Synthesis and crystal structure of N,N′ -(p-phenyl)-bis-(p-nitro) benzoylthiourea

Article abstract of DOI:10.1080/10426500701610952

N, N′ -(p-phenyl)-bis-(p-nitro)benzoylthiourea was synthesized and characterized by elemental analysis as well as IR and 1H NMR spectroscopy. The crystal structure of the title compound was determined by single crystal X-ray diffraction. It was crystallized in triclinic space group of P-1, a = 8.1084(12), b = 11.9185(13), c = 12.6061(15) A, α = 62.213(2)°, β = 71.266(2)°, γ = 88.014(3)°, Z = 1, V = 1011.0(2)A3. The intramolecular N-H ... O hydrogen bonding interactions between the N-H and the oxygen atom of C=O groups suport N, N′ -(p-phenyl)-bis-(p-nitro) benzoylthiourea framework. the solvent DMF molecules are accommodated in the framework by intermolecular N-H..O hydrogen bonds between N-H and the oxygen atom of DMF in the title compound, which help to assemble into supramolecular structure. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500701610952

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Phosphorus, Sulfur, and Silicon
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Synthesis and Crystal Structure
of N , N ′ -( p -phenyl)-bis-(p-
nitro)benzoylthiourea
Wen-Kui Dong a , Xiao-Qing Yang a , Lan-Qin Chai a ,
Yong-Qiang Tian a & Jian-Hua Feng a
a School of Chemical and Biological Engineering ,
Lanzhou Jiaotong University , Lanzhou, Gansu,
730070, P. R. China
Published online: 09 May 2008.
To cite this article: Wen-Kui Dong , Xiao-Qing Yang , Lan-Qin Chai , Yong-Qiang Tian
& Jian-Hua Feng (2008) Synthesis and Crystal Structure of N , N ′ -( p -phenyl)-bis-
(p-nitro)benzoylthiourea, Phosphorus, Sulfur, and Silicon and the Related Elements,
183:5, 1181-1187, DOI: 10.1080/10426500701610952
To link to this article: http://dx.doi.org/10.1080/10426500701610952
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Phosphorus, Sulfur, and Silicon, 183:1181–1187, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701610952
Synthesis and Crystal Structure of
N,Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea
Wen-Kui Dong∗, Xiao-Qing Yang, Lan-Qin Chai,
Yong-Qiang Tian, and Jian-Hua Feng
School of Chemical and Biological Engineering, Lanzhou Jiaotong
University, Lanzhou, Gansu, 730070, P. R. China
N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea was synthesized and characterized by
1
elemental analysis as well as IR and H NMR spectroscopy. The crystal structure of
the title compound was determined by single crystal X-ray diffraction. It was crystal-
lized in triclinic space group of P-1, a = 8.1084(12), b = 11.9185(13), c = 12.6061(15)
◦
◦
◦
3
˚
˚
A, α = 62.213(2) , β = 71.266(2) , γ = 88.014(3) , Z = 1, V = 1011.0(2)A . The in-
tramolecular N-H· · ·O hydrogen bonding interactions between the N-H and the
oxygen atom of C O groups suport N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea
framework. the solvent DMF molecules are accommodated in the framework by in-
termolecular N-H··O hydrogen bonds between N-H and the oxygen atom of DMF in
the title compound, which help to assemble into supramolecular structure.
Keywords Crystal structure; N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea; Synthesis;
X-ray diffraction
INTRODUCTION
The extensive applications of thiourea derivatives are paid much
attention. Besides their good biological activities,1−3 some thioureas
have good inhibition effect on the corrosion of mild steel in hy-
drochloric acid medium and they are excellent neutral ion carrier,4,5
which are also applied in the extraction of trace metals and the
separation of platinum group metal and in the a coordination
reaction etc.6−8 The existence of carbonyl and sulphur carbonyl
groups in benzoylthiourea enhances the coordination ability.
Received 4 July 2007; accepted 20 July 2007.
This work was supported by the Foundation of the Education Department of Gansu
Province (No. 0604-01) and the ‘Qing Lan’ Talent Engineering Funds of Lanzhou Jiaotong
University (No. QL-03-01A).
Address correspondence to Wen-Kui Dong, School of Chemical and Biological En-
gineering, Lanzhou Jiaotong University, Lanzhou, Gansu, 730070, P.R.China. E-mail:
dongwk@mail.lzjtu.cn
1181

