Theoretical studies of molecular structure and vibrational spectra of O-ethyl benzoylthiocarbamate

Article abstract of DOI:10.1016/j.saa.2006.09.011

O-Ethyl benzoylthiocarbamate has been synthesized and characterized by elemental analysis and FT-IR. The crystal structure was determined by X-ray diffraction analysis. Title compound crystallizes in the orthorhombic space group Pna2₁, with Z =

Full text of DOI:10.1016/j.saa.2006.09.011

Spectrochimica Acta Part A 67 (2007) 936–943
Theoretical studies of molecular structure and vibrational
spectra of O-ethyl benzoylthiocarbamate
a,b,∗
, Ulrich Fl o¨ rke , Nevzat K u¨ lc u¨ b
c
Hakan Arslan
a
Department of Chemistry, Faculty of Pharmacy, Mersin University, 33169 Mersin, Turkey
b
Department of Chemistry, Faculty of Arts and Science, Mersin University, 33343 Mersin, Turkey
c
Department of Chemistry, University of Paderborn, 33098 Paderborn, Germany
Received 10 July 2006; received in revised form 7 September 2006; accepted 11 September 2006
Abstract
O-Ethyl benzoylthiocarbamate has been synthesized and characterized by elemental analysis and FT-IR. The crystal structure was determined
˚
by X-ray diffraction analysis. Title compound crystallizes in the orthorhombic space group Pna2 , with Z = 4. Unit cell parameters a = 9.941(3) A,
1
3
˚
˚
˚
b = 9.352(3) A, c = 10.962(3) A and V = 1019.1(5) A . The molecular geometry and vibrational frequencies of O-ethyl benzoylthiocarbamate in the
ground state has 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 computational frequencies are in good agreement with
the observed results. Comparison of the observed fundamental vibrational frequencies of O-ethyl benzoylthiocarbamate and calculated results
by density functional B3LYP and Hartree–Fock methods indicate that B3LYP is superior to the scaled Hartree–Fock approach for molecular
vibrational problems.
©
2006 Elsevier B.V. All rights reserved.
Keywords: O-Ethyl benzoylthiocarbamate; Crystal structure; DFT; HF; Infrared spectrum; Molecular calculations
ꢀ
1
. Introduction
phenylenedicarbonyl)-bis(thiocarbamate) [11], and O,O -dime-
ꢀ
thyl-N,N -(m-phenylenedicarbonyl)-bis(thiocarbamate) [12].
Thiocarbamate derivatives have received much attention due
IR spectroscopy is usually considered as the most important
experimental method for chemists. The experimental and
theoretical vibrational spectrum assignment of thiocarbamate
derivatives has not been studied previously. Consideration
of all these factors motivated us to undertake the vibrational
spectroscopic studies of O-ethyl benzoylthiocarbamate.
The aim of this work is to calculate the molecular geometry
and vibrational spectra of O-ethyl benzoylthiocarbamate
by applying the Hartree–Fock and density functional using
Becke’s three-parameter hybrid method with the Lee, Yang,
and Parr correlation functional methods with 3-21G and
6-31G(d) basis sets. The calculated geometric parameters and
vibrational frequencies were analyzed and compared with
obtained experimental results.
to their interesting technological [1] and biological applica-
tions [2]. Most notably, acylthiocarbamate derivatives are used
as biosensors [3], elastase inhibitors [4], and they can exhibit
antineoplastic and antiinflammatory [5] effects. O-Alkyl-N-
acylthiocarbamate derivatives have been proposed as interme-
diates for regio- and chemoselective deoxygenation of primary
and secondary aliphatic alcohols [6]. In addition, O-alkyl-N-
aroylthiocarbamates are useful as selective extractants of heavy
metal ions in water solutions [7]. These derivatives are also
employed in studies of liquid–liquid extractions of silver(I) ions
[
8]. The synthesis, characterization and structure on some thio-
carbamate derivatives have been studied [9–15]. The crystal
structures of some derivatives have been reported in the litera-
ture are those of O-isopropyl-N-(2-furoyl)thiocarbamate [9], O-
ꢀ
ꢀ
benzyl-N-(2-furoyl)thiocarbamate [10], O,O -diethyl-N,N -(p-
2. Experimental
2.1. Synthesis
∗
Corresponding author at: Department of Chemistry, Faculty of Arts and Sci-
ence, Mersin University, Mezitli- C¸ iftlikk o¨ y u¨ Kamp u¨ s u¨ , 33343 Mersin, Turkey.
