Synthesis and crystal structure of n-(p-nitro)benzoyl-n'-(3-pyridyl) thiourea

Article abstract of DOI:10.14233/ajchem.2013.13968

In this study, N-(p-nitro)benzoyl-N'-(3-pyridyl)thiourea with the molecular formula C13H10N4O₃S has been synthesized and characterized structurally by 1H NMR and X-ray crystallography. There is a strong intramolecular N2-H₂···O1 hydrogen bond. In the crystal structure, intermolecular N1-H1···N4 hydrogen bonds link neighbouring molecules into an infinite zigzag chain supramolecular structure.

Full text of DOI:10.14233/ajchem.2013.13968

Asian Journal of Chemistry; Vol. 25, No. 8 (2013), 4334-4336
http://dx.doi.org/10.14233/ajchem.2013.13968
Synthesis and Crystal Structure of N-(p-Nitro)benzoyl-N'-(3-pyridyl)thiourea
*
GANG LI , MENG-MENG ZHAO, LI WANG, YU-HUA YANG, YU-JIE ZHANG and XIU-YAN DONG
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
*Corresponding author: E-mail: li_gang78@126.com
(Received: 26 April 2012;
Accepted: 11 February 2013)
AJC-12958
In this study, N-(p-nitro)benzoyl-N'-(3-pyridyl)thiourea with the molecular formula C13H10N4O3S has been synthesized and characterized
structurally by 1H NMR and X-ray crystallography. There is a strong intramolecular N2-H2···O1 hydrogen bond. In the crystal structure,
intermolecular N1-H1···N4 hydrogen bonds link neighbouring molecules into an infinite zigzag chain supramolecular structure.
Key Words: Thiourea, Synthesis, Crystal structure.
apparatus made in Beijing Taike Instrument Limited Company
and the thermometer was uncorrected.
INTRODUCTION
The extensive applications of thiourea derivatives are paid
much attention. Besides their good biological activities1-3, some
thioureas have good inhibition effect on the corrosion of mild
steel in hydrochloric acid medium and are excellent neutral
ion carrier4,5, which are also organic reaction catalyst in the
metal-catalyzed asymmetric reduction of carbonyl compounds
and carbonylative cyclization of o-hydroxy arylacetylenes6,7.
Studies of a number of substituted thioureas including N-
benzoyl-N'-thiourea indicate an intramolecular hydrogen bond
Synthesis: The p-nitrobenzoyl chloride (1.86 g, 10 mmol)
was reacted with ammonium thiocyanate (1.14 g, 15 mmol)
in CH2Cl2 (25 mL) solution under soild-liquid phase transfer
catalysis, using polyethylene glycol-400 (0.18 g) as the cata-
lyst, to give the corresponding p-nitrobenzoyl isothiocyanate,
which was reacted with 3-aminopyridine (0.85 g, 10 mmol),
to give the title compound. Yield 67.8 %, m.p. 443-445 K.
Anal. calcd. (%) for C13H10N4O3S: C, 51.65; H, 3.33; N, 15.88.
Found (%): C, 51.47; H, 3.45; N, 15.69. Selected IR data (KBr,
νmax, cm-1, pellet): 3344, 3173 (NH), 1680 (C=O), 1171 (C=S).
1H NMR (400 MHz, DMSO-d6, δ, ppm): 7.49 (dd, J = 8.4, 4.8
Hz, 1H, PyH), 8.12 (t, J = 8.2 Hz, 1H, PyH), 8.21 (dd, J =
20.4, 8.8 Hz, 2H, ArH), 8.34 (dd, J = 20.4, 8.8 Hz, 2H, ArH),
8.45 (dd, J = 27, 6.6 Hz, 1H, PyH), 8.74 (s, 1H, PyH), 12.13
(s, 1H, NH), 12.31 (s, 1H, NH).
between NH group and oxygen atom8,9. H NMR spectrum
1
shows that there is intramolecular hydrogen bond between the
pyridyl nitrogen atom and NH group10,11 and there is also
internolecular hydrogen bond between NH group and pyridyl
nitrogen atom of a neighboring molecule12. Here we report
the synthesis and crystal structure of N-(p-nitro)benzoyl-N'-
(3-pyridyl)thiourea.
A THF solution of the N-(p-nitro)benzoyl-N'-(3-pyridyl)-
thiourea was placed in a diethyl ether atmosphere, after several
days, along with diffusion of diethyl ether into the THF solution
of the title compound, colourless needle-shaped single crystals
suitable for X-ray crystallographic analysis were obtained.
X-Ray structure determination: The single crystal of
N-(p-nitro)benzoyl-N'-(3-pyridyl)thiourea, with approximate
dimensions of 0.37 mm × 0.17 mm × 0.15 mm was placed on
a Bruker Smart 1000 diffractmeter equipped with Apex CCD
area detector. The diffraction data were collected using a graphite
monochromated MoKα radition (λ = 0.71073 Å) at 298(2) K.
The structure was solved by using the program SHELXS-97
and Fourier difference techniques and refined by full-matrix
least-squares method on F2 using SHELXL-97. Details of the
data collection and refinements of the title compound are given
EXPERIMENTAL
p-Nitrobenzoyl chloride, 3-aminopyridine and poly-
ethylene glycol-400 were purchased and used without further
purification. The other reagents and solvents were analytical
grade reagents from Tianjin Chemical Reagent Factory. C, H
and N analyses were carried out with a GmbHVariuoELV3.00
automatic elemental analyzer. IR spectra in the range 4000-
400 cm-1 were recorded on a VERTEX70 FT-IR spectropho-
tometer using KBr pellets. The 1H NMR spectra were recorded
on a Mercury-400BB spectrometer at room temperature using
CDCl3 as solvent. X-Ray single crystal structure was deter-
mined on a Bruker Smart 1000 CCD area detector. Melting
points was measured by the use of a microscopic melting point

