Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and computational calculations on (nitrophenyl) octahydroquinolindiones by DFT method

Article abstract of DOI:10.1016/j.saa.2014.09.021

In the present study, 2′-nitrophenyloctahydroquinolinedione and its 3′-nitrophenyl isomer were synthesized and characterized by FT-IR, FT-Raman, ¹H NMR and ¹³C NMR spectroscopy. The molecular geometry, vibrational frequencies, ¹

Full text of DOI:10.1016/j.saa.2014.09.021

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Nuclear magnetic resonance, vibrational spectroscopic studies,
physico-chemical properties and computational calculations
on (nitrophenyl) octahydroquinolindiones by DFT method
M.A. Pasha a, , Aisha Siddekha a,b, Soni Mishra c, Sadeq Hamood Saleh Azzam a, S. Umapathy c
⇑
a Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore 560001, India
b Department of Chemistry, Smt. VHD Central Institute of Home Science, Bangalore 560001, India
c Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, 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
Comparison of the 20-nitrophenyl and 30-nitrophenyl isomers of octahydroquinolindiones.
ꢀ
ꢀ
The theoretical calculations were
made using 6-311++G (d,p) method.
Experimental IR and Raman spectra
are in agreement with the theoretical
results.
ꢀ
ꢀ
ꢀ
Complete wave number assignments
are performed on the basis of PED.
Isotropic chemical shifts for 1H and
13C NMR were calculated using GIAO.
Molecular electrostatic potential and
thermodynamic functions have been
investigated.
a r t i c l e i n f o
a b s t r a c t
In the present study, 20-nitrophenyloctahydroquinolinedione and its 30-nitrophenyl isomer were synthe-
sized and characterized by FT-IR, FT-Raman, 1H NMR and 13C NMR spectroscopy. The molecular geome-
try, vibrational frequencies, 1H and 13C NMR chemical shift values of the synthesized compounds in the
ground state have been calculated by using the density functional theory (DFT) method with the 6-
311++G (d,p) basis set and compared with the experimental data. The complete vibrational assignments
of wave numbers were made on the basis of potential energy distribution using GAR2PED programme.
Isotropic chemical shifts for 1H and 13C NMR were calculated using gauge-invariant atomic orbital (GIAO)
method. The experimental vibrational frequencies, 1H and 13C NMR chemical shift values were found to
be in good agreement with the theoretical values. On the basis of vibrational analysis, molecular electro-
static potential and the standard thermodynamic functions have been investigated.
Article history:
Received 22 February 2013
Received in revised form 10 September
2014
Accepted 11 September 2014
Available online xxxx
Keywords:
Octahydroquinolinediones
Raman spectroscopy
Vibrational spectroscopy
DFT
Ó 2014 Elsevier B.V. All rights reserved.
NMR
Computational studies
Introduction
Quinolinones are naturally occurring compounds; they exhibit a
broad spectrum of pharmacological activities which include anti-
cancer [1], antihypertensive [2], antiviral [2], and antibiotic [3]
⇑
Corresponding author. Tel.: +91 8022961337; fax: +91 8022961331.
E-mail address: m_af_pasha@ymail.com (M.A. Pasha).
http://dx.doi.org/10.1016/j.saa.2014.09.021
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

2
M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
activities. Toxicity of quinolinone is known to be low when com-
pared to that of other commonly used antimicrobial agents; hence,
quinolinones are considered to be relatively well-tolerated agents
[4]. They are potent chemotherapeutic agents and are used for
the development of inhibitors for the treatment of a broad range
of bacterial infections [5]. Inhibitory activity of quinolinones
against cathepsin V, a papain-like cysteine protease has been
reported [6]. 2(1H)-Quinolinones have been reported to exhibit
the cardiac stimulant activity [7] and methionyl-tRNA synthetase
inhibition [8]. Quinolinone derivatives have also been patented
for treating schizophrenia and related psychic disorders such as
acute mania, bipolar disorder, autistic disorder and depression [9].
Literature survey reveals that, there are reports on the synthesis
of quinolinones, but no structural study of such compounds seems
to be present. Detailed knowledge on the molecular structure and
spectral behavior of these compounds and their derivatives will aid
the understanding of chemical and biological properties. In the
present study, we describe the structural, vibrational, NMR and
reactivity analyses of the derivatives of quinolinones viz., 20-nitro-
phenyloctahydroquinolindione (20-NOHQ) and its isomer 30-nitro-
phenyloctahydroquinolindione (30-NOHQ) through spectral
measurements. Theoretical calculations were carried out by den-
sity functional theory (B3LYP) method using 6-311++G (d,p) basis
set. The calculated results were compared with the observed spec-
tral values and were analyzed in detail. The aim of this work is to
explore the molecular dynamics and the structural parameters
which govern the chemical behavior, and to compare predictions
made from the theory with the experimental observations.
filtered and washed with water; the dry solid residue was treated
with dichloromethane and filtered to get ZnO which could be
reused. The filtrate was then evaporated to get the desired product,
which was subjected to silica gel column chromatography [silica
gel G, 100–200 mesh] to get the pure product in 90% yield. The
structures of both the products were confirmed by their FT-IR, 1H
NMR, 13C NMR spectral analyses.
Experimental details
FT-IR spectra were recorded in the range 4000–400 cmꢁ1 on a
Bruker Optics Alpha-P FT-IR spectrophotometer with attenuated
total reflectance (ATR) module. The FT-Raman spectra were
recorded in solid phase on Bruker Optics Multi-RAM FT-Raman
spectrophotometer using Nd-YAG laser operating at 1064 nm as
an excitation source at the resolution of 4 cmꢁ1 1H NMR and 13C
.
NMR spectra were obtained using a Bruker instrument operating
at 400 MHz and 100 MHz respectively. Chemical shifts are
reported on d(delta) scale using tetra methyl silane as an internal
standard and CDCl3 as solvent. Elemental analysis was carried
out using vario MICRO V1.9.7 elemental analyzer. All the reactions
were monitored by thin-layer chromatography (TLC). All the chem-
icals and solvents used were commercial and of analytical grade.
Computational details
Calculations for electronic structure and geometry optimization
of the stable isomers of the molecule were done by DFT [15] using
the Gaussian 09 program [16] package employing 6-311++G (d,p)
basis sets and Becke’s three parameter (local, nonlocal, Hartree–
Fock) hybrid exchange functionals with Lee–Yang–Parr correlation
functionals (B3LYP) [17–19]. The absolute Raman intensities and
infrared absorption intensities were calculated in the harmonic
approximation at the same level of theory as used for the opti-
mized geometries from the derivatives of the dipole moment and
polarizability of each normal mode respectively. We have used
hybrid DFT B3LYP 6-311++G (d,p) method for vibrational frequency
calculations, which is known to be very appropriate; although GGA
is found to be accurate method for predicting many material prop-
erties including vibrational properties, for example: Sarrio et al.
[20] presented a comparative study between different DFT method
for vibrational property calculations of triatomic molecules and
concluded that GGA is more appropriate method than hybrid func-
tional method, and recently very accurate GGA based calculations
by Adjokatse et al. [21] also proved the accuracy of this method
in case of polymeric systems.
