Weak interaction and supramolecular structure of N-ethoxycarbonyl-N′- arylthiourea

Article abstract of DOI:10.1080/10426500601087392

Two kinds of N-ethoxycarbonyl-N′-arylthiourea were synthesized, and their structure was determined by X-ray diffraction. There are inter-and intramolecular hydrogen bonds in these compounds. In the crystals, the compounds were assembled to one-dimensional catenulate supramolecular structure by intermolecular hydrogen bonds. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon
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Weak Interaction and
Supramolecular Structure
of N -ethoxycarbonyl- N ′-
arylthiourea
Qi Lin a , Tai-Bao Wei a & You-Ming Zhang a
a College of Chemistry and Chemical Engineering,
Gansu Key Laboratory of Polymer Materials ,
Northwest Normal University , Lanzhou, Gansu, P.R.
China
Published online: 24 Feb 2007.
To cite this article: Qi Lin , Tai-Bao Wei & You-Ming Zhang (2007) Weak
Interaction and Supramolecular Structure of N -ethoxycarbonyl- N ′-arylthiourea,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:4, 863-871, DOI:
10.1080/10426500601087392
To link to this article: http://dx.doi.org/10.1080/10426500601087392
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Phosphorus, Sulfur, and Silicon, 182:863–871, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601087392
Weak Interaction and Supramolecular Structure
of N-ethoxycarbonyl-Nꢀ-arylthiourea
Qi Lin
Tai-Bao Wei
You-Ming Zhang
College of Chemistry and Chemical Engineering, Gansu Key Laboratory
of Polymer Materials, Northwest Normal University, Lanzhou, Gansu,
P.R. China
Two kinds of N-ethoxycarbonyl-Nꢀ-arylthiourea were synthesized, and their struc-
ture was determined by X-ray diffraction. There are inter- and intramolecular hy-
drogen bonds in these compounds. In the crystals, the compounds were assembled to
one-dimensional catenulate supramolecular structure by intermolecular hydrogen
bonds.
Keywords Hydrogen bond; supramolecular; thiourea
INTRODUCTION
Thiourea derivatives have been found to possess many impor-
tant biological activities;1 many of them are used as heribicides,2,3
insecticides4,5 and plant-growth regulators.6 In addition, owning to
their strong coordination ability,7,8 N-substituted- Nꢀ-ethoxycarbonyl
thioureas are extensively utilized as the collector for some precious
metals.9 Recently, these compounds have attracted considerable at-
tention for their potential uses as artificial receptors in supramolec-
ular chemistry because of their characteristic behavior based on strong
hydrogen-bond donors.10,11 In fact, the biological activity and the
Received June 26, 2006; Accepted September 20, 2006.
The authors gratefully acknowledge the support of the Natural Science Foundation
of China (No. 20371040), the Key Scientific and Technical Research Project of Ministry
of Education of China (205161), and the Youth Foundation of Gansu province (3YS051-
A25-010). At the same time, the authors thank the Key Laboratory of Eco-Environment-
Related Polymer Materials (Northwest Normal University), Ministry of Education of
China, for financial support.
Address correspondence to You-Ming Zhang, College of Chemistry and Chemical En-
gineering, Northwest Normal University, Lanzhou, 730070, Gansu, P.R. China. E-mail:
zhangnwnu@126.com.
863

864
Q. Lin et al.
FIGURE 1 The crystal structure of N-ethoxycarbonyl-Nꢀ-3-methylphenyl-
thiourea.
coordination ability of these kinds of compounds are closely related
to their structure. In view of this and as a part of our research on
supramolecular weak interaction and molecular recognition charac-
teristic of thiourea derivatives,12−14 we synthesized two kinds of N-
ethoxycarbonyl-Nꢀ-arylthiourea and obtained its unambiguous struc-
ture by X-ray analysis. There are inter- and intramolecular hydrogen
bonds in these compounds. In the crystals, the compounds were assem-
bled to a One-Dimensional (1D) catenulate supramolecular structure
by intermolecular hydrogen bonds.
RESULTS AND DISCUSSION
The molecular structure of N-ethoxycarbonyl-Nꢀ-3-methylphenyl-
thiourea (a) and N-ethoxycarbonyl-Nꢀ-4-fluorophenylthiourea (b) are
FIGURE 2 The crystal structure of N-ethoxycarbonyl-Nꢀ-4-fluorophenyl-
thiourea.

