Synthesis and crystal structure of a compound with two conformational isomers: N-(2-methylbenzoyl)-N′-(4-nitrophenyl)thiourea

Article abstract of DOI:10.1007/s10870-008-9413-z

The single crystal of the title compound (C₁₅H ₁₃N₃O₃S) with two conformational isomers was obtained from the solution of the title compound dissolved in the N,N-dimethylformamide (DMF) by slow evaporation at ro

Full text of DOI:10.1007/s10870-008-9413-z

J Chem Crystallogr (2008) 38:927–930
DOI 10.1007/s10870-008-9413-z
ORIGINAL PAPER
Synthesis and Crystal Structure of a Compound with Two
Conformational Isomers: N-(2-methylbenzoyl)-
N0-(4-nitrophenyl)thiourea
Qian-Jin Li Æ Chun-Long Yang
Received: 11 May 2007 / Accepted: 7 May 2008 / Published online: 30 May 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The single crystal of the title compound
(C15H13N3O3S) with two conformational isomers was
obtained from the solution of the title compound dissolved in
the N,N-dimethylformamide (DMF) by slow evaporation at
room temperature. The crystal is triclinic, space group P-1
relationship between the structure and its biological
activities [7, 8], we have prepared a few single crystals of
aroylthiourea compounds [9–11]. As part of our work, we
present the crystal structure of the title compound here, in
which there are two conformational isomers in the unit cell.
˚
with a = 10.418(2), b = 10.758(2), c = 14.494(3) A, a =
3
˚
71.07(3), b = 81.56(3), c = 85.61(3)8, V = 1519.2(5) A ,
Z = 2, C30H26N6O6S2, Dc = 1.379 g/cm3, l(MoKa) =
0.229 mm-1, S = 0.994, F(000) = 656, R = 0.0688 and
wR = 0.1695. In the unit cell, there are two independent
molecules having only slightly different bond lengths and
angles, but the corresponding dihedral angles of the two
molecules aredifferent. Intermolecular N–HꢀꢀꢀS andN–HꢀꢀꢀO
hydrogen bonds forming R2 (8) and R2 (12) rings, respec-
Experimental
Reagents and Apparatus
All the reagents were purchased commercially and used
without further purification. The melting point was deter-
mined using a WRS-1B digital melting-point apparatus and
uncorrected. IR spectra were recorded on a FTIR-Tensor27
spectrophotometer using KBr discs in the 4000–400 cm-1
region. Elemental analyses were performed on a Vario EL
III analyzer. The crystal data of the title compound were
collected on a Enraf Noius CAD4/PC X-ray single crystal
diffractometer.
2
2
tively, link the molecules into ribbons.
Keywords Thiourea ꢀ Benzoyl ꢀ Dihedral angle ꢀ
Hydrogen bond ꢀ Crystal structure
Introduction
Synthesis of the Title Compound
The title compound belongs to the family of aroylthiourea
derivatives, which have attracted much attention due to
their biological activities such as anti-virus, herbicidal,
pesticidal, plant growth regulating activity [1–4] and
coordination abilities [5]. In recent years, a convenient
method for the synthesis of 1,2,4-trizoles, N-substituted
and N,N-disubstituted thioureas using aroylthiourea com-
pounds as reactants was reported [6]. In order to study the
The title compound was prepared in three stages as shown
in Scheme 1 [11]. A total of 0.01 mol of benzoic acid was
added into 8 mL of SOCl2, the mixture was stirred and
refluxed for 4 h, then residual SOCl2 was removed under
reduced pressure to obtain benzoylchloride, which was
made to react with 0.015 mol NaSCN dissolved in 20 mL
acetonitrile for 1 h. The resulting solution was filtered, and
0.01 mol 4-nitroaniline was added into the filtrate, then the
mixture was stirred and refluxed for 2 h to get the title
compound by filtration. The single crystals suitable for
determination were obtained by slow evaporation from the
solution of the title compound dissolved in DMF at room
Q.-J. Li ꢀ C.-L. Yang (&)
