Spectroscopic (FT-IR, FT-Raman), first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis of 1,7,8,9-tetrachloro-10,10-dimethoxy-4-[3-(4- phenylpiperazin-1-yl)propyl]-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5- dione by density functio

Article abstract of DOI:10.1016/j.saa.2014.01.045

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 1,7,8,9-tetrachloro-10,10-dimethoxy-4-[3-(4- phenylpiperazin-1-yl)propyl]-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5- dione (TDPPAD) have been inve

Full text of DOI:10.1016/j.saa.2014.01.045

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Spectroscopic (FT-IR, FT-Raman), first order hyperpolarizability, NBO
analysis, HOMO and LUMO analysis of 1,7,8,9-tetrachloro-10,
10-dimethoxy-4-[3-(4-phenylpiperazin-1-yl)propyl]-4-azatricyclo
[5.2.1.02,6]dec-8-ene-3,5-dione by density functional methods
b
R. Renjith a, Y. Sheena Mary b, C. Yohannan Panicker a, , Hema Tresa Varghese ,
⇑
c
d
e
´
Magdalena Pakosinska-Parys , C. Van Alsenoy , T.K. Manojkumar
a Department of Physics, TKM College of Arts and Science, Kollam, Kerala, India
b Department of Physics, Fatima Mata National College, Kollam, Kerala, India
c Department of Medical Chemistry, Medical University of Warsaw, Oczki 3, 02-007 Warszawa, Poland
d Department of Chemistry, University of Antwerp, B2610 Antwerp, Belgium
e Indian Institute of Information Technology and Management-Kerala, Technopark Campus, Trivandrum, Kerala, 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 optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of
1,7,8,9-tetrachloro-10,10-dimethoxy-4-[3-(4-phenylpiperazin-1-yl)propyl]-4-azatricyclo[5.2.1.02,6]dec-
8-ene-3,5-dione have been investigated experimentally and theoretically using Gaussian09 software
package. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule.
The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has
been analyzed using NBO analysis. Mulliken’s net charges have been calculated and compared with
the atomic natural charges. Fist hyperpolarizability is calculated in order to find its role in non-liner
optics.
ꢀ
ꢀ
IR, Raman spectra and NBO analysis
were reported.
The wavenumbers are calculated
theoretically using Gaussian09
software.
The wavenumbers are assigned using
PED analysis.
The geometrical parameters are in
agreement with that of similar
derivatives.
ꢀ
ꢀ
a r t i c l e i n f o
a b s t r a c t
Article history:
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of
1,7,8,9-tetrachloro-10,10-dimethoxy-4-[3-(4-phenylpiperazin-1-yl)propyl]-4-azatricyclo[5.2.1.02,6]dec-
8-ene-3,5-dione (TDPPAD) have been investigated experimentally and theoretically using Gaussian09
software package. Gauge-including atomic orbital 1H NMR chemical shifts calculations were carried
out and compared with experimental data. The HOMO and LUMO analysis is used to determine the
charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative
Received 20 September 2013
Received in revised form 30 December 2013
Accepted 8 January 2014
Available online 21 January 2014
⇑
Corresponding author. Tel.: +91 9895370968.
E-mail address: cyphyp@rediffmail.com (C.Y. Panicker).
1386-1425/$ - see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2014.01.045

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
501
interaction and charge delocalization has been analyzed using NBO analysis. Molecular Electrostatic
Potential was performed by the DFT method and the infrared and Raman intensities have also been
reported. Mulliken’s net charges have been calculated and compared with the atomic natural charges. Fist
hyperpolarizability is calculated in order to find its role in non-liner optics. The calculated geometrical
parameters (SDD) are in agreement with that of similar derivatives.
Keywords:
FT-IR
FT-Raman
Azatricyclo
Hyperpolarizability
PED
Ó 2014 Elsevier B.V. All rights reserved.
Introduction
4-(3-bromopropyl)-4-azatricyclo[5.2.2.02,6] undecane-3,5,8-trione.
