Spectroscopic investigations and computational study of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl acetate

Article abstract of DOI:10.1002/jrs.2492

The Fourier transform Raman(FT-Raman)and Fourier transform infrared (FT-IR) spectraof2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl acetate were studied. The vibrational wavenumbers were examined theoretically using the Gaussian03 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. The simultaneous Raman and infrared (IR) activations of the C=O stretching mode in the carbamoylmoiety show a charge transfer interaction through a π-conjugated path. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of the C=O bond and increases the double bond character of the C-N bonds. The first hyperpolarizability and predicted IR intensities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar structures, which makes this compound an attractive object for future studies of nonlinear optics.Optimized geometrical parameters of the compound are in agreement with similar reported structures.

Full text of DOI:10.1002/jrs.2492

Research Article
Received: 21 May 2009
Accepted: 18 August 2009
Published online in Wiley Interscience: 6 October 2009
(www.interscience.wiley.com) DOI 10.1002/jrs.2492
Spectroscopic investigations and
computational study of 2-[acetyl(4-bromo-
phenyl)carbamoyl]-4-chlorophenyl acetate
C. Yohannan Panicker,a∗ Hema Tresa Varghese,b K. C. Mariamma,c
Koshy John,d Samuel Mathew,e Jarmila Vinsova,f Christian Van Alsenoyg
and Y. Sheena Maryh
TheFouriertransformRaman(FT-Raman)andFouriertransforminfrared(FT-IR)spectraof2-[acetyl(4-bromophenyl)carbamoyl]-
4-chlorophenyl acetate were studied. The vibrational wavenumbers were examined theoretically using the Gaussian03 set
of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. The
simultaneous Raman and infrared (IR) activations of the C O stretching mode in the carbamoyl moiety show a charge transfer
interaction through a π-conjugated path. From the optimized structure, it is clear that the hydrogen bonding decreases the
doublebondcharacteroftheC ObondandincreasesthedoublebondcharacteroftheC–Nbonds. Thefirsthyperpolarizability
and predicted IR intensities are reported. The calculated first hyperpolarizability is comparable with the reported values of
similarstructures, which makesthiscompoundan attractiveobjectforfuturestudiesofnonlinearoptics. Optimizedgeometrical
c
parameters of the compound are in agreement with similar reported structures. Copyright ꢀ 2009 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: salicylanilide; acetate; carbamoyl; FT-IR spectra; FT-Raman spectra; DFT and PED calculations
Introduction
(DFT) methods. Biagi et al.[17] reported the synthesis and biological
activity of novel, substituted benzanilides as potassium channel
activators. The spin-trapping behavior of carbamoyl substituted
derivatives toward different oxygen- and carbon-centered radicals
has been reported.[18] Kinetics and mechanism for the reactions of
N-methyl-N-phenylcarbamoyl chlorides with benzylamines in ace-
tonitrile were reported by Koh et al.[19] Matyk et al.[20] reported the
synthesis of a series of 64 derivatives of substituted heterocyclic
analogues of salicylanilides, and the compounds were evaluated
Salicylanilides have been the subject of intense interest in
medicinal chemistry, because of their ability to serve as inhibitors
of the protein tyrosine kinase epidermal growth factor receptor
relating to cancer, psoriasis and restenosis.[1,2] Salicylanilides
(2-hydroxy-N-phenylbenzamides) have been reported as a class of
compounds with a wide variety of interesting biological activities,
including antimycobacterial and antifungal effects.[1,3–9] They act
as inhibitors of the two-component regulatory system (TCS) in
bacteria.[10,11] The importance of electron-attracting substituents
in the salicyloyl ring and hydrophobic groups in the anilide moiety
for optimal activity has been noted, and the removal of the
2-OH group has been reported to result in the loss of activity.[10]
Imramovsky et al.[12] reported the synthesis and characterization
of a series of novel, highly antimicrobial salicylanilide esters of N-
protected amino acids. Anion-triggered, substituent-dependent
conformational switching of salicylanilides was reported by
Guo et al.[13] The synthesis and antimicrobial evaluation of
a series of variously ring-substituted salicylanilide acetates
were reported by Vinsova et al.[5] Boyce et al.[14] described the
structure–activity-relationship-guided conversion of bioactive
salicylanilides into a comparably bioactive derivative, which
was utilized as a tool for protein identification. Dahlgren et al.[6]
reported the design, synthesis and multivariate quantitative
structure–activity relationship of salicylanilides, and Singh
et al.[15] reported the synthesis of 5-chloro-3ꢁ-nitro-4ꢁ substituted
salicylanilides. Arslan et al.[16] reported the molecular structure
and vibrational spectra of 2-chloro-N-(diethylcarbamothioyl)
benzamide by Hartree–Fock (HF) and density functional theory
∗
Correspondenceto:C. Yohannan Panicker,DepartmentofPhysics,TKMCollege
of Arts and Science, Kollam 691005, Kerala, India.
E-mail: cyphyp@rediffmail.com
a
b
c
DepartmentofPhysics,TKMCollegeofArtsandScience,Kollam691005,Kerala,
India
Department of Physics, Fatima Mata National College, Kollam 691001, Kerala,
India
Department of Chemistry, M. E. S. College, Nedumkandam 685553, Kerala,
India
d
e
f
Department of Chemistry, Mar Thoma College, Thiruvalla 689103, Kerala, India
Department of Physics, Mar Thoma College, Thiruvalla 689103, Kerala, India
Department of Inorganic and Organic Chemistry, Charles University, 500 05
Hradec Kralove, Czech Republic
g
h
Department of Chemistry, University of Antwerp, B2610 Antwerp, Belgium
Thushara, Neethinagar-64, Pattathanam 691021, Kerala, India
c
J. Raman Spectrosc. 2010, 41, 707–716
Copyright ꢀ 2009 John Wiley & Sons, Ltd.

