The molecular structure and vibrational spectra of 2-chloro-N-(diethylcarbamothioyl)benzamide by Hartree-Fock and density functional methods

Article abstract of DOI:10.1016/j.saa.2007.02.015

2-Chloro-N-(diethylcarbamothioyl)benzamide (C₁₂H₁₅ClN₂OS) has been synthesized and characterized by elemental analysis and IR spectroscopy. The crystal and molecular structure of the title compound has been determined from

Full text of DOI:10.1016/j.saa.2007.02.015

Available online at www.sciencedirect.com
Spectrochimica Acta Part A 68 (2007) 1347–1355
The molecular structure and vibrational spectra of
2-chloro-N-(diethylcarbamothioyl)benzamide by
Hartree–Fock and density functional methods
c
a
Hakan Arslana,b,∗, Ulrich Florke , Nevzat Kulcu , Gun Binzet
¨
¨ ¨ a
¨
a Department of Chemistry, Faculty of Arts and Science, Mersin University, 33343-Mersin, Turkey
b Department of Chemistry, Faculty of Pharmacy, Mersin University, 33169-Mersin, Turkey
c Department of Chemistry, University of Paderborn, 33098-Paderborn, Germany
Received 12 October 2006; accepted 20 February 2007
Abstract
2-Chloro-N-(diethylcarbamothioyl)benzamide (C12H15ClN2OS) has been synthesized and characterized by elemental analysis and IR spec-
troscopy. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes
3
in the orthorhombic space group Pbca, Z = 8 with a = 9.581(3) A, b = 9.992(3) A, c = 26.640(8) A, V = 2550.5(13) A and Dcalc = 1.410 Mg/m3. The
molecular geometry and vibrational frequencies of 2-chloro-N-(diethylcarbamothioyl)benzamide in the ground state have been calculated using
the Hartree–Fock and density functional using Becke’s three-parameter hybrid method with the Lee, Yang and Parr correlation functional (B3LYP)
methods with 3-21G and 6-31G(d) basis sets. The calculated geometric parameters were compared to the corresponding X-ray structure of the title
compound. The raw B3LYP frequencies approximate the experimental data much better than the results of Hartree–Fock. The scaled B3LYP/6-
31G(d) results were more reliable than those obtained using the B3LYP/3-21G method with the mean absolute deviation about 13.7 cm−1. On the
basis of the comparison between calculated and experimental results, assignments of fundamental vibrational modes were examined.
© 2007 Elsevier B.V. All rights reserved.
˚
˚
˚
˚
Keywords: 2-Chloro-N-(diethylcarbamothioyl)benzamide; Thiourea; DFT; HF; Infrared spectrum; Molecular calculations
1. Introduction
metal ions in aqueous solutions. These chelates can be extracted
with CHCl3 and separated by chromatography [3]. The bio-
logical activities of complexes with thiourea derivatives have
been successfully screened against various bacteria and fungi.
Furthermore, some thiourea derivatives have been used com-
mercially as fungicides [4–7]. With all this in consideration, we
set our goal to examine the coordination behaviour of a series
of substituted benzoylthiourea derivatives that possess a number
of interesting properties [8–16]. In literature, there is no data on
the synthesis or characterization of the title compound proposed
in this study.
In this study, we synthesized and then, investigated the crys-
tal structure of 2-chloro-N-(diethylcarbamothioyl)benzamide.
Also, we calculated the molecular geometry and vibrational
spectra of title compound by applying the Hartree–Fock and
density functional using Becke’s three-parameter hybrid method
with the Lee, Yang and Parr’s correlation functional methods
with 3-21G and 6-31G(d) basis sets. The calculated geometric
parameters and vibrational frequencies were analyzed theoret-
ically and then, compared with obtained experimental results.
Thiourea derivatives and their transition metal complexes
have been known since the beginning of the 20th century, and
easily synthesized in good yields. The thiourea derivatives have
recently been attracted attention of scientists as they are highly
selective reagents for the pre-concentration and separation of
metal cations in different matrices [1]. The complexation capac-
ity of thiourea derivatives has been reported in several papers
[2,3]. Transition metal complexes with such thiourea deriva-
tives have been reported in literature and the structures with
O, S-binding to the metal ions were well defined in alkaline
media based on a series of physicochemical properties. N,N-
Dialkyl-Nꢀ-benzoyl thioureas form neutral chelates with lots of
∗
Corresponding author at: Department of Chemistry, Faculty of Arts and Sci-
ence, Mersin University, Mezitli-C¸ iftlikko¨yu¨ Kampu¨su¨, 33343-Mersin, Turkey.
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 © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2007.02.015

1348
H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
Table 1
Therefore, we made an intensive investigation and studied on
the structure and vibrational frequencies of the title compound.