Kossakowski et al. reported 4-Azatricyclo-[5.2.2.02,6]-undecane-
The piperazines or cyclizines are generally considered as ethy-
lenediamine derivatives or cyclic ethylenediamines and are a broad
class of chemical compounds with many important pharmacologi-
cal properties. This di-nitrogen moiety has been an inseparable
component of plethora of drugs. Piperazines have the chemical sim-
ilarity with piperidine, a constituent of piperazine in the black piper
plant. Piperazine is introduced into medicine as a solvent for uric
acid [1,2]. Recently, piperazine derivatives containing tetrazole
nucleus have been reported as an antifungal agent [3]. The pipera-
zine-based research has attracted considerable attention in recent
years. Piperazine and substituted piperazine nuclei had constituted
an attractive pharmacological scaffold present in various potent
marketed drugs. The incorporation of piperazine is an important
synthetic strategy in drug discovery due to its easy modificability,
proper alkality, water solubility, the capacity for the formation of
hydrogen bonds and adjustment of molecular physicochemical
properties [4–7]. A broad range of biological active compounds dis-
playing antibacterial [8–11], antifungal [3,12], anticancer [13–15],
anti-parasitic [16,17], anti-histamin [18], psychotolytic [19] and
anti-depressive activities [20] have been also found to contain this
versatile core. In particular, structurally simple 1-(1-naphthyl-
methyl)-piperazine, as the efflux pump inhibitor, could exert posi-
tive effect on tetracyclines and ciprofloxacin against their
resistant bacteria [21,22]. Moreover, benzotriazole-based pipera-
zine derivatives and N,N0-bis(alkyloxymethyl) piperazines had
moderate antibacterial and antifungal activities against pathogenic
bacterial strains and fungal strains [23,24]. These results once again
highlighted that piperazine core was an important backbone and
prompted us to design some active molecules with piperazine
nucleus. Azatricyclo-dec-8-ene-3,5-dione derivatives have anti
bacterial and anti fungal activities with other important biological
activities [25]. Panicker et al. [26] reported the quantum chemical
3,5,8-triones as potential pharmacological agents [28]. Recently
3,8-diazabicyclo-[3.2.1]-octane analogues and 4-azatricyclo-[5.
2.2.02.6]-undecane-3,5,8-triones derivatives have been investigated
as potential agents for the inhibitory effects of anti-proliferation and
HIV-1 multiplication in MT-4 cells respectively [29]. In the present
work, IR, Raman and 1H NMR parameters of the title compound are
described both experimentally and theoretically.
Experimental details
1,7,8,9-Tetrachloro-10,10-dimethoxy-4-azatricyclo[5.2.1.02,6]dec-
8-ene-3,5-dione (1) was synthesized (scheme 1) as previously
described [30]. 1,7,8,9-Tetrachloro-4-(3-chloropropyl)-10,10-dime-
thoxy-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (2) was prepared
as follows: A mixture of imide 1 (0.5 g, 0.00138 mol), 1-bromo-3-
chloropropane (0.6 g, 0.00415 mol) and anhydrous K2CO3 (0.5 g,
0.0036 mol) in acetonitrile (50 mL) was refluxed for 8 h. The inor-
ganic precipitate was filtered off, the solvent was evaporated [31].
The title compound, 1,7,8,9-tetrachloro-10,10-dimethoxy-4-[3-
(4-phenylpiperazin-1-yl)propyl]-4-azatricyclo[5.2.1.02,6] dec-8-ene-
3, 5-dione (3) was prepared as follows: A mixture of compound 2
(0.3 g, 0.0007 mol), 1-phenylpiperazine 0.21 g (0.0013 mol),
anhydrous K2CO3 (0.3 g, 0.0022 mol) and KI (0.2 g, 0.0012 mol) was
dissolved in acetonitrile (50 mL) and refluxed for 30 h. The solvent
was evaporated, then the residue was purified by column
chromatography (eluent: CH2Cl2ACH3OH, 95:5) [31]. Yield 75%,
m.p. 245.5–246 °C. Anal. Calculated: 48.06% C, 4.71% H, 7.01% N;
Found: 48.03% C, 4.59% H, 6.80% N.
