Synthesis and crystal structure of N-(1-Methyl-3-ethyl-4-chloropyrazol-5- yl)acyl-N-(4-fluorophenyl)thiourea

Article abstract of DOI:10.1007/s10870-009-9579-z

The title compound was synthesized by reaction of 1-methyl-3-ethyl-4- chloro-5-pyzolyl formaic isothiocyanate with 4-fluoroaniline and its crystal structure was determined by X-ray diffraction method. The compound crystallizes in the triclinic space group

Full text of DOI:10.1007/s10870-009-9579-z

J Chem Crystallogr (2009) 39:838–841
DOI 10.1007/s10870-009-9579-z
ORIGINAL PAPER
Synthesis and Crystal Structure of N-(1-Methyl-3-ethyl-4-
chloropyrazol-5-yl)acyl-N0-(4-fluorophenyl)thiourea
Changjun Zhang Æ Yanqiu Dang Æ Lin Jiang Æ
Liyin Wang
Received: 7 August 2008 / Accepted: 4 June 2009 / Published online: 18 June 2009
Ó Springer Science+Business Media, LLC 2009
Abstract The title compound was synthesized by reaction
of 1-methyl-3-ethyl-4-chloro-5-pyzolyl formaic isothiocy-
anate with 4-fluoroaniline and its crystal structure was
determined by X-ray diffraction method. The compound
Introduction
Since acylthiourea was synthesized by Schroepl in 1968
[1], a lot of acylthioureas have been prepared and their
properties have been studied. Many of these compounds
show high biological activities, such as herbicidal, fungi-
cidal, insecticidal, antitumor and regulating plant growth
activities [2–9]. Nowadays, the study of synthesis and
property of acylthioureas is still an active field in pesticide
research.
ꢀ
crystallizes in the triclinic space group P 1with a = 7.8510
˚
(10), b = 8.2731 (11), c = 11.9373 (15) A, a = 78.484 (2),
3
˚
b = 88.938 (2), c = 88.779 (2)°, V = 759.49 (17) A ,
Mr = 340.80, Dc = 1.490 mg/m3, and Z = 2. In the title
molecule, atoms in the acylthiourea moiety are able to form
a plane due to the intramolecular hydrogen-bond N1–H1–
O1, and makes a dihedral angle of 3.0° with the benzene
ring, while the acylthiourea makes a dihedral angle of
7.6° with the pyrazole ring. The preliminary biological
test shows that the title compound has some acaricidal
activity.
On the other hand, tebufenpyrad [N-(4-tertbutylbenze-
nyl)-4-chloro-3-ethyl-1-methylpyrzol- 5-yl formyl amine]
is an excellent acaricide [10], which contains substituted
pyrazole ring in the molecule. In order to seek highly
effective acaricides, we put the pyrazole moiety of te-
bufenpyrad into the acylthiourea molecule and synthesized
a novel acylthiourea, N-(1-methyl-3-ethyl-4-chloropyrazol-
5-yl)acyl-N0-(4-fluorophenyl)thiourea (3), and reported its
crystal structure. The procedure of synthesis is showed in
Scheme 1.
Keywords Acylthiourea ꢀ Synthesis ꢀ Crystal structure ꢀ
Acaricidal activity
Experimental
C. Zhang
Department of Chemistry and Chemical Engineering, Taishan
Medical College, 271000 Tai’an, People’s Republic of China
The melting point was measured on a XRC-1 microscopic
melting-point apparatus and uncorrected. The IR spectrum
was recorded in KBr pellets on a Shimadzu IR-440 infrared
spectrophotometer. The NMR spectrum was carried out on
Bruker AC-300 spectrophotometer (DMSO-d6 as solvent,
TMS as internal standard). Elemental analysis was per-
formed with a Vario EL III Elemental Analyzer.
1-Methyl-3-ethyl-4-chloro-5-pyzolyl formylic acid,
intermediates 1 and 2 were prepared in our laboratory
according to Ref. [11].
