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Green synthesis, crystal growth, and some physicochemical studies on an inter-molecular compound of anthranilic acid and m-nitro-benzoic acid system

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Abstract

The phase diagram of anthranilic acid (AA)–m-nitro benzoic acid (NBA) system, determined by the thaw–melt method, shows the formation of a 2:1 (AA:NBA) inter-molecular compound (IMC) and two eutectics E1 and E2 containing 0.084 and 0.917 mol fractions of AA, respectively, with one eutectic on either side of the IMC. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and the excess thermodynamic functions were calculated from the enthalpy of fusion data, obtained by the DSC method. While the spectroscopic investigations (IR and NMR) and optical studies suggest the presence of hydrogen bonding between the components, the powder X-ray diffraction spectra of eutectics and the IMC suggest that the eutectic E1 is a mechanical mixture of the IMC and NBA and the eutectic E2 is a mechanical mixture of the IMC and AA. A single crystal of cocrystal of AA and NBA was grown using slow evaporation technique at room temperature from its saturated solution in methanol solvent. Single-crystal analysis of the grown cocrystal shows the mode of the intermolecular hydrogen bonding in the molecule and the triclinic crystal structure with P − 1 space group.

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References

  1. Sangster J. Phase diagrams and thermodynamic properties of binary organic systems based on 1,2-,1,3-,1,4-diaminobenzene or benzidine. J Phys Chem Ref Data. 1994;23(2):295–338.

    Article  CAS  Google Scholar 

  2. Rai RN, Reddi RSB, Rai US. Developments and future directions of phase diagram, physicochemical and optical studies of binary organic complexes. Prog Cryst Growth Charact Mater. 2013;59(2):73–111.

    Article  CAS  Google Scholar 

  3. Okumuş M. Thermal characterization of binary mixture of some supramolecular liquid crystals. J Therm Anal Calorim. 2015;120(3):1603–8.

    Article  Google Scholar 

  4. Rai US, Singh M. An overview of the progress in solidification of binary monotectics. J Mater Chem Eng. 2013;1(2):75–84.

    CAS  Google Scholar 

  5. Singh NB, Agrawal T, Gupta P, Das SS. Solidification behavior of the benzamide + O-chlorobenzoic acid eutectic system. J Chem Eng Data. 2009;54(5):1529–36.

    Article  CAS  Google Scholar 

  6. Chem YP, Tang M, Cuo TC. Solid–liquid equilibria for binary mixtures of N-phenylacetamide with 4-aminoacetophenone, 3-hydroxyacetophenone and 4-hydroxyacetophenone. Fluid Phase Equilib. 2005;232(2):182–8.

    Article  Google Scholar 

  7. Rai RN, Ramasamy P, Lan CW. Synthesis and crystal growth of binary organic NLO material UNBA. J Cryst Growth. 2002;235(1):499–504.

    Article  CAS  Google Scholar 

  8. Horiuchi S, Tokura Y. Organic ferroelectrics. Nat Mater. 2008;7(5):357–66.

    Article  CAS  Google Scholar 

  9. Horiuchi S, Kumari R, Tokura Y. A supramolecular ferroelectric realized by collective proton transfer. Angew Chem Int Ed. 2007;46(19):3497–501.

    Article  CAS  Google Scholar 

  10. Abbott AP, Taib KE, Frisch G, Ryder KS, Weston D. The electrodeposition of silver composites using deep eutectic solvents. Phys Chem Chem Phys. 2012;14(7):2443–9.

    Article  CAS  Google Scholar 

  11. Sechiguchi K, Obi N. Studies on absorption of eutectic mixture. I. A comparison of the behavior of eutectic mixture of sulfathiazole and that of ordinary sulfathiazole in man. Chem Pharm Bull. 1961;9(11):866–72.

    Article  Google Scholar 

  12. Cherukuvada S, Nangia A. Eutectics as improved pharmaceutical materials: design, properties and characterization. Chem Commun. 2014;50(8):906–23.

    Article  CAS  Google Scholar 

  13. Springwl G, Norberg B, Robeyns K, Wouters J, Leyssess T. Advances in pharmaceutical co-crystal screening: effective co-crystal screening through structural resemblance. Cryst Growth Des. 2012;12(1):475–84.

    Article  Google Scholar 

  14. Desiraju GR. Supramolecular synthons in crystal engineering—a new organic synthesis. Angew Chem Int Ed Engl. 1995;34:2311–27.