C. Y. Panicker et al.
for in vitro antimycobacterial activity against Mycobacterium
tuberculosis, M. avium and two strains of M. kansasii. Methylene
group modifications of the N-(isothiazol-5-yl)phenylacetamides
synthesis and insecticidal activity were reported by Samaritoni
et al.[21] Several works have reported on the antimycobacterial
benzylsalicylamides,[22,23] and the activity of isoesters of sali-
cylanilides: 2-sulfanylbenzanilides, N-benzylsulfanylbenzamides
3-hydroxy picolinanilides, N-benzyl-3-hydroxypicolinamides.[24]
Vibrational spectroscopic study of acetate group was reported by
Ibrahim and Koglin.[25] Computational study of the IR spectrum
of acetic acid, its cyclic dimer and its methyl ester was reported
by Lewandowski et al.[26] The molecular structure of acetic
acid has been studied in the gas phase by both microwave
spectroscopy[27,28] and electron diffraction.[29] The assessment
of solid-state composition of an active salicylanilide compound
(N-[5-chloro-4-[(4-chlorophenyl)cyanomethyl]-2-methylphenyl]-
2-hydroxy-3,5-diiodobenzamide by FT-Raman spectroscopy
was reported by Spiegeleer et al.[30] Diclofenac sodium, which
consists of a phenylacetate group, a secondary amino group
and a dichlorophenyl ring, is a well-known representative of
nonsteroidal antiinflammatory drugs.[31] The present study is
on the analysis of FT-IR and FT-Raman spectra of 2-[acetyl(4-
bromophenyl)carbamoyl]-4-chlorophenylacetate; using the
computational method, theoretical wavenumbers have also been
calculated. This work is a part of our investigations of substituted
salicylanilide derivatives. The authors have reported the spectro-
scopic studies of 4-chloro-2-(4-bromophenylcarbamoyl)phenyl
acetate[32] and 4-chloro-2-(3,4-dichloro phenyl carbamoyl)
phenyl acetate.[33] To our knowledge, no theoretical HF or DFT
calculations, or detailed vibrational IR and Raman analyses, have
been performed on the title compound. A detailed quantum
chemical study will aid in understanding the vibrational modes of
the title compound and clarifying the experimental data available
for this molecule. DFT calculations are known to provide excellent
vibrational wavenumbers of organic compounds if the calculated
wavenumbers are scaled to compensate for the approximate
treatment of electron correlation, for basis set deficiencies and for
the anharmonicity effects.[34–39] DFT is now accepted as a popular
post-HF approach for the computation of molecular structure,
vibrational wavenumbers and energies of molecules by the ab
initio community.[40] In this work, by using HF, B3PW91 and B3LYP
methods we calculated the vibrational wavenumbers of the title
compound in the ground state to distinguish the fundamentals
from the many experimental vibrational wavenumbers and
geometric parameters. These calculations are valuable for
providing insight into the vibrational spectrum and molecular
parameters.
Experimental
The chemicals were purchased from Aldrich, USA. Melting point
(uncorrected) was determined on a Kofler block. Elemental
analyses were performed on an automatic microanalyser CHNS-O
CE instrument (FISONS EA 1110, Milano, Italy). Nuclear magnetic
resonance (NMR) spectra were measured in CDCl3 solution at
ambient temperature on a Varian Mercury-VxBB 300 spectrometer
(299.95 MHz for 1H and 75.43 MHz for 13C; Varian, Palo Alto,
CA, USA). The chemical shifts δ are given in ppm referenced
to tetramethylsilane (TMS) as internal standard. The coupling
constants (J) are reported in hertz. Mass spectra were measured
on ABI/MSD SCIEX API 3000 LC/MS/MS system (MSD SCIEX,
Concord, ON, Canada). The reaction was monitored and the
purity of the products checked by thin layer chromatography
(TLC) (Silufol UV 254, Kavalier Votice, Czech Republic and Merck
TLC plate Silica gel 60 F254). The plates were visualized using UV
light.
The FT-IR spectrum (Fig. 1) was recorded on a DR/Jasco FT-
IR-6300 spectrometer in KBr pellets. The spectral resolution was
4 cm−1. The FT-Raman spectrum (Fig. 2) was obtained on a Bruker
RFS 100/S, Germany. For excitation of the spectrum, the emission
of a Nd : YAG laser was used, with excitation wavelength 1064 nm
and maximal power 150 mW. The measurements were on solid
samples. One thousand scans were accumulated with a total
registration time of about 30 min. The spectral resolution after
apodization was 2 cm−1. The expanded IR and Raman spectra in
the region 500–2000 and 200–1800 cm−1 are given in Figs S1 and
S2 (Supporting Information).
N-(4-Bromophenyl)-5-chloro-2-hydroxyl benzamide (5 mmol)
was dissolved in chlorobenzene (15 ml), and acetyl chloride
was added (20 mmol). The mixture was refluxed for 5 h, and
concentrated to dryness in a vacuum evaporator. The crude
product was purified by crystallization from ethyl acetate.
Yield 45%; m.p. 114–116 ◦C; Anal./Calc. for C17H13BrClNO4
(410.65): 49.72% C, 3.19% H, 3.41% N; found: 50.09% C, 3.55%
H, 3.42% N; MS: 411.7(M + 1)+; 1H-NMR δ: 7.55–7.47(m, AAꢁ BBꢁ,
2H, H3ꢁ, H5ꢁ), 7.38–7.32 (m, 2H, H4, H6), 7.08–6.99 (m, 3H, H3, H2ꢁ,
H6ꢁ), 2.39 (s, 3H, CH3), 2.3 (s, 3H, CH3); 13C-NMR δ: 172.5, 168.5,
167.6, 145.8, 136.9, 132.8, 131.8, 131.3, 130.1, 128.7, 126.2, 124.5,
122.9, 25.9, 20.9.
Figure 1. FT-IR spectrum of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenylacetate.
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
J. Raman Spectrosc. 2010, 41, 707–716

Spectroscopic study of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl
Figure 2. FT-Raman spectrum of 2-[acetyl(4-bromophenyl)carbamoyl]-4- chlorophenyl acetate.
Computational Details
Calculations of the title compound were carried out
with Gaussian03 software program[41] using the HF/6–31G∗,
B3PW91/6–31G∗ and B3LYP/6–31G∗ basis sets to predict the
molecular structure and vibrational wavenumbers. Calculations
were carried out with Becke’s three-parameter hybrid model us-
ing the Lee–Yang–Parr correlation functional (B3LYP) method.