The FT-IR spectrum (Fig. 1) was recorded using KBr pellets on a
DR/Jasco FT-IR 6300 spectrometer. The FT-Raman spectrum (Fig. 2)
was obtained on a Bruker RFS 100/s, Germany. For excitation of the
spectrum the emission of Nd:YAG laser was used, excitation wave-
length 1064 nm, maximal power 150 mW, measurement on solid
sample. The 1H NMR spectra were recorded on a Bruker AVANCE
DFT study of 4-azatricyclo [5.2.2.02,6
Varghese et al. [27] reported the spectroscopic study of
] undecane-3,5,8-trione.
Scheme 1. Pathway of compound synthesis.

502
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
material in Table S1. The absence of imaginary wavenumbers on
the calculated vibrational spectrum confirms that the structure de-
duced corresponds to minimum energy. The assignments of the
calculated wavenumbers are aided by the animation option of
GAUSSVIEW program, which gives a visual presentation of the
vibrational modes [36]. The potential energy distribution (PED) is
calculated with the help of GAR2PED software package [37]. The
1H NMR data were obtained from the DFT method using basis set
6-31Gꢁ and potential energy surface scan studies have been carried
out to understand the stability of planar and non-planar structures
of the molecule. The HOMO and LUMO are calculated by B3LYP/
SDD method.
Results and discussion
IR and Raman spectra
The observed IR and Raman bands and calculated (scaled)
wavenumbers and assignments are given in Table 1. In the follow-
ing discussion, Phenyl ring is designated as R1, piperazine ring is
designated as R2, the imido fragment ring is designated as R3
and cyclohexene ring is designated as R4. For the title compound,
the assignments of the benzene ring vibrations are made by refer-
ring the case of benzene derivatives with mono-substitution as
summarized by Roeges [38]. According to Roeges [38], the CH
stretching modes for mono-substituted benzene are found in the
region 3105–3000 cmꢂ1. For the title compound the bands ob-
served at 3110 cmꢂ1 in the Raman spectrum is assigned as CH
stretching mode of the phenyl ring. The calculated (SDD) values
are at 3110, 3101, 3094, 3069 and 3062 cmꢂ1. The benzene ring
possesses six ring-stretching vibrations, of which the four with
the highest wavenumbers occurring respectively near 1600,
1580, 1490 and 1440 cmꢂ1 are good group vibrations. In the ab-
sence of ring conjugation, the band near 1580 cmꢂ1 is usually
weaker than that at 1600 cmꢂ1. The fifth ring-stretching vibrations
Fig. 1. FT-IR spectrum of TDPPAD.
t
Ph is active near 1335 35 cmꢂ1 and the intensity is, in general,
low or medium high [38,39]. The sixth ring-stretching vibration
or ring breathing mode
tPh appears as a weak band near
1000 cmꢂ1 in mono-substituted benzenes [38]. The bands
observed at 1559 and 1496 cmꢂ1 in the IR spectrum and at 1588,
1552 and 1315 cmꢂ1 in the Raman spectrum are assigned as
tPh
Fig. 2. FT-Raman spectrum of TDPPAD.
ring-stretching modes. As seen from Table 1, the SDD calculations
give these modes at 1593, 1553, 1486, 1430, and 1311 cmꢂ1. These
vibrations are expected in the region [38] 1620–1300 cmꢂ1. For the
title compound, the ring breathing mode is found at 1013 cmꢂ1
theoretically. There are five in-plane bending CH vibrations for
mono-substituted benzene. The band observed at 1069 cmꢂ1 in
the Raman spectrum is assigned as the in-plane bending vibrations
of CH modes. SDD calculations give these modes at 1329, 1184,
1157, 1071 and 1049 cmꢂ1. The out-of-plane CH deformations
DMX 400 spectrometer, operating at 400 MHz. The chemical shift
values are expressed in ppm relative to TMS as an internal
standard.
