Normal coordinate analysis and crystal structure of N,N-dimethyl-N′-(2-chloro-benzoyl)thiourea

Article abstract of DOI:10.1016/j.saa.2005.09.016

In the present paper, the crystal structural and vibrational analysis of the N,N-dimethyl-N′-(2-chloro-benzoyl)thiourea molecule is reported. The molecular structure of the title compound was determined by single crystal X-ray diffraction method. The compound crystallizes monoclinic, space group P2₁/c with a = 5.6601(13) A, b = 10.748(2) A, c = 17.778(4) A, β = 94.266(5)°, and V = 1078.5(4) A³ with Z = 4 for d_calc = 1.495 g/cm³. Calculations of the vibrational frequencies have been carried out on the basis of normal coordinate analysis using simple general valence force field in Wilson's GF matrix method with the SPSIM computer program. With the help of this modern technique we were able to complete the assignment of the vibrational spectrum of the title compound.

Full text of DOI:10.1016/j.saa.2005.09.016

Spectrochimica Acta Part A 64 (2006) 1065–1071
Normal coordinate analysis and crystal structure of
N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea
Hakan Arslana,∗, Nevzat Kulcu , Ulrich Florke
¨ ¨ a
¨
b
a Department of Chemistry, Faculty of Arts & Science, Mersin University, Mezitli-C¸ iftlikko¨yu¨ Campus, 33343 Mersin, Turkey
b Department of Chemistry, University of Paderborn, Paderborn, Germany
Received 30 May 2005; accepted 16 September 2005
Abstract
In the present paper, the crystal structural and vibrational analysis of the N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea molecule is reported. The
molecular structure of the title compound was determined by single crystal X-ray diffraction method. The compound crystallizes monoclinic,
◦
3
space group P21/c with a = 5.6601(13) A, b = 10.748(2) A, c = 17.778(4) A, β = 94.266(5) , and V = 1078.5(4) A with Z = 4 for dcalc = 1.495 g/cm3.
Calculations of the vibrational frequencies have been carried out on the basis of normal coordinate analysis using simple general valence force
field in Wilson’s GF matrix method with the SPSIM computer program. With the help of this modern technique we were able to complete the
assignment of the vibrational spectrum of the title compound.
˚
˚
˚
˚
© 2005 Elsevier B.V. All rights reserved.
Keywords: Crystal structure; Vibrational analysis; Normal coordinate analysis; Valence force field; Benzoyl thiourea
1. Introduction
lations are performed. Thus, whole vibrational spectrum of title
compound is explained.
N,Nꢀ-dialkyl-Nꢀ-benzoylthioureas are versatile ligands, able
to coordinate to transition metal centres either as monoanions
or as dianions [1–3]. There have been many studies of benzoyl-
substituted thioureas and related ligands coordinated to metals
[4], where the ligand typically bonds as a monoanion through S
and O, giving a six-membered ring system, though complexes
with neutral ligands are also known [5]. Study of compounds
of these type thioureas has recently received attention because
of their potential use as highly selective reagents for the pre-
concentration and separation of metal cations [6–8]. In addition,
thioureas have been shown to possess antitubercular, antithroid,
antihelmintic, antibacterial, insecticidal and rodenticidal prop-
erties [9–11].
We have recently begun to examine the coordination
behaviour of some series of N,Nꢀ-dialkyl-Nꢀ-benzoylthioureas
that posses a number of interesting properties [12–24]. We
discuss here the structure of one of them, N,N-dimethyl-Nꢀ-(2-
chloro-benzoyl)thiourea (HL). In addition, vibrational spectrum
of this compound is recorded and then normal coordinate calcu-
2. Experimental
2.1. Synthesis
N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea was obtained
as described in the literature [14]. A solution of 2-chlorobenzoyl
chloride (0.01 mole) in acetone (50 cm3) was added dropwise
to a suspension of potassium thiocyanate (0.01 mole) in ace-
tone (30 cm3). The reaction mixture was heated under reflux
for 30 min, and then cooled to room temperature. A solution
of dimethyl amine (0.01 mole) in acetone (10 cm3) was added
and the resulting mixture was stirred for 2 h. Hydrochloric acid
(0.1N, 300 cm3) was added and then the solution filtered. The
solid product was washed with water and purified by recrystalli-
sation from ethanol/dichloromethane mixture (1:1).