Crystal data and structure refinement for 2-chloro-N-(diethylcarbamothioyl)
benzamide
Empirical formula
Formula weight
Temperature (K)
C12H15ClN2OS
270.77
120(2)
2. Experimental
2.1. Synthesis
˚
Wavelength (A)
0.71073
Crystal system
Space group
Orthorhombic
Pbca
All chemicals used for the preparation of the title compound
were of reagent grade quality. Some of the solvents were dis-
tilled prior to use. The title compound was prepared by a similar
procedure that was reported in the literature [8]. A solution
of 2-chloro benzoyl chloride (0.01 mol, 1.17 mL) in acetone
(50 cm3) was added dropwise into a suspension of potassi-
umthiocyanate (0.01 mol, 0.9718 g) in acetone (30 cm3). The
obtained reaction mixture was heated under reflux for 30 min,
and then, cooled to room temperature. A solution of diethy-
lamine (0.01 mol, 0.53 mL) in acetone (10 cm3) was added and
the resultant mixture was stirred for 2 h. Next, hydrochloric acid
(0.1N, 300 cm3) was added and subsequently, the solution was
filtered. The resultant solid product was then washed with water
and purified by recrystallisation using ethanol/dichloromethane
mixture (1:1). 2-Chloro-N-(diethylcarbamothioyl)benzamide.
Yield: (2.5182 g) 93%, anal. calcd. for C12H15ClN2OS: C 53.2,
H 5.5, N 10.3. Found: C 52.6, H 5.5, N 10.4.
˚
Unit cell dimensions (A)
a = 9.581(3)
b = 9.992(3)
c = 26.640(8)
3
˚
Volume (A )
2550.5(13)
8
1.410
0.448
1136
Z
Density (calculated) (Mg/m3)
Absorption coefficient (mm−1
F(0 0 0)
)
Crystal size (mm × mm × mm)
0.52 × 0.10 × 0.08
Theta range for data collection (◦)
1.53–28.08
Index ranges
−12 ≤ h ≤ 12
−13 ≤ k ≤ 12
−35 ≤ l ≤ 31
19025
3107 [R(int) = 0.0750]
99.9
Semi-empirical from equivalents
0.9650 and 0.8004
Full-matrix least-squares on F2
3107/0/154
Reflections collected
Independent reflections
Completeness to theta = 28.08◦ (%)
Absorption correction
Maximum and minimum transmission
Refinement method
2.2. Instrumentation
Data/restraints/parameters
Goodness-of-fit on F2
1.045
The room temperature attenuated total reflection Fourier
transform infrared (FT-IR ATR) spectra of the 2-chloro-N-
(diethylcarbamothioyl)benzamide were registered using Varian
FTS1000 FT-IR spectrometer with Diamond/ZnSe prism
(4000–525 cm−1; number of scans, 250; resolution, 1 cm−1).
Elemental analyses were carried out on a Carlo Erba MOD 1106
instrument. Single crystal X-ray data were collected on a Bruker
AXSSMARTAPEXCCD, usingmonochromatedMoK␣radia-
tion. The structure was solved by direct and conventional Fourier
methods. Full-matrix least-squares refinement based on F2. All
buthydrogenatomsrefinedanisotropically, Hatomsonidealized
positions with ‘riding’ model. Programs used for calculations:
SHELXTL [17]. Further details concerning data collection and
refinement are given in Table 1.
Final R indices [I > 2sigma(I)]
R indices (all data)
Largest diff. peak and hole (e A
R1 = 0.0680, wR2 = 0.1546
R1 = 0.1545, wR2 = 0.1800
0.415 and −0.512
−3
˚
)
of GaussView 3.0 graphical interface for gaussian programs,
which gives a visual presentation of the shape of the vibrational
modes [21].
3. Results and discussion
The molecular structure which show the atom numbering
scheme, packing diagram and selected bond lengths and angles
of 2-chloro-N-(diethylcarbamothioyl)benzamide, are given in
Figs. 1 and 2 and Table 2, respectively. Both of the C(8)–S(1)
2.3. Calculations
The molecular structure of the title compound in the ground
state was optimized by Hartree–Fock and density functional
usingBecke’sthree-parameterhybridmethodwiththeLee, Yang
and Parr’s correlation functional methods with the standard 3-
21G and 6-31G(d) basis sets. The vibrational frequencies were
also calculated with these methods. These calculations were car-
ried out using Gaussian 03W program package on a double
Xeon/3.2 GHz processor with 4 GB Ram [18]. The frequency
values computed at these levels contain known systematic errors
[19]. We therefore used the scaling factor values of 0.8929,
0.9613, 0.9085 and 0.9614 for HF/6-31G(d), B3LYP/6-31G(d),
HF/3-21GandB3LYP/3-21G, respectively[20]. Theassignment
of the calculated wavenumbers is aided by the animation option
Fig. 1. The structure of 2-chloro-N-(diethylcarbamothioyl)benzamide. Thermal
ellipsoids are shown at the 50% probability level.

