Synthesis and characterisation a series of N-(3,4-dichlorophenyl)-N′-(2,3 and 4-methylbenzoyl)thiourea derivatives

Article abstract of DOI:10.1016/j.molstruc.2010.04.037

Three new compounds, N-(3,4-dichlorophenyl)-N′-(2-methylbenzoyl)thiourea (2a), N-(3,4-dichlorophenyl)-N′-(3-methylbenzoyl)thiourea (2b) and N-(3,4-dichlorophenyl)-N′-(4-methylbenzoyl)thiourea (2c) are isomers which have been successfully synthesised and characterised by typical spectroscopic techniques, namely IR and ¹H and ¹³C multi-nuclear magnetic resonance (NMR). The structure of 2a was determined by single crystal X-ray diffraction method and crystallised in the monoclinic system with space group C2/c, adopting configuration of the molecule is trans-cis. The infrared spectra of these compounds showed four significant stretching vibrations of ν(N{single bond}H), ν(C{double bond, long}O), ν(C{single bond}N) and ν(C{double bond, long}S) at 3261-3279 cm^-1, 1662-1680 cm^-1, 1345-1379 cm^-1 and 688-738 cm^-1, respectively. The ¹³C NMR chemical shift for the thiourea moiety appeared at ca. δ_C 180 ppm.

Full text of DOI:10.1016/j.molstruc.2010.04.037

Journal of Molecular Structure 975 (2010) 280–284
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis and characterisation a series of N-(3,4-dichlorophenyl)-N0-(2,3
and 4-methylbenzoyl)thiourea derivatives
a
a
b
M. Sukeri M. Yusof a, , Rabia’tun Hidayah Jusoh , Wan M. Khairul , Bohari M. Yamin
*
a Department of Chemical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Malaysia
b School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43650 Bangi, Selangor, Malaysia
a r t i c l e i n f o
a b s t r a c t
Three new compounds, N-(3,4-dichlorophenyl)-N0-(2-methylbenzoyl)thiourea (2a), N-(3,4-dichloro-
phenyl)-N0-(3-methylbenzoyl)thiourea (2b) and N-(3,4-dichlorophenyl)-N0-(4-methylbenzoyl)thiourea
(2c) are isomers which have been successfully synthesised and characterised by typical spectroscopic
techniques, namely IR and 1H and 13C multi-nuclear magnetic resonance (NMR). The structure of 2a
was determined by single crystal X-ray diffraction method and crystallised in the monoclinic system with
space group C2/c, adopting configuration of the molecule is trans–cis. The infrared spectra of these com-
Article history:
Received 19 January 2010
Received in revised form 26 April 2010
Accepted 26 April 2010
Available online 29 April 2010
Keywords:
pounds showed four significant stretching vibrations of m(NAH), m(C@O), m(CAN) and m(C@S) at 3261–
Methylbenzoylthiourea
Carbonylthiourea
Thiourea
3279 cmꢀ1, 1662–1680 cmꢀ1, 1345–1379 cmꢀ1 and 688–738 cmꢀ1, respectively. The 13C NMR chemical
shift for the thiourea moiety appeared at ca. dC 180 ppm.
Ó 2010 Elsevier B.V. All rights reserved.
Crystal structure
1. Introduction
reported derived from copolymerization of bisthiourea/thiourea/
glutaraldehyde which was successfully applied to determine Hg(II)
For the past few decades, thiourea derivatives have attracted
great attention as versatile ligands in numerous applications [1].
This is due to its unique properties which enable to coordinate with
various transition metal ions as monodentate or bidentate ligands
[2–5]. Thiourea derivatives for instance derived as substituted ben-
zoylthiourea or phenylthiourea derivatives are attractive model
compounds for the studies in solid-state chemistry due to their ten-
dency for the formation of intra- and intermolecular hydrogen
bonds of the NAH proton-donor groups to sulphur and carbonyl
oxygen atoms [7–25]. To date, these derivatives are widely used
in numerous applications such as in pharmaceutical industry for
potential therapeutic agents as antibacterial [26–28], anti-HIV
[28,29], anticancer drugs [30–32], antidepressants [33,34] and anti-
hyperlipidemic, antiallergic, antiparasitic, platelet antiaggregating,
antiproliferative activities [35–37]. Previous studies have reported
that the compounds containing thiourea moieties have been used
extensively and commercially as herbicides, fungicides and insecti-
cides agents in the agrochemical industries [23,38–41].
