Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Spectral and structural studies of the anti-cancer drug Flutamide by

density functional theoretical method
G. Mariappan, N. Sundaraganesan ⇑
Department of Physics (Engg.), Annamalai University, Annamalainagar 608 002, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 The FTIR and FT-Raman spectra of

3484

880
2932
IR intensity (arb units)

2999

1018

555
Flutamide were recorded.
1718
1602

 The vibrational frequencies were B3LYP/6-31G(d,p)

calculated by DFT method and

1127
1339

compared.
 UV–Vis spectra were recorded and
1496

compared with calculated ones.

 NMR and NBO analysis were also
1975
Transmittance (%)

2468
2563
2642

carried out.
2919
3055
3127

713
839
2984

655
903

Experimental
1244
1717

1541
3360

1345

1139

4 0 0 0 3 5 0 0 3 0 0 0 2 5 0 0 2 0 0 0 1 5 0 0 1 0 0 0 5 0 0

Wavenumber (cm -1)

a r t i c l e i n f o a b s t r a c t

Article history: A comprehensive screening of the more recent DFT theoretical approach to structural analysis is pre-
Received 5 July 2013 sented in this section of theoretical structural analysis. The chemical name of 2-methyl-N-[4-nitro-3-(tri-
Received in revised form 4 September 2013 fluoromethyl)phenyl]-propanamide is usually called as Flutamide (In the present study it is abbreviated
Accepted 7 September 2013
as FLT) and is an important and efficacious drug in the treatment of anti-cancer resistant. The molecular
Available online 18 September 2013
geometry, vibrational spectra, electronic and NMR spectral interpretation of Flutamide have been studied
with the aid of density functional theory method (DFT). The vibrational assignments of the normal modes
Keywords:
were performed on the basis of the PED calculations using the VEDA 4 program. Comparison of compu-
Flutamide
DFT
tational results with X-ray diffraction results of Flutamide allowed the evaluation of structure predictions
Vibrational assignments and confirmed B3LYP/6-31G(d,p) as accurate for structure determination. Application of scaling factors
UV–Vis for IR and Raman frequency predictions showed good agreement with experimental values. This is sup-
HOMO–LUMO ported the assignment of the major contributors of the vibration modes of the title compound. Stability of
NMR the molecule arising from hyperconjugative interactions leading to its bioactivity, charge delocalization
have been analyzed using natural bond orbital (NBO) analysis. NMR chemical shifts of the molecule were
calculated using the gauge independent atomic orbital (GIAO) method. The comparison of measured FTIR,
FT-Raman, and UV–Visible data to calculated values allowed assignment of major spectral features of the
title molecule. Besides, Frontier molecular orbital analyze was also investigated using theoretical
calculations.
Ó 2013 Elsevier B.V. All rights reserved.

Introduction nonsteroidal antiandrogen drug for the treatment of prostate can-

cer, has been associated with rare incidences of hepatotoxicity in
Flutamide (FLT) is an unusual example of an antiandrogenic patients. It is believed that bioactivation of FLT and subsequent
drug lacking a steroidal structure. Flutamide, a widely used covalent binding to cellular proteins is responsible for its toxicity.
It is used increasingly as part of total androgen ablation therapy
⇑ Corresponding author. Tel.: +91 9442068405. and in neoadjuvant treatment before radical prostatectomy [1].
E-mail address: [email protected] (N. Sundaraganesan). Although very useful and almost indispensable, it can produce

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.09.043
 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613 605

adverse biological effects such as clinical photosensitization which parameters, have become an accepted technique to gather insight
has been recognized to result from FLT [2]. FLT can cross the placen- into the molecular structure.
tal barrier and thus can have an impact on fetal development [3].
The capabilities of DFT method to reproduce the structural features
Experimental details
of benzamides, particularly in relation with intramolecular and
intermolecular C–H- - - -O hydrogen bonds, were also evaluated.
The compound Flutamide (solid state, light yellow crystalline
Crystal and molecular structure analysis of FLT and then bifur-
powder) was obtained from Sigma–Aldrich Chemical Company
cated helicoidal C–H. . .O hydrogen bonds have been analyzed by
with a stated purity 99% and used as such without any further
Cense et al. [4]. Vargas et al. [5] have investigated photochemistry
purification. The FTIR spectrum of the sample was carried out be-
and phototoxicity studies of Flutamide, a phototoxic anti-cancer
tween 400 and 4000 cm1 on a JASCO FT-IR-6300, spectrometer.
drug. Payen et al. [6] studied synthesis and biological activity of
The FT-Raman spectrum of the sample recorded using 1064 nm
ferrocenyl derivatives of the non-steroidal antiandrogens Flutam-
line of an Nd–YAG laser as the excitation wavelength in the region
ide and bicalutamide. A comparison between two doses of Flutam-
of 50–3500 cm1 on a Bruker RFS 100/S FT-Raman spectrometer.
ide (250 mg/d and 500 mg/d) in the treatment of hirsutism have
The detector is a liquid nitrogen cooled Ge detector. Five hundred
analyzed by Muderris et al. [7]. The detailed study and an electro-
scans were accumulated at 1 cm1 resolution using a laser power
chemical evidence of free radicals formation from Flutamide and
of 100 mW. The UV absorption spectrum of FLT molecule dissolved
its reactivity with endo/xenobiotics of pharmacological relevance
in Methanol and Ethanol is examined in the range 200–800 nm
investigated by Vergara et al. [8].
using Shimadzu UV-1800 PC, UV–Vis recording spectrometer. Data
In the present study, we have used the density functional theory
were analyzed by UV PC personal spectroscopy software, version
approach which was preferred in order to include exchange corre-
3.91. The experimental FT-IR and FT-Raman spectra along with
lation functions and to obtain an accurate electron density from
the theoretically simulated IR and Raman spectra using DFT/
the Kohn–Sham equations [9,10]. FTIR and FT-Raman spectroscopy
B3LYP/6-31G(d,p) level of calculations are shown in Figs. 1 and 2.
have been established as a useful technique to obtain information
The spectral measurements were carried out at Indian Institute
about the influence of structural analysis of certain molecule in the
of Technology, Chennai, India.
solid-state. The experimental wave numbers of both FTIR and
FT-Raman were reproduced fairly well by DFT calculations at the
B3LYP/6-31G(d,p) level. In addition to the theoretical vibrational Computational details
spectrum, density functional methods have also been used to cal-
culate the molecular geometry, the atomic charges and some other Quantum chemical calculations were used for FLT to carry out
molecular properties. Furthermore, the combination of DFT calcu- the optimized geometry and vibrational wavenumbers with 03
lations of chemical shifts and harmonic vibrations with nuclear version of the Gaussian program [11]. The vibrational modes were
magnetic resonance (NMR), FTIR and FT-Raman experimental assigned by means of visual inspection using the Gauss View
3484