Materials and methods
Synthesis
Occurrence of quinolinone scaffolds in a range of biologically
active compounds, natural products and in the designed medicinal
agents, necessitate the development of simple and efficient meth-
ods for the synthesis of quinolinones and their derivatives. Conven-
tional methods of synthesis include the base-catalyzed Friedlander
[10] and acid-catalyzed Knorr reactions [11]. Other reported meth-
ods are the Baylis–Hillman reaction [12], by the reduction of the
nitro group into amino group using Zinc–Acetic acid followed by
condensation sequence, and transition metal catalyzed cyclocarb-
onylation of 2-vinylanilines [13].
Reported methods are not completely satisfactory with regard
to the yield, reaction conditions, cost of the reagents, catalysts,
and due to involvement of multistep strategies.
Recently, we reported a multi-component synthesis of novel
octahydroquinolindiones using ZnO as a readily available, inexpen-
sive and environment friendly catalyst [14]. 20-NOHQ and 30-NOHQ
were prepared by this method by refluxing a mixture of 2-nitro-
benzaldehyde (1 mmol) or 3-nitrobenzaldehyde (1 mmol), diethyl
malonate (1 mmol), ZnO (0.025 g, 7.5 mol%) in water (10 mL) for
30 min; dimedone (1 mmol) and ammonium acetate (2 mmol)
were then added to the reaction mixture (Scheme 1) and refluxed
for the remaining period (90 min). The crude product obtained was
The normal-mode analysis was employed to calculate PED for
each of the internal coordinates using localized symmetry
[22,23]. For this purpose a complete set of 144 internal coordinates
was defined using Pulay’s recommendations [22,23]. The vibra-
tional assignments of the normal modes were proposed on the
basis of the PED calculations using the program GAR2PED [24].
Raman and IR spectra were simulated using a pure Lorentzian band
profile (fwhm = 10 cmꢁ1). Visualization and confirmation of the
O2N
O
CHO
O
O
O
ZnO/ H2O
O
O
+
NH OAc
4
+
+
Reflux
O
100-120 0
C
O
O2N
N
H
O
O
Scheme 1.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
3
Fig. 1. Optimized structures of octahydroquinolindione isomers (a) 20-NOHQ (b) 30-NOHQ.
calculated forms of the vibrations were done using the CHEM-
CRAFT program [25].
was calculated to be ꢁ1336.539 by DFT method and ꢁ1336.546
by Hartree respectively. The enthalpy difference between these
two molecules is 4.393 kcal/mol. Since these energy differences
are much larger than kT (at room temperature), there is almost
no possibility of coexistence of different molecules at room
temperature.
Calculated DFT vibrational wave numbers are known to be
higher than the experimental wave numbers as the anharmonicity
effects are neglected. The vibrational wave numbers were obtained
from the DFT calculations using a dual scaling procedure for the
fingerprint region (below 1800 cmꢁ1) and X-H stretching (above
1800 cmꢁ1) regions respectively [26,27]. Recently, a few good
papers using uniform scaling showed very good agreement
between calculated and experimental frequencies [28]. In addition
to uniform frequency scaling factors, dual scaling factors were
determined to improve the agreement between computed and
observed frequencies. The dual scaled error distributions are more
symmetric, compared with the uniform scaled frequency errors
[28]. All the calculated vibrational wavenumbers reported in this
study are the scaled values.
The optimized structures of the 20-NOHQ and 30-NOHQ mole-
cules were compared by superimposing them using a least-square
algorithm which minimizes the distances between the correspond-
ing non-hydrogen atoms (Fig. 2). The agreement between these
molecules shows that, the geometry optimization almost repro-
duces the different conformations (overall average deviation
0.078 Å). The main differences are due to the position of the nitro
group in the phenyl ring.
Molecular electrostatic potential
The molecular electrostatic potential (EPS) at a point r in the
Results and discussion
space around a molecule is (in atomic units):
Molecular geometry
Z
0
0
X
~
ZA
q
ðr Þdr
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
VðrÞ ¼
ꢁ
0
~
~
jr ꢁ rj
~
~
The molecular structures of both the isomers belong to C1 point
group symmetry. The optimized molecular structures of the iso-
mers were obtained from GAUSSIAN 09 program as shown in
Fig. 1. The minimum energy of the title compound and its isomer
RA ꢁ r
A
ZA is the charge on nucleus A, located at RA and
tronic density function for the molecule. The first term in the
q
(r0) is the elec-
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

4
M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
is incompletely shielded. By definition, the electron density isosur-
face is a surface on which molecule’s electron density has a partic-
ular value and that encloses a specified fraction of the molecule’s
electron probability density. Coloring the isosurface with contours
shows the electrostatic potential at different points on the electron
density isosurface. The electron density isosurface on to which the
electrostatic potential surface has been mapped are shown in
Figs. 3 and 4 for 20-NOHQ and 30-NOHQ respectively. The different
values of the electrostatic potential at the surface are represented
by different colors; red represents regions of most negative
electrostatic potential, blue represents regions of most positive
electrostatic potential and green represents regions of zero
potential. Potential increases in the order red < orange < yellow
< gre en < blue.
Vibrational analysis
The total number of atoms in the 20-NOHQ molecule is 50
resulting in 144 (3N-6) normal modes. Here, N is the number of
atoms in the molecule. The vibrational frequency and potential
energy distribution of each normal modes obtained by DFT/
B3LYP methods using 6-311++G (d,p) basis set for 20-NOHQ and
its isomer are summarized in Table 1. The title compound has
the molecular formula of C20H22O6N2, belongs to C1 point group
and has 144 normal modes of fundamental vibrations.
DFT calculations yield Raman scattering amplitudes which can-
not be taken directly to be the Raman intensities. The Raman scat-
tering cross section, orj/oX, which are proportional to Raman
intensity may be calculated from the Raman scattering amplitude
and predicted wavenumbers for each normal mode using the rela-
tionship [30,31].
Fig. 2. Comparison of the 20-nitrophenyl and 30-nitrophenyl isomers of
octahydroquinolindiones.
expression represents the effect of the nuclei; the second represents
that of electrons. The two terms have opposite signs and therefore
opposite effects. V(r) is their resultant at each point r; it is an indi-
cation of the net electrostatic effect produced at the point r by the
total charge distribution (electrons + nuclei) of the molecule. EPS
serves as a useful quantity to explain hydrogen bonding, reactivity
and structure–activity relationship of molecules [29].
Electrostatic potential correlates with dipole moment, electro-
negativity, partial charges and site of chemical reactivity of the
molecule. It provides a visual method to understand the relative
polarity of a molecule. While the negative electrostatic potential
corresponds to an attraction of the proton by the concentrated
electron density in the molecule, the positive electrostatic poten-
tial corresponds to repulsion of the proton by atomic nuclei in
regions where low electron density exists and the nuclear charge
0
1
!