2.2. Instrumentation and crystal structure determination
The solid-state infrared spectrum of HL studied was recorded
using in the form of KBr pellet by BOMEN MB102 FT-IR
instrument in the 4000–200 cm−1 ranges; the resolution was
1 cm−1. Single crystal X-ray data were collected on a Bruker
∗
Corresponding author. Tel.: +90 532 707 31 22; fax: +90 324 341 30 22.
E-mail address: arslanh@mersin.edu.tr (H. Arslan).
1386-1425/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2005.09.016

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H. Arslan et al. / Spectrochimica Acta Part A 64 (2006) 1065–1071
AXS SMART APEX CCD [25] using monochromated Mo K␣
(λ = 0.71073 A) radiation. Semi-empirical absorption correc-
Table 1
˚
Crystal data and structure refinement for title compound
tions has been carried out from equivalents [25]. The structure
was solved [25] by direct and conventional Fourier methods.
Full-matrix least-squares refinement [25] based on F2. Further
details concerning data collection and refinement are given in
Table 1.
Empirical formula
Formula weight (g)
Temperature (K)
Wavelength (Mo K␣) (A)
Crystal system
C10H11ClN2OS
242.72
120(2)
0.71073
Monoclinic
P21/c
˚
Space group
Unit cell dimensions
2.3. Normal coordinate analysis
˚
a (A)
5.6601(13)
10.748(2)
˚
b (A)
Calculationsofthefrequenciesandvibrationalactivitieswere
performed by using computer programs developed by Schrader
et al. [26,27] employing Wilson’s GF matrix method [28]. N,N-
dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea is calculated as an iso-
lated molecule with Cs point group symmetry. The 72 normal
modes of HL are distributed between the two species (Aꢀ and
Aꢀꢀ) of the Cs point group as
˚
c (A)
17.778(4)
94.266(5)
1078.5(4)
4
1.495
0.521
504
β (◦)
Volume (A )
3
˚
Z
Density (calculated) (Mg/m3)
Absorption coefficient (mm−1
F(0 0 0)
)
Crystal size (mm3)
0.43 × 0.20 × 0.11
Theta range for data collection (◦)
Index ranges
2.22–28.54
Γvib = 47Aꢀ + 25Aꢀꢀ
−7 ≤ h ≤ 7
−13 ≤ k ≤ 14
−23 ≤ l ≤ 23
10874
All of the species are both IR and Raman active. The geometric
parameters are transferred from single crystal X-ray structure
and to save Cs symmetry small adjustments were made on the
torsion angles of the title compound (Fig. 1, Table 2). A total of
87 force constants (61 diagonal and 26 non-diagonal) were used
for the HL to define the F-matrix. The initial set of valence
force constant and the corresponding non-diagonal constant
were transferred from related systems [29–40]. A zero order
calculation with the transferred force constant was performed.
The results indicated the reasonable agreement between the cal-
culated and the observed frequencies. The initial set of force
constant was refined by the method of least square technique by
keeping some interaction force constants fixed throughout the
refinement process. The only final diagonal force constants and
their description were shown in Table 3.
Reflections collected
Independent reflections
Completeness to theta = 28.54◦
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma(I)]
R indices (all data)
2724 [R(int) = 0.0993]
99.2%
Semi-empirical from equivalents
0.9450 and 0.8072
Full-matrix least-squares on F2
2724/1/146
1.175
R1 = 0.0675, wR2 = 0.0807
R1 = 0.1064, wR2 = 0.0850
0.979 and −0.668
−2
˚
Largest difference peak and hole (e A
)
Fig. 1. Molecular structure of N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea. Thermal ellipsoids are shown at the 50% probability level.

H. Arslan et al. / Spectrochimica Acta Part A 64 (2006) 1065–1071
1067
Table 3
Table 2
Force constant of N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea
◦
˚
Selected bond lengths (A) and angles ( )
Force constant
Related internal
coordinate
Force constant
valueb
Reference
Bond lengths
C7–O1
C8–S1
N1–C7
N1–C8
N2–C8
N2–C9
N2–C10
C6–C7
1.199(3)
1.669(3)
1.383(3)
1.398(3)
1.314(3)
1.450(3)
1.452(3)
1.500(4)
C1–Cl1
C1–C6
C5–C6
C1–C2
C2–C3
C3–C4
C4–C5
1.716(3)
1.383(4)
1.390(4)
1.381(4)
1.361(4)
1.365(4)
1.371(4)
No.