Vol. 25, No. 8 (2013)
Synthesis and Crystal Structure of N-(p-Nitro)benzoyl-N'-(3-pyridyl)thiourea 4335
in Table-1. The non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were added theoretically. CCDC: 647074.
RESULTS AND DISCUSSION
X-Ray crystallographic analysis revealed the crystal structure
of the title compound. And the structure is shown in Fig. 1.
Selected bond distances and angles are listed in Table-2. The
single crystal structure of the title compound is built up by
only the C13H10N4O3S molecule, in which all bond lengths are
in normal ranges. The X-ray diffraction anylisis of the title
compound revealed there is an intramolecular hydrogen
bonding N2-H2···O1 (d(H2..O1) = 1.98 Å; d(N2···O1) = 2.675(4)
Å; ∠N2-H2···O1 = 136.9º) between the carbonyl group and
the N2-H2 group, the six atoms (C2/N1/C1/N2/H2/O1) in the
hydrogen-bonded ring almost coplanar, the torsion angles of
C(2)-N(1)-C(1)-N(2) and C(1)-N(1)-C(2)-O(1) are -0.2(4)º
and 13.6(4)º, respectively. The C=O bond length is 1.221(3)
Å, longer than the average C=O bond length (1.200 Å), which
is due to intramolecular hydrogen bonding interactions.
A view of the intra- and inter- molecular hydrogen bonds
in a stacking of the title compound in the crystal lattice shows
it contains four molecules in a crystal packing. These mole-
cules are linked with another neighboring molecule by the
intermolecular hydrogen bondings of N2-H2···O1 (-x + 1, -y
+ 2, -z + 2) (d(H2··O1) = 2.569 Å; d(N2···O1) = 3.194(4) Å;
∠N2-H2···O1 = 130.33º) and N1-H1···N4 (-x + 3/2, y - 1/2,
TABLE-1
CRYSTAL DATA AND REFINEMENT
PARAMETERS FOR THE TITLE COMPOUND
Empirical formula
Formula weight
Temperature
C13H10N4O3S
302.31
298(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P2(1)/c
a = 9.3802(13) Å, b = 15.567(2) Å, c
Cell dimensions
= 9.6041(14) Å β = 110.217(2)
Volume
1316.0(3) Å3
Z
4
Density (calculated)
Absorption coefficient
F(000)
1.526 mg/m3
0.263 mm-1
624
Index ranges
-11 ≤ h ≤ 11, -16 ≤ k ≤ 18, -7 ≤ l ≤ 11
6580/2318 [R(int) = 0.0441]
2318
2318/0/190
1.019
Reflections collected/unique
Independent reflections
Data/restraints/parameters
Goodness of fit indicator
R [I > 2σ(I)]
R1 = 0.0425, wR2 = 0.0786
0.243 and -0.195 e Å
Largest diff. peak and hole
Fig. 1. Molecule structure of the title compound with atom numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn
at the 30 % probability level
TABLE-2
SELECTED BOND LENGTHS (Å) AND ANGLES (º) FOR THE TITLE COMPOUND
Bond
N(1)-C(2)
N(1)-C(1)
N(2)-C(1)
N(2)-C(10)
N(3)-O(3)
N(3)-O(2)
N(3)-C(6)
Lengths
1.366(3)
1.390(3)
1.334(3)
1.421(3)
1.218(3)
1.219(3)
1.474(3)
1.331(3)
Angles
129.4(2)
124.9(2)
123.7(3)
117.9(3)
118.4(2)
116.9(2)
114.6(2)
125.7(2)
119.72(19)
123.5(2)
Bond
N(4)-C(13)
O(1)-C(2)
S(1)-C(1)
C(2)-C(3)
C(3)-C(8)
C(3)-C(4)
C(4)-C(5)
Lengths
1.338(3)
1.222(3)
1.660(3)
1.490(4)
1.381(4)
1.385(3)
1.381(3)
1.375(3)
Angles
121.8(2)
114.7(2)
119.7(2)
121.7(2)
118.6(2)
120.8(3)
117.9(2)
122.6(2)
119.0(2)
118.4(2)
Bond
C(6)-C(7)
C(7)-C(8)
C(9)-C(10)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
–
Lengths
1.369(3)
1.380(3)
1.379(3)
1.371(3)
1.372(3)
1.372(3)
–
N(4)-C(9)
Bond
C(5)-C(6)
Bond
–
–
Bond
Angles
118.9(3)
120.1(3)
123.4(3)
118.7(2)
120.1(2)
121.2(2)
118.9(3)
118.8(3)
123.4(2)
–
C(2)-N(1)-C(1)
C(1)-N(2)-C(10)
O(3)-N(3)-O(2)
O(3)-N(3)-C(6)
O(2)-N(3)-C(6)
C(9)-N(4)-C(13)
N(2)-C(1)-N(1)
N(2)-C(1)-S(1)
N(1)-C(1)-S(1)
O(1)-C(2)-N(1)
O(1)-C(2)-C(3)
N(1)-C(2)-C(3)
C(8)-C(3)-C(4)
C(8)-C(3)-C(2)
C(4)-C(3)-C(2)
C(5)-C(4)-C(3)
C(6)-C(5)-C(4)
C(7)-C(6)-C(5)
C(7)-C(6)-N(3)
C(5)-C(6)-N(3)
C(6)-C(7)-C(8)
C(7)-C(8)-C(3)
N(4)-C(9)-C(10)
C(11)-C(10)-C(9)
C(11)-C(10)-N(2)
C(9)-C(10)-N(2)
C(10)-C(11)-C(12)
C(13)-C(12)-C(11)
N(4)-C(13)-C(12)
–

