Experimental and Quantum Chemical Calculations of 2-(3-Phenly-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl)-azomethine) Benzoic Acid Molecule

Year 2021, Issue: 21, 649 - 659, 31.01.2021

Gül Kotan , Haydar Yüksek

https://doi.org/10.31590/ejosat.813597

Abstract

2-(3-Phenyl-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl)-azomethine) benzoic acid molecule has been optimized using the 6-311G(d,p) basis set of DFT(B3LYP) and HF methods. Thus, the most stable geometrical conformer of the compound with different methods was obtained. 1H/ 13C-NMR chemical shifts, vibrational wavenumbers, thermodynamic parameters, molecular geometric optimizations (bond angles, bond lengths), HOMO-LUMO analyses, electronic properties, mulliken charges, dipole moment, total energy of the molecule were studied using Gaussian 09W software package. Gaussian results are drawn graphically with GaussView5.0 program. All quantum chemical computations were performed in the B3LYP functional of DFT method ve HF at the 6-311G(d,p) basis set. 1H/ 13C Nuclear magnetic Resonance spectral values were calculated in gas phase and in DMSO solvent according to GIAO method. Theoretical spectral values of the molecule were compared with experimental data obtained from the literature. In the Veda4f program, vibration types were determined and harmonic vibration frequencies were scaled with certain scale factors of different methods. In addition, thermodynamics properties (heat capacity CV0, entropy S0 and enthalpy H0), electronic properties (electronegativity (χ), electron affinity (A), global hardness (η), softness (σ), ELUMO-EHOMO energy gap (ΔEg) and ionization potential (I) were calculated. Also, the molecular surfaces such as the electron spin potential (ESP), molecular electrostatic potential (MEP), the total density, the electron density, the electrostatic potential of the molecule were visualized.

Keywords

2, 4-Triazole, B3LYP, HOMO-LUMO, GIAO

2-(3-Fenil-4,5-dihidro-1H-1,2,4-triazol-5-on-4-il)-azometin benzoik asid Molekülünün Deneysel ve Kuantum Kimyasal Hesaplamaları

Abstract

2-(3-Fenil-4,5-dihidro-1H-1,2,4-triazol-5-on-4-il)-azometin benzoik asit molekülü DFT (B3LYP) ve HF yöntemlerinin 6-311G (d, p) temel seti kullanılarak optimize edilmiştir. Böylece, farklı metotlarla bileşiğin en kararlı geometrik yapısı elde edilmiştir. Proton/ karbon NMR kimyasal kaymalar, titreşim dalga boyları, termodinamik parametreler, moleküler geometrik optimizasyonlar (bağ açıları, bağ uzunlukları), HOMO-LUMO analizleri, elektronik özellikler, mulliken yükleri, dipol momenti, molekülünün toplam enerjisi Gauss 09W paket yazılımı kullanılarak incelenmiştir. Gaussian sonuçları GaussView5.0 programı ile grafiksel olarak incelenmiştir. Tüm kuantum kimyasal hesaplamalar, 6-311G (d,p) temel setinde HF ve DFT yönteminin B3LYP fonksiyonu ile gerçekleştirildi. Proton/ Karbon-13 Nükleer manyetik Rezonans spektral değerleri, gaz fazında ve DMSO solventinde GIAO yöntemine göre hesaplanmıştır. Molekülün teorik spektral değerleri literatürden elde edilen deneysel verilerle karşılaştırılmıştır. Veda4f programında ayrı yöntemler kullanılarak belli skala faktörleri ile skala edilen harmonik titreşim frekansları hesaplanmıştır. Ayrıca termodinamik özellikler (ısı kapasitesi CV0, entropi S0 ve entalpi H0), elektronik özellikler (elektronegatiflik (χ), elektron ilgisi (A), küresel sertlik (η), yumuşaklık (σ), ELUMO-EHOMO enerji boşluğu (ΔEg) ve iyonlaşma potansiyeli (I) hesaplandı. Ayrıca, elektron spin potansiyeli (ESP), moleküler elektrostatik potansiyel (MEP), toplam yoğunluk, elektron yoğunluğu, molekülün elektrostatik potansiyeli gibi moleküler yüzeyler görselleştirildi.