H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
1349
Table 2
Optimized geometries of the 2-chloro-N-(diethylcarbamothioyl)benzamide in the ground state
Parameters
Experimental
Calculated (6-31G(d))
HF
Calculated (3-21G)
HF
B3LYP
B3LYP
˚
Bond lengths (A)
Cl(1)–C(1)
S(1)–C(8)
O(1)–C(7)
N(1)–C(7)
N(1)–C(8)
N(2)–C(8)
N(2)–C(11)
N(2)–C(9)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(9)–C(10)
C(11)–C(12)
1.733(4)
1.650(5)
1.213(5)
1.350(5)
1.415(5)
1.322(5)
1.452(5)
1.459(5)
1.362(6)
1.378(6)
1.373(6)
1.377(6)
1.361(6)
1.379(6)
1.483(6)
1.513(7)
1.484(7)
1.751
1.664
1.185
1.383
1.398
1.340
1.470
1.468
1.385
1.387
1.382
1.386
1.381
1.393
1.512
1.527
1.526
1.775
1.667
1.216
1.387
1.420
1.363
1.475
1.473
1.396
1.404
1.392
1.395
1.390
1.407
1.520
1.532
1.531
1.831
1.732
1.204
1.385
1.392
1.333
1.485
1.481
1.376
1.379
1.381
1.383
1.378
1.393
1.511
1.539
1.536
1.859
1.717
1.234
1.387
1.416
1.361
1.491
1.489
1.390
1.396
1.394
1.397
1.387
1.409
1.527
1.543
1.540
r
0.9927
0.9952
0.9942
0.9933
Bond angles (◦)
C(7)–N(1)–C(8)
C(8)–N(2)–C(11)
C(8)–N(2)–C(9)
C(11)–N(2)–C(9)
C(2)–C(1)–C(6)
C(2)–C(1)–Cl(1)
C(6)–C(1)–Cl(1)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(5)–C(4)–C(3)
C(4)–C(5)–C(6)
C(1)–C(6)–C(5)
C(1)–C(6)–C(7)
C(5)–C(6)–C(7)
O(1)–C(7)–N(1)
O(1)–C(7)–C(6)
N(1)–C(7)–C(6)
N(2)–C(8)–N(1)
N(2)–C(8)–S(1)
N(1)–C(8)–S(1)
N(2)–C(9)–C(10)
N(2)–C(11)–C(12)
122.3(4)
121.3(4)
123.5(4)
115.1(4)
121.1(4)
117.7(4)
121.1(4)
119.9(4)
119.7(4)
119.9(4)
121.0(4)
118.3(4)
124.5(4)
117.2(4)
121.2(4)
122.6(4)
116.1(4)
115.2(4)
125.7(3)
119.2(3)
111.5(4)
111.5(4)
127.4
120.4
123.1
116.1
121.3
117.1
121.5
119.6
120.0
119.8
121.2
118.0
126.7
115.3
124.4
120.5
115.1
113.4
124.8
121.7
114.0
113.7
126.0
119.9
123.4
116.4
121.9
115.5
122.6
119.8
119.8
119.7
122.1
116.8
129.5
113.7
123.2
119.7
117.0
113.2
124.9
121.9
114.1
113.7
126.7
120.5
123.3
116.1
122.4
115.2
122.4
119.4
119.7
119.8
121.5
117.1
129.1
113.7
124.2
119.5
116.2
114.4
123.4
122.1
113.0
112.6
125.5
119.8
123.2
116.9
122.9
113.3
123.7
119.4
119.4
119.8
122.4
115.9
131.7
112.3
123.5
119.4
117.1
117.5
123.9
122.5
113.4
112.4
r
0.8951
0.8687
0.8729
0.8137
˚
˚
(1.650(5) A) and C(7)–O(1) (1.213(5) A) bonds show typical
double-bond characteristics. However, the C–N bond lengths
˚
˚
C(7)–N(1) (1.350(5) A), C(8)–N(1) (1.415(5) A) and C(8)–N(2)
˚
(1.322(5) A) are shorter than the normal C–N single-bond
˚
length of about 1.48 A. The shortening of these C–N bonds
reveals the effects of resonance in this part of the molecule.