    Article  CAS  Google Scholar 

  15. Fan E, Vincent C, Geib SJ, Hamilton AD. Molecular recognition in the solid state: hydrogen-bonding control of molecular aggregation. Chem Mater. 1994;6:1113–7.

    Article  CAS  Google Scholar 

  16. Dean JA. Lange’s handbook of chemistry. New York: McGraw-Hill; 1985.

    Google Scholar 

  17. Singh M, Rai RN, Rai US. Synthesis, crystal growth and physicochemical studies on a novel organic inter-molecular compound; 3,5-dinitrobenzoic acid and salicylamide system. J Cryst Growth. 2015;419:114–22.

    Article  CAS  Google Scholar 

  18. Reddi RSB, Kant S, Rai US, Rai RN. Crystallization, thermal, phase diagram and microstructural studies of organic analog of metal–nonmetal monotectic alloy: 4-bromochlorobenzene–succinonitrile. J Cryst Growth. 2009;312:95–9.

    Article  CAS  Google Scholar 

  19. Sheldirck GM. Shelex-97, program for crystal structure refinement from diffraction data. Gottingen: University of Gottingen; 1997.

    Google Scholar 

  20. Rai US, Singh M, Rai RN. Solid state synthesis, structural, physicochemical and optical properties of an inter-molecular compound: 2-hydroxy-1,2-diphenylethanone-4-nitro-ophenylenediamine system. J Solid State Chem. 2017;253:63–72.

    Article  CAS  Google Scholar 

  21. Rai RN, Verma KBR. Phase diagram and dielectric studies of binary organic materials. Mater Lett. 2000;44:284–93.

    Article  CAS  Google Scholar 

  22. Singh M, Rai US, Rai RN. Some physicochemical and thermal studies on organic analog of a nonmetal-nonmetal monotectic alloy; 2-cyanoacetamide–4-chloronitrobenzene system. Am J Anal Chem. 2011;2:953–61.

    Article  CAS  Google Scholar 

  23. Reddi RSB, Ganesamoorthy S, Gupta PK, Rai RN. Phase equilibria, crystallization, thermal and microstructural studies on organic monotectic analog of nonmetal–nonmetal system; urea–4-bromo-2-nitroaniline. Fluid Phase Equilib. 2012;313:121–6.

    Article  Google Scholar 

  24. Rai US, Singh M, Rai RN. Some physicochemical studies on organic eutectics and intermolecular compounds. J Therm Anal Calorim. 2017. https://doi.org/10.1007/s10973-017-6429-7.

    Article  Google Scholar 

  25. Reddi RSB, Kumar Satuluri VSA, Rai US, Rai RN. Thermal, physicochemical and microstructural studies of binary organic eutectic systems. J Therm Anal Calorim. 2012;107:377–85.

    Article  CAS  Google Scholar 

  26. Reddi RSB, Kumar Satuluri VSA, Rai RN. Solid–liquid equilibrium, thermal and physicochemical studies of organic eutectics. J Therm Anal Calorim. 2012;107:183–8.

    Article  CAS  Google Scholar 

  27. Rai US, Singh M, Rai RN. Green synthesis, characterization and some physico-chemical studies on a novel intermolecular compound; 4-nitro-ophenylenediamine-N,N-dimethylaminobenzaldehyde system. J Mol Struct. 2017;1144:41–8.

    Article  CAS  Google Scholar 

  28. Kalsi PS. Spectroscopy of organic compounds. 6th ed. India: New Age Publication; 2005.

    Google Scholar 

  29. Naumov P, Ohashi Y. Packing-dependent photochromism: the case of photoinduced intramolecular proton transfer in 6-(2′,4′-dinitrobenzyl)-2,2′-bipyridine. Acta Cryst. 2004;B60:343–9.

    Article  CAS  Google Scholar 

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Acknowledgements

Authors thank the University Grant Commission (UGC), India, and BHU for financial support to MS.

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Authors and Affiliations

  1. Department of Chemistry, Centre of Advanced Study, Institute of Science, Banaras Hindu University, Varanasi, 221005, India

    U. S. Rai, Manjeet Singh & R. N. Rai

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  1. U. S. Rai
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  2. Manjeet Singh
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  3. R. N. Rai
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Correspondence to U. S. Rai.

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Rai, U.S., Singh, M. & Rai, R.N. Green synthesis, crystal growth, and some physicochemical studies on an inter-molecular compound of anthranilic acid and m-nitro-benzoic acid system. J Therm Anal Calorim 134, 1001–1009 (2018). https://doi.org/10.1007/s10973-018-7344-2

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