Abstract
The molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) 1H and 13C chemical shift values and several thermodynamic parameters of 4-allyl-2-(morpholin-4-ylmethyl)-5-(pyridin-4-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione in the ground state were calculated using density functional methods (BLYP and B3LYP) with the 6-31G(d) basis set. The results of the optimized molecular structure are given and compared with experimentally obtained X-ray diffraction. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. Vibrational mode assignments of the title compound were carried out using a total energy distribution calculation. The calculated 1H and 13C chemical shift values are compared with the experimental values. The molecular frontier orbital energies of the title compound were calculated using the BLYP and B3LYP/6-31G(d) levels. The obtained data for the title compound provided its molecular structure, while the IR and NMR analyses provide a basis for the future design of efficient materials containing a 1,2,4-triazole core.
Similar content being viewed by others
References
Jones D.H., Slack R., Squires S., Wooldridge K.R.H.: The activity of pyridine and quinoline derivatives against neurovaccinia in mice. J. Med. Chem 8, 676–680 (1965)
Mullican M.D., Wilson M.W., Connor D.T., Kostlan C.R., Schrier D.J., Dyer R.D.: Design of 5-(3,5-Di-tert-butyl-4 -hydroxyphenyl)-1,3,4-thiadiazoles, −1,3,4- oxadiazoles, and −1,2,4-triazoles as orally-active. J. Med. Chem 36, 1090–1099 (1993)
Porsolt R.D., Bertin A., Jalfre M.: Behavioural despair in mice: a primary screening test for antidepressants. Arch. Int. Pharmacol 229, 327–336 (1977)
Shams El-Dine S.A., Hazzaa A.A.B.: Synthesis of compounds with potential fungicidal activity. Pharmazie 29, 761–768 (1974)
Sughen J.K., Yoloye T.: Medicinal applications of indole derivatives. Pharm. Acta Helv 58, 64–68 (1978)
Unangst P.C., Shurum G.P., Connor D.T., Dyer R.D., Schrier D.J.: Novel 1,2,4-oxadiazoles and 1,2,4-thiadiazoles as dual 5-lipoxygenase and cyclooxygenase inhibitors. J. Med. Chem 35, 3691–3698 (1992)
Dinçer, M.; Özdemir, N.; Dege, N.; Çetin, A.; Cansız, A.; Şekerci, M.: 4-Allyl-2-(morpholin-4-ylmethyl)-5-(pyridin-4-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione. Acta Cryst. E 61, o1953–o1955 (2005)
Zamani K., Faghihi K., Sangi M.R., Zolgharnein J.: Synthesis of some new substituted 1,2,4-triazole and 1,3,4-thiadiazole and their derivatives. Turk. J. Chem 27, 119–125 (2003)
Cansız A., Koparır M., Demirdağ A.: Synthesis of some new 4,5-substituted-4H-1,2,4-triazole-3-thiol derivatives. Molecules 9, 204–212 (2004)
Moulton B., Zaworotko M.J.: From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids. Chem. Rev 101, 1629–1658 (2001)
Abramov Y.A., Volkov A.V., Coppens P.: On the evaluation of molecular dipole moments from multipole refinement of X-ray diffraction data. Chem. Phys. Lett 311, 81–86 (1999)
Handy N.C., Maslen P.E., Amos R.D., Andrews J.S., Murray C.W., Laming G.J.: The harmonic frequencies of benzene.Chem. Phys. Lett 197, 506–515 (1992)
Rauhut G., Pulay P.: Transferable scaling factors for density functional derived vibrational force fields. J. Phys. Chem 99, 3093–3100 (1995)
Casanovas J., Namba A.M., Leon S., Aquino G.L.B., da Silva G.V.J., Aleman C.: Calculated and experimental NMR chemical shifts of p-menthane-3,9-diols. A combination of molecular dynamics and quantum mechanics to determine the structure and the solvent effects. J. Org. Chem 66, 3775–3782 (2001)