from a real matrix [42]. On the other hand, thiourea and its deriv-
atives can serve as useful host material or inclusion compounds
exhibiting wide range applications in the development of electron-
ics and optoelectronics devices [43–45]. Thiourea and its deriva-
tives have been found as an effective corrosion inhibitors agent
because sulphur atom is easily protonated in acidic solution [46–
48]. Nowadays, these derivatives have been employed successfully
as catalyst in the palladium-catalyzed Suzuki and Heck reactions
because thiourea ligands are thermally stable and insensitive to
air and moisture which is the reaction may be conducted at ambi-
ent environment [49–51].
In the present study, we focus on the synthesis and character-
isation of three new synthetic derivatives which are 2,3 and 4-
methylbenzoyl with 3,4-dichlorophenyl groups as precursors at-
tached at the terminal of two nitrogen atoms as shown in Fig. 1.
Their structures were confirmed by several spectroscopic methods
namely IR, 1H and 13C NMR spectroscopy and single crystal X-ray
diffraction structural analysis. However, only 2a was obtained as
a single crystal and suitable for single crystal X-ray diffractometer
structural analysis.
Several studies have revealed that thiourea derivatives not only
have been using in medical and agriculture applications but also
they play major contribution in the environmental and industrial
applications. In the case of 1-benzoyl-3-propylthiourea, this com-
pound has great interest as effective adsorbent for removal of mer-
cury ions from aqueous solutions [24]. The chelating resin was
2. Experimental
2.1. Physical measurements
All reactions were carried out under an ambient atmosphere
and no special precautions were taken to exclude air or moisture
* Corresponding author.
E-mail address: mohdsukeri@umt.edu.my (M.S.M. Yusof).
0022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.04.037

M.S.M. Yusof et al. / Journal of Molecular Structure 975 (2010) 280–284
281
400.11 MHz): d 2.40 (s, 3H, Me); 7.42–7.50 (m, 2H, C6H3); 7.63–
7.70 (m, 2H, C6H4); 7.77 (d, JHH = 7 Hz, 1H, C6H4); 7.83 (s, 1H,
C6H4); 8.13 (s, 1H, C6H3); 11.64, 12.59 (2 ꢁ s, 1H, NH). 13C NMR
(DMSO-d6, 100.61 MHz): d 21.3 (s, Me); 125.4, 126.4, 126.6,
128.7, 128.9, 129.6, 130.9, 131.2, 132.4, 134.3, 138.4, 138.6
(12 ꢁ s, Ar); 168.7 (s, C@O); 180.1 (s, C@S).
2.4. Preparation of N-(4-methylbenzoyl)-N0-(3,4-
chlorophenyl)thiourea, 2c
In the similar manner as described above, the compound 2c was
obtained as colourless crystalline solids by recrystallisation from
Fig. 1. The proposed structures of the N-(3,4-dichlorophenyl)-N0-(2-meth-
ylbenzoyl)thiourea, 2a, N-(3,4-dichlorophenyl)-N0-(3-methylbenzoyl)thiourea, 2b
and N-(3,4-dichlorophenyl)-N0-(4-methylbenzoyl)thiourea, 2c.
methanol (0.26 g, 70%). IR (KBr pellets):
(C@O) (CAN)
1661.78 cmꢀ1 1374.75 cmꢀ1
738.12 cmꢀ1 1H NMR (DMSO-d6, 400.11 MHz): d 2.40 (s, 3H,
m ,
(NAH) 3278.56 cmꢀ1
m
,
m
,
m(C@S)
.
Me); 7.37 (pseudo-d, JHH=8 Hz, 2H, C6H4); 7.60–7.69 (m, 2H,
C6H3); 7.76 (s, 1H, C6H3); 8.13 (pseudo-d, JHH = 13 Hz, 2H, C6H4);
11.60, 12.61 (2 ꢁ s, 1H, NH). 13C NMR (DMSO-d6, 100.61 MHz): d
21.5 (s, Me); 120.7, 121.9, 126.5, 128.2, 128.7, 129.3, 129.5,
130.9, 131.0, 131.2 (10 ꢁ s, Ar); 168.4 (s, C@O); 180.2 (s, C@S).
during work-up. All chemicals were purchased from Sigma Aldrich
or MERCK and used as received without further purification. Infra-
red spectra of the synthesised compounds were recorded from KBr
pellets using FTIR Perkin Elmer 100 Spectrophotometer in the
spectral range of 4000–400 cmꢀ1
.