Molecular geometries were fully optimized by Berny’s optimiza-
tion algorithm using redundant internal coordinates. Harmonic
vibrational wavenumbers were calculated using analytic second
derivatives to confirm the convergence to minima on the poten-
tial surface. At the optimized structure (Fig. 3) of the examined
species, no imaginary wavenumbers were obtained, proving that
Figure 3. Optimized geometry of the molecule.
a true minimum on the potential surface was found. Parameters
corresponding to optimized geometries of the title compound are
given in Table S1 (Supporting Information). The DFT hybrid B3LYP
functional tends also to overestimate the fundamental modes;
therefore scaling factors have to be used for obtaining a consid-
erably better agreement with the experimental data. Therefore,
scaling factors of 0.9613 and 0.8929 were uniformly applied to the
DFT and HF calculated wavenumbers.[42] The observed disagree-
ment between theory and experiment could be a consequence
of the anharmonicity and of the general tendency of the quan-
tum chemical methods to overestimate the force constants at
the exact equilibrium geometry. The potential energy distribu-
tion (PED) was calculated with the help of GAR2PED software
package.[43]
C–Cl and C–Br vibrations
The vibrations belonging to the bond between the ring and
chlorineatomsareworthdiscussingheresincemixingofvibrations
is possible due to the lowering of the molecular symmetry and
the presence of heavy atoms on the periphery of the molecule.[44]
Mooney[45,46] assigned vibrations of C–Cl, C–Br and C–I in the
wavenumber range of 1129–480 cm−1. The C–Cl stretching gives
generally strong bands in the region 710–505 cm−1. For simple
organic chlorine compounds, C–Cl absorptions are in the region
750–700 cm−1.Sundaraganesanet al.[47] reportedC–Clstretching
at 704 (IR), 705 (Raman) and 715 (DFT) and the deformation
bands at 250 and 160 cm−1. The aliphatic C–Cl bands absorb[48]
at 830–560 cm−1, and putting more than one chlorine on a
carbon atom raises the C–Cl wavenumber. The C–Cl2 stretching
mode is reported at around 738 cm−1 for dichloromethane and
Results and Discussion
the scissoring mode δCCl2 at around 284 cm−1 [48,49]
Pazdera
.
IR and Raman spectra
et al.[50,51] reported the C–Cl stretching mode at 890 cm−1. For
2-cyanophenylisocyanide dichloride, the C–Cl stretching mode is
reported at 870 (IR), 877 (Raman) and 882 cm−1 (theoretical).[52]
Arslan et al.[16] reported the C–Cl stretching mode at 683
The observed IR and Raman bands with their relative intensities
and calculated scaled wavenumbers and assignments are given in
Table 1.
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
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C. Y. Panicker et al.
Table 1. Calculated vibrational wavenumbers (scaled), measured infrared and Raman bands positions and assignments of 2-[acetyl(4-
bromophenyl)carbamoyl]-4-chlorophenylacetate
HF/6–31G∗
B3PW91/6–31G∗
B3LYP/6–31G∗
υ
IR
υ
IR
υ
IR
IR
Raman
(cm−1
)
intensity
(cm−1
)
intensity
(cm−1
)
intensity
υ(cm−1
)
υ(cm−1
)
Assignmentsa
3077
3056
3049
3046
3046
3029
3026
2983
2980
2952
2950
2886
2879
1714
1682
1639
1612
1610
1593
1587
1502
1492
1469
1458
1455
1451
1417
1415
1399
1399
1324
1322
1287
1276
1223
1206
1199
1191
1187
1180
0.47
3.23
3155
3135
3133
3131
3129
3113
3113
3086
3077
3042
3041
2964
2959
1704
1649
1609
1599
1598
1591
1573
1492
1476
1466
1457
1452
1451
1400
1399
1397
1394
1336
1334
1309
1309
1267
1251
1213
1198
1183
1171
0.14
2.52
3145
3128
3122
3120
3120
3102
3100
3068
3062
3025
3025
2957
2949
1689
1632
1592
1584
1584
1577
1558
1487
1471
1470
1461
1456
1455
1403
1397
1394
1388
1312
1311
1309
1292
1267
1234
1200
1188
1181
1158
0.19
2.17
3158 w
3151 w
υC2H8 (91)
υC5H9 (99)
–
3136 w
0.72
0.17
0.46
–
–
υC28H30 (58) υC23H26 (21) υC27H29 (14)
υC1H7 (91)
5.95
4.33
0.44
–
–
0.29
0.36
4.94
–
–
υC23H26 (60) υC28H30 (23) υC22H21 (12)
υC22H21 (80) υC28H30 (18)
υC22H21 (80) υC23H26 (18)
υasMe I (97)
3.59
1.06
3.49
–
–
4.91
5.72
4.05
3090 w
3070 m
3082 w
3071 vs
5.74
4.01
5.38
9.56
7.46
8.89
υasMe II (93)
2.46
2.19
2.33
–
–
–
υasMe I (79) υasMe II (15)
υasMe II (84) υasMe I (13)
υsMe II (100)
3.06
1.32
2.35
3012 sh
2.27
1.45
1.72
2952 w
2963 w
2937 s
1733 m
1686 vs
1602 s
1589 s
–
3.01
2.74
2.76
2937 w
υsMe I (99)
247.39
94.15
538.84
20.73
3.14
170.63
58.32
304.44
23.29
11.31
6.82
165.47
55.95
280.31
29.67
23.27
5.68
1753 vs
υC12O13 (78)
1685 vs
υC32O33 (52) υC18O19 (21)
υC18O19 (42) υC32O33 (20)
υPh I (69)
–
1586 w
–
υPh II (60)
0.30
–
–
υPh I (72)
20.56
127.00
110.51
14.76
15.13
25.94
25.59
30.29
44.65
84.43
78.94
403.83
1.86
32.31
109.83
80.78
15.83
15.31
10.81
38.67
13.78
24.93
115.15
85.00
49.95
8.49
35.00
98.30
55.51
37.10
16.16
10.40
29.98
26.20
43.52
3.11
1559 w
–
υPh II (54) δCHC II (11)
δCHC I (60) υPh I (33)
δCHC II (36) δasMe II (14) υPh II (23)
δasMe II (76)
1490 s
1488 w
1472 w
–
–
–
–
–
–
δasMe I (96)
1453 w
1433 wbr
–
δasMe II (71)
1428 w
–
δasMe I (80)
δsMe I (92)
1397 s
1393 w
1369 s
–
–
δsMe II (90)