All other bond lengths fall within the expected ranges. The
conformation of the molecule with respect to the thiocarbonyl
and carbonyl moieties is twisted, as reflected by the tor-
sion angles O(1)–C(7)–N(1)–C(8) and C(7)–N(1)–C(8)–N(2)
of 5.63◦ and −76.78◦, respectively. Intermolecular hydrogen
˚
Fig. 2. Crystal packing viewed along [1 0 0] with hydrogen bonds as dashed
lines. H atoms not involved are omitted.
bonds N(1)–H· · ·O1 (−x + 0.5, y + 0.5, z) with H· · ·O 1.99 A
and N–H· · ·O 155◦ and C(5)–H· · ·Cl (−x + 0.5, y + 0.5, z) with

1350
H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
Fig. 3. Fifteen stable conformers of the title compound calculated at HF-/6-31G(d) level.
◦
numbering scheme given in Fig. 1. The correlation between the
experimental and calculated geometric parameters obtained by
the HF and DFT methods is given in Table 2. Based on our
calculations, DFT method correlates (r = 0.9952) well for the
bond length compared with the HF method. The largest differ-
ence between experimental and calculated DFT bond length is
˚
H· · ·Cl 2.81 A and C–H· · ·Cl 159 link molecules to endless
rows along [0 1 0].
The structure of the title compound shown in Fig. 1 is very
flexible. It has got several conformations (Figs. 3 and 4). To
establish the most stable conformation as the initial point for
further calculations, the molecule was submitted to a rigorous
conformation analysis around the free rotation bonds. This study
was performed with the software Spartan 04 [22]. Energetics,
gathered in Table 3, show that the Conformer 1 is the most stable.
But comparison of the theoretical and experimental geometry
of the title compound shows that the X-ray parameters fairly
well reproduce the geometry of the Conformer 21. Therefore,
further in this paper, we focus on this particular form of the title
compound.
˚
about 0.047 A. The bond angles provided by HF method is much
closer to experimental values (r = 0.8951). As a result, the opti-
mized bond lengths obtained by DFT-B3LYP/6-31G(d) method
and bond angles by ab-initio HF /6-31G(d) method show the best
agreement with the experimental values. The difference between
experimental and calculated geometric parameters comes from
the environment of the compound. It is clear that the experi-
mental results belong to solid phase and theoretical calculations
belong to gaseous phase.
The optimized structure parameters of title compound were
calculated at ab initio-HF and density functional theory-B3LYP
levels with the standard 3-21G and 6-31G(d) basis sets. The
results are tabulated in Table 2 in accordance with the atom
FT-IR spectrum of 2-chloro-N-(diethylcarbamothioyl)
benzamide is given in Fig. 5. Table 4 lists the vibrational
frequencies that were obtained using ab initio-HF and DFT-

H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
1351
Fig. 4. Twelve stable conformers of the title compound calculated at HF-/6-31G(d) level.
B3LYP calculations along with the experimental frequencies
and the approximate description of each normal modes. The
assignments for vibrational bands have been made by using
GaussView molecular visualization program. It is a well known
fact that the difference between the experimental and calculated
results arise from the presence of systematic errors due to
neglection of inharmonic effects, electronic correlation and
basis set deficiencies. It is obvious that the use of scaled factors
will further improve the agreement between the calculated and
observed fundamental vibrational frequencies. To compare
calculated values with experimental values a correlation
graphic was plotted in Figs. 6 and 7. As seen from Figs. 6 and 7,
experimental fundamentals are in better agreement with the
scaled fundamentals. Also, we found a better correlation for
DFT-B3LYP than HF method.
In order to investigate the performance and vibrational fre-
quencies for the title compound, the mean deviation, mean
absolute deviation and standard deviation (S.D.) between the
calculated harmonic and observed fundamental vibrational fre-
quencies for each method and basis set are also given in Table 5.
These results indicate that the B3LYP calculations approximate
the observed fundamental frequencies much better than the HF
results.
The experimental band at 3236 cm−1, correspond to the
stretching ␯N H vibrations of the hydrogen bond NH group. This
band disappears in the metal complex [8,10]. The appropriate
calculated frequency is positioned at 3446 cm−1 when DFT-
B3LYP/6-31G(d) method was applied. The difference between
experimental and calculated ␯N H is about 210 cm−1. This strik-
ing discrepancy comes from the formation of intermolecular
hydrogen bonding with N–H. Also, we note that the experi-
mental results belong to solid phase and theoretical calculations
belong to gaseous phase. This interpretation verifies presence
of ␯
stretching vibration mode. The difference between
C O
experimental (1655 cm−1) and calculated (1723 cm−1 with DFT
method) ␯C O is about 68 cm−1. It can easily be observed in the
correlation graphics of calculated and experimental frequencies
Fig. 5. Infrared spectrum of 2-chloro-N-(diethylcarbamothioyl)benzamide.

