The Malaysian Journal of Analytical Sciences Vol 15 No 1 (2011): 37 – 45






Siti Aishah Zakaria1, Siti Hajar Muharam1, Mohd Sukeri Mohd Yusof1,3*, Wan Mohd Khairul1,

Maisara Abdul Kadir1 & Bohari M. Yamin2


1Department of Chemical Sciences, Faculty of Science and Technology,

Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu.

2School of Chemical Sciences and Food Technology, Faculty of Science and Technology,

Universiti Kebangsaan Malaysia, 43650 Bangi, Selangor.

3Institue of Marine Biotechnology,

Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu.


*Corresponding author:




A series of pivaloylthiourea derivatives, N-(2-nitrophenyl)-N˘-(pivaloyl)thiourea (I), N-(3-nitrophenyl)-N˘-(pivaloyl)thiourea (II) and N-(4-nitrophenyl)-N˘-(pivaloyl)thiourea (III) were synthesised and characterised by typical spectroscopic methods and single crystal X-ray diffraction. The IR spectra show the important  stretching bands for ν(N-H), ν(C=O), ν(C-N) and ν(C=S) at around 3300 cm-1, 1600 cm-1, 1300 cm-1 and 700 cm-1, respectively. There are two vital chromophores, C=O and C=S were observed in the UV spectra with maximum absorption at 230 nm and 290 nm, respectively. The crystal structures of (II) and (III) have been determined by single crystal X-ray diffraction analysis. Both of the molecules adopt cis-trans configuration with respect to the position of the phenyl and pivaloyl groups relative to the thiono S atom, across their C-N bonds. There is an intramolecular hydrogen bond, N-H...O in both molecules that lead to the formation of a pseudo-six-membered ring. In the crystal lattice, the molecules are linked by intermolecular hydrogen bonds N-HS, C-HS and N-HO forming dimer (II) and 3-dimensional network (III). 1H NMR spectra show chemical shift at δH 12.70 – 12.88 ppm and δH 10.84 – 10.94 ppm were assigned for both NH proton. Whereas, the chemical shift for 13C NMR analysis for C=O and C=S presence at δC 179-180 ppm.


Keywords: Thiourea derivatives, Pivaloylthiourea, Crystal structure.



1.       Kelman, D.R., L.F. Szczepura, K.I. Goldberg, W. Kaminsky, A.K. Hermetet, L.J. Ackerman,  J.K. Swearingen, D.X. West. (2002) Structural, spectral and thermal studies of N-2-(4-picolyl)- and N-2-(6-picolyl)-N’-(2-bromophenyl)thiourea. J. Mol. Struct. 610: 143-150.

2.       Zhong, Z.,  R. Xing,  S. Liu,   L. Wang,   S. Cai,   P. Li. (2008) Synthesis  of  acylthiourea  derivatives  of  chitosan  and  their  antimicrobial   activities  in vitro. Carbohydrate Research. 343: 566-570.

3.       Fontŕs, C., M. Hidalogo, V. Salvadó, E. Anticó. (2005) Selective recovery and preconcentration of mercury with a benzoylthiourea-solid supported liquid membrane system. Analytica. Chim. Acta. 547: 225-261.

4.       Zhang, Y-M., L. Xian, T-B. Wei, L-X. Cai. (2003) N-Benzoyl-N’-(2-hydroxyethyl)thiourea. Acta. Cryst. E59: o817-o819.

5.       Bergendorff, O., C.M.L. Persson, C. Hansson. (2004) HPLC analysis of alkyl thioureas in an orthopaedic brace and patch testing with pure ethylbutylthiourea. Contact Dermatitis. 51: 273-277.

6.       Joseph, M., V. Suni, C.R. Nayar, M.R.P. Kurup, H.-K. Fun. (2004) Synthesis, spectral characterization and crystal structure of 2-benzoylpyridine N(4)-cyclohexylthiosemicarbazone. J. Mol. Struct. 705: 63-70.

7.       Campo, R.D., J.J. Criado, R. Gheorghe, F.J. González. (2004)  N-benzoyl-N’-alkylthioureas and their complexes with Ni(II), Co(III) and Pt(II) – crystal structure of 3-benzoyl-1-butyl-1-methyl-thiourea: activity against fungi and yeast.  J. Inorg. Biochem.  98: 1307-1314.

8.       Dong, Y., T.K. Venkatachalam, R.K. Narla, V.N. Trieu. (2004) N-Benzoyl-N’-(3-pyridyl)thiourea. Bioorg. Med. Chem. Lett. 10: 87-90.

9.       Mahajan, A., S. Yeh, M. Nell,  C.E.J.V. Rensburg,  K. Chilale. (2007) Synthesis of new 7-chloroquinolinyl thioureas and their biological investigation as potential antimalaria and anticancer agents. Bioorg. Med. Chem. Lett. 17: 5683-5685.