–
υPh I (39) δCHC I (45)
δCHC II (19) υPh II (39)
υPh II (81)
117.26
81.54
2.35
1385 w
–
–
–
δCHC I (90)
317.35
291.48
193.75
366.44
6.41
56.58
249.87
56.23
471.37
19.17
10.16
5.50
7.65
1304 s
–
1305 m
1282 w
1270 w
1222 m
–
υPh I (94)
291.12
28.45
504.41
12.60
9.84
υN20C24 (14) υC18N20 (11) υN20C32 (30)
δCHC II (56) υPh II (14)
υN20C32 (31) υC18N20 (24)
υN20C24 (46) υC4C18 (19)
υC3O11 (19) δCHC II (14) υPh II (22)
δCHC I (68)
–
1237 w
1219 vs
1195 w
–
9.20
1192 w
1188 w
1162 m
2.84
10.14
310.15
4.71
372.80
1162 m
υO11C12 (19) υC3O11 (13) υC12C14 (12) δMe I
(10)
1142
1111
1098
1091
1084
1078
1065
1061
1054
1043
1038
1027
1020
10.21
73.81
1.47
1148
1110
1103
1088
1071
1059
1052
1027
1013
1005
994
7.08
20.43
91.52
2.69
1142
1107
1096
1081
1063
1061
1056
1027
1012
1001
990
33.75
10.83
100.78
4.22
1138 m
1110 s
1100 m
–
1128 w
δCHC II (31) υC18N20 (10) υPh II (13)
δCHC I(57) υPh I (28)
δCHC II (63)
1101w
–
7.82
–
υPh II (52) δCHC II (16) υC6Cl10 (30)
δMe I(36) δCHC II (28)
υPh I (55) υC25Br31 (14)
δMe II (68)
1.60
38.60
5.56
4.14
–
1073 m
25.92
22.81
14.24
0.94
39.78
11.06
22.08
67.84
105.89
8.58
1062 w
–
–
16.91
16.03
60.70
78.29
9.44
–
1026 w
1012 m
1005 w
998 w
–
1031 wbr
δMe II (50)
1022 sh
δPh I (72) υPh I (16)
26.96
0.20
–
δMe I (39) υC12C14 (21) υO11C12 (10)
τCCCC I (22) δCHC I (35) γ CHC I (31)
γ CHC I (90)
–
983 w
–
56.25
67.70
987
0.49
981
0.40
965
0.00
960
0.01
–
γ CHC II (82)
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
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Spectroscopic study of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl
Table 1. (Continued)
HF/6–31G∗
B3PW91/6–31G∗
B3LYP/6–31G∗
υ
IR
υ
IR
υ
IR
IR
Raman
(cm−1
)
intensity
(cm−1
)
intensity
(cm−1
)
intensity
υ(cm−1
)
υ(cm−1
)
Assignmentsa
997
18.42
962
21.10
955
22.98
952 w
948 w
υC32C34 (22) δC4O19C18 (11) δN20O19C18 (11)
δCCC II (11)
972
904
887
880
877
852
818
27.96
33.35
5.31
922
888
858
839
837
829
791
21.18
19.65
66.96
1.34
919
878
850
837
834
825
786
20.36
17.48
70.40
1.25
–
910 w
887 m
–
γ CHC II (64) τPh II (17)
υC12C14 (40) υO11C12 (16) δCCC II (16)
γ CHC I (59)
886 m
844 s
840 w
–
22.52
36.49
34.64
24.52
–
γ CHC I (77)
7.14
4.24
826 w
822 w
787 w
γ CHC I (51)
35.50
29.58
31.14
28.97
807 m
778 m
γ CHC II (57) γ O11C2C4C3 (11)
γ O19C4N20C18 (14) τCCCC II (14) γ C18CCC II
(12) γ O11C2C4C3 (10)
777
28.15
761
46.48
755
55.73
–
759 w
γ O19C4N20C18 (19) υO11C12 (12) δCCC II (18)
δCCC I (12) τCCCC I (12)
758
733
2.44
736
717
1.78
732
712
1.69
737 w
713 m
734 w
711 m
τCCCC I(67) γ N20C22C27C24 (12) γ Br31CCC (10)
53.00
68.36
68.33
τCCCC II (12) δC3C12O11 (12) γ O11C2C4C3 (10)
δCCC I (18)
712
683
52.51
32.52
699
682
5.44
695
678
6.45
688 w
680 m
681 m
–
τCCCC II (42) γ O11C2C4C3 (14)
22.24
22.29
δCCC I (16) δCCC II (18) δC4N20C18 (16) δCO Me
I(12)
660
651
635
609
581
570
6.36
21.75
22.21
13.51
4.68
651
644
628
600
572
564
1.34
12.59
15.98
8.50
650
644
625
596
568
560
2.50
8.31
18.47
9.35
4.54
3.35
–
659 w
δCCC II (47) δCCC I (17)
638 w
621 w
599 m
566 m
–
–
631 m
599 w
–
δCCC I (47) τCCCC II (19)
δCCC I (28) γ O33C34N20C32 (13) τCCCC II (10)
γ O33C34N20C32 (34) δCC18C II (5)
γ O13C14O11C12 (24) δC14O13C12 (16)
4.65
16.09
2.02
–
τCCCC II (9) γ Cl10C1C5C6 (9) δC34O33C32 (18)
δCOMe II (16)
565
541
524
6.33
17.23
16.83
554
519
511
4.45
18.77
12.75
550
518
509
4.09
15.73
10.95
–
521 m
–
–
521 w
–
γ O13C14O11C12 (41) υC25Br31 (42) τCCCC II (16)
γ N20C22C27C24 (41) γ Br31C28C23C25(20)
τCCCC II (23) γ O11C2C4C3 (23) γ Cl11C1C5C6
(22)
480
458
0.61
3.30
468
457
1.06
2.17
466
455
1.22
1.73
–
470 w
448 w
τCCCC II (23) γ O11C2C4C3 (12) γ C18C3C5C4
(18) δC22N20C24 (14)
448 w
δC22N20C24 (15) δC27N20C24 (15) δCO11C (26)
δC34O33C32 (16)
436
428
0.09
5.41
424
421
0.08
5.80
425
421
0.05
3.76
–
430 w
–
τCCCC I (86)
418 w
τCCCC II (36) δC22N20C24 (16) δCOMe II (12)
δCO11C (12)
416
9.74
419
4.99
415
8.52
–
407 w
δMe I (27) δCCC II (10) δCO11C (18) δC O Me I
(18)
377
372
357
26.14
0.93
7.56
382
366
346
21.13
2.13
5.06
377
366
344
20.86
2.57
4.65
–
368 w
–
374 w
359 w
343 m
υC25Br31 (23) δCOMe II (33)
τCCCC II (23.) δCO11C (18) δC4O19C18 (16)
γ Br31CCC (29) τCCCC I (22) δC18C24N20 (11)
δC32C24N20 (11)
340
308
279
253
6.88
6.63
7.28
2.44
335
311
281
254
4.16
7.46
6.89
1.74
333
308
279
253
3.96
8.12
7.02
1.79
–
–
–
–
337 w
296 m
279 w
242 m
δCClC(30) γ ClCCCC(19)
δMeII CO (19) δC4N20C18 (24) δCO11C (20)
δCO Me I (31) δCCC II (18)
δCClC (22) δCO11C (13) δCBrC (16)
τC3O11C12O13 (12)
234
191
2.72
2.87
234
189
1.62
2.16
231
188
1.81
2.14
–
–
–
δCBrC (41) γ C24C18C32N20 (15)
197 s
τCCC18O19 (13) τCCC18N20 (13) γ ClCCC (11)
δC18C32N20 (18)
169
1.90
174
3.11
171
3.09
–
174 w
δCCN20 (14) τCCCC I (13) γ N20CCC (12) δCC18C
(11)
164
156
153
142
5.75
1.40
1.58
0.26
164
159
153
132
3.31
0.43
2.13
0.19
164
156
151
138
2.96
0.87
1.89
0.23
–
–
–
–
–
δC3C12O11 (26) τCCCC II (19) δC O ME II (13)
τCNC32O33 (20) τCNC32C34 (50)
τMe II (32) δCCN20 (34)
156 vs
–
–
τMe I (81)
c
J. Raman Spectrosc. 2010, 41, 707–716
Copyright ꢀ 2009 John Wiley & Sons, Ltd.