1H 400.11 MHz and 13C
100.61 MHz NMR spectra were recorded using Bruker Avance III
400 Spectrometer in DMSO-d6 as a solvent at room temperature
in the range between 0–15 ppm and 0–200 ppm. Room tempera-
ture diffraction data for 2a was collected on a Bruker SMART APEX
3. Results and discussion
3.1. Spectroscopic studies
4 K CCD diffractometer (Mo Ka radiation, k = 0.71073 Å). The struc-
Infrared spectra of these title compounds reveal all the expected
ture was solved and refined by using SHELX suit [26]. All non-
hydrogen atoms were refined anisotropically. The perspective view
of the molecule was obtained using ORTEP-32 for Windows [27].
Data collection: SMART [28]; cell refinement: SAINT [28]; data
reduction: structure: SHELXS 97 [29]; molecular graphics: SHELXL
97 [29]; software used to prepare material for publication: SHEL-
XTL [30] and PLATON: software to calculate the hydrogen bonds
[52].
frequency region of the m(NAH), m(C@O), m(CAN) and m(C@S). The
bands at 3279–3261 cmꢀ1 and 3236–3094 cmꢀ1 represent asym-
metric and symmetric stretching vibration respectively of the
v(NAH) in the secondary thioamide group. These assignments
were supported by the literature that mN(1)–H(1) can be seen at
above 3200 cmꢀ1 and the mN(2)–H(2) can be found at above
3000 cmꢀ1 have been examined due to the existence of intramolec-
ular hydrogen bonding [1–3,12–15,33,34,53–59]. The trans–cis
conformation of all studied compounds is related to the NAH
stretching frequencies range which are depends on the position –
NHC(S)NHC(O)– group vibrations and stabilised by hydrogen
bonding. The carbonyl band mC@O of 2a–c are clearly observed at
above 1660 cmꢀ1 which might be related to the resonance effect
with the phenyl rings and existence of intramolecular hydrogen
bonding with NAH [1–3,12–15,54–56]. The bands sp2 of the car-
bonyl stretching for 2a and b favour to absorb strongly at
1680 cmꢀ1 and 1664 cmꢀ1 compared to the 2c absorbs weakly at
1662 cmꢀ1. These vibrational frequencies occur at variation inten-
sities in IR spectra because of the polarity of the double bond and
electron donating methyl groups at ortho, meta or para position of
the substituent on the aromatic. The m(CAN) stretching frequencies
have been found at around 1345–1379 cmꢀ1. In fact, these vibra-
tional frequencies have been assigned by comparison with the
assignments of acylthiourea derivatives at 1400–1000 cmꢀ1
[3,12,15,54,56] and these assignments of thiourea derivatives were
also confirmed by [34,53,57,58]. Weiqun et al. reported the v(CAN)
stretching frequencies at ca. 1400 cmꢀ1 for the N-2-fluorobenzoyl-
N0-2-methoxyphenylthiourea [15]. Whilst, the m(CAS) stretching
vibration can be observed at 688–738 cmꢀ1 range that are in close
agreement with previously studied of other thiourea derivatives
[12,34,54,56–58]. For instance, these vibrational modes show a
good agreement with the 3-monosubstituted furoylthioureas ser-
ies in the wide range at ca. 700 cmꢀ1 [54]. The characteristic region
of the high frequency v(C@S) in the furoylthiourea derivatives are
described as large double bond character and the lower nucleo-
philic character of the sulphur atom in comparison with
alkylthioureas. Comparing to this report, it can be concluded that
the lowest frequency of the v(C@S) in the spectrum of 2b has less
double bond character between to the 2a and c. On other hand, the
2.2. Preparation of N-(2-methylbenzoyl)-N0-(3,4-
dichlorophenyl)thiourea, 2a
The mixture of 2-methylbenzoyl chloride (2.0 g, 13 mmol) with
the equimolar amount of ammonium thiocyanate (0.98 g,
13 mmol) and 3,4-dichloroaniline (2.10 g, 13 mmol) in 85 mL ace-
tone was put at reflux with constant stirring for ca. 4 h. The solu-
tion was poured into a beaker containing some ice blocks. Then,
the resulting white precipitate was filtered and washed with little
cold methanol, then dried in vacuum desiccator. Finally, the crude
product was purified by flash chromatography using (silica, hex-
ane: ethyl acetate 7:3) followed by recrystallisation from methanol
to afford the title compound as colourless single crystalline solids
(2.65 g, 66%). IR (KBr pellets):
1679.16 cmꢀ1 (CAN) 1379.21 cmꢀ1
NMR (DMSO-d6, 400.11 MHz): 2.44 (s, 3H, Me); 7.31 (d,
m
(NAH) 3270.93 cmꢀ1
(C@S) 722.00 cmꢀ1
,
m
(C@O)
.