880
2932
2999

1018

555
1718
1602
IR intensity (arb units)

B3LYP/6-31G(d,p)
1127
1339
1496
1975
2468
2563
2642
Transmittance (%)

2919
3055
3127

713
839
2984

655
903

Experimental
1244
1717

1541
3360

1345

1139

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Fig. 1. Comparison of experimental and theoretical (B3LYP/6-31G(d,p)) FT-IR spectra for FLT.
606 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613

1338
1586
B3LYP/6-31G(d,p)

106
1218
1496

1099
Raman Intensity (arb units)

1015
2934

1718

212
3002

667
851
3485

3115

1345
Experimental

86
1598

1245
1123
1040
1721
2948
3081

901
761

458
3500 3000 2500 2000 1500 1000 500
Wavenumber (cm -1)

Fig. 2. Comparison of experimental and theoretical (B3LYP/6-31G(d,p)) FT-Raman spectra for FLT.

program [12]. The basis set 6-31G(d,p) augmented by ‘d’ polariza- Results and discussion
tion functions on heavy atoms and ‘p’ polarization functions on
hydrogen atoms were used for better description of polar bonds Structural analysis
of molecules [13–14]. It should be emphasized that ‘p’ polarization
functions on hydrogen atoms are useful not only for reproducing The optimized parameters (bond lengths, angles, and dihedral
the out-of-plane vibrations involving hydrogen atoms but also angles) of the title compound have been obtained by using the
for a better description of the molecular geometry and other nor- B3LYP/6-31G(d,p) level of theory. The obtained results are com-
mal vibrational modes. The vibrational assignments of the normal pared with exact crystal structure of the title molecule [4] and
modes were also made on the basis of the PED calculated by using listed in Table S1 (Supplementary information). The B3LYP geome-
the VEDA 4 program [15]. Subsequent potential energy distribution try-optimized structure of FLT (Fig. 3) shows very close resem-
(PED) to each observed frequencies, predicts well the purity of the blance of the actual crystal structure of this molecule. The
fundamental modes and shows the reliability and accuracy of the optimized structure of the molecule is mainly planar, except the
spectral analysis. The graphical presentation of the calculated Ra- NO2, CF3 and CH3 groups, in agreement with the experimental re-
man and IR spectra were made using Gauss View program [12]. sults and in contrast with molecular mechanics calculations [25].
The absence of imaginary frequency modes for the optimized The calculated values of bond lengths are very close to the X-ray
structure of FLT at DFT level confirms a true minimum on the po- diffraction results of the FLT molecule. The minimum deviation
tential energy surface. As the hybrid B3LYP functional tends to identified due to the crystal forces deforming the ring structure,
overestimate the fundamental normal modes of vibration, the exactly at the substitution position of C5–C6 bond length
computed frequencies were scaled with appropriate values to (1.398 Å) differs from the C5–C10 bond (1.386 Å). The theoretical
bring harmonization between theoretical and experimental wave- data reproduced with the X-ray diffraction value on C–H- - - -O
numbers [16–18]. We know that DFT potentials systematically hydrogen bonds exactly at 2.18 Å [4] in O3–H21 bond distance.
overestimate the vibrational wavenumbers. These discrepancies While the high positive charge H21 (0.158 e) can also be calculated
are corrected either by computing anharmonic corrections explic- theoretically using B3LYP/6-31G(d,p) level of theory, which is
itly or by introducing a scaled field or directly scaling the calcu- demonstrated the intramolecular hydrogen bonding interaction
lated wavenumbers with the proper factor [19,20]. In our present with carbonyl group. The influence of this intramolecular
study, we have followed the scale factor of 0.9608 [19] for C–H- - - -O hydrogen bonding feature, results in the C10–H21 bond
B3LYP/6-31G(d,p) method. The TD-DFT calculations were also length contracted 1.080 Å among the other aromatic C–H bond
performed using the Gaussian program in Methanol and Ethanol lengths which are calculated around 1.083 Å.
as solvent medium. To simulate the solvent effect the IEFPCM Both the nitrogen atoms are bonded in para position of aromatic
(Polarization Continum Model) is used [21,22]. To investigate the ring in which amino (C–N = 1.471 Å) group dominates the increas-
reactive sites of the title compound the MEP were evaluated using ing bond length than the secondary amide (C–N = 1.400 Å) group. It
the B3LYP/6-31G(d,p) method. 1H and 13C NMR chemical shifts is noted that the high electronegativity and steric interaction be-
were calculated using the GIAO method [23,24] in deuterated tween the NO2 and CF3 group and also the C–H- - - -O hydrogen
DMSO. bonding interactions with the O16–H20 (2.378 Å). Two methyl
 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613 607

PED of the title molecule is given in Table 1. A complete assign-

ment of the fundamentals was proposed based on the calculated
PED values, infrared and Raman intensities. Any inadequacy noted
between the observed and the calculated frequencies may be due
to the two facts: one is that the experimental results belong to so-
lid phase and theoretical calculations belong to gaseous phase; the
another one is that the calculations have been actually done on a
single molecule contrary to the experimental values recorded in
the presence of intermolecular interactions.