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C. Y. Panicker et al.
Table 1. (Continued)
HF/6–31G∗
B3PW91/6–31G∗
B3LYP/6–31G∗
υ
IR
υ
IR
υ
IR
IR
Raman
(cm−1
)
intensity
(cm−1
)
intensity
(cm−1
)
intensity
υ(cm−1
)
υ(cm−1
)
Assignmentsa
126
116
108
95
0.87
9.62
2.24
1.16
126
117
109
94
0.91
8.30
2.03
0.93
125
117
107
97
0.80
9.79
2.37
1.10
–
–
–
–
–
δCC18C II (19) τO19C18N20C24 (15) δCClC (11)
τCCC18O19 (10)
–
105 s
–
τCCC18N20 (30) τCNC32O33 (16) τCNC32C34
(16) γ C18CCC (14) τC4C18N20C24 (14)
τC4C18 N20C24 (25) τO19C18N20C32 (25)
γ C24C18C32N20 (22) τCCC18O19 (19)
τC3O11C12C14 (34) τCCC18O19 (17) τCCC18N20
(17)
86
67
51
35
33
10.63
0.48
0.21
1.14
2.61
85
65
53
36
30
6.87
0.28
0.29
3.53
0.08
89
65
52
37
27
5.65
0.29
0.34
2.95
0.10
–
–
–
–
–
–
–
–
–
–
τCNC32O33 (41) τMe II(20)
τCCCC II (31) τCNC32O33 (18) τCNC32C34 (18)
τC3C4C18O19 (54) τC3O11C12C14 (10)
τC3O11C12O13 (60) δCO11C (13) δC3C12O11 (12)
τC18N20C24C22 (55) τO19C18N20C24 (14)
τCNC32O33 (13)
23
18
0.23
0.45
24
19
0.11
0.13
23
18
0.09
0.24
–
–
–
–
τC3C4C18O19 (56) τC4C18N20C24 (17)
τC4C18N20C24 (62) τCNC32O33 (16)
υ, stretching; δ, in-plane bending; γ , out-of-plane bending; τ, torsion; s, strong; m, medium; w, weak; v, very; br, broad; sh, shoulder; para and tri
substituted phenyl rings are designated as PhI, PhII ring; subscript; as, asymmetric; s, symmetric.
a PED, potential energy distribution, only contribution larger than 10% were given.
(experimental) and at 711, 736, 687, 697 cm−1 (theoretical).
The deformation bands[16] of CCl are reported at 431, 435 and
441 cm−1. For the title compound, the band at 1081 cm−1 is
assigned as C–Cl stretching mode. The deformation bands of
CCl are also identified. This is in agreement with the literature
data.[49,53,54] For 4-chlorophenylboronic acid, the CCl stretching
and deformation bands are reported at 571 (DFT) and at 287
and 236 cm−1, respectively.[55] Bromine compounds[56] show
stretchingvibrationsintheregion750–485 cm−1 duetoC–Br. The
CBr deformations[56] are found in the region 400–140 cm−1. For
p-bromoacetanilide, the stretching vibration of C–Br is reported at
515 (DFT) and 504 cm−1 (IR) by Jothy et al.[57] In the present case,
the band at 550 cm−1 is assigned as the C–Br stretching mode.
According to Colthup et al.,[48] in acetates the methyl next to the
C
O absorbs near 1374 cm−1 due to symmetric deformation; the
asymmetric methyl deformation absorbs weakly near 1430 cm−1
.
The methyl rocking generally appears in the regions 1050 30
and 975 45 cm−1 as a weak, moderate or sometimes strong
band, the wavenumber of which is coupled to the C–C stretching
vibrations, which occurs in the neighborhood of 900 cm−1. With
acetates, the rocking modes are clearly separated and show weak
to medium activity in the region[59] 1050 30 and 980 45
cm−1. The band at 1005 cm−1 in IR and 1073 cm−1 in Raman
spectrum is assigned to the rocking modes of the methyl group.
B3LYP calculations give these modes as 1001 and 1063 cm−1
.