ꢁ
ꢂ
4
@
rj
X
24p4
45
ð
m0
ꢁ
mj
Þ
h
@
A
h
i
¼
Sj
8p
2cmj
ꢁhcmj
@
1 ꢁ exp
kT
where Sj and
mj are the scattering activities and the predicted wave-
numbers, respectively of the jth normal mode, m0 is the wavenum-
Fig. 3. Molecular electrostatic potential mapped on the isodensity surface in the range from ꢁ5.76eꢁ2 (red) to +5.76eꢁ2 (blue) for 20-NOHQ calculated at the B3LYP/6-311G
(d,p) level of theory. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
5
Fig. 4. Molecular electrostatic potential mapped on the isodensity surface in the range from ꢁ6.51eꢁ2 (red) to +6.51eꢁ2 (blue) for 20-NOHQ calculated at the B3LYP/6-311G
(d,p) level of theory. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
ber of the Raman excitation line and h, c and k are universal con-
stants. The Raman intensities obtained using this relationship
match quite nicely with the experimentally observed intensities
as shown in Figs. 5 and 6.
the NH stretching internal coordinate and it is quite overestimated
in the calculations. In amides the out-of-plane NH deformation is
expected in the region 650 50 cmꢁ1 [35] and bands at 685 cmꢁ1
in the IR spectra, 660 cmꢁ1 in the Raman spectra are assigned as
this mode is calculated at 663 cmꢁ1
.
The compounds containing nitro group are readily identified ꢁb1y
Vibrational wavenumbers
asymmetric bands which observed in the region 1550–1490 cm
.
In the 20-NOHQ, band found at 1519 cmꢁ1 (IR) and 1524 cmꢁ1
(Raman) calculated at 1561 cmꢁ1 is attributed to NO2 asymmetric
stretching vibrations, and thus coincides well with the experimen-
tal observations.
Comparison of calculated wavenumbers at the B3LYP/6-311++G
(d,p) level with experimental values reveals an overestimation of
the wavenumber of the vibrational modes due to neglect of anhar-
monicity present in real system. Since the vibrational wavenum-
bers obtained from the DFT calculations are higher than the
experimental wavenumbers. Figs. 5–8 show a comparison between
experimental and calculated Raman and IR spectra for 20-NOHQ
and 30-NOHQ.
In 20-NOHQ, the bands at 1290, 1262, 1215, and 1182 cmꢁ1 (IR)
are assigned to CAH in-plane bending vibrations. Corresponding
bands are observed at 1287, 1249, 1211 and 1195 cmꢁ1 in 30-
NOHQ. The IR bands at 987, 957, 890, 787 and 743 cmꢁ1 are
assigned to CAH out-of-plane bending vibrations.
Ring vibrations
Methyl and methylene group vibrations
The CAH stretching vibration in ring is usually strong in both
the IR and Raman spectra. CAH stretching vibrations of aromatic
structures generally occur in the region 3100–2800 cmꢁ1 [32]
which is the characteristic of CAH stretching vibration. The IR
bands observed at 3099, 3090, 3075, and 3065 cmꢁ1, and Raman
bands at 3080 and 3069 cmꢁ1 are assigned to stretching vibrations
of the phenyl ring modes in Ring 3. These bands show a very good
agreement with the scaled vibrations obtained. The aromatic in-
plane CAH bending and out-of-plane bending vibrations normally
occur in the region 1300–1000 cmꢁ1 and 750–1000 cmꢁ1, respec-
Three methyl groups are present in the molecule. Two of them
are directly connected to the Ring 1, and the other one is connected
to the CH2 group in the side chain of Ring 2. The asymmetric
stretching mode of methyl group is expected to be around
2980 cmꢁ1 and symmetric stretching at 2870 cmꢁ1 [36,37]. In 20-
NOHQ, the modes appearing at 2997, 2825 and 2790 cmꢁ1 are
assigned to CH3 anti-symmetric stretching modes. The CH3 sym-
metric stretching normal modes are assigned to bands at 2753,
2736 and 2729 cmꢁ1 in the IR spectrum and at 2939, 2926 and
2779 cmꢁ1 in the Raman spectrum.
The symmetric and asymmetric bending vibrations of methyl
group are normally expected in the regions 1465–1440 cmꢁ1. The
asymmetric bending of methyl groups observed at 1427, 1410
and 1386 cmꢁ1 in the IR and 1425, 1414 and 1385 cmꢁ1 in the
Raman spectra are in good agreement with the calculated values.
The corresponding experimental wavenumbers for 30-NOHQ, are
observed at 1417 and 1374 cmꢁ1 in the IR spectrum.
tively [33]. The
and 2769 cmꢁ1 in the IR spectra and calculated to be at 2988 and
2935 cmꢁ1
The
t(CH) wavenumber in Ring 2 is assigned at 2908
.
t
(CH2) wavenumber in Ring 1 is assigned at 2857, 2743,
2722, and 2714 cmꢁ1 in the IR spectra and at 2775 and
2725 cmꢁ1 in the Raman spectra.
The N H stretching vibrations are weaker and sharper, and occur
in the region 3500–3300 cmꢁ1 [34]. This band is intense in infrared
spectra but not observed in Raman spectrum. For 20-NOHQ, the N H
stretch is calculated to be at 3591 cmꢁ1 corresponds to 3393 cmꢁ1
in IR spectrum. This is a pure mode having 99% contribution from