N-Ethoxycarbonyl-Nꢀ-Arylthiourea
865
TABLE I Crystal Data and Structure Refinement for a and b
Compounds
a
b
Formula
C11H14N2O2S
238.30
triclinic
colorless
P1
5.8380(10)
9.441(2)
11.595(2)
77.15(3)
87.89(3)
86.22(3)
621.6(2)
1.273
C10H11FN2O2S
242.27
Monoclinic
colorless
P21/n
9.718(2)
25.712(5)
9.878(2)
90.00
109.86(3)
90.00
Formula weight
Crystal system
Crystal color
Space group
˚
a (A)
˚
b (A)
˚
c (A)
α (deg)
β (deg)
γ (deg)
3
˚
V (A )
D
2321.4(8)
1.213
0.244
calcd. (g·cm−3
)
μ (mm−1
)
0.248
Total no. of reflns
No. of unique data
No. of params
R
1296
1138
290
0.0275
2263
1378
290
0.0402
Rw
0.0694
1.059
0.070, −0.059
0.0837
1.058
0.068, −0.061
Goodness of fit on F2
Largest peak/Hole in final
−3
˚
diff map (e A
)
shown in Figures 1 and 2. Unit-cell data are listed in Table I
and, selected bond distances and angles are listed in Tables II and
III. Coordinates and equivalent isotropic thermal parameters for
nonhydrogen atoms in the structure of a and b are listed in
Table IV.
In the molecule of compound a, there is an intramolecular hydro-
. . .
gen bond, N1-H O2, which forms a six-membered ring with C9, N2,
TABLE II Selected Bond Length (nm) for a and b
a
b
S1—C8
0.1618(3) N1—C8 0.1400(8) S1—C7 0.1678(4) N1—C6 0.1427(7)
O1—C9 0.1350(9) N2—C8 0.1395(8) O2—C8 0.1211(9) N2—C7 0.1366(8)
O2—C9 0.1176(9) N2—C9 0.1429(7) O1—C8 0.1326(8) N2—C8 0.1381(7)
O1—C10 0.1434(9) N1—C6 0.1428(6) O1—C9 0.1456(6) N1—C7 0.1331(8)
C4—C7 0.1598(1) C11—C10 0.1517(1) F1—C3 0.1353(9) C9—C10 0.1489(9)
C1—C6 0.1404(9) C5—C6 0.1376(9) C1—C6 0.1372(9) C5—C6 0.1376(9)
C1—C2 0.1376(9) C2—C3 0.1388(2) C1—C2 0.1389(9) C2—C3 0.1396(2)
C3—C4 0.1230(2) C4—C5 0.1414(1) C3—C4 0.1371(2) C4—C5 0.1372(9)