Symbola
1
2
K(1)
K(2)
C7–N1
C7–O1
C7–C6
N1–C8
N1–H1
C8–S1
C8–N2
C6–C5
C6–C1
C5–C4
C5–H5A
C4–C3
C4–H4A
C1–Cl1
N2–C9
C9–H9A
5.7902
7.9296
4.3240
6.3100
5.5075
4.0809
6.2350
5.7142
4.9261
6.1827
5.1874
6.0274
5.1874
3.4303
5.2537
4.8679
4.8679
0.5491
1.0530
0.5491
1.8231
0.3375
0.4321
1.0290
1.6050
1.0290
1.0178
0.9340
1.4832
0.4752
0.5120
0.8649
0.4230
1.2059
0.8283
0.8283
1.6400
1.2685
1.3570
0.6130
0.5563
0.5164
0.4686
0.5554
0.5698
0.0660
0.5820
0.2860
0.2467
0.2983
0.4319
0.2792
0.0706
0.0090
0.2000
0.2000
0.0390
0.0390
0.0390
0.0390
0.0270
[29]
[30]
[31]
[32]
[32]
[32]
[32]
[33]
[33]
[33]
[33]
[33]
[33]
[34]
[35]
[36]
[36]
[36]
[36]
[36]
[29]
[37]
[37]
[32]
[32]
[32]
[33]
[33]
[33]
[33]
[33]
[33]
[33]
[33]
[34]
[34]
[38]
[38]
[38]
[39]
[39]
[39]
[39]
[39]
[36]
[32]
[32]
[33]
[33]
[33]
[40]
[38]
[29]
[33]
[32]
[32]
[33]
[33]
[33]
[33]
[38]
3
K(3)
4
K(4)
5
K(5)
6
K(6)
7
K(7)
Bond angles
O1–C7–N1
O1–C7–C6
C7–N1–C8
N1–C8–S1
S1–C8–N2
C8–N2–C9
C8–N2–C10
8
K(8)
123.5(3)
C7–C6–C1
C7–C6–C5
C6–C1–C1
C6–C1–C2
C1–C2–C3
C2–C3–C4
C3–C4–C5
123.3(3)
9
K(9)
124.2(3)
125.6(2)
118.6(2)
124.5(2)
124.6(2)
121.2(2)
119.2(3)
120.6(2)
122.0(3)
117.8(3)
122.6(3)
118.7(3)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
K(10)
K(11)
K(12)
K(13)
K(14)
K(15)
K(16)
K(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
H(31)
H(32)
H(33)
H(34)
H(35)
H(36)
H(37)
H(38)
H(39)
H(40)
H(41)
H(42)
H(43)
H(44)
A(45)
A(46)
A(47)
A(48)
A(49)
A(50)
A(51)
A(52)
T(53)
T(54)
T(55)
T(56)
T(57)
T(58)
T(59)
T(60)
T(61)
C9–H9B
N1–C7–O1
N1–C7–C6
O1–C7–C6
C7–N1–C8
C7–N1–H1
C8–N1–H1
N1–C8–S1
N1–C8–N2
S1–C8–N2
C7–C6–C5
C5–C6–C1
C6–C5–C4
C6–C5–H5A
C4–C5–H5A
C5–C4–C3
C5–C4–H4A
C6–C1–C2
C6–C1–Cl1
C2–C1–Cl1
C8–N2–C9
C8–N2–C10
C9–N2–C10
N2–C9–H9A
N2–C9–H9B
3. Results and discussion
3.1. The crystal structure
The molecular structure of N,N-dimethyl-Nꢀ-(2-chloro-
benzoyl)thiourea, is depicted in Fig. 1. Selected bond distances
and angles of the title compound are presented in Table 2.
There are no significant differences in the bond distances and
bond angles from other thiourea derivatives [12,20–22,41,42].
The bond distances and angles in the thiourea moiety are typ-
ical for these compounds with the S1–C8 = 1.669(3) A and
C7–O1 = 1.199(3) A bonds showing the usual double-bond char-
acter. Also, the C–N bond distances C7–N1, C8–N1 and C8–N2
are significantly shorter than the normal C–N single bond
of about 1.48 A. The shortening of these C–N bonds con-
˚
˚
˚
firms the well-known effect of resonance in this part of the
molecule.