1182
W. -K. Dong et al.
Studies of a number of substituted thioureas including N-benzoyl-
Nꢀ-thiourea indicate an intramolecular hydrogen bond between NH
group and oxygen atom,9,10 which help to assemble into supramolec-
ular structure.11,12 Here, in continuation of our previous studies on
synthesis and structural characterization of N-(o-Chloro)benzoyl-Nꢀ-
(3-pyridyl)thiourea,13 a novel bis-benzoylthioureas,N,Nꢀ-(p-phenyl)-
bis-(p-nitro)benzoylthiourea N,Nꢀ-dimethylformamide disolvate has
been synthesized (Scheme 1) and structurally characterized by X-ray
crystallography.
SCHEME 1 Synthetic route to N,Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea.
RESULTS AND DISCUSSION
The title compound has been synthesized and characterized by elemen-
tal analysis, IR as well as 1H NMR spectroscopy and single crystal X-ray
diffraction analysis. The IR data of the title compound show two νN−H
stretching bands at 3341 and 3191 cm−1. The C O groups stretching
bands appears at 1675 cm−1. A strong band at 1152 cm−1 is observed
for the title compound and is assigned to νC stretching vibration.
S
The 1H NMR data of the title compound show that the chemical
shifts of hydrogen on nitrogen appear in the low field, which chemical
shifts are with 11.98 and 12.42 ppm. The chemical shifts (8.052, 8.187,
8.338 ppm) of hydrogen atoms on the benzene rings are in a lower field
than the average chemical shift (7.270 ppm) of hydrogen atoms on the
non-substituted benzene ring, which due to the substituted groups NO2
and C O of the benzene ring.
The crystal data and parameters relevant to the structure deter-
mination and refinement for the title compound are listed in Table I;
selected bond lengths and bond angles and hydrogen bonds parame-
ters are listed in Table II and Table III. The molecular structure in the

N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea
1183
TABLE I Crystal Data and Structure Refinement for the Title
Compound
3
˚
Formula
C34H48 N10O10S2 V/A
1011.0(2)
Mr
820.94
Triclinic/ P-1
Z
1
Crystal system/ Space
group
Dr/(mg·m−3
)
1.348
˚
˚
a/A
8.1084(1)
11.9185(1)
12.6061(2)
62.213(2)
71.266(2)
88.014(3)
λ/A
0. 71073
1.95–25.00
1.98
b/A
θ range/◦
µ/cm−1
T/K
˚
˚
c/A
α/◦
β/◦
γ /◦
298(2)
Block, Yellow
Crystal size
0.53 × 0.41
× 0.28 mm
Data collection
Bruker SMART
diffractometer
φ/ω scans
5258 measured
reflections
3499 independent
reflections
2056 reflections with
I > 2δ(I)
R(int) = 0.0482
θ
= 25.00
max
−9≤ h ≤ 8
−14≤ k ≤14
−14≤ l ≤14
Refinement
Refinement on F2
R [F2 >2σ(F2)] = 0.064
253 parameters
ω = 1/[σ2(F2o)+
(0.0925P)2+ 0.1348P]
Where P = (F2o+ 2Fc2)/3
ωR(F2) = 0.161
S = 1.014
−3
˚
ꢀρ
= 0.317 e A
max
−3
˚
3499 reflections
ꢀρmin = −0.317 e A
crystal with atom label1ing and a view of packing diagram along the
a-axis, resulting from intermolecular hydrogen bonding are shown in
Figure 1 and Figure 2, respectively.
A yellow block-shaped crystal of the title compound with approxi-
mate dimensions of 0.53 × 0.41 × 0.28 mm was mounted on a Bruker
Smart diffractometer equipped with an Apex CCD area detector. Inten-
sity data were collected using a graphite-monochromated MoKα radi-
˚
ation (λ = 0.71073 A) at 298 (2) K. The structure was solved by Direct
14
Methods (SHELXS 97)
and refined by full matrix least squares on
F2 using the program SHELXL 97.15 All hydrogen atoms were calcu-
lated. Hydrogens on nitrogens were located by difference Fourier maps,
˚
placed at N–H = 0.8600 A and refined isotropically. Hydrogens attached
˚
to carbons were located in their calculated positions (C–H = 0.9300 A),
2
˚
assigned fixed thermal parameters of U = 0.05 A and refined using
iso