,
m
,
m
1H
d
JHH = 8 Hz, 2H, C6H3); 7.43 (t, JHH = 4 Hz, 1H, C6H4); 7.51 (d,
JHH = 7 Hz, 1H, C6H4); 7.67 (s, 2H, C6H4), 8.16 (s, 1H, C6H3); 11.88,
12.52 (2 ꢁ s, 1H, NH). 13C NMR (DMSO-d6, 100.61 MHz): d 20.0
(s, Me); 125.3, 126.0, 126.5, 128.6, 128.7, 130.9, 131.1, 131.2,
131.5, 134.3, 136.6, 138.5 (12 ꢁ s, Ar); 170.9 (s, C@O); 180.0 (s,
C@S).
2.3. Preparation of N-(3-methylbenzoyl)-N0-(3,4-
dichlorophenyl)thiourea, 2b
In the similar manner as described above, compound 2b was
obtained as colourless crystalline solids (2.88 g, 85%). IR (KBr pel-
lets):
m
(NAH) 3260.55 cmꢀ1
,
m
(C@O) 1663.55 cmꢀ1
,
m
(CAN)
1344.93 cmꢀ1
,
m .
(C@S) 687.58 cmꢀ1
1H NMR (DMSO-d6,

282
M.S.M. Yusof et al. / Journal of Molecular Structure 975 (2010) 280–284
Table 1
Crystal data of 2a.
vibrational frequencies in this range are influenced by different po-
sition of the substituent methyl groups on the aromatic and prob-
ably due to the increased steric repulsion between the bulky
sulphur atom and the hydrogen in 3,4-dichlorophenyl and meth-
ylbenzoyl in aromatic nuclei. The bands observed at ca. 800 cmꢀ1
in the spectra corresponds to v(CACl) stretching vibrations with
the electronegativities of the meta and para chloro substituted of
phenyl ring compared to those v(CAF) stretching vibrations at ca.
1100 cmꢀ1 in the N-2-fluorobenzoyl-N0-4-methoxyphenylthiourea
[12] with bearing substituent effect in ortho fluoro group on the
aromatic. The FTIR spectra are shown in Fig. 2, respectively to its
designated molecule. In 1H NMR spectra of the 2a–c, one resonance
can be observed at dH 2.40–2.44 ppm as singlet which are due to
methyl proton substituents attached to the phenyl ring. The unre-
solved resonance of aromatic protons of 2a–c can be clearly ob-
served as distinctive multiplet resonances between dH 7.31–
8.16 ppm. These characteristics are strongly influenced by the o,
m and p-substituent methyl groups at the phenyl ring and due to
the overlapping proton signals in the aromatic rings. Two signals
noted as singlet, corresponds to one proton at ca. dH 11 ppm which
is assigned to the N(1)H proton which is substituted to the car-
bonyl and N(2)H proton and to the thione presence at ca. dH
12 ppm. These signals are different in term of chemical shift which
is due to the intramolecular hydrogen bonded NAH bonds in the
trans and cis conformations, respectively. As seen both NH signals
are very close chemical shifts between dH 11–12 ppm due to desh-
ielding aromatic ring. In 13C NMR spectra, signals of the methyl
carbon can be expected at above dC 20 ppm. Meanwhile, the aro-
matic carbon resonances can be found in between dC 120.7–
138.6 ppm which is corresponding to phenyl rings in the com-
pounds. The carbonyl and thione carbons can be clearly observed
at between dC 168.7–180.2 ppm and more slightly deshielded in
the spectra. Formation of intramolecular hydrogen bonding, the
increasing electronegatively of oxygen and sulphur atoms and dif-
ferent environment and conformations cause a deshielding effect
for these signals.
