Abstract
A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π<sup>∗</sup> and π → π<sup>∗</sup>), <sup>1</sup>H and <sup>13</sup>C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λ<inf>MAX</inf> absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.
| Original language | English |
|---|---|
| Pages (from-to) | 115-124 |
| Number of pages | 10 |
| Journal | Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy |
| Volume | 144 |
| DOIs | |
| Publication status | Published - 5 Jun 2015 |
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Keywords
- DFT
- N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea
- NMR
- TD-DFT
- Thiourea derivatives
- X-ray
ASJC Scopus subject areas
- Instrumentation
- Atomic and Molecular Physics, and Optics
- Analytical Chemistry
- Spectroscopy
Cite this
Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N′-(2-, 3- and 4-methylphenyl)thiourea derivatives. / Abosadiya, Hamza M.; Anouar, El Hassane; Hasbullah, Siti Aishah; Mohd. Yamin, Bohari.
In: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, Vol. 144, 05.06.2015, p. 115-124.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N′-(2-, 3- and 4-methylphenyl)thiourea derivatives
AU - Abosadiya, Hamza M.
AU - Anouar, El Hassane
AU - Hasbullah, Siti Aishah
AU - Mohd. Yamin, Bohari
PY - 2015/6/5
Y1 - 2015/6/5
N2 - A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π∗ and π → π∗), 1H and 13C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λMAX absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.
AB - A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π∗ and π → π∗), 1H and 13C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λMAX absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.
KW - DFT
KW - N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea
KW - NMR
KW - TD-DFT
KW - Thiourea derivatives
KW - X-ray
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UR - http://www.scopus.com/inward/citedby.url?scp=84929353408&partnerID=8YFLogxK
U2 - 10.1016/j.saa.2015.01.092
DO - 10.1016/j.saa.2015.01.092
M3 - Article
VL - 144
SP - 115
EP - 124
JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
SN - 1386-1425
ER -