In O-bonded–C( O)Me group,[59] the C O stretching vibration
exhibits a strong band at 1750 20 cm−1. Esters and lactones
have two characteristically strong absorption bands arising from
Acetate group vibrations
C
O and C–O stretchings. The intense C O stretching vibration
Methyl groups are generally referred to as electron-donating
substituents in the aromatic ring system.[58] The methyl group
attached to the acetate group is designated as Me I. In acetates,
the asymmetric vibrations of the methyl group are expected in the
region 2940–3040 cm−1 and symmetric vibrations in the region
2910–2930 cm−1, and usually the bands are weak.[59] Aromatic
occurs at higher wavenumbers than that in normal lactones. The
force constant of the carbonyl bond is increased by the electron-
attracting nature of the adjacent oxygen atom due to inductive
effect.[48] In the present case, the stretching mode C12 O13 is
observed at 1753 cm−1 in IR spectra and 1733 cm−1 in Raman
spectra and the calculated value for this mode is 1689 cm−1
.
acetyl substituents absorb in a narrow range 3000–3020 cm−1
,
The C–O next to the carbonyl is stiffer than the other bonds
due to resonance that tends to localize the high vibration in
the C–O bond. Acetates show a strong vibration in the region
1260–1320 cm−1, as υC–O band.[48] For phenyl acetate,[60] the
υCC( O)O stretching band is observed at 1215 cm−1. The band
at 1162 cm−1 in the Raman spectrum and 1158 cm−1 theoretically
(B3LYP) is assigned as υCC( O)O for the title compound. This
mode is not pure but contains significant contribution from other
modes. The deformation bands of C12 –O13 are also identified
(Table 1). For the acetate group[25,61] the deformation bands of
which sometimes coincides with a CH stretching mode of the
ring.[59] In the present case, the asymmetric methyl bands are
calculated to be at 3068, 3025 (B3LYP), and experimentally a band
isobservedintheRamanspectrumat3071 cm−1 andat3070 cm−1
in the IR spectrum. The symmetric methyl stretching vibration
is observed at 2937 cm−1 in both spectra and at 2949 cm−1
theoretically.
In contrasted to the weak absorptions of methyl stretching
vibrations, the methyl symmetric deformation absorb moderately
to strongly in the range 1365
25 cm−1 and asymmetric
C
O are reported at 642 and 581 cm−1 experimentally. In the
deformations in the region[59] 1390–1480 cm−1. The B3LYP
calculations give 1461, 1455 and 1403 cm−1 as asymmetric and
symmetric deformation bands.
present case, the C–C stretching mode of the acetate group is
observed at 886 (IR), 887 (Raman) and 878 cm−1 (theoretical).
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
J. Raman Spectrosc. 2010, 41, 707–716

Spectroscopic study of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl
According to literature, the C–C stretching mode is reported at
847 cm−1 experimentally and at 866 cm−1 theoretically.[25]
considering each molecule as a substituted benzene. Such an idea
has already been successfully utilized by several workers for the
vibrational assignment of molecules containing multiple homo-
and hetero-aromatic rings.[70,72–76] In the following discussion,
the di- and tri-substituted phenyl rings are designated as Ph
I and Ph II, respectively. The modes of the two phenyl rings
will differ in wavenumber, and the magnitude of splitting will
depend on the strength of interaction between different parts
(internal coordinates) of the two rings. For some modes, this
splitting is so small that they may be considered as quasi-
degenerate, whereas for other modes a significant amount of
splitting is observed.[72–74,77] The benzene ring possesses six
ring-stretching vibrations of which the four with the highest
wavenumbers occurring near 1600, 1580, 1490 and 1440 cm−1
are good group vibrations.[59] With heavy substituents, the bands
tend to shift to somewhat lower wavenumbers, and the greater
thenumberofsubstituentsonthering, thebroadertheabsorption
regions.[59] In the case of C O substitution, the band near
1490 cm−1 can be very weak.[59] The fifth ring-stretching vibration
is active near 1315 65 cm−1, a region that overlaps strongly with
that of the CH in-plane deformation.[59] The sixth ring-stretching
vibration, the ring breathing mode, appears as a weak band near
1000 cm−1 in mono, 1,3-di and 1,3,5-trisubstituted benzenes. In
the otherwise substituted benzenes, however, this vibration is
substituent sensitive and difficult to distinguish from the other
modes.
Carbamoyl group vibrations
The carbonyl stretching vibration[59,62]
C O is expected in the
region 1715–1680 cm−1, and in the present study the bands
observed at 1685 cm−1 in the IR spectrum and at 1686, 1602 cm−1
in the Raman spectrum are assigned as C32 O33 and C18 O19
stretching modes. B3LYP calculations give these modes at 1632
and 1592 cm−1. The intensity of the carbonyl group can increase
because of conjugation or formation of hydrogen bonds. The
increase in conjugation, therefore, leads to intensification of
Raman lines as well as increase in IR intensities. The mode
υC32 O33 is simultaneously active in IR and Raman spectra,
which clearly explains a charge transfer between the donor and
acceptor through a π-conjugated path.[63,64] Methyl groups are
generally referred to as electron-donating substituents in the
aromatic ring system[58] and the methyl group attached to the
carbamoyl moiety is designated as Me II. The observed bands
at 3012 and 2952 cm−1 in the IR and 2963 cm−1 in the Raman
spectrum are assigned to the stretching modes of the methyl
group II.[56,65] Absorption intensities in the IR spectrum provide
much information on the nature of chemical bonds and the
effects due to intramolecular environment. The electronic effect,
hyperconjugation, usually means the interaction of the orbitals of
a methyl group with the π orbitals of an adjacent C–C bond. In the
present case, the methyl group II hydrogen atoms are subjected
simultaneously to hyperconjugation and induction, which causes
the decrease of IR intensity as reported in the literature.[66] Thus
hyperconjugation and induction of the methyl group II, causing
changes in intensity in the IR spectrum, clearly indicate that the
methyl group II hydrogen atoms are directly involved in the
donation of electronic charges. The asymmetric and symmetric
bending modes of the methyl group II are normally expected
in the region 1465–1440 and 1390–1370 cm−1, respectively.
The B3LYP calculations give bands of Me II at 1470, 1456 and
1397 cm−1. The enhancement of intensity of the symmetric
bending mode at 1397 cm−1 in the IR spectrum is due to the
presence of C O adjacent to the methyl group,[67] which is
in good agreement with the calculated value. The strong IR
intensity of the symmetric mode suggests a large positive charge
localized on the hydrogen atoms, which further supports the
occurrance of hyperconjugation. A weak band is observed in the
Raman spectrum at 1451 cm−1 corresponding to the asymmetric
deformation of methyl group II.
In asymmetric trisubstituted benzenes, when all the three sub-
stituents are light, the wavenumber interval of the breathing
mode[49] is between 500 and 600 cm−1. When all the three sub-
stituents are heavy, the wavenumber appears above 1100 cm−1
.