4336 Li et al.
Asian J. Chem.
Fig. 2. Digram showing the intramolecular O-H···N and intermolecular O-H···N
6. Y. Nan, H. Miao and Z. Yang, Org. Lett., 2, 297 (2000).
7. J.A.J. Breuzard, M.L. Tommasino and F. Toucard, J. Mol. Catal. A:
Chem., 156, 223 (2000).
-z + 3/2) (d(H1··N4) = 2.22 Å; d(N1···N4) = 2.993(3) Å; ∠N1-
H1···N4 = 150.0°) (Fig. 2)13-15
.
8. W.K. Dong, X.Q.Yang. L.Q. Chai,Y.Q. Tian and J.H. Feng, Phosphorus
Sulfur Silicon Rel. Elem., 183, 1181 (2008).
ACKNOWLEDGEMENTS
9. W.K. Dong, X.Q. Yang and J.H. Feng, Acta Crystallogr., E62, o3459
(2006).
10. J. Valdés Martínez, S. Hernández Ortega and L.J. Ackeman, J. Mol.
Struct., 524, 51 (2000).
11. D.X. West, J.K. Swearingen and A.K. Hernetet, J. Mol. Struct., 522,
27 (2000).
12. V.M. Jesus, H.O. Simon and R. Manuel, J. Chem. Crystallogr., 34,
533 (2004).
13. W.K. Dong, G. Wang, S.S. Gong, J.F. Tong, Y.X. Sun and X.H. Gao,
Transition Met. Chem., 37, 271 (2012).
14. W.K. Dong,Y.X. Sun,Y.P. Zhang, L. Li, X.N. He and X.L. Tang, Inorg.
Chim. Acta, 362, 117 (2009).
15. W.K. Dong, J.G. Duan,Y.H. Guan, J.Y. Shi and C.Y. Zhao, Inorg. Chim.
Acta, 362, 1129 (2009).
The authors thank theYoung Scholars Science Foundation
of Lanzhou Jiaotong University for financial support of this
work.
REFERENCES
1. S.G. Teoh, S.H. Ang and H.K. Fun, J. Organomet. Chem., 580, 17
(1999).
2. V. Ravichandran and R.K. Agrawal, Med. Chem. Lett., 17, 2197 (2007).
3. R. Campo, J.J. Criado and E. Garcia, J. Inorg. Biochem., 89, 74 (2002).
4. S.D. Shetty and P. Shetty, Mater. Lett., 61, 2347 (2007).
5. M.R. Ganjali, P. Norouzi and T. Alizadeh, Sens. Actuators B, 120, 487
(2007).