Y. Dang
Department of Chemistry, Binzhou College, 256600 Binzhou,
People’s Republic of China
L. Jiang (&) ꢀ L. Wang
College of Chemistry and Material Science, Shandong
Agricultural University, 271018 Tai’an,
People’s Republic of China
e-mail: jiangl@sdau.edu.cn
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J Chem Crystallogr (2009) 39:838–841
839
C2H5
C2H5
SOCl2
COOH
C2H5
Cl
O
Table 1 Crystal data and structure refinement
Cl
Cl
KSCN
COCl
Chemical formula
CCDC deposit no.
Crystal description
Formula weight
Temperature (K)
Crystal system
C14H14ClFN4OS
N
N
N
C
N C S
N
N
N
684194
CH3
CH3
CH3
Colorless prism
340.80
2
1
Cl
O
C2H5
295 (2)
H2N
F
S
Triclinic
P-1
N
C
NH
C
NH
F
N
Space group
CH3
´
˚
Wavelength (A)
0.71073
3
´
˚
Unit cell dimensions (A)
Scheme 1 Synthesis route of compound (3)
a
7.8510 (10)
8.2731 (11)
11.9373 (15)
78.484 (2)
88.938 (2)
88.779 (2)
759.49 (17)
2
b
c
Synthesis of the Title Compound
a (°)
b (°)
c (°)
The title compound 3 was synthesized by reaction of 1-
methyl-3-ethyl-4-chloro-5-pyzolyl formyl isothiocyanate
(2) (0.92 g, 4 mmol) with 4-fluoroaniline (0.44 g, 4 mmol)
in acetonitrile (10 mL), with stirring for 3 h at 60 °C. After
evaporating the solvent at reduced pressure, the crude
product was obtained. Recrystallization from toluene gave
colorless powder of 3 (0.97 g) in 71% yield, m.p. 186–
187 °C. Anal. calcd. (%) for C14H14ClFN4OS: C, 49.06; H,
´
3
˚
Volume (A )
Z
Density (calculated) (mg m-3
Absorption coefficient (mm-1
)
1.490
)
0.406
F(000)
352
h range for data collection (°)
Limiting indices
2.5–28.9
–9 B h C 9; –10 B k C 10;
–14 B l C 14
1
4.21; N, 16.06. Found: C, 49.33; H, 4.11; N, 16.45. H
NMR(DMSO-d6), d: 1.27 (t, 3H,CH2–CH3, J = 5.7 Hz),
2.67 (q, 2H, CH2, J = 5.7 Hz), 4.16 (s, 3H, N–CH3), 7.10–
7.65 (m, 4H, Ph-H), 9.72 (s, 1H, NH), 12.13 (s, 1H, NH)
Reflections collected/unique
Absorption correction
3088/2609 (Rint = 0.0143)
Multi-scan (based on
symmetry-related
measurements)
ppm. IR (KBr) v: 3,343, 1,676, 1,573, 1,250 cm-1
.
Max. and min. transmission
Data/restraints/parameters
Goodness-of-fit on F2
0.9529, 0.8709
2069/0/209
Crystal Structure Determination
1.033
Final R indices [I [ 2r (I)]
R indices (all data)
R1 = 0.0382, wR2 = 0.0978
R1 = 0.0457, wR2 = 0.1031
0.298, –0.302
Suitable crystals for X-ray diffraction analysis were
obtained by slow evaporation from xylene at room tem-
perature. A single crystal of the title compound with
dimensions of 0.35 mm 9 0.20 mm 9 0.12 mm was
mounted on a glass fiber in a random orientation. The data
were collected at 295(2) K on a Bruker Smart APEX area-
detector diffractometer equipped with a graphite mono-
´
-3
)
˚
Largest diff. peak and hole (e A
´
˚
chromated MoKa radiation (k = 0.71073 A) by using u
and x scan modes.
The crystal structure was solved by direct methods and
expanded by using Fourier difference techniques with
SHELXS-97 program, and refined by full-matrix least-
squares techniques on F2 (w = 1/[r2(FO)2 ? (0.0538P)2 ?
0.1973P], where P = (F2O ? 2F2C)/3) using SHELXL-97.
Absorption correction was performed by the SADABS
program. The coordinates of non-hydrogen atoms were
obtained by successive difference Fourier synthesis, and
those of hydrogen atoms were added according to theo-
retical models. The crystal data and other structure
refinement parameters of the title compound are listed in
Table 1.