Amide group vibrations

The characteristic secondary amide bands in the stretching
region, associated with N–H stretch and the overtone of N–H
in-plane bending, can be observed in the IR spectrum. Usually
Fig. 3. Optimized molecular structure and atomic numbering of FLT.
the N–H stretching vibrations for secondary amides appear strong
and broad in the region 3390 ± 60 cm1 [31]. For the title com-
groups are super-imposed well in terms of structural data because pound, the very strong band at 3360 cm1 in the IR spectrum is as-
commonly all the C–H bond lengths of methyl group are calculated signed as N–H stretching mode. The calculated wavenumber for
around 1.09 Å. Noveron et al. [26] reported the bond lengths for the this mode is at 3485 cm1. The lowering of the N–H stretching
benzamide derivatives C5–N4, C1–N4, C1–C2, N4–H18 and C1–O3 wavenumber can be attributed to the red shifting by 125 cm1 in
as 1.395, 1.370, 1.494, 0.733 and 1.225 Å respectively and also the IR spectrum with a strong intensity from the computed wave-
Dereli et al. [27] calculated for 4-phenylsemicarbazide molecule number, which indicates the weakening of the N–H bond resulting
as C5–N4 (1.410 Å), N4–H18 (1.020 Å) and C1–O3 (1.240 Å) where in proton transfer to the neighboring oxygen [32]. As expected, this
as the corresponding values for our title molecule is 1.400, 1.387, mode is a pure stretching mode, and as it is evident from the PED
1.531, 1.010 and 1.222 Å respectively calculated by DFT/B3LYP column they are almost contributing 100%. The first overtone of
level of theory. These values are well in agreement with the exper- the N–H in-plane bending mode (3110 cm1) falling on the
imental counterparts (XRD) of C5–N4, C1–N4, C1–C2 and C1–O3 as N–H stretching band positions produces two bands of comparable
1.401, 1.379, 1.503, 1.213 Å respectively. intensities, equally displaced on either side of this wavenumber
According to the experimental and the literature data [28,29] resulting from Fermi resonance with one or more N–H stretching
the changes in bond lengths of C@O and C–N are consistent with [33]. In the present study, the NH2 bending frequency was found
the following interpretation: that is, hydrogen bond decreases at 1497 cm1 by B3LYP method is matching with medium FT-IR
the double bond character of C@O bond and increases the double band at 1495 cm1 showed good agreement in the FT-IR and FT-
bond character of C–N bond. On this basis of C1 atom the bond Raman spectra respectively.
angles are found to be C2–C1–O3 = 121.9° (120.7°), C2–C1–
N4 = 114.8° (115.5°) and N4–C1–O3 = 123.3° (123.7°) [30] and this C–H vibrations
asymmetry of exocyclic angles reveals both the interaction be- The C–H stretching vibration occurs above 3000 cm1 and is
tween H18 and H30 (2.101 Å) and O3 and H21 (2.18 Å). While typically exhibited as a multiplicity of weak to moderate bands,
the bond angle C10–C5–N4 is increased by 3.6° and N4–C5–C6 is compared with the aliphatic C–H stretch [34]. According to Roeges
reduced by 2.82° from 120° and this asymmetry reveals the inter- [31], the C–H stretching vibrations of the phenyl ring are expected
action between the amide moiety and the phenyl ring in which the in the region 3120–3000 cm1. In the present study, one can expect
number in parentheses is from the literature data [30]. Within the three C–H stretching vibrations. Among the three stretching vibra-
CF3 group FCF (F12–C11–F14) angle is increased to 108.9° com- tions the blue shifting of the ring C–H stretching wavenumbers are
pared to other FCF angles due to the steric interaction. As it is evi- at 3148 and 3115 cm1 (mode nos. 2 and 3) which indicates the
dent from the dihedral angle values C7–C8–N15–O16 (153.4°) and weakening of C–H bond resulting the intramolecular C–H- - - -O
C9–C8–N15–O17 (150.1°) give non-planarity of NO2 group. interactions to the neighboring oxygen atoms as O3–H21
(2.183 Å) and O16–H20 (2.378 Å) respectively. Substantially, the
observed FTIR bands at 3207 and 3127 cm1 are supported our cal-
Vibrational assignments culated wavenumbers. As expected, this mode is a pure stretching
mode, and as it is evident from the PED column they are almost
The most-significant calculated and experimental fundamental contributing 98%. Among the three aromatic C–H stretching vibra-
vibrational modes, together with their IR and Raman intensities, tions, the remaining one is observed within the spectral range at
are summarized in Table 1. As one can notice, the calculated values 3055 and 3080 cm1 in FTIR and FT-Raman spectra respectively.
agree well with the experimental data; however, some deviations The calculated wavenumber also gives good correlation with the
were observed for the vibrations involving electronegative atoms. observed wavenumber at 3092 cm1 with 99% of contribution.
All the calculated wavenumbers are in very good agreement with The C–H in plane bending vibration usually occurs in the region
the experimental values after which are scaled. The task of the 1390–990 cm1 and is very useful for characterization purpose
vibrational analysis is to find out the different vibrational modes [35]. The calculated frequencies are at 1287, 1245 and 1218 cm1
connected with specific molecular structure of title molecule. The by B3LYP/6-31G(d,p) level are assigned to C–H in plane bending
FLT consists of 30 atoms; hence it undergoes 84 normal modes of vibrations. The C–H in plane bending vibration are observed at
vibrations. Of the 84 normal modes of vibrations, 29 modes are 1274, 1244 cm1 in FTIR and 1244 cm1 in FT-Raman spectra for
stretching vibrations, 28 are bending modes of vibrations and the the title compound. The C–H out of plane deformation is usually
remaining 27 modes are tensional vibrations. The potential energy observed between 1000 and 700 cm1 [31]. The C–H out of plane
distribution (PED) was calculated and the fundamental vibrational bending mode is observed in FTIR spectrum at 963 and 839 cm1
modes were characterized by their PED. The recorded (FT-IR, and 840 cm1 in FT-Raman spectrum for the title compound. The
FT-Raman) and calculated vibrational wavenumber along with theoretical values are calculated for out of plane bending vibra-
their relative intensities and probable assignments along with tions are at 966, 850 cm1 B3LYP/6-31G(d,p) level of theory.
608 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613

Table 1
Comparison of the experimental and calculated vibrational spectra and proposed assignments of FLT.