1352
H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
Table 3
Energies of the different conformations of the title compound calculated at the
HF/6-31G(d) level*
Conformer
E (Hartree)
ꢀE (kcal/mol)
Dipole moment (D)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
−1503.919500
−1503.917330
−1503.917180
−1503.917185
−1503.916960
−1503.916750
−1503.916755
−1503.916050
−1503.915710
−1503.915600
−1503.915250
−1503.919030
−1503.909440
−1503.908860
−1503.908680
−1503.907050
−1503.906380
−1503.906190
−1503.903790
−1503.903660
−1503.919035
−1503.918700
−1503.918750
−1503.917920
−1503.917925
−1503.917750
−1503.917530
0.0000
1.3617
1.4558
1.4527
1.5938
1.7256
1.7225
2.1649
2.3782
2.4472
2.6669
0.2949
6.3126
6.6766
6.7895
7.8124
8.2328
8.3520
9.8580
9.9396
0.2918
0.5020
0.4706
0.9914
0.9883
1.0981
1.2362
3.98
4.27
5.46
5.45
6.05
5.58
5.58
5.74
5.72
6.01
6.09
4.06
6.86
5.63
8.16
6.78
7.79
8.14
8.37
6.72
4.07
4.02
4.03
3.95
3.94
3.06
5.76
Fig. 7. Correlation graphics of calculated and experimental frequencies of the
title compound.
*
Total energies, E.
of the title compound that there exists a big difference for ␯
N H
and ␯
stretching vibrations (Figs. 6 and 7).
C O
The characteristic ␯
stretching vibrations of substitute
C H
phenyl ring are expected to appear in 3040–3100 cm−1 fre-
quency ranges. The ␯C H stretching vibrations of the phenyl ring
were assigned to two bands observed at 3091 and 3062 cm−1
in IR spectrum of the title compound. The B3LYP/6-31G(d)-
calculated wavenumbers of these bands very well reproduced
the experimental ones. The difference between experimental and
calculated ␯C H is about 1, 11, 21 and 13 cm−1. The biggest dif-
ference (21 cm−1) is belongs to stretching vibration of C5–H5
bond. This discrepancy comes from the formation of intermolec-
ular hydrogen bonding with Cl· · ·H (Fig. 2).
Six bands at 3053, 3037, 2976, 2967, 2931 and 2872 cm−1
were observed in the spectrum. First three bands were asymmet-
ric ␯
stretching bands and the other bands symmetric ␯
C H
C H
stretching band for ethyl group. All these results agree with the
results of Arslan et al. [12,23,24].
In the nitrogen-containing thiocarbonyl compounds, the
assignment of the ␯C S stretching frequency has been controver-
sial. Thus, only the results from theoretical calculation analysis
can provide the clear-cut assignment for the title compound.
Based on the theoretical data obtained from calculations, two
bands at 1249 and 1130 cm−1 in the IR spectrum have been
assigned to the ␯
stretching vibrations coupled with the in-
C S
plane ring deformation.
Fig. 6. Correlation graphics of calculated and experimental frequencies of the
title compound.
The identification of ␯
vibrations is a difficult task since
C N
the mixing of vibrations is possible in 900–1300 cm−1 range

H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
1353
Table 4
Experimetal and calculated vibrational frequencies (in cm−1) of 2-chloro-N-(diethylcarbamothioyl)benzamidea
Experimental HF/6-31G(d)
DFT-B3LYP/6-31G(d)
HF/3-21G
Calc.
DFT-B3LYP/3-21G
Assignments
Calc.
Corr.
Inten.
Calc.
Corr.
Inten.
Corr.
Inten.
Calc.
Corr.
Inten.
3236
3091
3091
3091
3062
3053
3037
2976
2976
2976
2976
2967
2931
2931
2872
1655
1595
1566
1524
1485
1472
1460
1460
1460
1445
1445
1431
1411
1382
1382
1357
1342
1308
1285
1270
1249
1221
1203
1167
1143
1130
1107
1097
1078
1069
1051
1037
1006
989
3876
3409
3405
3391
3375
3345
3331
3314
3286
3276