Sebag A.B., Forsyth D.A., Plante M.A.: Conformation and configuration of tertiary amines via GIAO-derived 13C NMR chemical shifts and a multiple independent variable regression analysis. J. Org. Chem 66, 7967–7973 (2001)
Chesnut, D.B.: The ab initio computation of nuclear magnetic resonance chemical shielding. In: Lipkowitz, K.B., Boyd, D.B. (eds.) Reviews in Computational Chemistry, vol. 8, chap. 5, p. 245. VCH, New York (1996)
De Dios A.C.: Ab initio calculations of the NMR chemical shift. Prog. Nucl. Magn. Reson. Spectrosc 29, 229–278 (1996)
Forsyth D.A., Sebag A.B.: Computed 13 C NMR chemical shifts via empirically scaled GIAO shieldings and molecular mechanics geometries Conformation and configuration from 13 C. shifts. J. Am. Chem. Soc 119, 9483–9494 (1997)
Helgaker T., Jaszunski M., Ruud K.: Ab initio methods for the calculation of NMR shielding and indirect spin–spin coupling constants. Chem. Rev 99, 293–352 (1999)
Ditchfield R.: Molecular orbital theory of magnetic shielding and magnetic susceptibility. J. Chem. Phys 56(11), 5688–5691 (1972)
Wolinski K., Hinton J.F., Pulay P.: Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J. Am. Chem. Soc. 112(23), 8251–8260 (1990)
Cheeseman J.R., Trucks G.W., Keith T.A., Frisch M.J.: A comparison of models for calculating nuclear magnetic resonance shielding tensors. J. Chem. Phys 104(14), 5497–5509 (1996)
Avcı, D.; Başoğlu, A.; Atalay, Y.: Density functional theory and ab initio Hartree-Fock calculations of molecular structure and vibrational spectra of anilinium nitrate. Z. Naturforsch. 63a, 1–9 (2008)
Rauhut G., Puyear S., Wolinski K., Pulay P.: Comparison of NMR shieldings calculated from Hartree–Fock and density functional wave functions using gauge-including atomic orbitals. J. Phys. Chem 100(15), 6310–6316 (1996)
Ditchfield R., Hehre W.J., Pople J.A.: Self-consistent molecular-orbital methods. IX. An extended Gaussian? Type basis for molecular-orbital studies of organic molecules. J. Chem. Phys 54(2), 724–728 (1971)
Ditchfield R.: Molecular physics: an international journal at the interface between chemistry and physics. Mol. Phys 27(4), 789–807 (1974)
Rohlfing C.M., Allen L.C., Ditchfield R.: Proton chemical shift tensors in hydrogen-bonded dimers of RCOOH and ROH. Chem. Phys 87(1), 9–15 (1984)
Frisch, A.; Nielsen, A.B.; Holder, A.J.: Gaussview User Manual. Gaussian Inc., Pittsburg (2001)
Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Zakrzewski, V.G.; Montgomery, J.A. Jr.; Stratmann, R.E.; Burant, J.C.; Dapprich, S.; Millam, J.M.; Daniels, A.D.; Kudin, K.N.; Strain, M.C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G.A.; Ayala, P.Y.; Cui, Q.; Morokuma, K.; Salvador, P.; Dannenberg, J.J.; Malick, D.K.; Rabuck, A.D.; Raghavachari, K.; Foresman, J.B.; Cioslowski, J.; Ortiz, J.V.; Baboul, A.G.; Stefanov, B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R.L.; Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng, C.Y.; Nanayakkara, A.; Challacombe, M.; Gill, P.M.W.; Johnson, B.; Chen, W.; Wong, M.W.; Andres, J.L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E.S.; Pople, J.A.: Gaussian. Inc., Gaussian 98, Revision A.9, Pittsburgh PA (2001)
Baker J., Jarzecki A.A., Pulay P.: Direct scaling of primitive valence force constants: an alternative approach to scaled quantum mechanical force fields. J. Phys. Chem. A 102, 1412–1424 (1998)