College of Science, Nanjing Agricultural University, Nanjing
210095, People’s Republic of China
e-mail: chunlongyang@yahoo.com.cn
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J Chem Crystallogr (2008) 38:927–930
Scheme 1
O
C
O
C
O
NaSCN
reflux
+ SOCl2
NH2
OH
Cl
C
N
C
S
S
O
C
O2N
H
H
N
N
C
NO2
temperature. m.p: 176.6–178.1 °C. IR(KBr), m/cm-1):
3134(m), 3016(m), 1681(s), 1613(m), 1598(m), 1517(s),
1345(s), 1317(s), 1259(s), 1156(s), 1107(s). The elemental
analysis found for C15H13N3O3S: C, 57.10; H, 4.19; N,
13.32%. Calcd.: C, 57.13; H, 4.16; N, 13.33%.
Table 1 Crystal data and structure refinement
Chemical formula
CCDC Deposit No.
Color
C30H26N6O6S2
CCDC 646965
Yellow
Crystal dimensions (mm)
Formula weight
Crystal system
0.10 9 0.20 9 0.30
630.69
X-ray Crystallography
Triclinic
Space group
P-1
A yellow prism single crystal was mounted on a CAD4/PC
˚
Unit cell dimensions
equipped with MoKa(k = 0.71073 A) radiation at 293(2) K.
˚
a (A)
10.418(2)
10.758(2)
14.494(3)
71.07(3)
81.56(3)
85.61(3)
1519.2(6)
2
A total of 5945 reflections were collected using an x/2h
scanning method, of which 3184 were observed with
I [ 2r(I) and used in the structure solution and refinement.
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
The final R = 0.0688, wR = 0.1695 (w = 1/[r2(Fo ) +
2
(0.1000P)2], where P = (Fo2 + 2Fc2)/3), (D/r)max = 0.019,
3
˚
(Dq)max = 0.529 and (Dq)min = -0.278 e/A . The structure
3
˚
Cell volume (A )
was solved by direct methods and refined by full-matrix least-
squares techniques (SHELXTL97) [12, 13]. All non-hydro-
gen atoms were located by direct methods and subsequent
difference Fourier syntheses. The hydrogen atoms were
positioned geometrically and refined using a riding model,
with Uiso(H) = 1.2 Ueq(C, N). Crystal and structure refine-
ment data is shown in Table 1. Selected bond lengths and
bond angles are listed in Table 2, and the hydrogen bond
lengths and bond angles in Table 3.
Z
Density (calculated, g cm-3
Absorption coefficient (mm-1
)
1.379
)
0.229
Diffractometer
Nonius CAD4
Radiation
MoKa(k = 0.71073)
1.5–26.0
Theta min–max (°)
Reflections collected/unique
Range of h, k, l
5945/5945
-12:12, -12:13, 0:17
Full matrix least-squares on F2
Structure solution
Absorption correction
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices (all data)
Psi-scan
5945/0/397
Results and Discussion
0.994
R = 0.0688, wR = 0.1695
R = 0.1343, wR = 0.1993
0.53 and -0.28
293(2)
The bond lengths and angles are in normal range [14]
(Table 2), and in agreement with N-(4-methylbenzoyl)-N0-
(4-nitrophenyl)thiourea [15] and N-(4-methoxyphenyl)-N0-
(2-methylbenzoyl)thiourea [10]. In the unit cell, there are two
independent molecules (A and B, Fig. 1) having only slightly
different bond lengths and angles between them. The C7–C8
3
Largest feature (e/A )
˚
Temperature (K)
In molecule A, the plane D (defined by C8/C9/N1/N2/
˚
O1/S1, with a maximum deviation of 0.093(1) A for atom
˚
and C8–N1 bond lengths are 1.479(6) and 1.385(5) A,
˚
respectively; comparable with C22–C23 = 1.490(6) A and
˚
C23–N6 = 1.376(5) A, respectively. The bond angle of C7–
S1) makes dihedral angles of 59.2(2) and 52.39(18)8 with
2-methylphenyl and 4-nitrophenyl rings, respectively, and
the two phenyl rings incline to each other with an angle of
7.3(2)8. However, in molecule B, the plane E (defined by
C23/C24/N5/N6/O6/S2, with a maximum deviation of
C8–N1 = 114.7(4)8 is a slightly less than that of C22–C23–
N6 = 117.0(3)8. Thedifferenceinthebondlengthsandangle
above can be attributed to the different conformations of the
two molecules.
˚
0.057(1) A for atom S2) makes dihedral angles of 75.4(2)
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J Chem Crystallogr (2008) 38:927–930