The asymmetric and symmetric stretching bands of methylene
hydrogens (C42H2) in 20-NOHQ were observed at 2876 and
2781 cmꢁ1
.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

Table 1
Theoretical and experimental vibrational wavenumbers (cmꢁ1) of 20-NOHQ.a
Calculated
Unscaled
Observed
PEDb
Scaled
20-NOHQ
Scaled
30-NOHQ
IR
Raman
3591
3215
3197
3190
3175
3119
3105
3096
3093
3093
3091
3087
3086
3079
3056
3039
3038
3036
3026
3017
3010
3002
1787
1767
1711
1674
1645
1613
1573
1516
1513
1512
1507
1498
1496
1493
1487
1486
1474
1473
1464
1427
1426
1405
1399
1391
1387
1378
1363
1346
1338
1325
3468
3106
3088
3081
3067
3013
2999
2991
2988
2987
2986
2982
2981
2974
2952
2935
2934
2933
2923
2914
2908
2899
1774
1754
1699
1662
1633
1601
1561
1505
1502
1501
1496
1487
1485
1482
1477
1475
1463
1462
1453
1417
1416
1395
1389
1381
1377
1368
1353
1336
1328
1316
3468
3115
3096
3085
3071
3014
2999
2990
2989
2986
2983
2982
2975
2954
2943
2935
2932
2931
2923
2916
2905
2899
1780
1760
1708
1655
1645
1609
1569
1506
1501
1500
1495
1488
1484
1478
1476
1476
1462
1462
1453
1418
1415
1394
1391
1376
1363
1358
1352
1335
1330
1313
3393
3099
3090
3075
3065
3018
3001
2997
2908
2876
2869
2857
2825
2790
2781
2769
2753
2743
2736
2729
2722
2714
1719
1618
1520
–
–
–
–
1519
–
–
–
–
–
–
–
–
1468
–
1449
1427
1410
–
1386
–
–
–
–
–
3080
3069
3038
–
–
–
–
–
–
–
2962
2949
–
2939
–
2926
2779
2775
2725
1720
1614
1578
–
–
–
–
1524
–
–
–
–
t
(N38AH)(99)
R3[
R3[
R3[
R3[
Me3[
Me3[
Me2[
t
t
t
t
(CAH)](98)
(CAH)](100)
(CAH](94)
(CAH)](98)
t
t
t
(CH3)](68) + CH2[t(C42H)](31)
(C43AH45)](94) + CH2[
(C28AH31)](91)
t(C42H)](5)
R2[
CH2[
R1 (CH2)(34) + Me1[
R1[ (CH2)](48) + Me1[t
Me2[
Me1[
t
t
t
t
(C16AH50)](98)
(C42H)](64) + Me3[
(C11AH)](39)+ Me2[
(C11AH)](46)
t(C43AH)](33)
t
t(C28AH)](21)
t
t
(C28AH)](68) + Me1[
(C11AH)](87) + Me2[
t
t
(C11AH)](21) + R1[
(C28AH)](12)
t(C5AH8)](5)
CH2[
(C15AH19) (98)
Me3[ (C43AH)](99)
R1[ (CH2](96)
t(C42H)](97)
t
t
t
Me2[
Me1[
R1[
R1[
COO[
R2[
R1[
t
R3[
R3[
t
t
(C28AH)](81) + Me1[
(C11AH)](79) + Me2[
t
t
(C11AH13)](5)
(C28AH)](13)
t
t
(CH2)](93)
(CH2)](98)
t
(C18AO40)](66) + R2[
(C17@O49)](62) + COO[
(C@O](78) +
t
t
(C17AO49)](14) + R2 d(C16)(5)
(C18AO40)](15)
(C2@C3)(6)
(C@O](7) + R1[das ring](6)
t
t
t
(C2@C3)(58) + R1[
t
t
t
(CAC)](59) + R3[das ring](9) + d(CC21H)(6) + d(CN35C)(5) + d(CC23H)(5)
(CAC)](63) + d(C22H33)(10) + R3[dring](9)
t
(N35O) (79) +
d(C42H2)(68) + Me3[d(C43H46)]16) + Me3[das(HCH)](6)
R3[ (CAC)](28) + R3[d(CC21H)](33) + d(CN35C)(18)
Me2[ (CH)](51) + Me1[ (C6C11)]34) + Me2[d(C6C28)](5)
q(N35C22)(6)
t
q
q
Me2[das(CH)](45) + Me1[ds(CH)](41)
Me1[ds(CH)](43) + d(C42H2)(31) + Me3[das(CH)](18)
Me1[ds(CH)](37) + Me2[das(CH)](27) + R1[d(CH2)](18)
R2[d(CN38)](44) + R2[
Me1[ (C6C11)](50) + Me2[q
Me3[das(C43H)](91) + d(C42C43)(7)
d(C22H33)(22) + d(CC23H)(20) + R3[t(CAC)](29) + R2[d(C15H)](6) + d(CN35C)(5)
R1[d(CH2)](72) + Me2[das(CH)](12) + Me1[ds(CH)](7)
R1[d(CH2)](94)
Me2[ds(C28)](50) + Me1[ds(C11)](37)
Me3[ds(CH)](50) +
–
–
–
–
1466
–
1477
1425
1414
–
1385
–
–
t
(C2AN38)](23)
(CH)](35)
q
x(C42H2)(26) + t(C42C)(13)
Me1[d(C11)](54) + d(C28HC)(38)
x
R2[d(C15H)](36) + R2[
R1[x(CCH)](42) + R1[t
(C42H2)(43) + Me3[ds(CH3)](37)
q
(C15H)](12) + d(CN35C)(6)
(CAC)](15) + R1[das ring](6)
(N35O)(55) + d(NO2)(15) + R3[ (C22AN35)](15)
(C15H)](13) + R2[d(C16H)](9) + R2[
(CAC)](30) + R1[d(C@O)](7) + R2[ (C3AC15)](7) + R2[
(CAC)](66) + d(CC21H)(14) + d(C22H33)(6)
(C16H)](20) + R2[ (C16H)](14) + R2[d(C16H)](10) + R1[
1355
1354
–
–
–
1358
1344
–
–
–
t
t
R2[
R1[
R3[
R2[
x
(C15H)](22) + R2[
c
x
(C16H)](9) + R2[
c(C16H)](7) + t(C16AC18)](5) + x(C42H2)(5) + R2[q(C16)](5) + R2[t(C15AC16](5)
t
t
x
t
t(C17AN38)](5) + R2[d(C16H)](5) + R2[dring](5)
c
c
(CC1H)](6)

1323
1311
1301
1298
1281
1271
1248
1238
1212
1192
1188
1181
1176
1176
1164
1149
1136
1133
1105
1090
1070
1054
1034
1033
1008
1000
983
1314
1301
1292
1288
1271
1262
1239
1229
1203
1183
1180
1173
1168
1167
1156
1140
1128
1125
1097
1082
1062
1047
1027
1025
1001
992
1306
1297
1291
1290
1269
1263
1230
1220
1212
1183
1176
1171
1168
1164
1138
1128
1117
1104
1095
1084
1047
1027
1025
1010
997
–
–
1290
–
–
1262
1235
1216
1215
1182
–
1170
–
–
–
–
1294
–
–
R1[
R1[
R2[
x
x
(CH2)](39) + R2[
x
(C16H)](8) + R1[
(CH2)](21) + (C6AC28)(6) + R1[
(C18AO41)](12) + R2[ (C15H)](6) + R2[t(C16AC17](6) + R2[d(CO)](5)
c
(CH2)](7) + R2[
c
(C16H)](5)
(CH2)](34) + R1[
c
t
t(C4AC5)](5)
t
(C17AN38)](19) + COO[
t
x
c
(C42H2)(83) + Me3[d(C42C43)](7)
R1[
R3[
R2[
R2[
t
t
t
t
(CAC)](28) + R1[
(CAC)](20) + R2[d(C15H)](13) + d(CC21H)(11) + d(CN35C)(10) + R2[
(C2AN38)](16) + R2[ (C15H)](10) + R2[d(CH39N38)](8) + R2[ (C16H)](8) + R2[d(C15H)](6) + R1[dring](6)