Fig. 1 General view of the molecule with thermal ellipsoids drawn at
50% probability level
Results and Discussion
The molecular structure of the title compound (3) is shown
in Fig. 1. The selected bond lengths, bond angles and
123

840
J Chem Crystallogr (2009) 39:838–841
Table 2 Selected geometric
parameters (A, °)
´
˚
Selected bond lengths (A)
´
˚
N(1)–C(6)
1.418(2)
1.332(2)
1.403(2)
1.366(2)
1.357(2)
1.457(2)
S(1)–C(7)
1.651(2)
1.224(2)
1.386(2)
1.388(2)
1.473(2)
1.387(2)
N(1)–C(7)
O(1)–C(8)
C(1)–C(6)
C(5)–C(6)
C(8)–C(9)
C(9)–C(10)
N(2)–C(7)
N(2)–C(8)
N(3)–C(9)
N(3)–C(14)
Bond angles (°)
C(1)–C(6)–C(5)
C(6)–N(1)–C(7)
C(7)–N(2)–C(8)
N(1)–C(7)–N(2)
N(1)–C(7)–S(1)
Torsional angles (°)
C(6)–N(1)–C(7)–N(2)
C(6)–N(1)–C(7)–S(1)
C(7)–N(1)–C(6)–C(1)
C(7)–N(1)–C(6)–C(5)
C(7)–N(2)–C(8)–C(9)
119.58(17)
131.47(16)
129.94(16)
113.70(15)
129.75(14)
N(2)–C(7)–S(1)
N(2)–C(8)–O(1)
N(2)–C(8)–C(9)
N(3)–C(9)–C(10)
O(1)–C(8)–C(9)
116.55(13)
122.49(17)
115.13(15)
104.97(15)
122.38(16)
–179.16(17)
0.3(3)
C(7)–N(2)–C(8)–O(1)
C(8)–N(2)–C(7)–S(1)
C(8)–N(2)–C(7)–N(1)
N(2)–C(8)–C(9)–C(10)
O(1)–C(8)–C(9)–C(10)
–3.3(3)
–177.16(16)
2.4(3)
–3.5(3)
176.56(19)
176.38(17)
4.6(3)
–175.7(2)
Table 3 (An)isotropic
displacement parameters for: a
in P-1
Atom
U(1,1) or U
U(2,2)
U(3,3)
U(2,3)
U(1,3)
0.0092(2)
U(1,2)
Cl1
S1
0.0332(3)
0.0358(3)
0.0580(8)
0.0338(7)
0.0328(8)
0.0302(8)
0.0312(8)
0.0375(8)
0.0368(10)
0.0467(11)
0.0446(10)
0.0358(10)
0.0371(9)
0.0351(9)
0.0346(9)
0.0323(9)
0.0308(8)
0.0307(8)
0.0332(9)
0.0381(10)
0.0569(13)
0.0368(11)
0.0623(3)
0.0729(4)
0.0624(7)
0.0672(9)
0.0450(9)
0.0465(9)
0.0504(9)
0.0545(10)
0.0532(11)
0.0509(11)
0.0420(10)
0.0563(12)
0.0502(11)
0.0377(9)
0.0385(9)
0.0393(9)
0.0384(9)
0.0383(9)
0.0423(10)
0.0588(12)
0.0644(14)
0.0913(17)
0.0555(3)
0.0514(3)
0.0578(7)
0.0555(8)
0.0373(8)
0.0430(9)
0.0400(8)
0.0408(9)
0.0432(10)
0.0375(10)
0.0417(10)
0.0512(11)
0.0416(10)
0.0363(9)
0.0385(9)
0.0415(10)
0.0382(9)
0.0419(10)
0.0413(10)
0.0513(11)
0.0556(13)
0.0535(12)
-0.0021(2)
0.0044(3)
0.0071(2)
0.0023(2)
0.0127(6)
0.0097(6)
0.0002(6)
0.0044(7)
0.0056(6)
0.0061(7)
0.0027(8)
-0.0027(9)
0.0041(8)
0.0073(8)
-0.0007(8)
0.0001(7)
-0.0011(7)
0.0001(7)
-0.0008(7)
-0.0004(7)
0.0029(7)
0.0108(9)
0.0130(11)
0.0161(11)
0.0110(2)
-0.0066(6)
0.0068(6)
0.0055(6)
0.0021(6)
0.0014(6)
-0.0003(7)
0.0064(8)
0.0052(8)
-0.0063(8)
0.0018(8)
0.0066(8)
0.0003(7)
0.0016(7)
0.0008(7)
0.0016(7)
0.0012(7)
-0.0015(7)
-0.0027(8)
-0.0071(10)
0.0110(9)
F1
0.0087(6)
O1
N1
N2
N3
N4
C1
0.0144(7)
0.0010(7)
0.0003(7)
-0.0007(7)
0.0002(7)
-0.0015(8)
0.0017(8)
C2
C3
-0.0038(8)
-0.0054(9)
-0.0008(8)
-0.0062(7)
-0.0078(7)
-0.0043(7)
-0.0056(7)
-0.0074(7)
-0.0060(8)
0.0009(9)
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
0.0062(10)
0.0067(12)
torsional angles are listed in Table 2, and (An)isotropic
displacement parameters for: a in P-1 are given in Table 3.