Computational details
Calculations of the title compound are carried out with Gauss-
ian09 program [32] using the B3LYP/6-31Gꢁ and B3LYP/SDD basis
sets to predict the molecular structure and vibrational wavenum-
bers. Molecular geometry was fully optimized by Berny’s optimiza-
tion algorithm using redundant internal coordinates. Harmonic
vibrational wavenumbers were calculated using the analytic
second derivatives to confirm the convergence to minima on the
potential surface. The DFT hybrid B3LYP functional and SDD meth-
ods tend to overestimate the fundamental modes; therefore scaling
factor of 0.9613 has to be used for obtaining a considerably better
agreement with experimental data [33]. The Stuttgart/Dresden
effective core potential basis set (SDD) [34] was chosen particu-
larly because of its advantage of doing faster calculations with rel-
atively better accuracy and structures [35]. Then frequency
calculations were employed to confirm the structure as minimum
points in energy. Parameters corresponding to optimized geometry
(SDD) of the title compound (Fig. 3) are given as Supporting
c
CH of mono-substituted benzene derivative modes are expected
in the range [38] 1000–730 cmꢂ1. In general, the
CH out-of-plane
deformations with the highest wavenumbers have a weaker inten-
sity than those absorbing at lower wavenumbers. The stronger CH
band occurring in the region 775 45 cmꢂ1
CH umbrella mode)
c
c
(c
tends to shift to lower (higher) wavenumbers with increasing elec-
tron donating (attracting) power of the substituent, but seems to
be more sensitive to mechanical interaction effects. The lowest
wavenumbers for this umbrella mode are found in the spectra of
mono-substituted benzene [39–41]. For the title compound the
bands at 979 cmꢂ1 in the Raman spectrum and 754 cmꢂ1 in the
IR spectrum are assigned as the out-of-plane CH deformations of
the phenyl ring. The bands at 980, 959, 872, 814 and 752 cmꢂ1
are the theoretically calculated values for the
cCH deformation
modes. The
c
CH band at 754 cmꢂ1 in the IR spectrum and the

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
503
Fig. 3. Optimized geometry (B3LYP/SDD) of TDPPAD.
phenyl ring deformation mode at 500 cmꢂ1 in the IR spectrum
form a pair of strong bands characteristics of mono-substituted
benzene derivatives [38,42].
bands can increase owing to conjugation or formation of hydrogen
bonds [45,46]. The carbonyl band of cyclic imides is shifted to high-
er wavenumber if the ring is strained [46]. The carbonyl groups in
the imide fragment give rise to bands [46,48] in the region of
1720–1790 cmꢂ1. For the title compound, the C@O stretching
bands are observed at 1698 cmꢂ1 in the IR spectrum, 1677,
1609 cmꢂ1 in the Raman spectrum and at 1678, 1611 cmꢂ1 theo-
retically (SDD).
In aromatic methoxy compounds,
tasCH3 are expected in the
region [38] 2985 20 and 2955 20 cmꢂ1. For the title compound,
computed wavenumbers of modes (SDD) corresponding to the
t
asCH3 group are 3075, 3065, 3057 and 3047 cmꢂ1. The bands
observed at 3042 cmꢂ1 in the IR spectrum and at 3081 and
3057 cmꢂ1 in the Raman spectrum was assigned as these modes.