3271
3262
3246
3215
3210
2021
1802
1767
1711
1682
1656
1650
1647
1643
1633
1631
1602
1588
1573
1566
1534
1519
1474
1429
1414
1401
1364
1330
1301
1272
1249
1229
1214
1209
1197
1178
1150
1137
1131
1101
1093
1010
999
3461
3044
3040
3028
3014
2987
2974
2959
2934
2925
2921
2913
2898
2871
2866
1805
1609
1578
1528
1502
1479
1473
1471
1467
1458
1456
1430
1418
1405
1398
1370
1356
1316
1276
1263
1251
1218
1188
1162
1136
1115
1097
1084
1080
1069
1052
1027
1015
1010
983
35.93 3585
7.49 3237
4.48 3227
13.09 3214
2.91 3199
20.32 3157
15.97 3154
15.43 3133
16.75 3127
96.52 3125
50.82 3120
14.49 3079
4.59 3062
34.68 3059
12.76 3056
287.46 1792
27.55 1650
5.95 1620
667.24 1552
22.50 1543
3.40 1538
42.79 1529
5.07 1519
15.08 1519
2.37 1512
1.92 1507
14.53 1476
126.85 1463
54.54 1442
19.07 1435
107.93 1412
50.95 1397
104.71 1356
88.03 1339
161.52 1319
328.86 1300
209.32 1280
13.00 1252
124.91 1198
115.62 1197
2.82 1178
10.59 1150
10.93 1134
27.88 1121
39.60 1118
19.60 1090
24.03 1071
19.46 1047
1.36 1026
13.50 1001
3446
3112
3102
3090
3075
3035
3032
3012
3006
3004
2999
2960
2944
2941
2938
1723
1586
1557
1492
1483
1478
1470
1460
1460
1453
1449
1419
1406
1386
1379
1357
1343
1304
1287
1268
1250
1230
1204
1152
1151
1132
1105
1090
1078
1075
1048
1030
1006
986
49.42
4.00
5.12
13.14
3.13
3841
3412
3408
3390
3373
3328
3322
3305
3285
3275
3268
3260
3249
3214
3210
1937
1772
1733
1722
1703
1680
1674
1665
1659
1658
1651
1610
1591
1578
1571
1528
1521
1474
1437
1425
1381
1357
1347
1304
1270
1258
1245
1229
1224
1207
1201
1168
1161
1148
1129
1066
1060
997
3490
3100
3096
3079
3065
3024
3018
3002
2985
2975
2969
2961
2951
2920
2917
1760
1610
1574
1565
1547
1526
1521
1513
1507
1506
1500
1463
1445
1434
1428
1388
1382
1340
1305
1295
1255
1233
1224
1185
1154
1143
1131
1116
1112
1097
1091
1061
1055
1043
1026
968
68.45 3527
3.81 3241
0.47 3236
6.62 3222
2.39 3208
15.12 3156
10.92 3150
7.43 3134
7.44 3130
63.57 3128
36.11 3122
6.14 3083
6.83 3074
24.18 3066
9.37 3063
175.87 1729
23.67 1628
58.86 1588
497.77 1576
65.32 1575
4.66 1567
11.14 1560
4.17 1558
0.90 1554
13.44 1530
40.75 1513
19.98 1486
95.57 1469
22.20 1462
15.41 1454
107.24 1412
7.11 1401
53.98 1364
16.94 1326
164.51 1318
444.17 1311
48.45 1269
303.75 1243
96.77 1230
76.72 1201
11.07 1177
2.44 1147
43.81 1137
31.13 1134
10.61 1124
21.99 1079
21.15 1063
12.11 1061
17.60 1059
26.94 1020
22.87 1003
3390
3116
3110
3098
3084
3034
3028
3013
3009
3007
3001
2963
2955
2947
2945
1662
1565
1527
1515
1514
1507
1500
1497
1494
1470
1455
1428
1413
1406
1398
1357
1347
1311
1275
1267
1261
1220
1195
1183
1155
1132
1103
1093
1090
1080
1037
1022
1019
1018
980
119.90
5.25
6.00
5.81
3.10
20.95
16.04
10.59
27.97
2.32
17.46
39.56
3.23
22.08
10.06
113.82
12.01
23.47
245.79
102.39
42.99
59.53
8.37
67.24
11.27
42.71
14.16
47.50
27.41
20.94
44.44
22.88
22.20
76.01
90.05
6.19
392.37
203.66
89.02
66.13
45.48
36.68
28.63
61.85
4.22
3.53
11.14
8.90
34.59
3.19
15.52
2.01
0.05
8.80
37.39
3.54
17.88
11.07
67.98
15.85
29.44
10.98
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␯
␦
␦
␦
␦
␦
␦
␦
␯
␯
␦
␦
␦
␦
␦
␦
␦
␦
␯
␦
␦
␦
␦
␯
␦
␦
␦
␦
␦
␯
␯
␯
NH
CH, sym, Ph
CH, sym, Ph
CH, asym, Ph
CH, asym, Ph
CH, asym, et
CH, asym, et
CH, asym, et
CH, asym, et
CH, sym, et
CH, sym, et
CH, sym, et
CH, sym, et
CH, sym, et
CH, sym, et
24.77
11.50
15.08
11.76
36.69
21.66
40.48
30.23
14.18
11.32
187.57
16.69
5.05
C
O
CC
CC
443.64
100.20
4.65
9.71
4.17
CH, CH3 + ␦NH
CH, et + ␦NH
CH, et
CH, et
CH, et
3.44
CH, et