Tel.: +90 532 707 31 22; fax: +90 324 341 30 22.
A solution of benzoyl chloride (0.01 mol) in acetone (50 cm3)
E-mail address: arslanh@mersin.edu.tr (H. Arslan).
was added dropwise to a suspension of potassium thiocyanate
1
386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.09.011

H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
937
3
Table 1
(
0.01 mol) in acetone (30 cm ). The reaction mixture was heated
Summary of crystallographic data and parameters of the title compound
under reflux for 30 min, and then cooled to room temperature.
A solution of ethanol (0.01 mol) in acetone (30 cm ) was added
dropwiseandtheresultingmixturewasstirredfor2 h. Coldwater
250 cm ) was added and then the solution filtered. The solid
3
Empirical formula
Formula weight
Temperature
C10H11NO2S
209.26
120(2) K
3
(
Wavelength
0.71073 A˚
product was washed with water and purified by recrystallisation
from ethanol/dichloromethane mixture (1:1). Anal. Calcd. for
C10H11NO2S: C, 57.4.; H, 5.3; N, 6.7. Found: C, 57.2; H, 5.2;
N, 6.8.
Crystal system
Space group
Unit cell dimensions
Orthorhombic
Pna2(1)
a = 9.941(3)
A˚ , b = 9.352(3) A˚ ,
c = 10.962(3) A˚
1019.1(5) A˚
3
Volume
Z
4
3
2
.2. Instrumentation
Density (calculated)
Absorption coefficient
F(0 0 0)
1.364 Mg/m
0.290 mm
440
−
1
The room temperature attenuated total reflection Fourier
transform infrared (FT-IR ATR) spectra of the O-ethyl ben-
zoylthiocarbamate were registered using Varian FTS1000 FT-IR
Crystal size
Theta range for data collection
Index ranges
0.40 mm × 0.22 mm × 0.20 mm
◦
2.86–28.08
−13 ≤ h ≤ 13, −12 ≤ k ≤ 12,
−
1
spectrometerwithDiamond/ZnSeprism(4000–525 cm ;num-
−14 ≤ l ≤ 13
−
1
Reflections collected
Independent reflections
Completeness to theta = 28.08
7685
ber of scans: 250; resolution: 1 cm ). Elemental analyses were
carried out on a Carlo Erba MOD 1106 instrument. Single crys-
tal X-ray data were collected on a Bruker AXS Smart Apex
CCD, using monochromated Mo K␣ radiation. The structure
was solved by direct and conventional Fourier methods. Full-
2135 [R(int) = 0.0497]
99.2%
Semi-empirical from equivalents
0.9443 and 0.8929
◦
Absorption correction
Maximum and minimum
transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F
Final R indices [I > 2σ(I)]
R indices (all data)
2
Full-matrix least-squares on F2
2135/1/127
1.059
matrix least-squares refinement based on F . All but hydrogen
atoms refined anisotropically, H-atoms on idealized positions
with ‘riding’ model. Programs used for calculations: SHELXTL
16]. Further details concerning data collection and refinement
2
R1 = 0.0444, wR2 = 0.1014
R1 = 0.0524, wR2 = 0.1052
0.14(12)
0.342 and −0.278 einstein A˚
[
are given in Table 1.