The CAN stretching modes are reported [49] in the range 1100–
1300 cmꢂ1. Silverstein et al. [50] assigned CAN stretching absorp-
tion in the region 1382–1266 cmꢂ1 for aromatic amines. In the
The symmetrical stretching mode tsCH3 is expected in the range
2845 45 cmꢂ1 in which all the three CH bonds extend and
contract in phase [38]. For the title compound SDD calculations
give values 2956 and 2947 cmꢂ1 as symmetrical methyl group
stretching modes. With methyl esters the overlap of the regions
in methyl asymmetrical deformations are active (1465 10 and
1460 15 cmꢂ1) is quite strong, which leads to many coinciding
wavenumbers [38]. This is obvious, not only for the asymmetric
deformation, but also for the symmetric deformation [38] mostly
displayed in the range 1450 20 cmꢂ1. The intensity of these
absorptions is only weak to moderate. The SDD calculations give
values 1471, 1462, 1457, 1455 cmꢂ1 and 1449, 1428 cmꢂ1 as das
CH3 and dsCH3, respectively, for the title compound. The bands
observed at 1463 cmꢂ1 (Raman) are assigned as the deformation
bands of the methyl group. The methyl rocking vibration [38] has
been observed at 1190 45 cmꢂ1. The second methyl rock [38]
absorb at 1150 30 cmꢂ1. The bands calculated (SDD) at 1158,
1155, 1118 and 1109 cmꢂ1 were assigned as rocking modes of
the methyl group. These modes are observed at 1118 cmꢂ1 in the
Raman spectrum.
present case, the
1328 cmꢂ1 in the Raman spectrum and at 1338, 1335, 1325, 1140,
1124 cmꢂ1 theoretically corresponding to
52AN47 13AN15
16AN15, C19AN15 and C31AN38 respectively. Kas’yan et al. [51]
reported the CN stretching in the region 1350–1100 cmꢂ1 and
Nakanishi [48] reported the range as 1300–1200 cmꢂ1
For bridging methylene groups [47] the CH2 (at C19, C28, C31
tCN stretching modes are observed at
C
,
C
,
C
.
)
vibrations are observed in the region of 2800–3000, 1200–1400,
875–1150 and 600–850 cmꢂ1. The vibrations of these CH2 groups
(the asymmetric stretch tasCH2, symmetric stretch tsCH2, the scis-
soring vibration and wagging vibration) appear in the regions of
2940–3005, 2870–2940, 1420–1480 and 1320–1380 cmꢂ1, respec-
tively [38,40,52]. These bands are observed at 2949 cmꢂ1 in the IR
spectrum, 3028, 3008, 2966, 2951, 2811 cmꢂ1 in the Raman spec-
trum and in the ranges of 3031–2965, 2954–2801, 1473–1419,
1390–1298 cmꢂ1 theoretically (SDD) for the title compound
respectively. According to literature [50] scissoring mode of the
CH2 group give rise to characteristic band near 1465 cmꢂ1 in IR
and Raman spectra. These modes are unambiguously correlated
with the strong bands in the region of 1402–1482 cmꢂ1 observed
experimentally. The twisting and rocking vibrations of the CH2
group appear in the region [38] of 1200–1280 and 740–
900 cmꢂ1, respectively. These modes are also assigned (Table 1).
For the title compound the twisting vibrations are observed at
1290 cmꢂ1 in the IR spectrum, 1285, 1242 cmꢂ1 in the Raman spec-
trum and at 1283, 1244, 1236 cmꢂ1 theoretically. The rocking
deformations are observed at 868, 825 cmꢂ1 in the IR spectrum,
830 cmꢂ1 in the Raman spectrum and at 867, 833, 809 cmꢂ1 theo-
retically and these modes are not pure, but contain significant con-
tributions from other modes also. In the bridging methylene group,
for C28AC31 and C19AC28, CAC stretching modes are found at 1037
and 1020 cmꢂ1 respectively.
A methoxy group attached to an aromꢂa1tic ring give CAOAC
stretching modes in the range 1200–900 cm [40]. The SDD calcu-
lation gives 1145, 1065 and 961, 947 cmꢂ1 as asymmetric and
symmetric CAOAC stretching vibrations. The bands observed at
1145 cmꢂ1 in the IR spectrum and at 1148, 1065, 946 cmꢂ1 in
the Raman spectrum were assigned as CAOAC stretching vibra-
tions. The skeletal CAO deformation can be found in the region
[38] 320 50 cmꢂ1. Klimentova et al. [43] reported the asymmetric
and symmetric CAOAC stretching vibrations in the range, 1214–
1196 cmꢂ1 and 1093–1097 cmꢂ1. Castaneda et al. [44] reported
the methoxy vibrations at 1252, 1190, 1172, 1028 and 1011 cmꢂ1
.