Keywords

1,2,4-Triazol, B3LYP, HOMO-LUMO, GIAO

References

• Ben Salah, B., Chaari, N., Rekik, A., Ben Hsouna, A., Trigui, M., & Kossentini, M. (2015). Synthesis, Crystal Structure, and Antibacterial Activity of 1, 2, 4‐Triazoles and 1, 2, 4‐Triazol‐3‐one. Journal of Heterocyclic Chemistry, 52(6), 1769-1775.
• Choi, C.H., Kertesz, M., (1998). Bond length alternation and aromaticity in large annulenes, J. Chem. Phys., 108, 6681-6688.
• Dennington, R., Keith, T., Millam, J. (2009). GaussView. Version 5. Semichem Inc. Shawnee Mission KS.
• Fukui, K., (1982). Role of Frontier Orbitals in Chemical Reactions. Science, 747-754.
• Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X. et al., (2009). Gaussian 09. Revision C.01. Gaussian. Inc. Wallingford. CT.
• Goszczyńska A., Kwiecień, H., Fijałkowski, K. (2015). Med. Chem. Res., 24, pp 3561.
• Guo-Qiang H, Li-Li H, Song-Qiang X, Wen-Long H. (2008), Design, synthesis and antitumor activity of asymmetric bis(s-triazole Schiff-base)s bearing functionalized side-chain, Chin J. Chem, 26, 1145-1149.
• Hearn, M.J., Cynamon, M.N., Chen, M.F., Coppins, R., Davis, J., Kang, H.J.O., Noble, A., Tusekine, B., Terrot, M.S., Trombino, D., Thai, M., Webster, E.R., Wilson, R. (2009). Eur.J.Med. Chem., 44,4169.
• Hunashal, R. D., Ronad, P. M., Maddi, V. S., Satyanarayana, D., & Kamadod, M. A. (2014). Synthesis, anti-inflammatory and analgesic activity of 2-[4-(substituted benzylideneamino)-5-(substituted phenoxymethyl)-4H-1, 2, 4-triazol-3-yl thio] acetic acid derivatives, Arabian Journal of Chemistry, 7(6), 1070-1078.
• Jamróz, M. H. (2004). Vibrational Energy Distribution Analysis. VEDA 4 program, Warsaw.
• Kotan, G., Yüksek, H. (2019). 3-Fenil-5-(4-pridil)-1,2,4-triazol Molekülünün DFT(B3LYP/B3PW91)/HF ile Spektroskopik, Geometrik, Termodinamik ve Elektronik Analizi, Avrupa Bilim ve Teknoloji Dergisi, No. 17, pp. 933-943.
• Mahdavi, M., Akbarzadeh, T., Sheibani, V., Abbasi, M., Firoozpour, L., Tabatabai, S. A., Foroumadi, A. (2010). Synthesis of two novel 3-amino-5-[4-chloro-2-phenoxyphenyl]-4H-1, 2, 4-triazoles with anticonvulsant activity, Iranian journal of pharmaceutical research, IJPR, 9(3), 265.
• Merrick, J. P., Moran, D., Radom, L. (2007). An Evaluation of Harmonic Vibrational Frequency Scale Factors. Journal of Physical Chemistry, 111(45), 11683-11700.
• Mulliken, R. S. (1955). Electronic Population Analysis on LCAO–MO Molecular Wave Functions, International Journal of Chemical Physics., 23, 1833-1840.
• Murray, J.S., Peralta-Inga, Z., Pelitzer, P., (1999). Int. J. Quant. Chem., 75 (3), 267-273.