3.2. Normal coordinate analysis
H
H
H
9A–C9–H9B
9A–C9–H9C
9B–C9–H9C
FT-IR part of the vibrational spectrum of the title compound
was the only spectral source. This was not a serious problem
in the compound because of both Aꢀ and Aꢀꢀ modes are active
in both Raman and infrared in Cs point group symmetry. The
IRspectrumof the N,N-dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea
molecule is shown in Fig. 2. The frequencies observed in the IR
spectrum along with their relative intensities, the correspond-
ing calculated frequencies together with the respective potential
energy distributions (PEDs) and mode assignments are collected
in Table 4. Here, the normal mode description following each
fundamental in the last column is due to Wilson [28]. As seen
from Table 4, the agreement between experimental and cal-
culated frequencies for fundamental is good. The calculated
frequencies do not differ so much from the experimental ones
that the maximum difference between two spectra is not more
than 10 cm−1. The average absolute error of the calculated fre-
quencies was found less than 0.1%. We also studied the relativity
between the calculation and the experimental values, obtained
C7
N1
C8
C6
C5
C4
C1
N2
C7–N1
C7–C6
N1–C8
C8–N2
C6–C5
C6–C1
C5–C4
C2–C1
N2–C9
a
K, stretching; H, in-plane; A, out-of-plane bending; T, torsion force constant.
Units: K (mdyn/A); H (mdynA/rad ).
b
2
˚
˚

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H. Arslan et al. / Spectrochimica Acta Part A 64 (2006) 1065–1071
Fig. 2. Infrared spectrum of the title compound.
linear function formula y = 1.0007x − 1.6793, r2 = 0.9999. The
linear corrected is shown in Fig. 3. The linear properties of the
equation are very satisfactory. The vibrational bands observed in
IR spectrum gave sufficient proof for the control of the accuracy
of the valence force field developed for the compound.
The strong absorb νC=O band in the IR spectrum of com-
pound appears at about 1710 cm−1. Our calculations con-
firmed the assignment of one absorption at 1705 cm−1 to
C=O stretching vibration in agreement with the literature data
[14,21,22,30,44]. νC=O vibration frequency (1710 cm−1) of the
title compound decreases by ca. 102 cm−1 in the complex form
and this information is good agreement with the literature data
[14,19,23,24,43–45]. Similar interpretations are valid for νC=S
band. The C=S stretching vibration is calculated in 1199 cm−1
that is in agreement with the literature data [32,43,45]. For C=S
One band with strong at 3166 cm−1 was observed in the N,N-
dimethyl-Nꢀ-(2-chloro-benzoyl)thiourea spectrum. On the basis
of NCA calculations and literature data, this band was assigned
to the N–H stretching absorption [14,21,22,32]. Because this
band is disappear in the nickel complex [14,23,24,43–45]. The
N–H stretching force constant given by Bleckmann et al. [32]
was modified to give a better fit to the experimental value and
˚
stretching, a force constant of 4.0809 mdyn/A (Table 3, No. 6)
was used after the modification of C=S stretching force constant
of thiourea as given by Bleckmann et al. [32].
˚
used as 5.5075 mdyn/A (Table 3, No. 5).
Characteristic Car–H stretching vibrations of substituted ben-
zenes are expected to appear in 3060–3095 cm−1 frequency
ranges. Our calculations confirmed the assignment of absorp-
tion at 3091 cm−1 to Car–H stretching vibrations, which is in
agreement with the literature data [33].
The C–N stretching vibrations are calculated in 1641, 1484,
1240 and 1160 cm−1 that is in agreement with the literature data
[29,32,35]. For conjugated systems with aromatic ring attached
to the carbon atom, the C–N absorption was observed at high
frequencies in comparison with other systems where this absorp-
tion was observed in the 1641 and 1484 cm−1 frequencies.
The characteristic skeletal stretching modes of semi-
unsaturated carbon–carbon bonds lead to appearance of a group
of four bands in the 1663–1509 cm−1 region. A change of the
dipole-moment of substituted benzenes during the stretching
modes generally occurs and as a result the bands of strong to
Two bands at 3019 and 2924 cm−1 were observed in the spec-
trum. First band is asymmetric C–H stretching band and the
other band symmetric C–H stretching band for methyl group.