Mode Nos. Experimental wavenumbers/cm1 Theoretical wavenumbers/cm1/B3LYP/6-31G(d,p) Vibrational assignments with PED (P10%)
a b
FT-IR FT-Raman Unscaled Scaled IIR IRA
1 3360vs 3627 3485 24.37 4.98 tNH(100)
2 3207w 3276 3148 10.20 3.02 tCH(98)
3 3127s 3242 3115 1.62 3.88 tCH(98)
4 3055m 3080w 3218 3092 3.44 3.49 tCH(99)
5 3142 3019 25.27 6.28 tCH(36)
6 3138 3015 1.61 0.71 tCH(38)
7 3123 3001 38.88 10.13 tCH(29)
8 2984s 2985w 3121 2999 16.24 1.95 tCH(30)
9 2941m 2947w 3053 2933 16.06 18.35 tCH(39)
10 3050 2930 28.73 0.17 tCH(35)
11 2880w 2907w 3024 2905 31.88 4.01 tCH(98)
12 1716vs 1721m 1789 1719 131.92 17.76 tOC(82)
13 1611s 1610s 1667 1602 132.32 28.62 tCC(20) + tON(15)
14 1597w 1597s 1652 1587 126.49 62.25 tON(18) + tCC(16)
15 1541s 1540m 1626 1563 62.02 8.53 tCC(22) + tON(17) + dHNC(10)
16 1495w 1558 1497 558.23 34.35 dHNC(41)
17 1470w 1533 1473 116.15 0.14 dHCC(24)
18 1528 1468 3.40 2.22 dHCH(29) + dHCC(14) + cCHCH(15)
19 1516 1456 15.19 9 dHCH(27) + cCHCH(15)
20 1446w 1507 1448 1.41 3.01 cCHCH(29) + dHCH(27) + dHCC(12)
21 1499 1440 1.02 7.25 dHCH(31)
22 1391 1436 1380 14.55 1.57 tCC(22) + + dHCH(20) + dHCC(11)
23 1429 1373 0.66 2.3 dHCC(16) + dHCH(12) + cCHCH(11)
24 1410 1355 2.72 0.78 dHCC(20) + dHCH(17) + cCHCH(13)
25 1344s 1345vs 1400 1345 146.15 52.3 tON(23) + dHCC(14)
26 1393 1339 299.09 100 dHCC(37) + tON(18)
27 1321vs 1319s 1362 1309 86.27 33.2 tCC(25)
28 1274m 1339 1287 331.19 26.41 tCC(18) + tNC(16) + dHCC(12)
29 1337 1285 1.33 3.46 sHCCN(72)
30 1244vs 1244s 1296 1245 73.91 7.79 dHCC(28) + tCC(10)
31 1268 1218 89.99 32.94 tNC(22) + dHCC(21)
32 1173m 1187w 1229 1181 225.85 0.89 tFC(44)
33 1211 1163 43.26 13.69 cCHCH(18) + cCCCC(12)
34 1205 1158 103.26 1.56 tFC(22) + dHCC(11)
35 1138w 1143m 1173 1127 307.41 4.1 tNC(13) + dHCC(13) + tFC(12)
36 1123s 1168 1122 74.75 3.46 tNC(21) + tCC(15) + dHCC(15)
37 1102w 1144 1099 43.32 31.32 tNC(15) + dCCC(15) + dHCC(14) + tFC(11)
38 1121 1077 0.11 2.27 tCC(24) + cCHCH(12) + dHCC(11)
39 1117 1074 16.82 4.47 dHCC(29) + cCHCH(14) + tCC(11)
40 1040s 1041s 1058 1016 62.37 23.21 dCCC(28) + tFC(15)
41 963w 1006 966 0.96 0.64 cCCCH(52) + sHCCC(43)
42 977 939 0.26 3.41 cCHCH(25) + dHCC(22) + tCC(18)
43 931w 969 931 10.14 2.56 tCC(19) + dNCO(11)
44 902vs 901w 941 904 2.33 0.01 cCHCH(32) + dHCC(16) + sHCCN(16)
45 917 881 32.61 6.61 tCC(20)
46 862s 900 865 30.20 1.46 sHCCN(84)
47 886 852 1.82 4.32 tCC(25)
48 839s 840w 885 850 14.04 3.31 cCCCH(32) + sHCCC(32)
49 847 814 33.21 8.23 dONO(48)
50 754s 769 739 10.69 2.45 cOCON(51)
51 760 730 7.28 3.83 cCFFF(14) + tFC(13) + dCCC(12)
52 712s 755 726 0.06 0.3 cOCNC(61)
53 714 686 9.05 5.29 sCCCC(24) + cOCON(16)
54 655vs 694 667 4.81 9.74 tCC(19)
55 669 642 1.50 1.41 dCCC(24) + dONO(15) + tNC(10)
56 660 634 8.24 1.96 dCCC(16) + cCFFF(14)
57 657 631 2.62 3.5 sCCCC(24) + sCCCN(13)
58 605 582 4.19 1.92 dCNO(18) + dFCF(10)
59 579 556 58.76 0.83 sHNCC(86)
60 551 529 2.31 2.26 cCCFF(38) + dCNO(16)
61 520 500 3.00 2.04 dFCF(45) + dCNO(11)
62 478m 480 461 4.34 1.03 tNC(14)
63 456w 465 447 1.07 3.66 sCCCC(52)
64 417 400 4.91 0.19 cCCCC(20) + dNCO(16) + dCCN(12)
65 386 371 8.36 3.79 dCCF(23)
66 354 340 1.12 0.2 dCCF(19) + cCCCC(18)
67 325 312 0.80 1.77 dCCF(33) + sCCCC(25)
68 320 307 1.34 3.62 sCCCC(15) + dCCC(14) + sCCCN(12) + sCCNC(10)
69 314 302 8.14 1.62 dCCC(33) + dNCO(10)
70 274 263 2.53 3.83 tCC(14) + dCCF(15) + cCFFF(12)
71 257 247 2.81 1.9 sHCCC(40)
72 227w 245 235 5.11 2.41 dCCC(26) + sHCCC(11) + cOCNC(11)
73 220 211 0.50 14.63 dCCN(15)
 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613 609

Table 1 (continued)