In the title compound, torsion angles of C6–N1–C7–N2,
C7–N2–C8–C9 and C8–N2–C7–S1 are all near to 180°
with deviations in the range of 0.8–3.6°, whereas torsion
angles of C7–N2–C8–O1, C8–N2–C7–N1 are both near to
0° with deviations in 3.3 and 2.4°, respectively, which
indicates that the atoms in acylthiourea moiety (C8, O1,
123

J Chem Crystallogr (2009) 39:838–841
841
Supplementary Material
Table 4 Hydrogen-bonding geometry
D–HꢀꢀꢀA
D–H
HꢀꢀꢀA
DꢀꢀꢀA
D–HꢀꢀꢀA
CCDC 684194 contains the supplementary crystallographic
data for this paper. This data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, by e-mailing
data_request@ccdc.cam.ac.uk.
N(1)–H–O(1)
N(2)–H–Cl(1)
0.86(2)
0.80(2)
1.90(2)
2.43(2)
2.642(2)
3.148(2)
143.2(2)
149.0(2)
Symmetry codes: –x, –y, –z
N2, C7, S1 and N1 atoms) are able to form a plane. These
atoms are coplanar due to the intramolecular hydrogen
bond N–HꢀꢀꢀO (Table 4). Besides, there are two other
planes in the title compound, one is benzene ring plane and
the other is pyazole ring plane. The dihedral angle between
acylthiourea moiety and benzene ring is 3.0°, while that
between acylthiourea moiety and pyazole ring is 7.6°.On
the other hand, N1–C6, N2–C7 bond distances are
References
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25:1053
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23:215–217
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Chem 24:1284
´
˚
1.418(2), 1.403(2) A, respectively, both shorter than the
´
˚
normal N–C bond (1.470 A) [12], but longer than the
´
˚
typical C=N bond (1.320 A) [13]. Moreover, N1–C7,
´
˚
N2–C8 bond distances are 1.332(2) and 1.366(2) A,
respectively, near to the typical C=N bond because of the
N–C=O(or S) delocalisation system. So we deduce that N1
atom conjugates with carbonyl and benzene ring, while N2
conjugates with carbonyl and C=S double bond, which
means the atoms of acylthiourea moiety are able to make
up a conjugative system.
12. Zeng ZQ (2004) Organic chemistry. China Advanced Education
Press, Beijing, p 7
13. Lu RJ, Yang HZ, Zhao GF, Liu HY (1996) Chem J Chin Univ
17:1231
14. Mu LY (1994) Research method of plant chemical protection.
China Agriculture Press, Beijing, p 61
Biological test was performed using Leaf-dip method
according to reference [14], and commercial acaricide
‘‘cyhalothrin’’ was used as the reference compound. The
preliminary biological test shows that the title compound
exhibits some acaricidal activity against Tetranychus Cin-
nabarinus, which the median lethal concentration (LC50) is
0.337 g/L, but the activity is lower than that of the refer-
ence compound (LC50 is 0.031 g/L).
123