˚
For these bands, a force constant of 4.8679 mdyn/A (Table 3,
No. 16) was used after modification of C–H stretching force
constant as given by Ozpozan [36].
Fig. 3. The linear corrected between the calculation and FT-IR spectrum.

H. Arslan et al. / Spectrochimica Acta Part A 64 (2006) 1065–1071
1069
Table 4
Observed and calculated planar and non-planar fundamentals (cm−1
)
No.
Species
Wavenumber
Observed (IR)
PED (%)
Assignmentsa
Calculated (IR–Raman)
1
2
3
4
5
6
7
8
9
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀꢀ
A
3166
3091
3091
3091
3091
3019
3019
3019
3019
2924
2924
1710
1663
1637
1591
1563
1509
1484
1471
1457
1432
1430
1390
1375
1292
1270
1240
1201
1160
1130
1093
1043
1037
1009
972
962
952
909
887
869
815
782
752
721
694
684
647
613
602
547
503
470
449
434
–
3166
3095
3093
3091
3090
3028
3025
3015
3015
2920
2920
1705
1657
1641
1600
1556
1507
1487
1468
1457
1438
1429
1384
1380
1291
1271
1238
1199
1159
1132
1086
1033
1033
1009
978
960
955
910
885
869
823
779
749
723
696
682
647
611
598
544
496
99% K(5)
74% K(11), 25% K(13)
87% K(13), 12% K(11)
96% K(13)
89% K(13), 10% K(11)
54% K(17), 45% K(16)
53% K(16), 47% K(17)
91% K(16), 10% K(17)
84% K(16), 16% K(17)
62% K(16), 36% K(17)
63% K(16), 36% K(17)
25% K(2), 11% K(15)
21% K(12), 13% K(8)
38% K(7), 18% K(4), 17% K(15)
25% K(10), 22% K(2)
23% K(12), 23% K(10), 15% K(2)
24% K(10), 17% H(33), 13% H(30), 13% H(31)
55% H(44), 12% K(4), 10% H(40)
53% H(44), 16% H(42)
39% H(42), 28% K(44), 11% H(40)
28% H(33), 16% K(12), 13% K(10)
49% H(42), 15% H(40)
66% H(43), 16% H(42)
67% H(43), 16% H(42)
30% K(3), 19% K(9), 11% K(12)
21% K(9), 16% K(10), 13% K(12)
16% H(40), 14% K(15), 15% K(4)
47% H(33), 11% K(6)
16% K(15), 15% H(41)
11% K(8), 11% H(23)
16% K(8), 10% K(10)
41% H(33), 37% K(10)
84% H(40)
63% H(33), 34% K(12)
35% K(12), 30% H(33)
25% K(1), 19% H(23), 19% H(41), 17% H(22)
94% H(40)
νN–H
νC–H
νC–H
νC–H
νC–H
νC–H
Aꢀꢀ
Aꢀ
Aꢀꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀ
Aꢀꢀ
A
νC–H
νC–H
νC–H
νC–H
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
νC–H
νC=O
νC–C
νC–N
νC–C, νC=O
νC–C, νC=O
νC–C, δC–C–H
δH–C–H
δH–C–H
δH–C–H
δC–C–H, νC–C
δH–C–H
δH–C–H
δH–C–H
νC–C
νC–C
δN–C–H, νC–N
δC–C–H, νC=S
νC–N, δN–C–H
νC–C, δC–N–H
νC–C
δC–C–H, νC–C
δN–C–H
Aꢀꢀ
Aꢀ
Aꢀꢀ
A
δC–C–H, νC–C
νC–C, δC–C–H
νC–N, δC–N–H
δN–C–H
Aꢀꢀ
Aꢀꢀ
Aꢀꢀ
Aꢀꢀ
A
66% H(41), 17% H(40)
17% H(40), 18% K(15), 14% H(41)
86% A(50)
25% K(15), 10% K(6)
73% A(50), 17% A(49)
δN–C–H
δN–C–H, νC–N
γC
νC–N, νC=S
γC
δC–C–C, νC–Cl
γC
Aꢀꢀꢀ
A
19% H(32), 10% K(14)
Aꢀꢀ
Aꢀꢀꢀ
A
33% A(45), 16% A(48), 17% A(50), 14% A(49)
46% A(47), 20% T(56), 12% A(52)
18% H(32), 18% K(9), 12% H(29)
43% A(50), 20% A(45), 11% A(49)
14% K(15), 13% K(8)
γC, τC–N
δC–C–C, νC–C
γC
Aꢀꢀꢀ
A
νC–N, νC=C
γC
δC–N–C, νC–N
γC
Aꢀꢀꢀ
A
52% A(50), 37% A(49)
21% H(39), 21% H(37), 16% K(15)
53% A(51), 13% A(48), 11% A(45)