Mode Nos. Experimental wavenumbers/cm1 Theoretical wavenumbers/cm1/B3LYP/6-31G(d,p) Vibrational assignments with PED (P10%)
a b
FT-IR FT-Raman Unscaled Scaled IIR IRA
74 216 207 1.01 0.25 sHCCC(47)
75 207 199 1.23 4.04 dCCN(31) + sHCCC(10)
76 176 169 0.52 8.12 dCCC(38) + dCCN(13)
77 134m 157 151 0.09 5.99 sCCCC(51)
78 110 106 0.32 38.55 sCCCN(31) + sCCNC(20) + sCCCC(10)
79 98 94 0.40 10.25 sCCCF(36) + sCCCN(13) + dCCF(10)
80 86s 88 84 1.21 5.96 dCCN(23) + dCNC(19) + dCCC(12) + sCCCF(11)
81 54 52 3.89 26.06 sCNCC(29) + sCCNO(24) + sCCCC(13)
82 43 41 2.01 27.24 sCCNO(36) + sCNCC(26) + sCCCF(22)
83 36 34 1.25 5.63 sCCNC(35) + sCNCC(19) + sCCCN(19)
84 17 16 0.00 39.68 sCCCN(80)
m-Stretching; d-in-plane-bending; c-out-of-plane bending; s-torsion; w-weak; s-strong; vs-very strong; vw-very weak; m-medium.
a
IIR-IR Intensity (Km mol1).
b
IRa-Raman intensity (Arb units) (intensity normalized to 100%).

Isopropyl group vibrations to PED (82%), this mode is not contaminated with other vibrations
The isopropyl group consists of two methyl groups attached to a suggesting that it is a pure mode. In keto-groups, the C@O in-plane
carbon that also has a C–H bond. The C–H moiety in the isopropyl bending vibration is found theoretically at 400 cm1 by B3LYP/6-
functional group is called methane group [36]. The antisymmetric 31G(d,p) level of theory. However, the experimental observation
C–H stretching mode of CH3 is expected around 2980 cm1 and does not support this kind of vibration. The C@O out-of-plane
CH3 symmetric stretching is expected at 2870 cm1 [37,38]. For bending vibration computed by B3LYP level at 235 cm1 show
the methyl group compound, the asymmetric stretching mode ap- good agreement with recorded weak FT-Raman band at
pears in the range 2825–2870 cm1, lower in magnitude compared 227 cm1. An analysis by PED calculations shows that this vibra-
to its value in CH3 (compounds) (2860–2935 cm1) whereas the tion is coupled with ring bending mode as shown in Table 1.
asymmetric stretching modes for both the type of compounds lie
in the same region 2925–2985 cm1 [37,38]. In the present calcu- Nitro group vibrations
lation, these modes are at the following wavenumbers: 3019, 3015, Commonly aromatic nitro compounds have strong absorptions
3001 and 2999 cm1 for CH3 asymmetric stretching vibrations and due to asymmetric and symmetric stretching vibration of the nitro
2933, 2930 cm1 for CH3 symmetric vibrations, while the experi- group at 1570–1485 and 1370–1320 cm1 respectively [41]. Usu-
mental observation for asymmetric CH3 stretching mode is ally the symmetric vibration is stronger than the asymmetric one
observed at 2984 cm1 and 2985 cm1 in FTIR and FT-Raman spec- in the Raman spectra and contrary holds in infrared [42,43]. This
tra respectively. Furthermore the symmetric stretching mode is could be due to the electron withdrawing substituent adjacent to
observed in both the spectra at 2941 and 2947 cm1 respectively. the nitro group that tends to increase the frequency of asymmetric
The asymmetric bending vibrations of the methyl groups should vibration and decrease symmetric vibration. Based on the above
appear between 1410 and 1550 cm1 [39]. In many molecules observation and literature data the strong asymmetric stretching
the symmetric deformation appears with an intensity from med- bands are measured at 1611, 1597 and 1541 cm1 in FTIR and
ium to strong and expected in the range of 1380 ± 25 cm1 [31]. 1610, 1597 and 1540 cm1 in FT-Raman spectrum. And the sym-
The title molecule obeys this statement. Asymmetric deformation metric bands are observed at 1344 and 1345 cm1 in FTIR and
vibration contributes to the bands calculated at 1468, 1456, 1448 FT-Raman spectra respectively. The calculated wavenumbers are
and 1440 cm1, the symmetric deformation vibrations (umbrella well reproduced in the experimental observations which are as-
mode) are calculated at 1380, 1373 and 1355 cm1 calculated by signed as asymmetric and symmetric stretching modes at 1602,
B3LYP level. Experimentally, asymmetric mode is observed at 1587, 1563 cm1 and 1345, 1339 cm1 respectively. The in-plane
1446 cm1 and symmetric mode is observed at 1391 cm1 in FTIR bending modes are calculated at 814 and 642 cm1 while the
spectrum. No bands are appeared in the FT-Raman spectrum. out-of-plane bending vibrations are assigned at 739, 726 and
686 cm1. As expected, these modes are pure modes as it is evident
Carbonyl group vibrations from the PED column.
The carbonyl stretching wavenumber have been extensively
studied by infrared spectroscopy [40]. This multiple bonded group Trifluromethyl group vibrations
is highly polar and therefore gives rise to an intense infrared The trifluromethyl group stretching vibrations are falling in the
absorption band in the region 1700–1800 cm1. The carbon–oxy- range of 1290–1200 cm1 [44,45]. In the present study, the med-
gen double bond is formed by pp–pp bonding between carbon ium and weak bands are observed in FTIR and FT-Raman spectra
and oxygen. Because of the different electronegativities of carbon at 1173 and 1187 cm1 respectively. The CF3 stretching wavenum-
and oxygen atoms, the bonding electrons are not equally distrib- bers are calculated in our theoretical study are at 1181, 1158, and
uted between the two atoms. The intensity of these bands can 1099 cm1 are assigned to the C–F stretching modes. Furthermore,
increase due to conjugation or formation of hydrogen bonds. The the calculated wavenumbers are at 582 and 500 cm1 in our title
following two resonance forms contribute to the bonding of the compound is assigned to CF3 in-plane-bending modes. Mode nos.
carbonyl group >C@O M C+AOA. The lone pair of electrons on 56, 60 and 70 are assigned as CF3 out-of-plane bending vibrations
oxygen also determines the nature of the carbonyl group [40]. In at 529 and 263 cm1. And also the CF3 torsional modes are calcu-
our present case, one can expect only one C@O stretching vibration lated at 84 and 41 cm1.
corresponding to the C1@O3 mode. The experimental wavenumber
observed as a very strong band in the FT-IR and FT-Raman spec- Phenyl ring modes
trum at 1716 and 1721 cm1 respectively, are assigned to C@O The aromatic carbon–carbon stretching vibration occurs in the
stretching vibration, which shows good agreement with that of cal- region 1620–1400 cm1 called ring modes. Usually the bands
culated value by B3LYP level at 1719 cm1. In this study, according appear between the range of 1630–1680 cm1, it is most likely a
610 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613