The C@O stretching frequency appears strongly in the IR spec-
trum in the range 1600–1700 cmꢂ1 because of its large change in
dipole moment. The carbonyl group vibrations give rise to charac-
teristics bands in vibration spectra and its characteristic frequency
used to study a wide range of compounds. The intensity of these
The hydrocarbon CH stretching vibrations occur [40] above
2900 cmꢂ1 and CH deformations absorb weakly in the region of

504
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
Table 1
IR, Raman bands and calculated (scaled) wavenumbers of TDPPAD and assignments.
B3LYP/6-31Gꢁ
B3LYP/SDD IR
Raman
Assignmentsa
t
IRI
RA
t
IRI
RA
t
t
3107
3103
3093
3074
3069
3065
3063
3059
3046
3023
3005
2998
2996
2969
2966
2963
2960
2957
2957
2951
2948
2942
2912
2878
2864
2812
2790
1709
1643
1611
1603
1566
1511
1506
1500
1492
1490
1489
1488
1483
1477
1474
1469
1461
1457
1441
1429
1403
1386
1383
1372
1365
1356
1354
1351
1349
1334
1314
1310
1299
1295
1288
1282
1267
1257
1247
1232
1227
1206
1201
1191
1176
1167
0.32
29.49
50.50
9.92
18.68
12.28
9.00
270.37
4.39
3110
3101
3094
3075
3069
3065
3062
3057
3047
3031
3013
3007
3002
2980
2972
2968
2965
2957
2956
2954
2950
2947
2921
2884
2870
2822
2801
1678
1611
1594
1593
1553
1486
1481
1476
1473
1471
1468
1466
1462
1457
1455
1449
1444
1430
1428
1419
1390
1370
1368
1358
1353
1345
1338
1335
1329
1325
1311
1298
1283
1281
1274
1270
1255
1244
1236
1220
1213
1195
1187
1184
1161
1158
2.59
38.05
50.91
14.86
15.67
18.03
9.02
16.85
27.15
18.87
3.05
304.37
1.44
–
–
–
–
–
–
–
–
3042
–
–
–
–
–
–
–
–
–
–
–
2949
–
–
–
2873
2831
–
1698
–
1589
–
1559
1496
–
–
–
–
–
–
–
–
–
–
1445
–
–
1404
1379
1371
–
–
–
1346
–
–
–
–
–
–
1290
–
–
3110
–
–
3081
–
–
–
3057
–
3028
–
3008
–
–
–
–
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
CH (R1) (99)
CH (R1) (94)
CH (R1) (95)
asCH3 (96)
CH (R1) (100)
asCH3 (99)
CH (R1) (93)
asCH3 (93)
asCH3 (98)
asCH2 (98)
C4AH10 (53),
asCH2 (97)
C4AH10 (47), tC5AH12 (53)
asCH2 (R2) (95)
asCH2 (R2) (95)
asCH2 (R2) (90)
asCH2 (96)
asCH2 (R2) (75),
sCH3 (88)
108.04
62.93
135.91
79.50
48.11
29.49
23.20
11.84
127.20
40.97
35.14
64.66
96.71
31.31
145.28
78.31
28.12
51.26
131.77
37.86
56.86
74.66
110.47
102.26
55.38
19.60
0.32
23.39
92.06
3.69
15.64
13.14
4.87
10.96
7.92
48.13