(C17AN38)](10) + R2[ (C15H)](8) + R2[ (C16H)](6) + R2[d(CO)](6) + R2[d(C15H)](6) + R1[dring](5) + R1[
(C22AC25)](19) + R3[dring](7) + d(CN35C)(6) + d(CC23H)(6) + R2[dring](5)
R3[d(CCH)](48) + d(CN35C)(9) + COO[ (C18AO41)](7) + R3[ (C21AC23)](6) + R2[d(C16H)](5)
COO[ (C18AO41)](20) + R2[d(C16)](15) + d(C22H33)(10) + R2[ (C16H)](6) + d(CC23H)(6)
(C2AN38)](9) + R1[ (CC1H)](9) + (C6AC11)(8) + Me2[ (C6C28)](15) + R1[ (CC1H)](6) + d(C6C11)(5) + R1[d(CC6C)](5)
(CH2)](36) + Me2[ (C6C28)](5)
c
(CH2)](24) + R1[
x
(CC6C)](12) + Me2[d(C6C28)](7) + Me1[das(CH)](7)
1261
1238
t
(C17AN38)](9) + R2[q(C15H)](7)
x
x
x
x
t(C3AC4)](5)
1217
1190
–
1188
–
t(C15AC20)(32) + R3[t
t
t
t
c
R2[
R1[
t
c
c
t
q
x
q
–
q(C42H2)(48) + Me3[d(C42C43)](25) + Me3[
q
(C42C43)](9) +
(C22AN35)](8) + d(CC23H)(6) + d(CC20C)(5)
(C6AC28)(12) + R1[ (CC6C)](10) + (C6AC11)(8) + R1(dring)(6) + R1[
(C42C43)](37) + (C42C)(20) + d(C42H2)(13) + d(CO41C)(6) + (C42C)(5)
(C1AC2)](20) + R2[ (CAC)](25) + R2[dring](9)
(C15AC16](27) + R3[dring](10) + R1[ (C4AC5)](6) + R3[
(C22AN35)](12) + R2[ (C15AC16](10)
(CAC)](61) + d(CN35C)(5)
c(C42H2)(5) + Me3[das(CH)](5)
–
1150
1134
–
R3[
R1[
t
c
(CAC)](26) + d(C22H33)(15) + R3[
(CC5H)](17) +
t
1141
–
–
1100
–
1066
–
–
1015
–
987
–
–
t
q
t
q(CC5H)](6) + R1[c(CC1H)](5) + d(C6C11)(5)
Me3[
q
t
t
–
R1[
R2[
t
t
t
1099
1078
1069
1047
–
1018
–
988
978
–
941
–
–
–
–
t
t(C22AN35)](6)
R3[dring](38) + R3[
t
t
R3[
t
t
(C42C)(18) + R1[
t
t
(C4AC5)](11) + R2[
(C15AC16](7) + Me2[d(C6C28)](6) + Me1[das(CH)]5) + d(C6C11)(5) + Me3[
(C42C)(13)
O(H34AC21AC26AC23)(38) + O(H33AC23AC25AC26)(24) + O(H24AC20AC23AC21)(15) + R3[puckring](14) + O(H27AC22AC25AC22)(5)
(C16AC18)](16) + (C42C) (13) + R1[ (CAC)](10) + R2[dring](5) + R1[ (C1AC6)](5) + R2[ (C17AN38)](5)
R1[ (CCH)](15) + d(C6C11)(12) + (C6AC11)(10) + (C16AC18)](8) + R2[ (C3AC15)](5) + (C42C)(5) + R1[
O(H27AC22AC25AC22)(34) + O(H24AC20AC23AC21)(23) + O(H33AC23AC25AC26)(19) + O(H34AC21AC26AC23)(6) + R3[
Me2[ (C6C28)](40) + (C6AC)(24) + Me1[das(CH)]12) + d(C6C11)(10)
R1[ (CAC](31) + Me2[ (C6C28)](16) + d(C6C11)(17) + Me1[das(CH)]7) + R1[
R2[O(O49AC16AN38AC17)](11) + R2[ (C16)](11) + R3[dring](8) + R2[ (C16AC17](6) + doop(C18AC16)(5) + R2[
(CCH)](19) + Me1[das(CH)](5)
(CCH)](50) + O(C4AO9AC3AC5)(10) + doop(C2@C3)(5)
t(C15AC16](8) + R1[dring](13)
t
(C42C)(30) + R2[
q(C42C43)](5)
Me2[d(C6C28)](34) + Me1[das(CH)](20) + t
995
974
948
945
941
937
927
921
t
t
t
t
t
976
970
944
937
934
921
897
q
t
t
t
t
t(C4AC5)](5)
977
951
944
941
928
903
sring](5)
957
–
932
–
q
t
q
t
q(CC5H)](5)
q
t
q(C15H)](5)
R1[t
(CAC)](31) + t(C6AC28)(15) + R1[q
–
R1[q
893
883
876
845
839
824
886
877
869
839
833
818
907
896
869
840
832
817
890
–
861
839
–
891
–
864
845
–
O(H24AC20AC23AC21)(23) + O(H27AC22AC25AC22)(20) + R3[puckring](10) + O(N35AC20AC25AC22)(7) + O(H34AC21AC26AC23)(5)
d(NO2)(27) + R3[dring](21) + R3[ (C22AN35)](8) + (C15AC20)(6)
(C42C)(37) + Me3[ (C42C43)](12) + O(H24AC20AC23AC21)(5) + O(H27AC22AC25AC22)(5) +
R1[dring](11) + doop(C2@C3)(8) + R2[puckring](8) + d(C18O41)(5) + d(CO41C)(5)
d(NO2)(26) + (C15AC20)(13) + R3[ (CAC)](12)+R2[ (C15H)](4)
(C6AC28)(23) + R1[dring](9) + d(C18O41)(5) + doop(C2@C3)(5)
t
t
t
q
x(C42H2)5)
t
t
q
–
–
t
812
803
772
758
727
722
806
797
766
752
721
716
808
808
764
735
721
713
813
787
–
743
–
814
793
754
747
720
–
q
(C42H2)(43) + Me3[d(C42C43)](38) + c(C42H2)(14)
O(N35AC20AC25AC22)(26) + doop(NO2)(20) + O(H34AC21AC26AC23)(16) + R3[puckring](14) + O(H24AC20AC23AC21)(6) + O(H33AC23AC25AC26)(6)
R3[puckring](9) + O(H33AC23AC25AC26)(8) + doop(C15C20) (6) + R2[ (C16AC17](6) + (C6C28)(6) + d(C18O41)(5)
R3[puckring](25) + O(H33AC23AC25AC26)(16) + O(N35AC20AC25AC22)(10) + doop(C18AC16)(9) + O(H27AC22AC25AC22)(6)
R3[puckring](17) + doop(NO2)(14) + R2[dring](9) + R2 O(O49AC16AN38AC17)(6) + R1[
R3[puckring](29) + doop(NO2)(10) + doop(C15C20)(5)
t
t
t(C3AC4)](6) + O(H34AC21AC26AC23)(5)
–
716
680
668
654
627
619
603
575
562
556
512
508
490
467
710
675
663
649
623
614
599
571
557
552
509
505
487
464
691
689
658
644
621
613
591
569
559
527
507
499
488
463
–
–
doop(C18AC16)(22) + R2[O(O49AC16AN38AC17)](13) + R3[puckring](7) + R3[das ring](5)
R3[dring](36) + d(NO2)(9) + R3[puckring(7) + R3[ (C22AN35)](6) + R3[ (C20AC22)](5)
R2[O(H39AC2AC17AN38)(29) + R2 O(O49AC16AN38AC17)(16) + R3(puckring)(7) + R2[
O(C4AO9AC3AC5)(18) + R3(das ring)(14) + R3(dring)(13) + R1[ (CH2)](5)
doop(C2@C3)(21) + R2[puckring](11) + R3[(das ring)](9) + O(C4AO9AC3AC5)(8) + R2[O(H39AC2AC17AN38)](5) + R1[d(C@O)](5)
R2[O(H39AC2AC17AN38)](14) + R3(puckring)(8) + R2[d(C@O)](7) + O(C4AO9AC3AC5)(6) + R1[d(C@O)](6) + R3[(das ring)](5) + doop(C18O41)(5)
doop(C2@C3)(21) + R3[puckring](6) + R2 O(H39AC2AC17AN38)(6) + d(CC20C)(6) + R2[puckring](6) + R2 O(O49AC16AN38AC17)(5) + R3[das ring](5) + R2[