Parameter
Data
Empirical formula
Formula weight
Crystal system
Space group
Unit cell dimensions
C
15H12Cl2N2OS
339.23
Monoclinic
C2/c
a = 10.888(3) Å, a = 90°
b = 10.533(3)Å, b = 100.803(5)°
c = 28.131(7)Å,
3168.9(13) A3
8, 1.422 Mg/m3
1392
c = 90°
Volume
Z, Calculated density
F(0 0 0)
Crystal size
Theta range for data collection
Limiting indices
0.50 ꢁ 0.33 ꢁ 0.17
2.71–28.35°
ꢀ14 <= h <= 13
ꢀ14 <= k <= 14
ꢀ37 <= 1 <= 34
Reflections collected/unique
Completeness to theta = 26.00
Max. and min. transmission
Refinement method
11,536/3928 [R(int) = 0.0237]
99.5%
0.9138 and 0.7740
Full-matrix least-squares on F2
3928/0/198
Data/restraints/parameters
Goodness-of-fit on F2
1.042
Final R indices [I > 2 sigma(I)]
R indices (all data)
Largest diff. peak and hole
R1 = 0.0544, wR2 = 0.1299
R1 = 0.0756, wR2 = 0.1404
0.322 and ꢀ0.192 eAꢀ3
compound, 2a is analogous to the previously reported, 1-ben-
zoyl-3-(3,4-dichlorophenyl)thiourea [20], N-(3,4-dichlorophenyl)-
N0-(phenylacetyl)thiourea [21] and N-(butanoyl)-N0-(3,4-dichloro-
phenyl) thiourea [22] with the difference of 2-methylphenyl is re-
placed by the benzoyl, butanoyl and phenylacetyl groups (Fig. 3).
The compound adopts trans–cis configuration with respect to the
position of the 2-methylphenyl and 3,4-dichlorophenyl group rel-
ative to the S1 atom across their C9–N1 and C9–N2 bonds, respec-
tively (Fig. 3), comparable to those other methylbenzoylthiourea
derivatives reported [18–19,23–24].
The bond length and angles (Table 2) are similar and in the
range of previously reported [35–37]. The bond lengths N2–C9
(1.329(3) Å) and N1–C8 (1.377(3) Å) are shorter than the normal
C–N (1.472 Å) bond length indicate of partial double bond charac-
ter [12]. These can be attributed to the presence of resonance in
this fragment agreement with the literature [6,12] and forming a
planar six-membered ring with N2–H2ꢂ ꢂ ꢂO1 hydrogen bond. The
3.2. Crystal structure determination of 2a
Molecule 2a is discrete, crystallised in monoclinic crystal sys-
tem with C2/c space group, unit cells a = 10.888(3) Å,
b = 10.533(3) Å, c = 28.131(7) Å and b = 100.803(5)°. The crystallo-
graphic and refinement data of 2a is shown in Table 1. The title
100.0
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0.0
4000.0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
400.0
cm-1
Fig. 2. IR spectra of all the synthesised compounds.

M.S.M. Yusof et al. / Journal of Molecular Structure 975 (2010) 280–284
283
There is an intramolecular hydrogen bond, N2–H2Aꢂ ꢂ ꢂO1 clos-
ing a pseudo-six-membered ring (O1ꢂ ꢂ ꢂH2A–N2–C9–N1–C8–O1).
In the crystal lattice, the molecules are linked by intermolecular
hydrogen bonds N1–H1Aꢂ ꢂ ꢂS1 and N2–H2Aꢂ ꢂ ꢂO1 (Table 3), forming
one-dimensional network along the a-axis (Fig. 4).