21% H(27), 14% K(8), 12% K(14)
42% T(55), 39% A(46), 15% T(53)
25% K(6), 25% H(38), 12% H(39)
26% K(14), 20% H(36)
38% A(47), 32% T(56), 14% A(52)
11% K(14), 10% H(35)
21% H(20), 15% H(18)
Aꢀꢀꢀ
A
468
445
435
369
365
325
281
257
δC–C–C, νC–Cl
τC–N, γC
νC=S, δC–N–C
νC–Cl, δC–C–Cl
γC, τC–N, γN
νC–Cl, δC–C–Cl
δC–C–O, δN–C–O
γC, τC–C
δN–C–N, δN–C–S
τC–C
Aꢀꢀ
Aꢀ
Aꢀ
Aꢀꢀ
Aꢀꢀ
A
–
–
–
–
–
–
–
Aꢀꢀꢀ
51% A(48), 22% A(51), 13% T(59)
17% H(25), 14% H(26), 13% H(18)
85% T(59)
A
227
202
180
Aꢀꢀ
Aꢀꢀ
45% A(52), 35% T(61), 18% T(56)
γN, τC–N

1070
H. Arslan et al. / Spectrochimica Acta Part A 64 (2006) 1065–1071
Table 4 (Continued )
No.
Species
Wavenumber
PED (%)
Assignmentsa
Observed (IR)
Calculated (IR–Raman)
63
64
65
66
67
68
69
70
71
72
Aꢀꢀꢀ
A
–
–
–
–
–
–
–
–
–
–
166
139
122
110
86
61
53
42
27
21% H(24), 17% H(21), 12% H(26)
18% H(27), 16% H(25), 16% H(35)
95% T(61)
33% T(59), 21% T(57), 20% T(60)
38% A(46), 31% T(55)
37% H(19), 22% H(21), 22% H(27)
30% T(58), 25% T(53), 16% T(60)
38% T(61), 21% T(58), 11% T(56)
47% T(53), 13% T(61)
δN–C–S, δN–C–N
δC–C–C, δN–C–N, δC–C–Cl
τC–N
Aꢀꢀ
Aꢀꢀ
Aꢀꢀꢀ
Aꢀꢀ
Aꢀꢀ
A
τC–C
γN, τC–N
δC–C–N, δC–N–C, δC–C–C
τC–C, τC–N
τC–N, τC–C
τC–N
Aꢀꢀ
Aꢀꢀ
10
92% T(54)
τC–C
a
ν, stretching; δ, in-plane; γ, out-of-plane; τ, torsional vibrations.
medium intensity are expected for the aromatic CC modes. All
observed bands are in full agreement with the literature data
[33].
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4. Conclusion
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Molecular structure of title compound was determined by
single crystal X-ray diffraction method. These crystal struc-
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culations. A detailed IR study of the N,N-dimethyl-Nꢀ-(2-
chloro-benzoyl)thiourea molecule on the basis of simple general
valence force field and normal coordinate analysis calculations
helped to assign the vibrational modes of the uncoordinated HL.
It is apparent from Table 4 that out of the 72 fundamentals, 54
could be observed in the present case. The close agreements
between the observed and calculated frequencies confirm the
validity of the present assignment.
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Supplementary material
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Crystallographic data for the structure reported in this paper
have been deposited at the Cambridge Crystallographic Data
Centre (CCDC) with quotation number CCDC-273278 for HL
and can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [Fax: +44 1223 336 033,
e-mail: deposit@ccdc.cam.ac.uk].
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Acknowledgement
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USA, 2002.
This work was supported by Mersin University Research
Fund (Project No. BAP.ECZ.TB.HA.2004-3).
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