Absolute structure parameter
Largest difference between
peak and hole
−
3
2
.3. Calculations
The molecular structure of the O-ethyl benzoylthiocarbamate
in the ground state is optimized by Hartree–Fock and den-
sity functional using Becke’s three-parameter hybrid method
with the Lee, Yang, and Parr correlation functional meth-
ods with the standard 3-21G and 6-31G(d) basis sets. The
vibrational frequencies were also calculated with these meth-
ods. These calculations were carried out using Gaussian 03W
program package on a double Xeon/3.2 GHz processor with
2
2
tances show usual C sp –N sp single bond character. Thus ␲–␲
conjugation is observed along the S(1)–C(8)–O(2), but not along
O(1)–C(7)–N(1) and N(1)–C(8)–S(1), as reported by Schr o¨ der
˚
et al. [21] and Morales et al. [9]. S(1)–C(8) (1.619(3) A) and
˚
O(1)–C(7) (1.205(3) A) are double bonds. O(1)–C(7) bond
length compares well with that from other thiourea deriva-
tives (d(C O) = 1.213(3) [22]; 1.224(2) [23]; 1.216(2) [24]) but
S(1)–C(8) bond is shortened (d(C S) = 1.676(4) [25]; 1.664(2)
4
GB RAM [17]. The frequency values computed at these lev-
els contain known systematic errors [18]. We therefore, have
used the scaling factor values of 0.8929, 0.9613, 0.9085, and
[
22]; 1.6696(17) [23]; 1.666(2) [24]). Crystal packing shows
intermolecular hydrogen bonds N1–H· · ·O1(x + 0.5, −y + 0.5,
0
.9614 for HF/6-31G(d), B3LYP/6-31G(d), HF/3-21G, and
z) which link molecules to endless rows along [1 0 0].
B3LYP/3-21G, respectively [19]. The assignment of the cal-
culated wavenumbers is aided by the animation option of
GaussView 3.0 graphical interface for gaussian programs, which
gives a visual presentation of the shape of the vibrational modes
The structure of the title compound shown in Fig. 1 is very
flexible. It has got several conformations (Fig. 3). To establish
the most stable conformation as the initial point for further
calculations, the molecule was submitted to a rigorous confor-
mation analysis around the free rotation bonds. This study was
performed with the software Spartan 04 [26]. Energetics gath-
ered in Table 3 shows 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 4. Therefore,
further in this paper, we focus on this particular form of the title
compound.
[
20].
3
. Results and discussion
The molecular structure and packing diagram of O-ethyl ben-
zoylthiocarbamate is depicted in Figs. 1 and 2, respectively.
Selected bond lengths and angles of the compound are pre-
˚
sented in Table 2. The C(8)–O(2) bond distance (1.318(3) A)
indicates double bond character in agreement with literature
The optimized structure parameters of O-ethyl benzoylth-
iocarbamate calculated at ab initio-HF and density functional
theory-B3LYP levels with the standard 3-21G and 6-31G(d)
˚
˚
data (d(C–O) = 1.290(6) A [9] and d(C–O) = 1.300(7) A [15].
˚
˚
The C(7)–N(1) (1.378(3) A) and C(8)–N(1) (1.370(3) A) dis-

9
38
H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
Fig. 1. The structure of O-ethyl benzoylthiocarbamate. Thermal ellipsoids are shown at the 50% probability level.
Fig. 2. The crystal packing viewed along [0 0 1] with hydrogen bonds as dashed lines. H-atoms not involved are omitted.