4. Conclusion
The derivatives of methylbenzoylthiourea which are N-(3,4-
dichlorophenyl)-N0-(2-methylbenzoyl)thiourea, 2a, N-(3,4-dichlo-
rophenyl)-N0-(3-methylbenzoyl)thiourea, 2b and N-(3,4-dichloro-
phenyl)-N0-(4-methylbenzoyl)thiourea, 2c have been successfully
prepared and fully characterised by typical spectroscopic methods.
The molecular structure of N-(3,4-dichlorophenyl)-N0-(2-meth-
ylbenzoyl)thiourea, 2a was determined using single crystal X-ray
diffractometer and exhibit monoclinic crystal system. Their confor-
mation is analogous to other benzoylthioureas and the presence of
inter- and intramolecular hydrogen bonding are supported by the
IR spectra, NMR measurements and single crystal X-ray diffrac-
tometer data. These derivatives are currently bring great potential
and interest in the coordination chemistry as polydentate ligands
to bind with wide range of metal ions for numerous promising
applications in the near future.
Fig. 3. The ORTEP diagram of 2a, showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 50% probability level. The dashed line indicates
hydrogen bonds.
Table 2
Selected bond lengths (Å) and angles (°) for 2a.
Bond lengths (Å)
S1–C9 1.667(2)
O1–C8 1.216(3)
N1–C8 1.377(3)
N1–C9 1.392(3)
N2–C9 1.329(3)
Cl1–C13
Cl2–C14
1.730(2)
1.727(3)
Bond angles (°)
O1–C8–C6
N1–C8–C6
N2–C9–N1
N2–C9–S1
N1–C9–S1
123.9(2)
C8–N1–C9
128.55(19)
126.65(19)
118.9(2)
118.4(2)
121.11(18)
5. Supplementary material
113.28(19)
116.11(19)
125.69(17)
118.19(16)
C9–N2–C10
C12–C13–Cl1
C15–C14–Cl2
C13–C14–Cl2
Crystallography has been deposited with the Cambridge Crys-
tallography Data Centre, 12 Union road, Cambridge CB22 1EZ, UK
(fax: +44 1223 336 033; email: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk) and is available on request quoting the
deposition number CCDC 761512.
central thiourea moiety (S1/N1/N2/C9), 2-methylphenyl (C1–C7),
and 3,4-dichlorophenyl (C10–C15/Cl1/Cl2) groups are essentially
planar with maximum deviation of 0.027(2) Å for atom N2 from
the least-squares plane. The central thiourea moiety makes dihe-
dral angles with the 2-methylphenyl and 3,4-dichlorophenyl frag-
ments of 59.72(9)° and 47.38(7)°, respectively. Plane of 2-
methylphenyl and 3,4-dichlorophenyl group are inclined to each
other at an angle of 12.63(8)°.
Acknowledgement
The authors gratefully acknowledge Ministry of Higher Educa-
tion Malaysia for FRGS research Grant No: 59001, Ministry of Sci-
ence Technology and Innovation (MOSTI), HRD (S&T) National
Science Fellowship (NSF) for the postgraduate scholarship, Univer-
siti Malaysia Terengganu and Universiti Kebangsaan Malaysia for
providing research facilities.
Table 3
Hydrogen bond geometry (Å, °).
References
D–Hꢂ ꢂ ꢂA
D–H
Hꢂ ꢂ ꢂA
Dꢂ ꢂ ꢂA
D–Hꢂ ꢂ ꢂA
N1–H1Aꢂ ꢂ ꢂS1i
N2–H2Aꢂ ꢂ ꢂO1
N2–H2Aꢂ ꢂ ꢂO1ii
0.91(3)
0.94(3)
0.94(3)
2.66(3)
1.88(3)
2.47(3)
3.559(2)
2.663(3)
3.101(3)
166(3)
140(3)
350(4)
[1] H. Arslan, U. Flörke, N. Külcü, G. Binzet, Spectrochim. Acta Part A 68 (2007)
1347.
[2] H. Arslan, D.S. Mansuroglu, D. VanDerveer, G. Binzet, Spectrochim. Acta Part A
72 (2009) 561.
Symmetry codes: (i) -1/2 ꢀ x, 1/2 ꢀ y, 1 ꢀ z; (ii) 1/2 ꢀ x, 1/2 ꢀ y, 1 ꢀ z.
[3] G. Binzet, F.M. Emen, U. Flörke, T. Yesßilkaynak, N. Külcü, H. Arslan, Acta
Crystallogr. E65 (2009) o81.