17.56
58.84
14.55
100.67
26.53
9.82
75.30
14.41
47.19
6.44
115.09
47.13
296.33
211.83
1.40
92.33
59.59
11.39
5.26
9.31
40.90
6.28
8.06
39.42
5.80
0.89
1.38
0.47
11.94
0.20
CH, Ph + ␦CH, et
CN + ␦CH, et + ␦NH
CC + ␦CH, Ph
CH, et
CH, et
CH, et
CH, et
NH, + ␦CH, Ph + ␦CH, et
CH, Ph
CH, Ph + ␯
CC
CH, et + ␯
CN
S + ␯CC + ␦CH, Ph
C
CH, et + ␯
CN
CH, Ph + ␯CN + ␦NH
CH, Ph
CH, Ph + ␯
C=S + ␦CH, et
CH, Ph
CH, Ph + ␯CN + ␦CH, et
CH, Ph + ␯CN + ␦CH, et
CH, et
CH, Ph + ␦CH, et
CC + ␦CH, Ph
CC + ␦CH, Ph
CN
CN + ␯
CC
CH, Ph
CH, Ph
955
922
911
871
853
842
796
778
748
740
719
680
962
932
907
882
852
839
773
760
756
727
719
687
␥
␥
976
902
892
887
886
785
769
756
754
724
711
667
3.99
5.16
970
944
918
886
873
804
791
786
756
748
715
682
964
899
893
887
828
802
785
766
762
725
697
671
963
906
890
850
826
810
799
773
8.64
18.04
3.33
935
929
923
861
834
817
797
792
754
726
698
␦
␦
CH, et
CCC, Ph + ␦CNC
9.99
993
992
879
861
847
844
811
796
11.77
36.26
20.47
10.79
6.08
979
936
909
892
879
851
827
810
␥
CH, Ph
21.47
17.24
21.75
4.75
25.75
7.83
14.29
34.49
111.88
16.70
21.07
47.65
5.33
␦CNC + ␥CH, et
␥
␥
␥
␥
␥
␯
CH, et
CCC, Ph
CH, et
CCC, Ph
CCC, Ph + ␥CN
Cl + ␥CCC, Ph
46.66
0.88
752
736
697
7.45
14.87
8.09
C
665
747
26.87
656
768
37.85
␥CCC, Ph

1354
H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
Table 4 ( Continued )
Experimental
HF/6-31G(d)
DFT-B3LYP/6-31G(d)
HF/3-21G
Calc.
DFT-B3LYP/3-21G
Assignments
Calc.
Corr.
Inten.
Calc.
Corr.
Inten.
Corr.
Inten.
Calc.
Corr.
Inten.
619
609
553
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
702
685
613
564
532
524
497
483
470
451
399
375
330
327
274
250
220
213
186
166
154
122
102
88
627
612
547
504
475
468
444
431
420
403
356
335
295
292
245
223
196
190
166
148
138
109
91
15.06
7.14
2.51
4.95
54.77
5.58
29.09
41.46
14.76
15.07
7.81
6.57
2.09
1.29
1.92
0.28
0.22
0.51
0.15
0.85
0.15
1.11
0.91
4.18
0.39
1.90
1.54
2.71
648
613
562
515
510
482
464
453
435
430
379
346
315
309
256
240
218
196
188
159
139
115
100
79
623
589
540
495
490
463
446
435
418
413
364
333
303
297
246
231
210
188
181
153
134
111
96
9.46
732
699
652
600
568
540
504
486
484
452
400
370
333
323
281
244
225
222
200
181
161
135
120
98
665
635
593
545
516
490
458
441
439
411
364
336
303
293
255
221
204
202
181
164
146
123
109
89
10.89
9.01
55.39
3.85
1.19
12.24
12.79
17.10
7.69
23.27
14.40
8.34
1.41
4.59
0.98
0.76
0.44
0.04
0.14
0.89
0.17
0.63
1.65
4.40
0.85
1.86
2.15
3.56
669
648
596
548
523
492
468
461
445
421
382
344
330
307
251
237
233
221
200
156
132
121
108
88
643
623
573
527
502
472
450
443
428
405
367
331
317
295
242
228
224
212
192
150
127
116
104
85
15.32
19.10
38.66
4.73
6.42
2.46
4.35
11.25
8.19
18.67
2.99
9.16
2.62
4.87
1.44
0.90
0.35
0.55
0.43
1.15
0.22
1.02
0.62
2.13
1.16
0.91
1.64
2.94
␥
␥
␥
␥
␥
␥
␥
␦
CCC, Ph
CCC, Ph
CH, Ph
1.67
2.62
38.73
44.74
6.58
14.11
17.18
11.32
14.50
3.44
6.22
0.81
3.27
0.99
0.20
0.59
0.35
0.53
0.67
0.24
1.36
0.96
3.12
0.20
2.09
1.20
2.27
NH
NH + ␥C
CCC + Ph
C
Cl + ␥CH
C
␥
CH, et, Ph
␶
CCCC
␥
NH
␦
␦
␦
CCN + ␦CNC
CCN + ␦CCC
CCN + ␦CCC
␶
␶
␶
CC, et
CC, et
CC, et
␦
CCC
␶CC, et + ␦CNC
␦
CNN
␶
CC
␦CNN + ␶
CCCC
␶
␶
CN + ␶
CN + ␶
CCCC
CCCC
79
60
39
34
76
68
40
36
67
44
38
14
71
42
37
14
76
50
35
10
69
45
32
9
82
38
34
15
79
37
33
14
␦
␦
CNN + ␶
CCCC
CNN + ␶
CCCC
–
–
␶
␶
CN + ␶
CN + ␶
CCCC
CCCC
13
13
a
␯, Stretching; ␦, in-plane bending; ␥, out-of-plane bending; ␶, torsion; sym, symmetric; asym, asymmetric; et, ethyl group; Ph, phenyl group.