H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
939
Table 2
The experimental and calculated structure parameters of the O-ethyl benzoylthiocarbamate
Parameters
Experimental
Calculated (6-31G(d))
HF
Calculated (3-21G)
HF
B3LYP
B3LYP
Bond lengths ( A˚ )
S(1)–C(8)
O(1)–C(7)
O(2)–C(8)
O(2)–C(9)
N(1)–C(8)
N(1)–C(7)
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)
r
1.619(3)
1.205(3)
1.318(3)
1.449(3)
1.370(3)
1.378(3)
1.373(4)
1.391(4)
1.371(4)
1.373(4)
1.373(4)
1.390(4)
1.481(3)
1.478(4)
1.642
1.185
1.317
1.432
1.367
1.397
1.382
1.391
1.387
1.385
1.385
1.390
1.501
1.516
0.9924
1.645
1.213
1.352
1.448
1.384
1.407
1.392
1.402
1.398
1.396
1.395
1.403
1.503
1.520
0.9937
1.700
1.204
1.335
1.465
1.352
1.400
1.380
1.387
1.385
1.384
1.383
1.387
1.492
1.524
0.9891
1.693
1.231
1.353
1.485
1.375
1.409
1.391
1.401
1.398
1.397
1.395
1.401
1.500
1.528
0.9906
◦
Bond angles ( )
C(8)–O(2)–C(9)
C(8)–N(1)–C(7)
C(2)–C(1)–C(6)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
C(5)–C(4)–C(3)
C(4)–C(5)–C(6)
C(5)–C(6)–C(1)
C(5)–C(6)–C(7)
C(1)–C(6)–C(7)
O(1)–C(7)–N(1)
O(1)–C(7)–C(6)
N(1)–C(7)–C(6)
O(2)–C(8)–N(1)
O(2)–C(8)–S(1)
N(1)–C(8)–S(1)
O(2)–C(9)–C(10)
r
119.0(2)
127.5(2)
119.9(3)
120.3(3)
120.2(2)
120.4(3)
119.8(3)
119.4(2)
123.0(2)
117.5(2)
122.2(2)
122.3(2)
115.5(2)
107.0(2)
125.3(2)
127.71(19)
107.0(2)
122.9
130.2
120.2
120.0
120.1
120.0
120.2
119.5
123.2
117.2
124.1
122.2
113.7
106.4
126.1
127.5
110.9
0.9633
120.4
129.9
120.4
120.1
120.0
120.1
120.3
119.3
123.8
116.9
123.9
122.5
113.7
105.7
126.7
127.5
110.1
0.9784
123.3
129.6
120.3
119.9
120.1
120.0
120.0
119.7
123.8
116.5
123.6
122.4
113.9
107.0
124.7
128.3
109.7
0.9695
119.2
128.7
120.5
119.9
119.9
120.1
120.1
119.4
124.8
115.7
123.6
122.4
113.9
105.9
126.0
128.1
109.9
0.9806
◦
˚
basis sets are listed in Table 2 in accordance with the atom
numbering scheme given in Fig. 1. The correlation between the
experimental and calculated geometric parameters obtained by
the several methods is shown in Table 2. Owing to our calcula-
tions, DFT method correlates well for the bond length and angle
compare with the HF method. The largest difference between
experimental and calculated DFT bond length and angle is about
0.042 A and 3.1 for the 6-31G(d) basis set. As a result, the opti-
mized bond lengths and angles by DFT method show the best
agreement with the experimental values.
FT-IR spectrum of O-ethyl benzoylthiocarbamate is given in
Fig. 4. Table 4 lists the vibrational frequencies obtained using
ab initio-HF/6-31G(d), 3-21G and DFT-B3LYP/6-31G(d) and 3-
21G calculations together with the experimental frequencies and
Table 3
Energies of the different conformations of the title compound calculated at the DFT-B3LYP/6-31G(d) level
Conformer
E (Hartree)
ꢀE (kcal/mol)
E0 (Hartree)
Dipole moment (D)
1
2
3
4
5
6
7
8
−991.089382
−991.088162
−991.088059
−991.084483
−991.083553
−991.083490
−991.078116
−991.076703
0.0000
0.7655
0.8298
3.0743
3.6578
3.6973
7.0693
7.9557
124.565600
124.666710
124.678950
124.290090
124.401190
124.380160
124.537420
124.473490
2.4784
2.3349
2.4229
5.9063
5.7150
5.7716
5.5980
5.1666
E: total energies; E0: energies corrected for zero-point energy vibrational.

9
40
H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
Table 4
Experimental and calculated vibrational frequencies (in cm 1) of O-ethyl benzoylthiocarbamate
−
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.