[4] H. Arslan, U. Flörke, N. Külcü, Acta Chim. Slov. 51 (2004) 787.
[5] H.H. Nguyen, U. Abram, Inorg. Chem. Commun. 11 (2008) 1478.
[6] D.R. Kelman, K.A. Claborn, W. Kaminsky, K.I. Goldberg, D.T. Lib, D.X. West, J.
Mol. Struct. 654 (2003) 145.
[7] S.S.S. Raj, K. Puviarasan, D. Velmurugan, G. Jayanthi, H.-K. Fun, Acta Crystallogr.
C55 (1999) 1318.
[8] G.M.S. El-Bahy, B.A. El-Sayed, A.A. Shabana, Vib. Spectrosc. 31 (2003) 101.
[9] P. Wagner, S. Niemczyk-Baltro, M. Kubicki, Acta Crystallogr. C59 (2003) o83.
[10] W. Yang, Z. Weiqun, Z. Zhang, J. Mol. Struct. 828 (2007) 46.
[11] Z. Weiqun, L. Kuisheng, Z. Yong, L. Lu, J. Mol. Struct. 657 (2003) 215.
[12] Z. Weiqun, L. Baolong, Z. Liming, D. Jiangang, Z. Yong, L. Lude, Y. Xujie, J. Mol.
Struct. 690 (2004) 145.
[13] B.M. Yamin, S. Yousuf, M.S.M. Yusof, R.H. Jusoh, Acta Crystallogr. E64 (2008)
o832.
[14] H. Kogen, K. Tago, M. Arai, E. Minami, K. Masuda, T. Akiyama, Bioorg. Med.
Chem. Lett. 9 (1999) 1347.
[15] R. Vig, C. Mao, T.K. Venkatachalam, L. Tuel-Ahlgren, E.A. Sudbeck, F.M. Uckun,
Bioorg. Med. Chem. 6 (1998) 1789.
[16] S.A. Khan, N. Singh, K. Saleem, Eur. J. Med. Chem. 43 (2008) 2272.
[17] R.B. Patel, K.H. Chikhalia, C. Pannecouque, E. de Clercq, J. Braz. Chem. Soc. 18
(2007) 312.
[18] A. Mahajan, S. Yeh, M. Nell, C.E.J. Van Rensburg, K. Chibalea, Bioorg. Med.
Chem. Lett. 17 (2007) 5683.
Fig. 4. Packing diagram of N-(3,4-dichlorophenyl)-N0-(2-methylbenzoyl)thiourea,
2a, viewed down the c axis. The dashed lines denote intermolecular hydrogen
bonds.

284
M.S.M. Yusof et al. / Journal of Molecular Structure 975 (2010) 280–284
[19] K. Bhandari, S. Srivastava, G. Shankar, Bioorg. Med. Chem. 12 (2004) 4189.
[39] B.M. Yamin, S. Yousuf, M.S.M. Yusof, T.N.D.T. Zakaria, Acta Crystallogr. E64
(2008) o1227.
[40] M.S.M. Yusof, M.A. Hamid, R.N.H.R. Ramli, B.M. Yamin, Acta Crystallogr. E62
(2006) o3242.
_
[20] S. Karakusß, G. Küçükgüzel, I. Küçükgüzel, E. de Clercq, C. Pannecouque, G.
Andrei, R. Snoeck, F. Sßahin, Ö.F. Bayrak, Eur. J. Med. Chem. 44 (2009) 3591.
[21] S.-Y. Ke, S.-J. Xue, ARKIVOC x (2006) 63.
[22] W. Zheng, S.R. Yates, S.K. Papiernik, M. Guo, Environ. Sci. Technol. 38 (2004)
6855.
[41] P.A. Yonova, G.M. Stoilkova, J. Plant Growth Regul. 23 (2005) 280.
[42] A.M. Donia, A.A. Atia, A.M. Heniesh, Sep. Purif. Technol. 60 (2008) 46.
[43] P. Jara, J. Merchan, N. Yutronic, G. González, J. Inclusion Phenom. Macrocyclic
Chem. 36 (2000) 101.
[44] N. Yutronic, V. Manriquez, P. Jara, O. Witke, J. Merchán, G. González, J. Chem.