Table 5
ular structure of the compound have been determined from
single crystal X-ray diffraction data. We have also calculated
the geometric parameters and vibrational frequencies of the
2-chloro-N-(diethylcarbamothioyl)benzamide by using B3LYP
and HF method with the standard 3-21G and 6-31G(d) basis sets.
Wehaveusedthescalingfactorvaluesof0.8929, 0.9613, 0.9085,
and 0.9614 for HF/6-31G(d), B3LYP/6-31G(d), HF/3-21G and
B3LYP/3-21G, respectively, in order to fit the theoretical results
with experimental ones. Scaling factors results seemed to be
in a good agreement with experimental ones. In comparison to
the experimental results, the calculated vibrational frequencies
obtained by B3LYP method are much better than those of the
Hartree–Fock method. A high level of conformity between the
scaled B3LYP/6-31G(d) and experimental results indicate that
the density functional theory is a very promising method for
molecular vibrational analysis. The difference between exper-
imental and calculated geometrical parameters and vibrations
mode can come from the difference of the state. In fact, it is
evident gas state vibration frequencies are larger than those of
solid state. Moreover, solid states of the compound include a lot
of intra- and inter-molecular interactions.
Mean deviation, mean absolute deviation and S.D. between the calculated and
observed fundamental vibrational frequencies for the title compound
DFT-B3LYP
6-31G(d)
HF
3-21G
6-31G(d)
3-21G
Mean deviation
Mean absolute deviation
S.D.
6.0
13.7
13.1
13.9
20.1
13.0
0.9
25.2
12.8
32.9
35.5
12.9
region. However, with the help of the animation option of
GaussView 3.0 graphical interface for gaussian programs, the
␯
C N
vibrations were identified and assigned in this study. The
IR bands appearing at 1270, 1221 and 1143 cm−1 were assigned
to ␯C N vibrations coupled with the ␦CH for the title compound.
The carbon–carbon stretching vibrations of the title com-
pound have been observed at 1595, 1566 and 1431 cm−1. The
in-plane and out-of-plane bending vibrations of C–C group are
presented in Table 3. All these assignment are in good agreement
with literature [12,24,25]. The C–H in-plane bending vibrations
assigned at 1050–1200 cm−1 are in the same range found in the
literature [12,26,27].
Supplementary material
4. Conclusions
Crystallographic data for the structure reported in this paper
have been deposited at the Cambridge Crystallographic Data
Centre (CCDC) with quotation number CCDC-613210 and can
Title compound has been synthesized and characterized by
elemental analysis and IR spectroscopy. The crystal and molec-

H. Arslan et al. / Spectrochimica Acta Part A 68 (2007) 1347–1355
1355
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].
[15] H. Arslan, N. Duran, N.O. Sahin, N. Ku¨lcu¨, Asian J. Chem. 18 (3) (2006)
1710.
[16] H. Arslan, D. Vanderveer, F. Emen, N. Ku¨lcu¨, Zeitschrift fu¨r Kristallogra-
phie NCS 218 (2003) 479.
[17] Bruker, SHELXTL (Version 6.10), Bruker AXS Inc., Madison, WI, USA,
2002.
Acknowledgement
[18] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R.
Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant,
J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi,
G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara,
K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala,
K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski,
S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D.
Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul,
S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I.
Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A.
Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W.
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Gilliland, GaussView, Version 3.07, Semichem Inc., Shawnee Mission, KS,
2003.
[22] Spartan 04, Wavefunction Inc., Irvine, CA 92612, USA, 2004.
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[24] H. Arslan, T. Ozpozan, Asian J. Chem. 18 (3) (2006) 1815.
[25] W. Zhou, L. Zhu, Y. Zhang, Z. Yu, L. Lu, X. Yang, Vib. Spec. 36 (1) (2004)
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This work was supported financially by the Mersin University
Research Fund (Project no. BAP.ECZ.F.TB.(HA).2006-1).
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