PQS version 3.3, Parallel Quantum Solutions, 2013 Green Acres Road, Fayetteville, Arkansas 72703
Dinçer, M.; Avcı, D.; Atalay, Y.; Şekerci, M.: Molecular structure and vibrational and chemical shift assignments of 5-(2-Hydroxyphenyl)-4-(p-tolyl)-2,4-dihydro-1,2,4-triazole-3-thione by DFT and ab initio HF calculations. J. Mol. Mod. 14, 823–832 (2008)
Şekerci, M.; Atalay, Y.; Yakuphanoğlu, F.; Avcı, D.; Başoğlu, A.: A theoretical study on 1-(thiophen-2-yl-methyl)-2- (thiophen-2-yl)-1H-benzimidazole. Spectrochim. Acta A 67, 503–508 (2007)
Atalay Y., Yakuphanoğlu F., Şekerci M., Avcı D., Başoğlu A.: Theoretical studies of molecular structure and vibrational spectra of 2-amino-5-phenyl-1,3,4-thiadiazole. Spectrochim. Acta A 64, 68–72 (2006)
Lee S.Y., Boo B.H.: Molecular structures and vibrational spectra of pyrrole and carbazole by density functional theory and conventional ab initio calculations. J. Phys. Chem 100(37), 15073–15078 (1996)
Lee S.Y., Boo B.H.: Density functional theory study of vibrational spectra of fluorene. J. Phys. Chem 100, 8782–8785 (1996)
Atalay, Y.; Avcı, D.; Başoğlu, A.; Okur, İ.: Molecular structure and vibrational spectra of melamine diborate by density functional theory and ab initio Hartree-Fock calculations. J. Mol. Struct.: Theochem. 713, 21–26 (2005)
Zhao P.S., Xu J.M., Zhang W.G., Jian F.F., Zhang L.: Synthesis, characterization, and quantum chemical calculational studies on 3-p-methylphenyl-4-amino-1,2,4-triazole-5-thione. Struct. Chem 18, 993–1000 (2007)
Genç, S.; Dege, N.; Çetin, A.; Cansız, A.; Şekerci, M.; Dinçer, M.: 5-(2-Hydroxyphenyl)-4-(p-tolyl)-2,4-dihydro-1,2,4- triazole-3-thione. Acta Cryst. E60, o1340–o1342 (2004)
Scott A.P., Radom L.: Harmonic vibrational frequencies: an evaluation of Hartree–Fock, Møller–Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J. Phys. Chem 100, 16502–16513 (1996)
Palafox M.A., Gill M., Nunez N.J., Rastogi V.K., Mittal L., Sharma R.: Scaling factors for the prediction of vibrational spectra. II. The aniline molecule and several derivatives. Int. J. Quant. Chem 103, 394–421 (2005)
Avcı D., Cömert H., Atalay Y.: Ab initio Hartree-Fock calculations on linear and second-order nonlinear optical properties of new acridine-benzothiazolylamine chromophores. J. Mol. Mod 14, 161–169 (2008)
Atalay, Y.; Avcı, D.; Başoğlu, A.: Linear and non-linear optical properties of some donor-acceptor oxadiazoles by ab initio Hartree-Fock calculations. Struct. Chem. 19, 239–246 (2009)
Abboud, J-LM.; Foces-Foces, C.; Notario, R.; Trifonov, R.E.; Volovodenko, A.P.; Ostrovskii, V.A.; Alkorta, I.; Elguero, J.: Basicity of N-H- and N-methyl-1,2,3-triazoles in the gas phase in solution, and in the solid state—an experimental and theoretical study. Eur. J. Org. Chem. 16, 3013–3024 (2001)
Palmer M.H., Christen D.: An ab initio study of the structure, tautomerism and molecular properties of the C- and N- amino-1,2,4-triazoles. J. Mol. Struct 705, 177–187 (2004)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Avcı, D., Atalay, Y., Cömert, H. et al. DFT Calculations on the Molecular Structure, Vibrational and Chemical Shift Assignments of 4-Allyl-2-(morpholin-4-ylmethyl)-5-(pyridin-4-yl)-2,4-Dihydro-3H-1,2,4-Triazole-3-Thione. Arab J Sci Eng 36, 607–620 (2011). https://doi.org/10.1007/s13369-011-0059-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13369-011-0059-3