Soc. Perkin Trans. 2 (2000) 1757.
[45] C.-K. Lam, T.C.W. Mak, Tetrahedron 56 (2000) 6657.
[46] C.B. Shen, S.G. Wang, H.Y. Yang, K. Long, F.H. Wang, Corros. Sci. 48 (2006) 1655.
[47] M.A. Quraishi, F.A. Ansari, D. Jamal, Mater. Chem. Phys. 77 (2002) 687.
[48] L.N. Tang, F.P. Wang, Corros. Sci. 50 (2008) 1156.
[49] D. Yang, Y.-C. Chen, N.-Y. Zhu, Org. Lett. 6 (2004) 1577.
[50] M. Dai, B. Liang, C.H. Wang, J.H. Chen, Z. Yang, Org. Lett. 6 (2004) 221.
[51] T.Y. Zhang, M.J. Allen, Tetrahedron Lett. 40 (1999) 5813.
[52] A.L. Spek, Acta Cryst. D65 (2009) 148–155.
[23] X. Xu, X. Qian, Z. Li, Q. Huang, G. Chen, J. Fluorine Chem. 121 (2003) 51.
[24] O. Olkhovyk, V. Antochshuk, M. Jaroniec, Eng. Aspects 236 (2004) 69.
[25] G. De Munno, B. Gabriele, G. Salerno, Inorg. Chim. Acta 234 (1995) 181.
[26] G.M. Sheldrick, Programs for Crystal Structure Analysis (Release 97-2),
Gottingen University, Germany, 1997.
[27] L.J. Farrugia, ORTEP-3 for windows, J. Appl. Cryst. 30 (1997) 565.
[28] Bruker, SADABS (Version 2.01), SMART (Version 5.603) and SAINT (Version
6.36a), Bruker AXS Inc, Madison, Wisconsin, USA, 2000.
[29] G.M. Sheldrick, SHELXTS97 and SHELXTL97, University of Gottingen, Germany,
1997.
[30] G.M. Sheldrick, SHELXTL, Version 5.1. Bruker AXS, Inc., Madison, Wisconcin,
USA, 1997.
[31] A.L. Spek, J. Appl. Cryst. 36 (2003) 7.
[32] Z. Weiquin, L. Baolong, C. Yang, Z. Yong, L.L.Y. Xujie, J. Mol. Struct.
(THEOCHEM) 715 (2005) 117.
[53] A. Vijay, D.N. Sathyanarayana, Spectrochimica Acta. 49A (1993) 156.
[54] O. Estévez-Hernández, E. Otazo.-Sánchez, J.L. Hidalgo-Hidalgo de Cisneros, I.
Naranjo-Rodríguez, E. Reguera, Spectrochimica Acta Part A 62 (2005) 964.
[55] Y.-F. Yuan, S.-M. Ye, L.-Y. Zhang, J.-T. Wang, H.-G. Wang, Polyhedron 16 (1997)
2271.
[56] J. Dillen, M.G. Woldu, K.R. Koch, Acta Cryst. E62 (2006) o5225.
[57] J. Dillen, M.G. Woldu, K.R. Koch, Acta Cryst. E62 (2006) o4819.
[58] J. Dillen, M.G. Woldu, K.R. Koch, Acta Cryst. E62 (2006) o5228.
[59] Y. Mido, M. Sakoda, K.-I. Fujiwara, J. Mol. Struct. 350 (1995) 205.
[33] H.M. Badawi, Spectrochim. Acta Part A 72 (2009) 523–527.
[34] L. Bencivenni, S.N. Cesaro, A. Pieretti, Vib. Spectrosc. 18 (1998) 91.
[35] M.K. Rauf, A. Badshah, U. Flörke, A. Saeed, Acta Crystallogr. E62 (2006) o1380.
[36] M.S.M. Yusof, A.M. Pazil, M.A. Kadir, B.M. Yamin, Acta Crystallogr. E63 (2007)
o1302–o1303.
[37] M.S.M. Yusof, Z.I.M. Saadum, B.M. Yamin, Acta Crystallogr. E63 (2007) o4285.
[38] B.M. Yamin, S. Yousuf, M.S.M. Yusof, R.H. Jusoh, Acta Crystallogr. E64 (2008)
o833.