R2[O(H39AC2AC17AN38)](20) + doop(C2@C3)(16) + R2[dring](10)
699
685
657
–
609
602
577
566
545
517
–
694
660
644
–
–
598
–
569
548
519
–
484
459
t
t
sring](5)
q
q(C15H19)](5)
q
(N35C22)(17) + O(N35AC20AC25AC22)(10) + doop(C2@C3) (10) + R3[
R3[ ring](14) + R3[puckring](8) + R1[d(C@O)](10) + R1[das ring](6) + doop(C15C20)(9)
R1[das ring](18) + d(C18OO)(10) + d(CC20C)(7) + R2[O(O49AC16AN38AC17)](6)
R2[dring](15) + R1[d(C@O)](10) + R1(dring)7) + R1[d(CC6C)](7) + R3[ ring](6)
R2[d(CO)](15) + R3[ ring](13) + doop(C2@C3) (9) + doop(C15C20)(7) + R1[das ring](12) + R2[O(H39AC2AC17AN38)](6)
R3[ ring](13) + R1[d(CC6C)](16) + R1[das ring(13) + d(C18O41) (6) + R1(das ring)(5) + d(C18OO) (5) + doop(C2@C3)(5)
sring](15) + R3[puckring](7)
s
s
485
464
s
s
(continued on next page)

Table 1 (continued)
Calculated
Observed
PEDb
Unscaled
Scaled
20-NOHQ
Scaled
30-NOHQ
IR
Raman
431
415
402
393
383
355
344
318
299
287
276
270
252
247
227
220
215
204
168
162
152
130
116
102
90
428
412
399
390
380
352
342
315
297
284
274
268
250
245
226
218
213
202
167
161
151
129
115
101
90
429
425
393
392
378
353
345
313
305
284
276
272
253
247
227
219
208
201
169
165
163
133
110
94
424
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
423
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
R1[
R3[
R3[
x
s
t
(CC6C)](26) + R1[das ring](17) + R1[
ring](53) + O(N35AC20AC25AC22)(21) +
(C22AN35)](18) + R1[ (CC6C)](17) + R3[dring](8) + R3[
q
(CC6C)](5) + R2[d(CO)](5)
q(N35C22)(5)
q
sring](7)
R1[d(CC6C)](13) + d(C42H2)(9) + R2[dring](8) + R1[das ring](8) + R1[
d(C42H2)(33) + R1[ (CC6C)](20) + d(C18O41)(5)
R3[ ring](10) + R1[ (CC6C)](8) + R1[ (CC6C)](7) + R1[d(C@O)](7) + R2[dring](6) + d(C42H2)(5) + R2[dring](5)
R1[d(CC6C)](30) + R1[das ring](11) + R1[ (CC6C)](8)
d(CC20C)(17) + doop(C2@C3)(10) + R2[ ring](9) + d(N35C)(9) + R1[d(CC6C)](6) +
d(CC20C)(13) + d(N35C)(12) + d(CO41C)(10) + d(C18OO)(9) + R2 (C16)(6) + R1[
R1[ (CC6C)](21) + Me2[ (CH3)](8) + d(CO41C)(6) + Me1[ (CH3)](5) + R1[d(C@O)](5)
(C18O41)(12) + R3[ (CH)](7) + R2[d(CO)](5) + Me2[ (CH3)](5)
(CH3)](17) + Me1[ (CH3)](15) + Me2[ (CH3)](8) + R3[ ring](6) + d(CO41C)(5)
(CH3)](25) + R3[ ring](13) + R1[ (CC6C)](10) + O(N35AC20AC25AC22) (9) +
(CH3)](18) + R2[dring](7) + O(N35AC20AC25AC22)(6) + d(N35C)(6) + (C15AC20)(5) + R3[das ring](5) + R2[
(CH3)](35) + Me2[ (CH3)](25)
(CH3)](16) + R1[das ring](7) + Me3[
(CH3)](25) + R1[ (CC6C)](15) + O(N35AC20AC25AC22)(10) + Me3[
(C16)](9) + (C16AC18)](7) + R2[dring](7) + d(CC20C)((7) + O(N35AC20AC25AC22)(5)
R2[O(H39AC2AC17AN38)](24) + R2[ ring](18) + R1[dring](15) + R2[puckring](15) + R3[dring](5)
R2[O(H39AC2AC17AN38](19) + R2[ ring](15) + (C18O41) (12) + R2[puckring](9) + R1[dring](5) + R1[
d(CO41C)(13) + (C18O41)(10) + d(C18O41)(7) + O(N35AC20AC25AC22)(7) + R2[puckring](7)+ d(C42H2) (6) + R3[
ring(C21)](32) + O(N35AC20AC25AC22)(13) + R3[ ring](21)
ring](41) + R2[O(H39AC2AC17AN38)](8) + R1[dring](12) + R2[
q
(CC6C)](7) + R1[x(CC6C)](5) + R3[t(C22AN35)](5)
q
s
q
x
x
s
q(N35C22)(5)
q
t(CC6C)](6) + R1[d(CC6C)](5)
t
s
s
Me3[
Me3[
Me1[
Me3[
Me1[
Me2[
Me2[
s
s
s
s
s
s
s
(CH3)](37) +
s
t
s
s
s
s
s
t
q(N35C22)(5)
t
sring](5) + R3[sring](5)
s
s
(CH3)](7) + O(N35AC20AC25AC22)(6)
(CH3)](5)
t
s
d(N35C)(21) + R2[
q
t
s
s
s
sring](5)
s
sring](5)
R3[
R1[
R1[
R1[
NO2[
NO2[
R1[
R2[
R2[
NO2[
R2[
s
s
s
s
s
s
c
ring](7) + doop(C2@C3)(5) + R2[puckring)(5)
(C16H)](7) + R2[O(H39AC2AC17AN38)](5)
(C16H)](6) + R1[dring](5)
ring](9) + R2 O(H39AC2AC17AN38)(9) + R2[puckring](6)
(C18O41)(10) + R2[puckring](8) + (O41C42)(7) + doop(C2@C3)(6) + (C18C16)(6)
ring)(13) + (O41C42)(8) + [ (NO2)](5) + R3[
ring](20) + R2[O(H39AC2AC17AN38)](6) + R2[ (C15H)](6)
(NC)(13) + R1[ ring](6) + R2[O(H39AC2AC17AN38)](6)
ring](14) + R2[ ring](13) + dCC20C)(7) + R2[ (C15H)](6)
ring](51) + R2[puckring](20) + NO2[ (NC)](9) + d(CC20C)(5)
(C18C16)(32) + (O41C42)(30) + R2[ ring](10) + NO2[ (NC)](5)
ring](23) +
ring](30)+
s
s
(C18C16)(11) + R1[dring](10) +
(C18C16)(14) + NO2[ (NC)](7) + R3[
ring](11) + R2[
s
(C18O41)(7) + R2[
83
74
63
55
40
33
27
21
s
s
s
ring](6) + R2[c
80
64
61
52
47
30
17
13
79
63
61
52
46
30
17
12
s
s
(NC)](18) + R3[
s
(NC)](20) +
s
s
s
s
s
s
ring](16) + R[puckring](15) + R2 O(H39AC2AC17AN38)(15) + R2[
ring](18) + doop(C15C20)(14) + R1[
ring](32) + R2[ ring)(17) + NO2[
(NC)](38) + R3[
s
s
s
sring](5)
s
c
s
s
s
s
s
s
q
s
s
17
s
s
s
s
a
Proposed assignment and potential energy distribution (PED) for vibrational normal modes. Types of vibration: t, stretching; d, deformation; O, out-of-plane bending; x, wagging; c, twisting; q, rocking; s, torsion.
b
Potential energy distribution (contributing P5) for 20-NOHQ.