3
3
3
3
3
3
3
3
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
256, w
106, vw
090, vw
076, vw
065, vw
060, vw
042, vw
030, vw
993, w
963, w
942, vw
697, s
3865
3411
3393
3383
3371
3362
3355
3310
3285
3277
3217
2024
1809
1783
1720
1669
1657
1645
1630
1613
1577
1547
1475
1463
1428
3451
3046
3030
3021
3010
3002
2996
2955
2933
2926
2872
1807
1615
1592
1536
1490
1480
1469
1455
1440
1408
1381
1317
1306
1275
58.96 3591
3.94 3228
20.36 3214
29.88 3203
8.18 3193
1.51 3184
12.02 3158
26.93 3142
44.24 3128
17.10 3093
22.14 3062
262.47 1811
19.02 1661
4.06 1640
588.31 1553
14.85 1539
19.17 1533
2.83 1515
2.17 1513
6.90 1494
40.58 1442
32.70 1421
9.65 1369
199.84 1359
753.82 1348
3452
3103
3090
3079
3069
3061
3036
3020
3007
2973
2944
1741
1597
1577
1493
1479
1474
1456
1454
1436
1386
1366
1316
1306
1296
27.99
4.69
19.52
24.47
3.35
7.22
19.22
6.24
21.50
30.71
17.68
149.80
10.71
3.38
379.77
95.87
82.44
3.36
33.27
5.06
41.67
54.53
1.40
3792
3402
3389
3378
3367
3358
3344
3297
3284
3271
3215
1947
1777
1752
1694
1675
1670
1661
1658
1621
1577
1544
1505
1456
1432
3445
3091
3079
3069
3059
3051
3038
2995
2984
2972
2921
1769
1614
1592
1539
1522
1517
1509
1506
1473
1433
1403
1367
1323
1301
74.11 3530
3.70 3233
7.91 3222
18.74 3211
6.73 3200
0.66 3190
8.18 3165
13.86 3142
26.41 3132
8.88 3095
13.60 3067
166.58 1742
13.41 1633
5.11 1614
482.90 1572
5.06 1553
47.28 1552
64.98 1539
6.92 1525
6.53 1504
12.83 1459
17.74 1416
9.29 1392
109.18 1349
861.18 1337
3394
3108
3098
3087
3076
3067
3043
3021
3011
2976
2949
1675
1570
1552
1511
1493
1492
1480
1466
1446
1403
1361
1338
1297
1285
33.17
6.46
8.36
15.02
2.93
8.69
νNH
νCH, sym, Ph
νCH, sym, Ph
νCH, asym, Ph
νCH, asym, Ph
νCH, asym, Ph
νCH, asym, et
νCH, asym, et
νCH, asym, CH3
νCH, sym, CH2
νCH, sym, CH3
12.38
2.10
19.12
20.56
13.16
84.93
8.68
7.40
11.46
5.54
119.85
156.56
206.86
11.59
13.01
33.64
29.24
135.81
366.54
νC
O
598, w
582, vw
518, s
νCC
νCC
δNH
489, m
472, m
452, m
449, w
437, w
388, w
358, vw
325, w
306, m
289, vs
δNH + δCH, Ph
δCH, CH3 + δNH
δCH, CH3
δCH, CH2
δCH, Ph + νCC
δCH, et
δCH, et
δCH, Ph
279.76
74.32
νCC + δCH, Ph
δCH, Ph +
νCN + δCH, CH3
νCN + δCH,
CH3 + νC–O
νCC + νCN + δCH,
Ph
1
1
264, vs
232, m
1400
1348
1250
1204
201.05 1330
85.75 1271
1279
1222
319.24