866
Q. Lin et al.
TABLE III Selected Bond Angle (◦) and Torsion Angle (◦)
a
b
N1—C8—S1
N1—C8—N2
N1—C6—C1
N2—C8—S1
O2—C9—N2
O1—C9—O2
O1—C9—N2
C9—O1—C10
C8—N2—C9
C6—N1—C8
C5—C4—C7
C3—C4—C7
C4—C5—C6
126.4(5)
113.8(6)
119.8(6)
119.8(4)
127.6(6)
126.9(6)
105.4(5)
114.8(5)
127.4(5)
119.5(6)
113.1(7)
123.3(7)
116.8(6)
120.3(6)
5.3(10)
N1—C7—S1
N2—C7—S1
N1—C6—C1
N1—C7—N2
O2—C8—N2
O1—C8—O2
O1—C8—N2
C8—O1—C9
C7—N2—C8
C6—N1—C7
C2—C3—F1
C4—C3—F1
C6—C5—C4
C4—C3—C2
C6—N1—C7—S1
C8—N2—C7—S1
C7—N1—C6—C1
F1—C3—C4—C5
C8—N2—C7—N1
C7—N2—C8—O2
C7—N2—C8—O1
124.6(4)
118.1(4)
118.7(5)
117.3(4)
125.7(6)
125.4(5)
108.8(5)
116.3(5)
127.2(5)
126.1(4)
119.0(7)
119.5(8)
120.2(6)
121.4(7)
−3.4(7)
C4—C3—C2
C6—N1—C8—S1
C9—N2—C8—S1
C8—N1—C6—C1
C7—C4—C5—C6
C9—N2—C8—N1
C8—N2—C9—O2
C8—N2—C9—O1
179.0(6)
−79.1(9)
−179.9(7)
0.6(10)
−176.4(4)
131.5(5)
−179.7(7)
3.1(8)
−6.2(12)
−8.3(9)
177.8(6)
172.9(5)
and C8 atoms (Figure 1); the mean deviation from the best plane of the
˚
five non-H atoms is 0.0203 A. Moreover, the carbonyl and the thiocar-
bonyl moieties point approximately in opposition. The compound adopts
a cis-trans configuration, where the phenyl group and the ethoxycar-
bonyl moiety lie, respectively, cis and trans relative to the S atom across
the thiourea C N bonds. The torsion angles of C6-N1-C8-S1 and C9-
N2-C8-S1 are 5.34◦ and 179.04◦. This configuration facilitates the for-
mation of the two ꢀpairs of centrosymmetric intermoꢀlecular hydrogen-
ꢀ
ꢀ
ꢀ
ꢀ
. . .
. . .
. . .
S, and N
. . .
O, N H O (Figure 3), which
bonds N H S , N
H
H
connect the molecules into a 1D catenulate supramolecular structure
along the b axis direction. Moreover, from Figure 3 we can find the
parallel packing of the phenyl rings in the crystal of compound a; how-
ever, the distance between the centers of two parallel phenyl rings is
0.5838 nm, which is out of the accepted range of the intermolecular
π − π interaction.15
In the crystal of compound b, there is a six-membered ring formed by
. . .
intramolecular hydrogen bond N1-H O2 alike compound a (Figure 2).
The mean deviation from the best plane of the five non-H atoms is
˚
0.0205 A. The compound also adopts a cis-trans configuration, the tor-
sion angles of C6-N1-C7-S1 and C8-N2-C7-S1 are −3.44◦ and 3.14◦,

867

868
Q. Lin et al.
FIGURE 3 The 1D catenulate supramolecular structure of compound a.
respectively. However, unlike compound a, the molecules of b only
form one pair of centrosymmetric intermolecular hydrogen bonds,
ꢀ
ꢀ
ꢀ
. . .
. . .
N H S and N
H
S, which connect compound b to dimers, and
these dimers are linked together by another intermolecular hydrogen
ꢀ
. . .
bond, C H F, and form a 1D zigzag catenulate supramolecular struc-
ture (Figure 4). It is obvious that from the hydrogen-bonding geometry
FIGURE 4 The 1D zigzag catenulate superamolecular structure of compound
b.

N-Ethoxycarbonyl-Nꢀ-Arylthiourea
869
TABLE V Data of Hydrogen Bond for a and b
. . .
A/
nm
. . .
. . .
D—H/
nm
H
D A/ D—H A/
. . .
D—H
Compounds
A
nm
deg
Symmetry code
a
N1—H1· · ·O2 0.0900 0.2013 0.2715
N1—H1· · ·O2 0.0900 0.2498 0.3183
N2—H2· · ·S1 0.0900 0.2468 0.3352
N1—H1· · ·O2 0.0900 0.1975 0.2686
N2—H2· · ·S1 0.0900 0.2490 0.3376
C10—H2· · ·F1 0.0960 0.2540 0.3447
133.90
133.25
167.23
134.89
168.22
157.50
x−1, y+1, z
x+1, y−1, z
b
x+1/2, −y+1/2, z+1/2
−x+1/2, y+3/2, −z−1/2
. . .
(Table V), we can find that the intramolecular hydrogen bond N H
O
is stronger than the intermolecular hydrogen bonds, and intermolecu-
ꢀ
ꢀ
. . .
. . .
lar hydrogen bond N H O is stronger than N H S .
The spectroscopic data are in agreement with the crystal structure:
the IR spectra of compound a exhibited the N H stretching vibration
absorption in 3212 and 3152 cm−1, and compound b exhibited the N H
stretching vibration absorption in 3220 and 3167 cm−1, respectively,
which is in accord with the intramolecular and the intermolecular hy-
1
. . .
. . .
drogen bonds N H O and N H S. In H NMR spectra, the N H
proton peaks are observed in 11.43 ppm and 8.30 ppm; these two peaks
shifted to low field, which is in accord with the intramolecular and in-
termolecular hydrogen bonds, respectively. The same cases also can be
observed in compound b; the N H proton peaks of compound b are
observed in 11.38 ppm and 8.36 ppm. Moreover, owning to the forma-
. . .
tion of intermolecular hydrogen bonds C H F, the C H proton peak
shifted to low field in 1.67 ppm. Other protons on this methyl group gave
. . .
tri-peaks in 1.37 ppm (J = 7.2); this confirms the existence of C H
intermolecular hydrogen bonds in compound b.
F
EXPERIMENTAL
Melting points (m.p.) were determined with a digital electrothermal
apparatus without calibration. IR spectra were recorded in KBr on
1
a Nicilet NEXUS 670 FT-IR spectrophotometer, and H NMR spectra
were recorded on a JNM-ECP400 instrument using TMS as the inter-
nal reference. Elemental analysis was determined on a PE-2400 CHN
instrument. The X-ray diffraction were determined on CAD4 Enraf-
Nonius X-ray instruments. The synthesis of a,b were according to our
previous works16: we added powdered potassium thiocynate (KSCN)
(1.17 g, 12 mmol) to an ethyl acetate solution (15 mL) of ethyl chlo-
roformate (1.09 g, 10 mmoles) and N,N,Nꢀ,N-tetramethylethane-1,2-
diamine (TMEDA) (0.01 g, 0.1 mmoles). The reaction mixture was

