Abstract
In this work, 3-nitroanilinium nitrate (3NAN) has been synthesized and crystallized successfully by solution growth combined with solvent evaporation technique. 3NAN molecular structure has been optimized with Density Functional Theory (DFT) using B3LYP function and Hartree–Fock method with a 6–311 + + G(d,p) basis set. The geometrical parameters of the title molecules have been analyzed. The computed vibrational spectra were compared with experimental result which show appreciable agreement. Thermal stability of the crystal was analyzed with TGA/DTA and the melting points of the salt identified at 209 ºC. HOMO–LUMO energy calculations have shown the charge transfer within the molecule. The possible pharmaceutical/biological activity of the salts confirmed by the Frontier Molecular Orbital (FMO) analysis have lower band gap value. The antimicrobial activity of grown crystals has been tested against certain potentially threatening microbes.
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Becke, A.D.: Density‐functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5653 (1993)
Bhuvaneswari, N., Priyadharsini, N., Sivakumar, S., Venkatachalam, K., Siva, V.: Growth, vibrational, optical, thermal, magnetic and dielectric behavior of organo-metallic tetramethyl ammonium cadmium chloride crystal. J. Therm. Anal. Calorim. 136, 411–417 (2018)
Bishop, D.M., Champagne, B., Kirtman, B.: Molecular vibration and nonlinear optics. J. Chem. Phys. 109, 9987–9994 (1998)
Chitradevi, A., Suresh Kumar, S., Athimoolam, S., Asath Bahadur, S., Sridhar, B.: Single crystal XRD, vibrational spectra, quantum chemical and thermal studies on a new semi-organic crystal: 4-Aminium antipyrine chloride. J. Mol. Struct. 1099, 58–67 (2015). https://doi.org/10.1016/j.molstruc.2015.06.022
David, W.I.F., Shankland, K., Vandestreek, J., Pidcock, E., Motherwell, W.D.S., Cole, J.C.: DASH: a program for crystal structure determination from powder diffraction data. J. Appl. Cryst. 39, 910–915 (2006)
Dennington, R., Keith, T., Millam, J., Gauss View Version 5.0.8 Semichem Inc., Shawnee Mission KS, (2013)
Drozd, M., Dudzic, D.: Guanidinium perchlorate ferroelectric crystal. Study of vibrational properties based on experimental measurements and theoretical calculations. Spectrochim. Acta Part A 115, 345–356 (2013). https://doi.org/10.1016/j.saa.2013.06.023
Fleming, I.: Frontier Orbitals and Organic Chemical Reactions. John Wiley & Sons, New York (1976)
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J.: Gaussian 09, Revision B.01. Gaussian Inc., Wallingford (2010)
Hohenberg, P., Kohn, W.: Inhomogeneous electron gas. Phys. Rev. B 136, 864–871 (1964)
Jain, A.K., Mehta, S.C., Shrivastava, N.M.: Hypoglycemic and antihyperglycemic effects of newly synthesized sulfonyloxy derivatives of azalactone in normal and alloxan diabetic rabbits. Indi. J. Pharmaco. 37, 395–396 (2005)
Jean, Y., Volatron, F.: An Introduction to Molecular Orbitals. Oxford University Press, Oxford (2005)
Karthiga Devi, P., Venkatachalam, K.: Growth, spectroscopic, mechanical, thermal, antimicrobial and DFT studies of piperidinium hydrogen oxalate. J. Mater Sci: Mater Electron. 28, 8061–8073 (2017). https://doi.org/10.1007/s10854-017-6512-7
Krishnakumar, V., Nagalakshmi, R.: Terahertz generation in 3-Nitroaniline single crystals. Cryst. Growth Des. 8, 3882–3884 (2008)
Lee, C., Yang, W., Parr, R.G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. 37, 785–789 (1988)
Mary Novena, L., Suresh Kumar, S., Athimoolam, S., Saminathan, K., Sridhar, B.: Single crystal, vibrational and computational studies of Theophylline (a bronchodilator drug) and its chloride salt. J. Mol. Struct. 1133, 294–306 (2017). https://doi.org/10.1016/j.molstruc.2016.11.087
Palafox, M.A.: Scaling factors for the prediction of vibrational spectra. I. Benzene molecule. Int. J. Quant. Chem. 77, 661–684 (2000)
Prabavathi, N., Nilufer, A., Krishnakumar, V.: Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation, conformational stability, NLO Properties, HOMO-LUMO and NBO Analysis of Hydroxyquinoline Derivatives by Density Functional Theory Calculations. Spectrochim. Acta A 114, 449–474 (2013). https://doi.org/10.1016/j.saa.2013.05.011
Reis, H., Papadopoulos, M.G., Calaminici, P., Jug, K., Köster, A.M.: Calculation of macroscopic linear and nonlinear optical susceptibilities for the naphthalene, anthracene and meta-nitroaniline crystals. Chem. Phys. 261, 359 (2000)
Schlegel, H.B.: Optimization of equilibrium geometries and transition structures. J. Comput. Chem. 3(2), 214–218 (1982)
Siva, V., Shameem, S., Suresh Kumar, S., Raja, M., Athimoolam, S., Asath Bahadur, S.: Structural, spectral, Quantum chemical and thermal studies on a new NLO crystal: Guanidinium Cinnamate. J. Mat. Sci: Mat. Electr. 28, 12484–12496 (2017a). https://doi.org/10.1007/s10854-017-7070-8
Siva, V., Suresh Kumar, S., Suresh, M., Raja, M., Athimoolam, S., Asath Bahadur, S.: N-H∙∙∙O hydrogen bonded novel nonlinear optical semiorganic crystal (4-methoxyanilinium trifluoroacetate) studied through theoretical and experimental methods. J. Mol. Struct. 1133, 163–171 (2017b). https://doi.org/10.1016/j.molstruc.2016.11.088
Siva, V., Asath Bahadur, S., Shameem, A., Murugan, A., Athimoolam, S., Suresh, M.: Supramolecular architecture, hydrogen bonding assembly and Hirshfeld surface analysis of charge transfer adipate salt of 4-methoxyaniline. Chem. Data Collect. 24, 100281 (2019)
Thangarasu, S., Siva, V., Athimoolam, S., Asath Bahadur, S.: Molecular structure, spectroscopic and quantum chemical studies on benzoic acid and succinic acid co-crystals of 2-Aminopyrimidine. J. Theor. Comput. Chem. 17(4), 1850021 (2018)
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The authors are grateful to the management of Kalasalingam Academy of Research and Education, Krishnankoil, India for their support.
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Thangarasu, S., Siva, V., Asath Bahadur, S. et al. Structural, vibrational, quantum chemical calculations, thermal and antimicrobial studies on nitrate salt of 3-nitroaniline. Opt Quant Electron 53, 570 (2021). https://doi.org/10.1007/s11082-021-03146-w
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DOI: https://doi.org/10.1007/s11082-021-03146-w