1184
W. -K. Dong et al.
◦
˚
TABLE II Selected Bond Lengths [A] and Bond Angles [ ] for the
Title Compound
Bond
Dist.
Bond
Dist.
Bond
Dist.
N(1)-C(1)
N(1)-C(2)
N(2)-C(5)
N(2)-C(1)
N(3)-O(2)
N(3)-O(3)
N(3)-C(9)
O(1)-C(5)
S(1)-C(1)
1.330(4) C(2)-C(4)
1.406(4) C(2)-C(3)
1.367(4) C(3)-C(4)
1.400(4) C(5)-C(6)
1.212(4) C(6)-C(7)
1.222(4) C(6)-C(11)
1.475(4) C(7)-C(8)
1.216(4) C(8)-C(9)
1.651(4) C(9)-C(10)
1.373(5) C(10)-C(11)
1.392(5) N(4)-C(12)
1.379(5) N(4)-C(13)
1.494(5) N(4)-C(14)
1.377(5) N(5)-C(15)
1.387(4) N(5)-C(16)
1.375(5) N(5)-C(17)
1.376(5) O(4)-C(12)
1.367(5) O(5)-C(15)
1.375(5)
1.301(5)
1.440(6)
1.450(5)
1.311(7)
1.388(6)
1.479(7)
1.221(4)
1.212(8)
Bond angles
Deg.
Bond angles
Deg.
Bond angles
Deg.
C(1)-N(1)-C(2)
C(5)-N(2)-C(1)
O(2)-N(3)-O(3)
O(2)-N(3)-C(9)
O(3)-N(3)-C(9)
131.7(3) N(1)-C(1)-N(2)
127.6(3) N(1)-C(1)-S(1)
123.2(3) N(2)-C(1)-S(1)
118.2(3) N(2)-C(1)-S(1)
118.6(3) C(4)-C(2)-C(3)
114.2(3) N(2)-C(5)-C(6)
127.7(3) C(7)-C(6)-C(11)
114.2(3) C(7)-C(6)-C(5)
118.1(3) C(11)-C(6)-C(5)
118.7(3) C(8)-C(7)-C(6)
125.4(3) C(7)-C(8)-C(9)
115.8(3) C(10)-C(9)-C(8)
116.5(3)
119.8(3)
122.9(3)
117.1(3)
120.9(3)
117.7(3)
123.0(3)
C(12)-N(4)-C(13) 120.5(4) C(4)-C(2)-N(1)
C(12)-N(4)-C(14) 121.8(4) C(3)-C(2)-N(1)
C(13)-N(4)-C(14) 117.7(4) C(4)#1-C(3)-C(2) 121.2(3) C(12)-C(11)-C(10) 118.6(2)
C(15)-N(5)-C(16) 125.6(6) C(2)-C(4)-C(3)#1 120.1(3) C(10)-C(9)-N(3)
118.8(3)
118.2(3)
123.9(7)
125.4(4)
C(15)-N(5)-C(17) 119.2(5) O(1)-C(5)-N(2)
C(16)-N(5)-C(17) 115.2(5) O(1)-C(5)-C(6)
123.8(3) C(8)-C(9)-N(3)
119.7(3) O(5)-C(15)-N(5)
C(9)-C(10)-C(11) 118.5(3) C(10)-C(11)-C(6) 120.1(3) O(4)-C(12)-N(4)
Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y+1,-z.
a riding model. The final refinements converged at R1 = 0.0645, wR2 =
0.1607 with ω = 1 / [σ2(Fo2)+ (0.0925P)2+ 0.1348P], where P = (F2o+
2F2c ) / 3. All non-hydrogen atoms were refined with anisotropic displace-
ment parameters. The largest differential peak and hole were 0.317 and
−0.317 e A−3. The structural plots were drawn with SHELXL 97 soft-
˚
ware package.
The X-ray crystallographic analysis of the title compound revealed
the carbonyl and thiocarbonyl moieties point in approximately opposite
TABLE III Hydrogen Bonds Parameters for the Title Compound
D-H· · ·A
D-H
H· · ·A
D· · ·A
D-H· · ·A
N(1)-H(1N)· · ·O(1)
N(2)-H(2N)· · ·O(4)∗
0.86(2)
0.86(2)
1.867(2)
2.006(2)
2.602(3)
2.821(3)
142.37(2)
157.73(2)
Symmetry transformations used to generate equivalent atoms: *: x-1, y, z.

N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea
1185
SCHEME 2 Molecular structure in the crystal with atom numbering of the
title compound. Intramolecular H-bonds are indicated by dashed lines.
directions, there is intramolecular hydrogen bonding N1-H1· · ·O1
˚
˚
(d(H1· · ·O1) = 1.867(2) A; d(N1· · ·O1) = 2.602(3) A; N1-H1· · ·O1
= 142.37◦) between the carbonyl group and the N1-H1 group, the
six atoms (C5/N2/C1/N1/H1/O1) in the hydrogen-bonded ring almost
coplanar, the torsion angles of C(5)-N(2)-C(1)-N(1) and C(1)-N(2)-C(5)-
O(1) are −3.8(5)◦ and 1.4(6)◦, respectively. The formtion of coplanar
hydrogen-bonded ring promotes the stability of the thiourea com-
pounds, which is difficult for the oxygen atom on carbonyl of ben-
zoylthioureas to particpate in the coordination with metal ions.16,17
˚
The C O bond length is 1.216(4) A, longer than the average C O
˚
bond length (1.200 A), which is due to intramolecular hydrogen bonding
SCHEME 3 View of packing diagram along the a-axis in the crystal structure
of the title compound. Intermolecular H-bond are indicated by dashed lines.