929
˚
Table 2 Selected bond lengths (A), bond angles (°) and torsion angles (°)
S1–C9
1.654(4)
1.666(3)
1.216(5)
1.214(4)
1.479(6)
1.490(6)
1.385(5)
1.384(5)
1.424(5)
1.330(5)
1.419(4)
1.329(5)
1.382(4)
1.376(5)
C8–N1–C9
O1–C8–C7
O1–C8–N1
N1–C8–C7
N1–C9–N2
S1–C9–N2
128.7(3)
123.7(4)
121.6(4)
114.7(4)
115.3(3)
125.2(3)
119.5(3)
129.5(3)
121.4(4)
121.4(3)
117.0(3)
116.2(3)
124.7(2)
119.1(3)
C9–N1–C8–O1
3.5(6)
172.7(3)
-8.4(5)
S2–C24
O1–C8
C24–N6–C23–C22
C8–N1–C9–N2
O6–C23
C7–C8
C23–N6–C24–S2
C10–N2–C9–S1
C25–N5–C24–N6
C9–N2–C10–C11
C9–N2–C10–C15
C24–N5–C25–C26
C24–N5–C25–C30
C2–C7–C8–O1
-173.1(3)
1.4(5)
C22–C23
N1–C8
-179.0(3)
56.6(6)
S1–C9–N1
N1–C9
C23–N6–C24
O6–C23–N6
O6–C23–C22
N6–C23–C22
N5–C24–N6
S2–C24–N5
S2–C24–N6
-126.4(4)
131.9(4)
-51.3(5)
-53.5(6)
126.4(4)
-108.4(5)
75.8(5)
N2–C10
N2–C9
N5–C25
N5–C24
N6–C24
N6–C23
C2–C7–C8–N1
C17–C22–C23–O6
C17–C22–C23–N6
˚
and 47.32(18)8 with 2-methylphenyl and 4-nitrophenyl
rings, respectively, and the two phenyl rings are inclined to
each other with an angle of 28.1(2)8. The corresponding
dihedral angles formed by the two phenyl rings in the
crystal of 1-benzoyl-3-(2,6-dichlorophenyl)thiourea [16]
are 72.43(14) and 75.11(4)8, and 1-(3-chlorobenzoyl)-3-(2,6-
dichlorophenyl)-thiourea [17] 68.69(5) and 63.30(5)8.The
different dihedral angles of the two molecules indicate that
the two molecules show two different conformations, due
to the different rotation of 2-methylphenyl rings about the
C7–C8 or C22–C23 bonds.
Table 3 Hydrogen bond lengths (A) and bond angles (°)
D–HꢀꢀꢀA
d(DꢀꢀꢀH)
d(HꢀꢀꢀA)
d(DꢀꢀꢀA)
\(DHA)
N1–H1A–S2
N2–H2A–O1
N2–H2A–O6i
N5–H5B–O1ii
N5–H5B–O6
N6–H6B–S1
C1–H1C–O1
C4–H4A–O2iii
C30–H30A–S2
0.86
0.86
0.86
0.86
0.86
0.86
0.96
0.93
0.93
2.62
1.93
2.34
2.36
1.96
2.69
2.54
2.51
2.86
3.473(4)
2.627(4)
3.025(4)
3.056(4)
2.653(4)
3.531(4)
2.992(6)
3.412(8)
3.214(4)
174
137
136
139
136
166
109
165
104
In the crystal structure, the intramolecular N2–H2AꢀꢀꢀO1
and N5–H5BꢀꢀꢀO6 hydrogen bonds are a result of the planar
conformation of plane D or E [8, 10]. The two intermo-
lecular N–HꢀꢀꢀS hydrogen bonds (Table 3) link the two
independent molecules into a dimer forming a simple
Symmetry transformations used to generate the equivalent atoms: i: x,
1 + y, z; ii: x, -1 + y, z; iii: 1 + x, y, -1 + z
R2 (8) ring [18] (Fig. 1). The dimers are further linked by
2
the intermolecular N–HꢀꢀꢀO hydrogen bonds, which form
the R2 (12) rings sharing an edge with the R2 (8) rings.
2
2
This creates ribbons running in the [010] direction (Fig. 2).
Ribbons are further linked together by the intermolecular
C4–H4AꢀꢀꢀO2 hydrogen bonds forming C(15) chains run-
ning along [101] direction.
Supplementary Material
Hydrogen atom positions and complete tables of bond
distances and angles have been deposited with the Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK. Additional crystallographic data
can be obtained from the authors (C.L.Y.).
Fig. 1 Molecular structure of the title compound with 50% thermal
ellipsoids. Dashed lines indicate hydrogen bonds
123

930
J Chem Crystallogr (2008) 38:927–930
Fig. 2 A view of part of the
crystal structure, showing the
ribbons built from R22(8) and
R22(12) rings. Dashed lines
indicate intermolecular
hydrogen bonds. Atoms marked
with a hash (#), an asterisk (*)
and ampersand (&) are at the
symmetry positions (-1 + x,
-1 + y, 1 + z), (-1 + x, y,
1 + z) and (x, -1 + y, z),
respectively
Acknowledgments We are grateful to H.-Q. Wang for the data
collection and refinement.
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11. Li QJ, Yang CL, Xie XQ (2007) Acta Cryst E63:o773–o774
12. Sheldrick GM (1997) SHELXS97. Structure determination pro-
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