C@C (double bond) stretching vibration. Ring modes are lower in Table 2
wavenumber than C@C stretches because the bond order of aro- The observed (in deuterated DMSO) and predicted 1H and 13C NMR isotropic chemical
shifts (with respect to TMS, all values in ppm) for FLT.
matic carbon–carbon bonds is lower than in alkenes. The lowering
a a
of the force constant causes the difference between the spectra of Atom Experimental B3LYP/6- Atom Experimental B3LYP/6-
the two functional groups [36]. In the present work, the frequencies position (DMSO) 31G(d,p) position (DMSO) 31G(d,p)

observed in the FT-IR spectrum at 1611, 1541, 1391 and 1321 cm1 C1 176.4 179.31 H18 10.62 8.09
and predicted wavenumber by B3LYP level at 1602, 1563, 1380 and C2 35.2 49.24 H19 8.29 7.79
C5 144.0 148.08 H20 8.17 8.38
1309 were assigned to C–C stretching vibrations. The same vibra- C6 117.1 123.49 H21 8.06 9.01
tions in the FT-Raman spectrum are observed at 1610, 1540 and C7 126.1 133.31 H24 1.13 1.62
1319 cm1. The ring breathing mode at 1040 cm1 in FT-IR and C8 141.1 148.15 H25 1.13 1.22
the same vibration in FT-Raman at 1041 cm1 coincide exactly with C9 127.6 135.02 H26 1.13 1.23
C10 122.0 124.42 H27 1.13 1.28
the predicted value at 1016 cm1. The PED of this vibration is a
C11 123.4 135.11 H28 1.13 1.22
mixed mode as it is evident from Table 1 mixed with C–F stretching C22 19.1 30.17 H29 1.13 1.27
mode. The in-plane deformations are at higher frequencies than C23 19.1 30.52 H30 2.63 3.01
those of out-of-plane vibrations. Shimanouchi et al. [46] gave the a
Taken from Ref No. [47].
frequency data for these vibrations for different benzene deriva-
tives as a result of normal coordinate analysis. The calculated values
of mode nos (51, 55–56) are assigned to C–C–C deformation of phe-
nyl ring. The theoretically computed C–C–C out-of-plane and in- aid for the assignment of the experimental data and for the study
plane bending vibrational modes have been found to be consistent of our title molecule.
with recorded spectral value. The PED of these vibrations is not pure The range for 13C NMR chemical shift of the typical organic mol-
modes as it is evident from the last column of PED in Table 1. ecule usually is >100 ppm [48,49], the accuracy ensures reliable
interpretation of spectroscopic parameters. It is true from the
C–N vibrations above literature value, in our present study, the title molecule
The identification of C–N stretching vibrations is a very difficult FLT also falls with the above literature data except with the isopro-
task, since the mixing of several bands is possible in this region. pyl carbon atoms (C2, C22 and C23). Usually, the carbonyl carbon
However, with the help of the animation option of Gauss View enhanced the chemical shift to the shielded region. Notwithstand-
3.0 graphical interface for Gaussian programs and PED value from ing the fact and the adjacent electronegativity environment of
VEDA 4 program, the C–N stretching vibrations are identified and nitrogen impact to the present case for C1 chemical shift as it is ob-
assigned in this study. In the present work, the bands observed served at shielded region of 176.4 ppm in the experimental value
at 1138 and 1102 cm1 in FT-IR spectrum and at 1143 and and 179.31 ppm for calculated value. Among the ring carbon
1123 cm1 in FT-Raman spectrum have been assigned to, C–N chemical shifts, C5 and C8 carbon atoms fall in deshielding region
stretching vibrations for amide and nitro group respectively. The at 144.0 and 141.1 ppm and which is exactly correlated with the
corresponding calculated wavenumbers are assigned at 1127, calculated chemical shifts at 148.08 and 148.15 ppm respectively.
1122 and 1099 cm1 for C–N stretching modes which gives good The signals for aromatic carbons were observed at 117.1–
correlation with the experimental one. 144 ppm in 13C NMR spectrum for the title molecule, since those
carbon atoms which belong to phenyl also exactly correlate with
theoretically predicted value at 123.49–148.15 ppm.
Correlation coefficient
The H atom is the smallest of all atoms and mostly localized on
In order to investigate the performance and vibrational wave-
the periphery of molecules. Therefore their chemical shifts would
numbers for the title compound, the correlation coefficient be-
be more susceptible to intermolecular interactions in the aqueous
tween the calculated harmonic and observed fundamental
solution as compared to that for other heavier atoms. Another
vibrational frequencies are 0.999 for both the cases by B3LYP
important aspect is that, hydrogen attached or nearby electron
method 6-31G(d,p) basis set were also calculated which are shown
withdrawing atom or group can decrease the shielding and moves
in Fig. S2 (Supplementary information). As we can see the correla-
the resonance of attached proton towards to a higher frequency. By
tion graph, experimental fundamentals are in good agreement
contrast electron donating atom or group increases the shielding
with the scaled fundamental and are found to be better correlation
and moves the resonance towards to a lower frequency. In this
for DFT method.
study, the signals of the aromatic proton were observed at 8.06–
8.29 ppm it is well known the aromatic protons fall in the shielded
1 13
H and C NMR spectral analysis region. The calculated proton NMR chemical shifts show moderate
agreement with the experimental values except for isopropyl and
The characterization of the title compound was further en- amide protons. The chemical shifts obtained and calculated for
hanced by the use of 1H and 13C NMR spectroscopy. In the present the hydrogen atoms of methyl groups are quite low. All values
investigation we took the experimental chemical shift values from are 63 ppm [50] due to shielding effect. It is true from above liter-
the literature data [47] as shown in Table 2. The isotropic chemical ature data in our present study all the isopropyl protons at C22 and
shifts are frequently used as an aid in identification of reactive or- C23 appear as doublet with six protons integral at 1.13 ppm shows
ganic as well as ionic species. It is recognized that accurate predic- good agreement with computed chemical shift values and are
tions of molecular geometries are essential for reliable calculations shown in Table 2. The computed methine H atom (H30) chemical
of magnetic properties. Therefore, full geometry optimization of shift by B3LYP level (3.01 ppm) is in good agreement with experi-
FLT were performed by using B3LYP/6-31G(d,p) level of theory. mental value at 2.63 ppm which is also fall in shielding region.
Then, Gauge-Including Atomic Orbital (GIAO) 1H and 13C chemical
shift calculations of the compound have been made by the same le-
vel of theory. Density functional theory shielding calculations are Natural bond orbital analysis
rapid and applicable to large systems, but the paramagnetic contri-
bution to the shielding tends to be overestimated. In this sense, The Natural bond orbital analysis provides an efficient method
theoretical calculations of the chemical shifts may be used as an for studying intra and intermolecular bonding and interaction
 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613 611