1186
W. -K. Dong et al.
interactions. There are two N,Nꢀ-dimethylformamide molecules in the
structure of N,Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea.
A view of the inter-molecular hydrogen bond in a packing diagram
along a-axis in the crystal lattice of the title compound shows it contains
a molecule in a crystal packing. There are intermolecular hydrogen
˚
bondings N2-H2· · ·O4(x-1, y, z) (d(H2· · ·O4) = 2.006(2) A; d(N2· · ·O4)
= 2.821(3) A; N1-H1· · ·O1 = 157.73◦) between the carbonyl group of
˚
N,Nꢀ-dimethylformamide and the N2-H2 group. There are π-π interac-
tions between two benzene rings of neighboring molecules in the crystal
packing along a-axis and the distance between two benzene rings planes
˚
is 1.132(3) A.
The crystal structure shows that thioureas are good donors of hy-
drogen bondings, which may form inter- and intramolecular hydrogen
bondings, and the intermolecular hydrogen bonding assembled into
supramolecule. There are the π-π interaction between the aromatic
rings, which help to assemble into supramolecular structure.11,12
EXPERIMENTAL
All chemicals were of analytical reagent grade and were used with-
out further purification. C, H, and N analyses were obtained using a
VarioEL V3.00 automatic elemental analysis instrument. The IR spec-
tra in the range of 400–4000 cm−1 were recorded with a VERTEX70
FT-IR spectrophotometer using KBr pellets. 1H NMR spectra were ob-
tained with a German Bruker AVANCE DRX-400 spectrometer. The sin-
gle crystal structure determination by X-ray diffraction was performed
with a Bruker Smart diffractometer equipped with an APEX CCD area
detector. Melting points were obtained using a X4 microscopic melting
point apparatus ( Beijing Taike Instrument ) and are uncorrected.
Synthesis
(p-Nitro)benzoyl chloride (1.86 g, 10 mmol) was reacted with ammo-
nium thiocyanate (1.14 g, 15 mmol) in CH2Cl2(25 ml) solution un-
der soild-liquid phase transfer catalysis, using polyethylene glycol-400
(0.18 g) as the catalyst, to give the corresponding (p-nitro)benzoyl
isothiocyanate under stirring at the room temperature, followed by
slow addition of 15 ml CH2Cl2 solution dissolved p-phenylenediamine
(1.60 g, 0.01 mmol). The corresponding yellow compound precipitated
immediately. The product was filtered, washed with water and CH2Cl2,
dried, and recrystallized from THF to give the title compound (N,Nꢀ-
(p-phenyl)-bis-(p-nitro)benzoylthiourea). Yield: 72.6%. m.p. 243–244◦.

N, Nꢀ-(p-phenyl)-bis-(p-nitro)benzoylthiourea
1187
Elemental analysis – found: C, 50.38%; H, 3.07%; N, 16.02%; calcd.
for C34H48N10O10S2: C, 50.27%; H, 3.15%; N, 15.99%. Selected IR data
(cm−1, KBr pellet): 3341, 3191 (νNH), 1675 (νC O), 1152 (νC S).1H NMR
(400 MHz, DMSO-d6, δ, ppm): 8.052 (d, J = 17.2 Hz, 4H, ArH), 8.187
(d, J = 8.2 Hz, 4H, ArH), 8.338 (dd, J = 17.2, 7.2 Hz, 4H, ArH), 11.98
(s, 2H, NH), 12.42 (s, 2H, NH).
A DMF solution of the title compound was placed in a diethyl ether
atmosphere, after several days, along with diffusion of diethyl ether
into the DMF solution of the title compound, yellow block-shaped single
crystal suitable for X-ray crystallographic analysis were obtained.
Further details of the crystal structure investigation may be ob-
tained from the the Cambridge Crystallographic Data Centre, Postal
Address: CCDC, 12 Union Road, CAMBRIDGE CB2 1EZ, UK.
Telephone: (44) 01223 762910
Fax: (44) 01223 336033; E-mail:
deposit@ccdc.cam.ac.uk on quoting the depository number CCDC
652645.
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