centre; CCDC Nos. 919166 for 1a, 919167 for 1b, 919168 for 1c, 919169 for 1d, 919171 for 1e, 924125 for 1f. This material is available free of charge via internet at http://www.ccdc.cam.ac.uk or E-mail: deposit@ccdc.cam.ac.uk.

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ORUGANTI, M., PALLEPOGU, R. & TRIVEDI, D.R. Identification of robust synthon in the molecular salts of 2-aminothiazole with substituted benzoic acids: A case study. J Chem Sci 126, 1291–1302 (2014). https://doi.org/10.1007/s12039-014-0693-x

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  • DOI: https://doi.org/10.1007/s12039-014-0693-x

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