among bonds, and also provides a convenient basis for investigat- C8–C9 (24.45 kJmol1); C6–C7 ? C5–C10 (19.04 kJmol1), C8–C9
ing charge transfer or conjugative interaction in molecular sys- (16.89 kJmol1); C8–C9 ? C5–C10 (17.03 kJmol1), C6–C7
tems. Some electron donor orbital, acceptor orbital and the (22.38 kJmol1); on the phenyl ring of the title molecule. While
interacting stabilization energy resulting from the second order the oxygen and nitrogen lone pairs (O3, O16, O17 and N4), have
micro disturbance theory are reported. The interaction result is a the greater interactions energy contribution in their (r⁄, p⁄) anti-
loss of occupancy from the localized NBO of the idealized Lewis bonding orbitals. Furthermore, the p⁄ (C15–O17) NBO conjugates
structure into an empty non-Lewis orbital. For each donor (i) and with respective bonds of p⁄ (C8–C9) resulting to maximum stabil-
acceptor (j), the stabilization energy E(2) associated with the delo- ization of 14.49 kJ mol1 in the antibonding interactions.
calization i ? j is estimated as

Fði; jÞ
2 Electronic properties
Eð2Þ ¼ DEij ¼ qi
ej  ei
The TD-DFT method is able to detect accurate absorption wave-
Some electron donor orbital, acceptor orbital and the interacting lengths at a relatively small computing time which correspond to
stabilization energy resulted from the second-order-micro-distur- vertical electronic transitions computed on the ground state geom-
bance theory, where qi is the donor orbital occupancy, ei and ej etry, especially in the study of solvent effect for vertical excitation
are diagonal elements and F(i,j) is the off diagonal NBO Fock matrix energy of electronic spectra [53–55]. To investigate the nature of
element reported [51,52]. The intramolecular hyperconjugative electronic transitions, the electronic spectra of FLT molecule were
interactions are formed by the orbital overlap between p(C–C) calculated using the time-dependent density functional theory
and geminal p⁄(C–C) bond orbitals which results intra-molecular (TD-DFT) approach at the B3LYP/6-31G(d,p) level on the basis of
charge transfer (ICT) causing stabilization of the system are pre- fully optimized ground-state structure. Calculations are performed
sented in Table 3. These interactions are observed as an increase for Methanol and Ethanol environment. Molecules allow strong p–
in electron density (ED) in (C–C) and (N–O) antibonding orbital that p⁄ and r–r⁄ transitions in the UV–Vis region with high extinction
weakens the respective bonds. The electron density of conjugated coefficients. It is targeted to understand the nature of electronic
double bond of FLT (1.6 e) clearly demonstrates strong delocaliza- transitions, positions of experimental absorption peaks, calculated
tion as evident from Table 3. The exception of the electron density absorption peaks (kmax), vertical excitation energies, oscillator
(ED) value of 1.985 e occurs for N15–O17 may be the reason of high strengths (f) and assignments of the transitions of the FLT molecule
electronegativity environment. We could see the strong intramolec- were calculated according to Frank Condon principle and the re-
ular hyperconjugative interaction of p-electrons with the greater sults are presented in Table 4 along with experimental UV–Vis
energy contributions from C5–C10 ? C6–C7 (19.16 kJmol1), spectrum recorded in ethanol and methanol as solvent are shown

Table 3
Second order Perturbation theory analysis of Fock Matrix in NBO basis for FLT.

Donor (i) ED (i)(e) Acceptor (j) ED (j)(e) E(2)a kJ mol1 E(j)-E(i)b a.u F(i,j)c a.u
p(C5–C10) 1.599 p⁄(C6–C7) 0.338 19.16 0.28 0.066
p⁄(C8–C9) 0.370 24.45 0.28 0.074
p⁄(C5–C10) 0.366 19.04 0.29 0.068
p(C6–C7) 1.707 p⁄(C8–C9) 0.370 16.89 0.29 0.064
r⁄(C11–F12) 0.104 3.75 0.51 0.041
r⁄(C11–F14) 0.107 6.32 0.52 0.054
p(C8–C9) 1.650 p⁄(C5–C10) 0.366 17.03 0.29 0.063
p⁄(C6–C7) 0.338 22.38 0.28 0.071
p(N15–O17) 1.985 LP(3)O16 1.444 11.72 0.19 0.078
p⁄(N15–O17) 0.613 6.85 0.34 0.051
r(C9–H20) 1.976 r⁄(C7–C8) 0.029 5.02 1.07 0.065
LP(2)O3 1.861 r⁄(C1–C2) 0.068 19.38 0.62 0.1
r⁄(C1–N4) 0.080 27.53 0.69 0.125
LP(1)O3 1.974 RY⁄(1)C1 0.018 16.45 1.5 0.141
LP(1)N4 1.659 p⁄(C1–O3) 0.250 55.92 0.29 0.115
p⁄(C5–C10) 0.366 37.89 0.29 0.094
LP(2)O16 1.895 r⁄(C8–N15) 0.103 13.11 0.56 0.077
r⁄(N15–O17) 0.063 18.76 0.7 0.103
LP(2)O17 1.895 r⁄(C8–N15) 0.103 12.78 0.56 0.076
r⁄(N15–O16) 0.062 19.72 0.7 0.106
p⁄(N15–O17) 0.613 p⁄(C8–C9) 0.370 14.49 0.12 0.054

ED means Electron Density.

a
E(2) means energy of hyper conjugative interactions.
b
Energy difference between donor and acceptor i and j NBO orbitals.
c
F(i,j) is the Fock matrix element between i and j NBO orbitals.