870
Q. Lin et al.
stirred at r.t. for 5 h. Then m-toluidine (1.07 g, 10 mmol) was slowly
added to the reaction mixture with constant stirring. The reaction mix-
ture was stirred at r.t. for 5 h again. After evaporating the solvent in
vacuum, the precipitation was washed with 10 mL 75% ethanol three
times and 15 mL H2O three times; recrystallization from DMF-EtOH-
H2O gave compound a, yield 94%, m.p. 102–103◦C, IR (KBr): ν = 3212
(NH), 3152(NH), 1714 (C O), 1603, 1538, 1474, (C C) 1242 (C S);
1HNMR (CDCl3): dH = 11.43 (s, 1H, NH), 8.30 (s, 1H, NH), 7.29 (m,
4H, ArH), 4.35 (q, 2H, CH2), 2.40 (s, 3H, CH3), 1.36, (t, 3H, CH3); anal.
calcd. for C11H14N2O2S: C, 55.44; H, 5.92; N, 11.76. Found: C, 55.41; H,
5.92; N, 11.78. Compound b was synthesized in a similar method, yield
90%, m.p. 187–188◦C. IR (KBr): ν = 3220 (NH), 3167 (NH), 1726 (C O),
1565, 1534, 1510 (C C), 125 (C S). 1HNMR (CDCl3): dH = 11.38 (s, 1H,
NH), 8.36 (s, 1H, NH), 6.99–7.67 (m, 4H, ArH), 4.36 (q, 2H, CH2), 1.37
(t, J = 7.2, 2H, CH3), 1.67 (s, 1H, CH3). Anal. Calcd. for C10H11N2O2SF:
C, 49.57; H, 4.58; N, 11.56. Found: C, 49.49; H, 4.58; N, 11.76.
The single crystal was obtained from the slow evaporation of EtOAc
solution of compound a, b for one week, respectively. Intensity data
were collected at 293(2) K on a CAD4 Enraf-Nonius diffractometer with
˚
graphite-monochromated Mo Ka (λ = 0.71073 A) radiation, using the
φ-ω scan mode. Data collection and reduction were performed using
MOLEN PC software. The structure was solved by direct methods using
the SHELXS-97 program and successive difference Fourier syntheses
to yield the positions of all non-hydrogen atoms, which were refined by
full-matrix least-squares method on F2 with temperature factors and
anistropical thermal parameters using SHELXTL program.
CONCLUSION
The synthesis and 1D catenulate supramolecular structure of two N-
ethoxycarbonyl-Nꢀ-arylthioureas have been reported. The compounds
a and b were synthesized in high yields. In the crystal of compounds a
and b, there are inter- and intramolecular hydrogen bonds. The com-
pounds were assembled to 1D catenulate supramolecular structure by
the intermolecular hydrogen bonds. The 1H NMR and IR confirmed the
existence of inter- and intramolecular hydrogen bonds.
Crystallographic data have been deposited to the Cambridge Crystal-
lographic Data Center, CCDC 602850 for a and 602851 for b. Copies of
the information may be obtained free of charge from the Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk; web site: http://www.ccdc.ac.uk);
web site upon request.

N-Ethoxycarbonyl-Nꢀ-Arylthiourea
871
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