In the case of mixed substituents,[49] the wavenumber is expected
to appear between 600 and 750 cm−1. The band calculated
at 1081 cm−1 is assigned as the ring-breathing mode of the
phenyl ring Ph II. According to Varsanyi,[49] for para substituted
benzene, the ring-breathing mode is expected in the interval
1050–1100 cm−1,andinthepresentcasethebandat1062 cm−1 in
IR and 1061 cm−1 by theory (B3LYP) is assigned the ring-breathing
mode of Ph I. For the phenyl ring Ph II, the δCH in-plane bending
vibrations are expected in the region 1090–1265 cm−1 [40,44,59]
.
The CH out-of-plane deformations[59] are observed between 1000
and 700 cm−1. Generally, the CH out-of-plane deformations with
the highest wavenumbers have a weaker intensity than those
absorbing at lower wavenumbers. In the case of trisubstituted
benzenes, two γ CH bands are observed at 890 50 and 815 45
cm−1 in the IR spectrum, and thebands at 910, 822 cm−1 in Ra-
man, 807 cm−1 IR and 919, 825 cm−1 (B3LYP) are assigned to these
modes. The strong CH out-of-plane deformation band occurring
at 840 50 cm−1 is typical for para-substituted benzene.[59] For
the title compound, a band is observed at 844 cm−1 in the IR
spectrum, which finds support from computational results. The
IR bands in the 2880–1936 cm−1 region and their broadening
support intramolecular hydrogen bonding.[32]
The C–N stretching vibration[59] is moderately to strongly active
in the region 1275 55 cm−1. El-Shahawy et al.[68] observed a
band at 1320 cm−1 in the IR spectrum as the υC–N mode. Primary
aromatic amines with nitrogen directly on the ring absorb at
1330–1260 cm−1 duetostretchingofthephenylcarbon–nitrogen
bond.[16,48] Sandhyarani et al.[69] reported υC–N at ∼1318 cm−1
,
and Anto et al.[70] and Ambujakshan et al.[71] reported υC–N at
1332, 1331 (IR), 1315 (Raman), 1315 and 1323 cm−1 (HF). For
the title compound, the C–N stretching modes are observed at
1219, 1237 (IR), 1222 cm−1 (Raman) and at 1292, 1234, 1200 cm−1
(theoretical). All these modes are not pure but contain significant
contribution from other modes.
Geometrical parameters and first hyperpolarizability
To the best of our knowledge, no X-ray crystallographic data of
this molecule has yet been established. However, the theoretical
results obtained are almost comparable with the reported
structuralparametersoftheparentmolecules. Thebondsoflength
C18 O19 = 1.2439 Å, C32 O33 = 1.2438 Å, C12 O13 = 1.2267
Å show typical double bond characteristics. However, the C–N
bondlengthsC18 –N20 (1.4149 Å), C24 –N20 (1.4529 Å)andC32 –N20
Phenyl ring vibrations
As the identification of all the normal modes of vibration of
large molecules is not easy, we tried to simplify the problem by
c
J. Raman Spectrosc. 2010, 41, 707–716
Copyright ꢀ 2009 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/jrs

C. Y. Panicker et al.
(1.4170 Å) are shorter than the normal C–N single bond length of
about1.48 Å. TheshorteningoftheseC–Nbondsrevealstheeffect
ofresonanceinthispartofthemolecule.[16] Foraphenylcarbamoyl
derivative, Kubicki[78] reported Cphenyl –N bond length as 1.414 Å
and that of the N–C( O) as 1.352 Å. The C O and C–N bond
lengths in benzamide, acetamide, formamide are, respectively,
the bond angles for the carbamoyl group are C18 –N20 –C24
=
116.6◦, C18 –N20 –C32 = 125.9◦, C24 –N20 –C32 = 117.5◦,
C3 –C4 –C5 = 118.5◦, C5 –C4 –C18 = 116.5◦, O19 –C18 –N20
=
120.2◦, C4 –C18 –O19
=
119.7◦, C4 –C18 –N20
=
120.0◦,
C22 –C24 –C27 = 120.5◦ and N20 –C24 –C27 = 120.1◦. The cor-
responding values reported for a similar compound[87] are 117.0,
123.7, 118.5, 119.0, 124.2, 122.6, 120.6, 115.1, 122.2 and 119.1◦. The
1.2253, 1.2203, 1.2123 and 1.3801, 1.3804, 1.3683 Å.[79] The C
bonds C18 O19, C32 O33, C12 O13 and C–N bonds C24 –N20
O
,
B3LYP calculations give the dihedral angles C28 –C27 –C24 –N20
=
C18 –N20, C32 –N20 are 1.2439, 1.2438, 1.2267, 1.4529, 1.4149,
1.4170 Å respectively, in the present case. According to the
literature,[80–83] the changes in bond lengths in C O and C–N
are consistent with the following interpretation: hydrogen bond
decreases the double bond character of the C O bond and
increases the double bond character on C–N bond. The angles
O11 –C12 –O13 and O13 –C12 –C14 are increased by 2.2◦ and 7.8◦
and the angle O11 –C12 –C14 is reduced by 10◦ at C12 position
from 120◦, revealing the repulsion between the methyl group MeI
180.0◦, O19 –C18 –C4 –C3 = −136.3◦, N20 –C18 –C4 –C3 = 40.9◦,
O19 –C18 –C4 –C5 = 37.1◦, and N20 –C18 –C4 –C5 = −145.7◦
around the benzamide group, whereas the corresponding re-
ported values[88] for a similar derivative are 178.5, −16.8, 163.8,
161.6 and −17.8◦. The deviations are due to the presence of
COCH3 group attached with N29. The C18 –N29 bond is twisted
from the phenyl rings I and II as is evident from the torsion an-
gles C27 –C24 –N20 –C18 = −112.5◦, C22 –C24 –N20 –C18 = 67.3◦,
N20 –C18 –C4 –C3 = 40.9◦ and N20 –C18 –C4 –C5 = −145.7◦. At C4
position, the angles C5 –C4 –C18 is reduced by 3.5◦ and C3 –C4 –C18
is increased by 4.7◦ from 120◦, and this asymmetry of exocyclic
angles reveals the interaction between O19 and the phenyl ring II.