M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
9
Fig. 5. FT-Raman spectrum of 20-NOHQ.
Fig. 6. FT-Raman spectrum of 30-NOHQ.
Fig. 7. FT-IR spectrum of 20-NOHQ.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

10
M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
Fig. 8. FT-IR spectrum of 30-NOHQ.
Carbonyl group vibrations
and 1H NMR spectra in DMSO-d6 are presented in Fig. 9. The singlet
observed at 10.86 ppm is assigned to N H and this has been com-
puted to be at 6.12 ppm. The phenyl protons resonate as the mul-
tiplet at 7.49–8.26 ppm experimentally and these have been
predicted in the range 7.33–9.50 ppm. A singlet at 2.35 and
2.40 ppm correspond to the methylene hydrogens of the ring and
the singlet at 4.09 to the methylene protons of the side chain. In
the 13C NMR spectrum, C18 in Ring 2 and C22 in Ring 3 appear
at lower chemical shift of 161.8 and 133.3 ppm due to neighboring
electronegative oxygen and nitrogen atoms. C42 appears at higher
field of 54.8 ppm due the methyl and the ester groups attached to
it. The carbonyl carbon C4 at 191.30 ppm, methyl carbons C11,
C28, and C43 at 26.1, 27.6, and 16.2 are in good agreement with
the predicted chemical shifts. It is observed from Table 2 that the
predicted chemical shift values are in closer agreement with the
experimental values. The experimental and theoretical values of
1H and 13C NMR for 30-NOHQ are given in the Table S2 as a supple-
mentary material.
Esters show a very strong band for the C@O group in the range of
17,501,735 cmꢁ1. Stretching mode of C18O40 in 20-NOHQ, is
observed at 1719 cmꢁ1 in IR as a very strong band and at
1720 cmꢁ1 in Raman as a weak band. A very strong band of the
amide carbonyl stretching vibration is observed at 1618 cmꢁ1 in
the IR and 1614 cmꢁ1 in the Raman spectra. The cyclic ketone
appears at 1520 cmꢁ1 in the IR spectra and 1578 cmꢁ1 in the Raman
spectra. In 30-NOHQ, these modes appear at 1736, 1587, 1525 cmꢁ1
in the IR and 1612, 1578, 1551 cmꢁ1 in the Raman spectra. It is
observed from Table 1 that the calculated vibrational frequencies
of both the isomers are very close to the experimental values.
NMR spectra
1H and 13C NMR chemical shifts were calculated at the B3LYP/6-
311++G (d,p) level. The experimental and theoretical values of 1H
13
and C NMR spectra of 20-NOHQ are given in Table 2. The 13C
Table 2
Thermodynamic properties
Observed and calculated NMR chemical shifts (d ppm) for 20-NOHQ.
Atom
d
d
Da
Atom
d
d
Da
Thermal properties such as thermal diffusivities, specific heat
capacities etc. of octahydroquinolindiones are crucially important
from the viewpoint not only of fundamental aspects for academia
but also of various processing and applications of the octahydroqu-
inolindiones. On the basis of vibrational analysis and statistical
thermodynamics, the standard thermodynamic functions: heat
capacity (C°p,m), entropy (S°m) and enthalpy (H°m) were obtained
and listed in Table 3. As observed from Table 3, values of heat
capacity, entropy and enthalpy increase with the increase of tem-
perature from 100 to 500 K which is attributed to the enhancement
of molecular vibration with increase in the temperature.
(Calculated) (Expt.)
(Calculated) (Expt.)
C1
C2
C3
C4
C5
C6
C11
C15
C16
C17
C18
C20
C21
C22
C23
C25
C26
C28
C42
C43
46.36
153.64
118.92
203.83
55.89
46.8
115.2
148.8
191.6
32.3
ꢁ0.44
H7
H8
2.49
1.70
1.89
0.75
0.77
1.35
4.93
8.38
9.50
0.45
0.55
1.22
0.69
7.33
7.53
6.12
2.61
2.22
1.87
9.56
8.30
3.76
2.35
2.4
2.4
0.14
38.44
ꢁ0.70
ꢁ0.51
ꢁ0.36
ꢁ0.34
ꢁ1.00
0.48
1.14
2.03
ꢁ0.66
ꢁ0.56
0.11
ꢁ29.88 H10
12.23
23.59
13.13
5.49
H12
H13
H14
H19
H24
H27
H29
H30
H31
H32
H33
H34
H39
H44
H45
1.11
1.11
2.35
4.45
7.24
7.47
1.11
1.11
1.11
1.11
7.08
7.44
10.86
1.23
1.23
1.23
4.09
4.09
6.05
43.23
31.59
59.07
56.06
30.1
26.1
31.9
47.4
27.17
8.66
ꢁ6.59
24.82
5.68
171.51
186.62
140.98
146.61
161.08
140.39
140.02
131.96
25.63
178.1
161.8
135.3
122.7
133.3
129.5
115.2
121.5
27.6
The correlation between these thermodynamic properties and
temperatures T are shown in Fig. 10. The correlation equations
for octahydroquinolindiones are as follows:
23.91
27.78
10.89
24.82
10.46
ꢁ1.97
ꢁ0.42
0.25
0.09
ꢁ4.74
Cꢂ
¼ Y ¼ 1:4506 þ 0:30045T ꢁ 4:56ꢃ10ꢁ5T2 ðR2 ¼ 0:99953Þ
1.38
p;m
0.99
0.64
5.47
4.21
37.46
24.83
54.8
16.2
ꢁ17.34 H46
Sꢂ ¼ Y ¼ 60:6378þ0:32287T ꢁ3:88357ꢃ10ꢁ5T2 ðR2 ¼ 0:99999Þ
m
8.63
H47
H48
H50
ꢁ2.29
Hꢂ ¼ Y ¼ 249:5756þ0:00344T þ1:3922910ꢁ4T2 ðR2 ¼ 0:99999Þ
m
a
dcalculated ꢁ dexpt
.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
11
13
Fig. 9. 1H NMR and C NMR spectra of 20-NOHQ.
Table 3
Thermodynamic properties of 20-NOHQ at different temperatures at B3LYP/6-311++G
(d,p) level.
These equations could be used for the further studies on the
title compound. For instance, when the interaction of octahydroqu-
inolindiones with any other compound is studied, these thermody-
namic properties could be obtained from the above equations and
then can be used to calculate the change in Gibbs free energy of the
reaction, which will in turn help to judge the spontaneity of the
reaction.
T (K)
Hm (kcal/mol)
Cp,m (Cal/mol K)
Sm (Cal/mol K)
100
200
300
400
500
251.324
255.818
263.108
273.282
286.08
31.627
58.547
87.469
115.523
139.685
92.439
123.897
153.867
183.512
212.414
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

12
M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
Fig. 10. Temperature dependence of the thermodynamic values H°m, C°p,m, and S°m of 20-NOHQ.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021

M.A. Pasha et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (2014) xxx–xxx
13
[12] K.Y. Lee, J.N. Kim, Bull. Korean Chem. Soc. 23 (2002) 939–940.
[13] J. Ferguson, F. Zeng, N. Alwis, H. Alper, Org. Lett. 15 (2013) 1998–2001.