Table 4
The experimental and computed absorption wavelength k (nm), excitation energies E(eV), absorbance and oscillator strengths (f) of FLT in ethanol, methanol solutions.

Experimental TD-DFT/B3LYP/6-31G(d,p)
Ethanol Methanol Ethanol Methanol
k(nm) Abs. k(nm) Abs. k(nm) E(eV) F(a.u) k(nm) E(eV) F(a.u)
– – – – 343.95 3.605 0.288 344.21 3.602 0.289
296 0.885 293 0.575 308.69 4.016 0.014 309.35 4.008 0.012
229 1.22 231 0.808 303.18 4.089 0.102 303.09 4.091 0.099
612 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613

1.4

1.2 Ethanol 0.8

Methanol

1.0

Absorbance (a.u)
Absorbance (a.u)

0.6
0.8

0.6 0.4

0.4
0.2
0.2

0.0 0.0
200 250 300 350 400 450 300 400
Wavelength (nm) Wavelength (nm)

Fig. 4. The UV–Visible spectrum (Ethanol and Methanol) of FLT.

in Fig. 4. As can be seen from the Table 4 TD-DFT/B3LYP method by B3LYP/6-31G(d,p) level of theory. The frontier orbital gap helps
predicts one intense band in electronic transitions for the ethanol to characterize the chemical reactivity and kinetic stability of the
and methanol solvents at 4.016 eV (308.69 nm) and 4.008 eV molecule. A molecule with a small frontier orbital gap is more
(309.35) with the oscillator strength 0.014 and 0.012 respectively polarizable and is generally associated with a high chemical reac-
is in good agreement with the measured experimental data in eth- tivity, low kinetic stability and is also termed as soft molecule
anol at 0.885 eV (296 nm) and methanol at 0.575 eV (293 nm). The [56]. The eigen values of HOMO and LUMO and their energy gap re-
difference may be due to Bathochromic shift (red shift). Comparing flect the chemical activity of the molecule. A greater HOMO–LUMO
these values with the corresponding experimental values, TD-DFT energy gap has been taken as an indication of a high stability of the
method for both the solvent media is useful to predict UV–Vis title molecule shown in Fig. S3 (Supplementary information).
spectrum. According to the DFT/B3LYP features the HOMO–LUMO energy val-
The transitions that are formally forbidden by the selection ues are calculated as
rules are often not observed. However, theoretical treatments are
rather approximate, and in certain cases forbidden transitions are HOMO energy ¼ 7:0993 eV
observed, although the intensity of the absorption tends to be LUMO energy ¼ 2:5425 eV
much lower than for transitions that are allowed by the selection HOMO  LUMO energy gap ¼ 4:5568 eV
rules. The n ? p⁄ transition is the most common type of forbidden
transition. Here the energy required to bring about transitions The molecular orbitals show that the electron density in the HOMO
from the highest occupied energy level (HOMO) in the ground state mostly centered on the phenyl ring and carbonyl group while in
to the lowest unoccupied energy level (LUMO) is less than the LUMO the electron density predominantly located on the phenyl
energy required to bring about a transition from a lower occupied ring and nitro group, indicating a charge transfer of the type
energy level. The typical carbonyl compound undergoes n ? p⁄ n ? p⁄ upon excitation.
transition around 280–290 nm and p ? p⁄ transitions around
190 nm. Most of these n ? p⁄ transitions are forbidden and hence Conclusion
are of low intensity. Notwithstanding the fact, the title molecule
having the possibilities of conjucation effect in the solution state The spectroscopic techniques such as FTIR, FT-Raman, NMR and
and carbonyl group exhibits to the n ? p⁄ transitions. Molecular UV–visible supported by the recent development of computational
orbital coefficients analysis based on optimized geometry indicate tool such as DFT method allow the structural analysis of our title
that, for the title compound, the frontier molecular orbitals are molecule to be conducted in a seamless way. In this review, the
mainly composed of p-atomic orbitals, so the electronic transitions experimental approach to molecular properties has been shown
are mainly derived from the contribution of bands n ? p⁄ within by some examples of FTIR, FT-Raman, NMR and UV–Visible spec-
the FLT molecule. troscopy. The theoretical support has been addressed by example
of DFT/B3LYP/6-31G(d,p) calculations, and the peculiarities and
Frontier molecular orbital analysis limitations of the theoretical approach to the analysis have been
considered. Both the nitrogen atoms are bonded in para position
Investigation of molecular orbitals and the spatial distribution of aromatic ring in which amino (C–N = 1.471 Å) group dominates
of other molecular properties are useful for many purposes. MOs the increasing bond length than the secondary amide (C–
can provide important insight into bonding and other chemical N = 1.400 Å) group. It is noted that the high electronegativity and
properties. The analysis of the wave function indicates that the steric interaction between the NO2 and CF3 group and also the C–
electron absorption corresponds to the transition from the ground H- - - -O hydrogen bonding interactions with the O16–H20
to the first excited state and is mainly described by one-electron (2.378 Å). The vibrational frequencies of the fundamental modes
excitation from the highest occupied molecular orbital (HOMO) of the compound have been precisely assigned and analyzed and
to the lowest unoccupied orbital (LUMO). Highest occupied molec- the theoretical results were compared with the experimental
ular orbital (HOMO) and lowest unoccupied molecular orbital vibrations. The experimental data are deviated substantially from
(LUMO) are very important parameters for quantum chemistry. the calculated results according to the intermolecular hydrogen
The HOMO–LUMO energy gap for FLT molecule was calculated bonds and the crystal forces, which deforming the structure. The
 G. Mariappan, N. Sundaraganesan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 604–613 613

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