Analysis of organic molecules having conjugated π-electron
systems and large hyperpolarizability using IR and Raman
spectroscopy has evolved as a subject of research.[89] The potential
application of the title compound in the field of nonlinear optics
demands the investigation of its structural and bonding features
contributingtothehyperpolarizabilityenhancement,byanalyzing
the vibrational modes using the IR and Raman spectra. The
ring-stretching bands at 1586, 1369, 1304, 1195, 1138, 1110 and
1012 cm−1 observed in the IR spectrum have their counterparts
in the Raman spectrum at 1589, 1385, 1305, 1192, 1128, 1101 and
1022 cm−1, respectively, and their relative intensities in IR and
Raman spectrum are comparable.
The first hyperpolarizability (β0) of this novel molecular system
is calculated using the DFT method, based on the finite-field
approach. In the presence of an applied electric field, the
energy of a system is a function of the electric field. The first
hyperpolarizability is a third-rank tensor that can be described by
a 3 × 3 × 3 matrix. The 27 components of the 3D matrix can be
reduced to 10 components because of Kleinman symmetry.[90]
The components of β are defined as the coefficients in the
Taylor series expansion of the energy in the external electric field.
When the electric field is weak and homogeneous, this expansion
becomes
and O13
.
The C–C bond lengths in the phenyl rings I and II lie in the range
1.3930–1.3987 Å and 1.3875–1.4080 Å, respectively, while the
C–C bond length of benzene[84] is 1.399 Å and of benzaldehyde[85]
is 1.3973Å. In contrast, the value of angles C5 –C4 –C18 (116.5◦) and
C4 –C18 –O19 (119.7◦) are smaller than those of benzaldehyde,[85]
121.0◦ and 123.6◦. These differences are ascribed to the steric
repulsion between the H9 and methyl group MeII hydrogen
atoms. The dihedral angle C5 –C4 –C18 –N20 was determined to be
−145.7◦ by the B3LYP method. On the contrary, the equilibrium
structure of benzaldehyde is planar.[85] The steric repulsion in the
present case is also considered to cause a nonplanar skeleton. The
C4 –C18 bond length (1.4964 Å) is larger than the corresponding
length in benzaldehyde[85] (1.4794 Å) by about 0.017Å. The C–Cl
bond length (1.8206) given by B3LYP calculations is in agreement
with the value obtained by Arslan et al.[16] The substitution of
chlorine in the phenyl ring shortens the C–C bond lengths C1 –C6,
C5 –C6 of the benzene ring. Chlorine is highly electronegative and
tries to obtain additional electron density. It attempts to draw
it from the neighboring atoms, which move closer in order to
share the electrons more easily as a result. Due to this, the bond
angle C1 –C6 –C5 is found to be 121.6◦ in the present calculation,
which is 120◦ for normal benzene. Kurt[55] reported the bond
lengths and angles as follows: C–Cl = 1.757 Å, C1 –C6 = 1.391 Å,
C5 –C6 = 1.391 Å, C1 –C6 –C5 = 121.2◦, C1 –C6 –Cl10 = 119.4◦.
The experimental values[86] are 1.736 Å, 1.365 Å, 1.369Å, 121.2◦
and 119.7◦.
ꢀ
ꢀ
ꢀ
1
2
1
6
For acetate group, Ibrahim and Koglin[25] reported C12 –C14
,
E = E0 −
µiFi −
αijFiFj −
βijkFiFjFk
C14 –H15–17, C12 –O11, C12 O13 bond lengths as 1.52, 1.102,
1.364 and 1.214 Å respectively, whereas in the present case
the corresponding values are 1.4949, 1.0902–1.0968, 1.416 and
1.2267Å. For the title compound, the bond angles of the acetate
group are: C14 –C12 –O11 = 110.0, C14 –C12 –O13 = 127.8◦ and
C12 –C14 –H15–17 = 108.7–110.8◦, which are in agreement with
the reported values[25] 113.0, 126.6, 122.0 and 107◦. The strong
steric repulsion between the phenyl ring II and the amide group is
confirmed by the nonplanarity of the benzamide, where the amide
group is turned by −136.3◦ (C3 –C4 –C18 –O19) with respect to the
benzene ring.[83] Siddiqui et al.[87] reported the bond lengths for
phenylcarbamoylgroupsasfollows:N20 –C18 = 1.3314–1.3384 Å,
N20 –C24 = 1.4294–1.4404 Å, C18 –O19 = 1.2363–1.2413 Å,
C4 –C3 = 1.3893 Å, C4 –C5 = 1.4033 Å, C4 –C18 = 1.5053 Å,
C24 –C22 = 1.4034 Å and C24 –C27 = 1.4038 Å. For the title
compound, the corresponding values are 1.4149, 1.4529, 1.2439,
1.4080, 1.4068, 1.4964, 1.3987 and 1.3976 Å. In the present study,
i
ij
ijk
ꢀ
1
−
γ ijklFiFjFkFl + . . .
(1)
24
ijkl
where E0 is the energy of the unperturbed molecule, Fi is the
field at the origin, µi, αij, βijk and γ ijkl are the components
of dipole moment, polarizability, the first hyper polarizabilities
and second hyperpolarizibilites, respectively. The calculated first
hyperpolarizabilityofthetitlecompoundis1.62×10−30 esu,which
is comparable with the reported values of similar derivatives,[32]
but experimental data are not readily available. We conclude that
the title compound is an attractive object for future studies of its
nonlinear optical properties.
The calculated (B3LYP) results give the following thermody-
namic parameters: self consistent field (SCF) energy is −4042.77
a.u.; zero point vibrational energy is 693.12 kJ/mol; entropy is
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
J. Raman Spectrosc. 2010, 41, 707–716

Spectroscopic study of 2-[acetyl(4-bromophenyl)carbamoyl]-4-chlorophenyl
Figure 4. Correlation graph.
166.94 cal/mol-K; specific heat capacity at constant volume is References
82.08 cal/mol-K; E (thermal) is 183.16 kcal/mol; and the dipole
moment is 2.41 debye.
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ꢁ
ꢂ
ꢂ
ꢃ
n
ꢀ
ꢄ
ꢅ
1
2
RMS =
υci alc − υei xp
(2)
n − 1
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The RMS error of the observed Raman and IR bands are found
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12.03 and 14.01 for B3LYP methods, respectively. Small differences
between experimental and calculated vibrational modes are
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