10.    Shen, C.B., D.Y. Han, Z.M. Ding. (2007) The inhibition effect of thiourea on bulky nanocrystallized ingot iron in acidic sulfate solution. Mater. Chem. Phys. 109: 417-421.

11.    Yang, W., W. Zhou, Z. Zhang. (2007) Structural and spectroscopic study on N-2-fluorobenzoyl-N’-4-methoxyphenylthiourea. J. Mol. Struct. 828: 46-53.

12.    Rode, J.E., J.C. Dobrowolski., Z. Rzączyńska. (2002) DFT conformation and IR spectra of 1,1-dicarboxycyclobutane. J. Mol. Struct. 642: 147-156.

13.    Weiqun, Z., L. Baolong, L. Zhu, D. Jiangang, Z. Yong, L. Lude, Y. Xujie. (2004) Structural and spectral studies on N-(4-chloro)benzoyl-N’-(4-tolyl)thiourea. J. Mol. Struct. 690: 145-150.

14.    Gambino, D., E. Kremer, E.J. Baran. (2002) Infrared spectra of new Re(III) complexes with thiourea derivatives. Spectrochim. Acta A. 58: 3085-3085.

15.    Fernández, E.R., J.L. Manzano, J.J. Benito, R. Hermosa, E. Monte, J.J. Criado. (2005) Thiourea, triazole and thiadiazine compounds and their metal complexes as antifungal agents. J. Inorg. Biochem. 99: 1558-1547.

16.    Allen, F.H., O. Kennard, D.G. Watson, L. Brammer, A.G. Orpen,  R. Taylor. (1987) Table of body length determined by X-ray and neutron diffraction. Part I. Body length in organic compounds. J. Chem. Soc. Perkin Trans ii. 1-9.

17.    Shoukat, N., M.K. Rauf, M. Bolte, A. Badahah. (2007) 1-(2-Chlorophenyl)-3-pivaloylthiourea. Acta Cryst. E63: o920-o922.

18.    Sultana, S., M.K. Rauf, M. Ebihara, A. Badshah. (2007a) N-(3-Bromofenil)-N’-pivaloylthiourea. Acta Cryst. E63: o2602.

19.    Sultana, S., M.K. Rauf, M. Ebihara, A. Badshah. (2007b) N-(pyrimindin-2-il)-N’-pivaloylthiourea. Acta Cryst. E63: o2674.

20.    Sultana, S., M.K. Rauf, M. Ebihara, A. Badshah. (2007c) 1-(4-Nitrophenyl)-3-pivaloylthiourea. Acta Cryst. E63: o2801.

21.    Yusof, M.S.M., N.I.A. Ramadzan, B.M. Yamin. (2006) N-(3-phenylthiourea)-N’-pivaloylthiourea. Acta Cryst. E62: o5513-o5514.

22.    Dillen, J., M.G. Woldu, K.R. Koch. (2006a) N,N-Di-n-butil-N’-pivaloylthiourea. Acta Cryst. E62: o4819-o4820.

23.    Dillen, J., W. Ghebreysus, K.R. Koch. (2006b) N,N-(Heptane-2,6-diyl)-N’-(3,4,5-methoxy-benzoyl)thiourea. Acta. Cryst. E62: o5225-o5227.

24.    Rauf, M.K., A. Badshah, U. Flörke, (2006a) 1-Benzoyl-3-[3-(trifluoromethyl)phenyl]thiourea. Acta. Cryst. E62: o2452-o2453.

25.    Saeed, A.,  U. Flörke. (2006) 1-(2-Chlorophenyl)-3-(4-methylbenzoyl)thiourea. Acta. Cryst. E62: o2403-o2405.

26.    Rauf, M.K., A. Badshah,  M. Bolte. (2006b) 1-(3-Chlorobenzoyl)-3-(2,4,6-trichlorophenyl)-thiourea. Acta. Cryst. E62: o2444-o2445.

27.    Borowiak, T., Dutkiewicz, J.G. Sośnicki, T.S. Jagodziński, P.E. Hansen. (2008) Secondary thioamide group deformations in different surroundings: The case of intramolecular N-HN hydrogen bond – An X-ray study combined with theoretical calculations. J. Mol. Struct. 892: 438-445.

28.    Valdés-Martínez, J., S. Hernández-Ortega,  D.X. West, L.J. Ackerman, J.K. Swearingen,  A.K. Hermetet. (1999) Structural and spectral studies of N-(2-pyridyl)-N’-tolylthioureas. J. Mol. Struct. 4278: 219-226.


Previous                    Content                    Next