111.02
1372
1362
1246
1237
136.90 1323
19.60 1256
1272
1208
170.29
84.60
1182, vs
1175, vs
1158, vs
1149, s
1335
1305
1290
1246
1192
1165
1152
1113
507.51 1217
23.65 1208
73.91 1196
10.77 1171
1170
1161
1150
1126
11.86
328.14
2.74
1335
1314
1275
1258
1213
1194
1158
1143
9.06 1245
374.99 1232
174.68 1197
2.81 1150
1197
1184
1151
1106
67.98
16.11
160.68
225.91
δCH, Ph
δNH + δCH, Ph
δCH, Ph + νC
νC–O + δCH,
S
232.19
CH3 + δCH, Ph
δNH + δCH, Ph
δCH, Ph + δCH,
CH3
1
1
094, s
073, m
1228
1207
1096
1078
3.76 1141
46.14 1123
1097
1080
8.53
16.29
1231
1209
1118
1098
29.21 1138
16.99 1131
1094
1087
16.61
4.14
1
060, w
1187
1060
4.38 1109
1066
62.35
1202
1092
1.36 1087
1045
157.37
δCH, Ph + δCH,
CH3
1
1
030, m
011, vs
1141
1136
1019
1014
49.55 1062
10.08 1039
1021
999
17.04
131.29
1181
1171
1073
1064
88.01 1063
1.17 1052
1022
1011
2.85
6.58
δCH, Ph + δCO
νCN + ␯CC + δCH,
Ph
995, s
962, m
932, s
1117
1113
1091
997
994
974
108.08 1018
0.37 1008
979
969
943
8.21
0.36
1.46
1140
1124
1112
1036
1021
1010
5.74 1041
60.51 1021
31.18 1017
1001
982
978
38.10
2.29
137.82
δCCC, Ph + νCO
γCH, Ph
γCH, Ph + γCCC,
Ph
1.49
981
9
9
16, m
10, m
1065
1014
951
905
3.28
50.29
945
941
908
905
15.51
31.70
1088
1001
988
909
131.22
26.35
970
939
933
903
1.73
41.80
γCH, Ph
γCH, Ph + γCH,
CH3
857, m
812, w
799, m
753, m
715, m
705, vs
964
931
893
875
802
796
861
831
797
781
716
711
0.56
16.08
7.89
2.78
118.13
12.72
866
858
815
806
752
721
832
825
783
775
723
693
0.73
7.09
4.82
5.49
3.87
58.40
997
965
909
898
890
813
906
877
826
816
809
739
0.56
65.36
15.62
164.37
22.89
64.95
876
857
841
831
775
739
842
824
809
799
745
710
0.25
13.39
3.55
9.30
161.19
7.98
γCH, Ph
γCH, Ph
γCH, et
γCH, Ph
δCCC, Ph + νCO
γCH,
Ph + νC S + δCNC
γCCC, Ph
δCCC, Ph
6
6
6
6
85, vs
77, vs
35, s
765
750
728
678
683
670
650
605
10.16
56.75
31.55
1.28
700
681
665
633
673
655
639
609
0.67
41.81
48.74
0.69
793
777
717
710
720
706
651
645
6.82
13.19
42.17
0.86
730
720
678
658
702
692
652
633
31.09
5.94
30.20
0.93
γNH
15, s
γCCC, Ph

H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
941
Table 4 (Continued)
Experimental HF/6-31G(d)
DFT-B3LYP/6-31G(d)
HF/3-21G
DFT-B3LYP/3-21G
Assignments
Calc.
Corr.
Inten.
Calc.
Corr.
Inten.
Calc.
Corr.
Inten.
8.32
Calc.
Corr.
Inten.