Conclusions
[14] S.H.S. Azzam, A. Siddekha, M.A. Pasha, Tetrahedron Lett. 53 (2012) 6306–6309.
[15] P. Hohenberg, W. Kohn, Phys. Rev. 136B (1964) 864–871.
[16] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson,
H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida,
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian,
J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J.
Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A.
Voth, P. Salvadorm, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels,
M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman,
J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B. Stefanov, G. Liu, A.
Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-
Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W.
Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision C.02, Gaussian
Inc., Wallingford, CT 06492, 2003.
Vibrational, electronic, NMR, reactivity and structural aspects of
20-NOHQ and its isomer 30-NOHQ were studied in detail based on
B3LYP/6-311++G (d,p) method, and the results were compared
with the experimental results. A detailed normal coordinate anal-
ysis of all the normal modes along with PED assignment has been
made indicating the composition of each normal mode. Compari-
son between the calculated and experimental vibrational frequen-
cies indicate that the results are in good agreement with
experimental values. The 13C and 1H NMR spectra of the com-
pounds were recorded, assignment of the chemical shifts were
done for calculated and experimental values. The thermodynamic
properties of the title compounds at different temperatures were
calculated, and the correlations between C°p,m, S°m, H°m and tem-
peratures have also been given for both the compounds.
[17] C.T. Lee, W.T. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785–789.
[18] R.G. Parr, W. Yang, Density Functional Theory of Atoms and Molecules, Oxford
University Press, New York, 1989.
[19] A.D. Becke, J. Chem. Phys. 98 (1993) 5648–5652;
G.A. Petersson, A. Bennett, T.G. Tensfeldt, M.A. Allaham, W.A. Shirley, J.
Mantzaris, J. Chem. Phys. 89 (1988) 2193–2218.
Appendix A. Supplementary material
[20] C. Clavaguera-Sarrio, N. Ismail, C.J. Marsden, D. Begue, C. Pouchan, Chem. Phys.
302 (2004) 1–11.
[21] S.K. Adjokatse, A.K. Mishra, U.V. Waghmare, Polymer 53 (2012) 2751–2757.
[22] P. Pulay, G. Fogarasi, F. Pang, J.E. Boggs, J. Am. Chem. Soc. 101 (1979) 2550–
2560.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.09.021.
[23] G. Fogarasi, X. Zhou, P.W. Taylor, P. Pulay, J. Am. Chem. Soc. 114 (1992) 8191–
8201.
References
[24] J.M.L Martin, C. Van Alsenoy, Gar2ped, University of Antwerp, 1995.
[25] G.A. Zhurko, D.A. Zhurko, Chemcraft, 2005, <http://www.chemcraftprog.com>.
[26] M.D. Halls, J. Velkovski, H.B. Schlegel, Theor. Chem. Acc. 105 (2001) 413421.
[27] S. Mishra, P. Tandon, A.P. Ayala, Spectrochim. Acta Part A 88 (2012) 116–123.
[28] A.K. Mishra, P. Tandon, J. Phys. Chem. 113 (44) (2009) 14629–14639.
[29] C. Santhosh, P.C. Misra, J. Mol. Model. 3 (1997) 172–181.
[30] G.A. Guirgis, P. Klaboe, S. Shen, D.L. Powell, A. Gruodis, V. Aleksa, C.J. Nielsen, J.
Tao, C. Zheng, J.R. Durig, J. Raman Spectrosc. 34 (2003) 322–336.
[31] P.L. Polavarapu, J. Phys. Chem. 94 (1990) 8106–8112.
[32] L.J. Bellamy, The Infrared Spectra of Complex Molecules, John Wiley, New York,
1956.
[33] G. Keresztury, Raman spectroscopy: theory, in: J.M. Chalmers, P.R. Griffiths
(Eds.), Handbook of Vibrational Spectroscopy, vol. 1, John Wiley & Sons, New
York, 2002.
[34] L.J. Bellamy, The IR spectra of Complex Molecules, John Wiley and Sons, New
York, 1975.
[35] N.P.G. Roges, A Guide to the Complete Interpretation of the Infrared Spectra of
Organic Structures, Wiley, New York, 1994.
[36] R.M. Silverstein, G.C. Bassler, T.C. Morrill, Spectrometric identification of
organic compounds, third ed., John Wiley & Sons, New York, NY, 1974. p. 239.
[37] J. Mohan, Organic Spectroscopy-Principles Applications, Narosa Publishing
House, New Delhi, 2001.
[1] (a) G. Claassen, E. Brin, C. Crogan-Grundy, M.T. Vaillancourt, H.Z. Zhang, S.X.
Cai, J. Drewe, B. Tseng, S. Kasibhatla, Cancer Lett. 274 (2009) 243–249;
(b) Z.-J. Ni, P. Barsanti, N. Brammeier, A. Diebes, D.J. Poon, S. Ng, S. Pecchi, K.
Pfister, P.A. Renhowe, S. Ramurthy, A.S. Wagman, D.E. Bussiere, V. Le, Y. Zhou,
J.M. Jansen, S. Ma, T.G. Gesner, Bioorg. Med. Chem. Lett. 16 (2006) 3121–3124.
[2] A. Afonso, J. Weinstein, M.J. Gentles, (Schering Corp.) WO 9203327, 1992.
[3] (a) R.M. Forbis, K.L. Rinehart Jr., J. Am. Chem. Soc. 95 (1973) 5003–5013;
(b) H.M. Hassanin, S.M. El-edfawy, Heterocycles 85 (2012) 2421–2436.
[4] J.C. Lanter, Z. Sui, M.J. Macielag, J.J. Fiordeliso, W. Jiang, Y. Qiu, S. Bhattacharjee,
P. Kraft, T.M. John, D. Haynes-Johnson, E. Craig, J. Clancy, J. Med. Chem. 47
(2004) 656–662.
[5] G. Anquetin, J. Greiner, P. Vierling, Tetrahedron 61 (2005) 8394–8404.
[6] P.D. Duarte, R.P. Severino, P.C. Vieira, D. Brömme, A.G. Corrêa, 4th Brazilian
Symposium on Medicinal Chemistry, Brazilian Chemical Society (SBQ).
[7] C.T. Alabaster, A.S. Bell, S.F. Campbell, P. Ellis, C.G. Henderson, D.A. Roberts, K.S.
Ruddock, G.M. Samuels, M.H. Stefaniak, J. Med. Chem. 31 (1988) 2048–2056.
[8] Farhanullah, S.Y. Kim, E.-J. Yoon, E.-C. Choi, S. Kim, T. Kang, F. Samrin, S. Puri, J.
Lee, Bioorg. Med. Chem. 14 (2006) 7154–7159.
[9] US 8247420 B2, US 12/124, 985, 2012.
´
[10] F. Domınguez-Fernandez, J. Lopez-Sanz, E. Perez-Mayoral, D. Bek, R.M. Martın-
´
Aranda, A.J. Lopez-Peinado, J. Cejka, Chem. Cat. Chem. 1 (2009) 241–243.
[11] M. Marull, O. Lefebvre, M. Schlosser, Eur. J. Org. Chem. (2004) 54–63. and
references cited therein.
Please cite this article in press as: M.A. Pasha et al., Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and com-
putational calculations on (nitrophenyl) octahydroquinolindiones by DFT method, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2014), http://dx.doi.org/10.1016/j.saa.2014.09.021