• Neelakantan, M. A., Esakkiammal, M., Mariappan, S. S., Dharmaraja, J., & Jeyakumar, T. (2010). Synthesis, characterization and biocidal activities of some schiff base metal complexes, Indian Journal of Pharmaceutical Sciences, 72(2), 216.
• Ocak, N., Çoruh, U., Kahveci, B., Şaşmaz, S., Vazquez-Lopez, E. M., Erdönmez, A. (2003). 1-Acetyl-3-(p-chlorobenzyl)-4-(p- chlorobenzylidenamino)-4,5-dihydro-1H-1, 2, 4- triazol-5-one. Acta Cryst. Sec. E., 59(6), 750-752.
• Sarac, K. (2020). Synthesis, Experimental and Theoretical Characterization of 4-(((4-Ethyl-5-(Thiophene-2-yl)-4H-1, 2, 4-Triazol-3-yl) Thio) Methyl)-6-Methoxycoumarin, Russian Journal of Physical Chemistry B, 14, 19-28.
• Serin, S., Gök, Y., (1988), Hidroksi Schiff Bazı Metal Komplekslerinin Tekstil Boyamacılığında Kullanabilirliğinin İncelenmesi, T. Kimya D.C., 12, 325-331.
• Sudha, N., Abinaya, B., Kumar, R. A., Mathammal, R., (2018). Synthesis, Structural, Spectral, Optical and Mechanical Study of Benzimidazolium Phthalate crystals for NLO Applications, Journal of Lasers Optics & Photonics, 5(2), 1-6.
• Sumangala, V., Poojary, B., Chidananda, N., Arulmoli, T., & Shenoy, S. (2013). Synthesis and biological evaluation of some Schiff bases of 4-amino-5-(4-methylsulfonyl) benzyl-2, 4-dihydro-3H-[1, 2, 4]-triazole-3-thione, Medicinal Chemistry Research, 22(6), 2921-2928.
• Şen, F., Dinçer, M., Yılmaz, İ., Çukurovalı, A. (2017). Spectral and structural analysis on 2-(4-Allyl-5-Mercapto-4H-1,2,4-Triazol-3-yl) Acetic acid: Experimental and theoretical (HF and DFT) studies, Journal of Molecular Structure, 1137, 193-205.
• Ustabas, R., Çoruh, U., Sancak, K., Ünver, Y., Vazquez-Lopez, E.M. (2007). 1-(benzoylmethyl)-4-[(2,4-dichlorobenzylidene)amino]-3-(2- thienylmethyl)4,5-dihydro-1H-1,2,4-triazol-5-one. Acta Cryst. Sec. E., 63, 2982- 3051.
• Wolinski, K., .Hilton, J. F., Pulay, P. J. (1990). Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations, Journal of the American Chemical Society, 112, 512.
• Yüksek, H., Akdeniz, F., Bahçeci, Ş. (2006). Bazı Potansiyel biyolojik aktif 4,5-dihidro-1H-1,2,4-triazol-5-on Türevlerinin Sentezi ve Yapılarının Aydınlatılması, Kimya 2006, XX. Ulusal Kimya Kongresi, Kayseri, Bildiri Özetleri Kitabı, OKS-03.
• Zacharias, A. O., Varghese, A., Akshaya, K. B., Savitha, M. S., & George, L. (2018). DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-(1-(2, 4-difluorophenyl)-2-(1H-1, 2, 4-triazol-1-yl) ethylidene) thiosemicarbazide, Journal of Molecular Structure, 1158, 1-13.
• Zhang, H. Y., & Shi, D. Q. (2014). Synthesis and Herbicidal Activities of 3‐Trifluoromethyl‐5‐[3‐(trifluoromethyl) phenoxy]‐1, 2, 4‐Triazol‐4‐Schiff Bases, Journal of Heterocyclic Chemistry, 51(S1), E344-E348.