5
5
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
92, s
80, m
657
636
536
477
456
450
368
345
286
244
230
185
137
114
79
587
568
479
426
407
402
329
308
255
218
205
165
122
102
71
33.19
4.27
5.02
6.32
0.43
2.05
10.81
5.88
3.79
0.42
1.38
0.76
3.21
1.61
0.87
0.43
0.72
0.12
610
593
490
441
420
417
341
324
268
222
220
172
121
101
73
586
570
471
424
404
401
328
311
258
213
211
165
116
97
24.05
7.20
3.38
3.85
1.40
0.12
6.46
4.98
3.94
2.27
0.09
0.94
2.96
1.35
0.76
0.42
0.59
0.08
662
597
539
473
470
464
369
337
288
260
220
192
157
118
79
601
542
481
422
420
414
329
301
257
232
196
171
140
105
71
607
569
487
440
428
426
348
321
273
228
226
181
139
109
76
584
547
468
423
411
410
335
309
262
219
217
174
134
105
73
12.83
8.54
3.77
1.19
1.64
2.58
6.43
8.61
5.23
2.34
1.69
1.46
3.05
1.18
0.81
0.34
0.64
0.55
γNH
3.85
7.99
1.30
3.13
4.29
11.95
9.58
5.52
1.57
2.51
1.17
3.81
1.19
0.92
0.55
1.14
0.30
γCH, et + γCOC
τCCCC + τCCCN
δCCO
τCCCC + τCCNC
τCCCC
δCO
τCOC2H5
τCOC2H5
τCCCH, et
τCCCN
τCCCC + τCCNC
τCNCO
τSCOC2H5
τSCOC2H5
τCNCO
70
64
37
29
69
40
31
62
36
28
67
38
30
72
43
31
64
38
28
71
40
28
68
38
27
τCNCO
τCNCS, τCCNC
s, strong; vs, very strong; m, medium; w, weak; vw, very weak; blank, not observed or measured; ν, stretching; δ, in-plane bending; γ, out-of-plane bending; τ,
torsion; sym, symmetric; asym, asymmetric; et, ethyl group; Ph, phenyl group.
the approximate description of each normal modes. The vibra-
tional bands’ assignments have been made by using GausView
molecular visualization program. To make comparison with
experimental, we present correlation graphics in Figs. 5 and 6
based on calculations. As we can see from Figs. 5 and 6, exper-
imental fundamentals are in better agreement with the scaled
fundamentals and are found to have a good correlation for DFT-
B3LYP than HF.
Fig. 3. Eight stable conformers of the title compound calculated at HF/6-31G(d) level.

9
42
H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
Fig. 4. FT-IR spectrum of O-ethyl benzoylthiocarbamate recorded at room temperature.
In the heterocyclic compounds, νN–H vibration occurs
3
1G(d)), 189 cm 1 (HF/3-21G) and 138 cm (DFT/3-21G).
− −1
−
1
in the region 3500–3000 cm . The IR band appearing at
This striking discrepancy can come from the formation of inter-
molecular hydrogen bonding with N–H. This interpretation is
verifying with νC O stretching vibration mode. The difference
−1
3
256 cm
is assigned to νN–H stretching mode of vibra-
tions. This vibration mode calculated at 3451, 3452, 3445
−
1
−
1
−1
and 3394 cm for HF and DFT methods. This band is cal-
between experimental (1697 cm ) and calculated (1741 cm
−
1
−1
with DFT-B3LYP/6-31G(d) method) νC O is about 44 cm 1. It
can be easily observed in the correlation graphics of calculated
and experimental frequencies of the title compound that the big
difference is observed for νN–H and ␯C O stretching vibrations
−
culated and observed at 3632 cm (non-scaling), 3491 cm
scalling; 0.9613) and 3236 cm
−
1
(
(
by Zhou et al. for N-
morpholinothiocarbonyl)benzamide, respectively [27]. The
difference between experimental and calculated νN–H stretching
−
1
−1
mode is about 196 cm (DFT/6-31G(d)), 195 cm (HF/6-
(Fig. 5).
Fig. 5. Correlation graphics of calculated and experimental frequencies of the
title compound.
Fig. 6. Correlation graphics of calculated and experimental frequencies of the
title compound.

H. Arslan et al. / Spectrochimica Acta Part A 67 (2007) 936–943
943
Characteristic aromatic νC–H stretching vibrations of sub-
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1
stituted benzenes are expected to appear in 3050–3100 cm
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[
[
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1
pound have been observed at 1598, 1582, 1437 and 1306 cm
.
6
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[
[
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1
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1
δ
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(
PhH
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iocarbamate by using B3LYP and HF method with the standard
3
-21G and 6-31G(d) basis sets. We have used the scaling factor
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Acknowledgement
[
3
This work was supported by the Mersin University Research
Fund (project no. BAP.ECZ.F.TB.(HA).2006-1).
[