15.35
7.97
18.83
20.52
7.43
34.97
2.56
4.84
9.44
6.74
1.68
3.78
6.11
7.52
8.42
15.74
4.35
10.61
14.26
6.25
15.80
12.19
6.32
50.02
57.78
111.77
66.09
34.13
27.75
20.16
7.93
132.73
36.82
28.53
96.78
88.15
47.17
35.58
60.52
205.75
32.05
55.75
93.41
65.75
80.14
115.44
102.38
50.69
26.97
0.63
22.27
94.03
3.04
10.75
8.84
3.20
7.99
8.21
8.86
4.68
4.89
9.41
17.78
3.44
28.93
2.79
3.14
5.75
8.28
4.98
2.18
2.61
3.82
6.34
14.36
4.42
5.78
12.51
7.61
10.29
10.72
3.76
4.81
6.15
13.98
4.903
2.04
2.10
12.82
1.37
9.24
17.21
11.44
1.39
9.84
0.80
t
C5AH12 (47)
9.86
0.69
22.52
21.02
28.11
40.91
22.18
51.49
11.52
44.36
4.31
41.37
50.92
69.20
83.25
64.79
29.05
433.08
47.09
176.87
10.82
20.57
30.01
14.61
42.48
41.31
48.13
28.68
23.56
1.97
41.51
22.51
67.52
38.81
59.90
38.25
8.76
2966
–
–
–
tCH2 (11)
sCH2 (79),
sCH2 (89),
sCH3 (100)
t
t
sCH2 (R2) (6)
sCH2 (R2) (6)
3.73
2951
–
2902
2878
–
2822
2811
1677
1609
–
1588
1552
–
–
–
–
–
–
–
1463
–
–
–
1445
–
–
1409
–
–
–
–
–
34.92
40.19
55.99
84.52
98.37
64.22
32.91
501.17
15.30
256.96
12.65
30.21
34.34
6.18
23.58
25.70
151.44
16.62
33.64
4.74
sCH2 (R2) (95)
sCH2 (R2) (96)
sCH2 (R2) (91)
sCH2 (R2) (91)
sCH2 (94)
C@O (77), dR3 (11)
C@O (77)
C@C (R4) (57),
CAC (R1) (62),
CAC (R1) (67)
CAC (R1) (77)
t
t
CAC (R1) (10)
C@C (R4) (22)
dasCH2 (R2) (60), dasCH2 (12)
dasCH2 (R2) (80), dasCH2 (11)
dasCH2 (64)
dasCH3 (84)
dasCH2 (R2) (62)
dasCH2 (R2) (74), dasCH2 (16)
dasCH3 (91)
dasCH3 (41), dCH2 (29), dasCH2 (R2) (13)
dasCH3 (39), dCH2 (37), dasCH2 (R2) (9)
dsCH3 (83)
dasCH2 (90)
dCH (R1) (20),
dsCH3 (91)
6.21
9.77
16.23
0.05
4.57
8.18
13.84
14.07
0.08
5.96
8.91
tCAC (R1) (44)
4.87
1.85
dasCH2 (93)
1.56
dsCH2 (44), dsCH2 (R2) (33)
dsCH2 (R2) (52), dsCH2 (11)
dsCH2 (48), dsCH2 (R2) (15)
dsCH2 (R2) (57)
dsCH2 (R2) (35), dsCH2 (24)
dsCH2 (R2) (53), dsCH2 (12)
tC52AN47 (52), dsCH2 (R2) (12), dCH (R1) (10)
dCH2 (10), dC13AN15 (R3) (48)
dCH (R1) (62), dCH (R2) (8)
15.98
111.67
2.32
13.42
8.07
51.23
78.87
81.94
253.65
1.88
45.87
41.29
0.75
44.67
10.70
54.14
122.85
5.04
248.21
2.12
6.80
13.65
8.91
30.51
24.72
23.46
48.00
1.09
11.96
58.02
14.35
19.68
5.87
1345
–
–
–
1328
1315
1301
1285
–
t
t
C16AN15 (R3) (46), dsCH2 (17)
CAC (R1) (63)
5.39
6.02
dsCH2 (56), dsCH2 (R2) (11)
dCH2 (48), dCH2 (R2) (23)
dC4AH10 (66), dC5AH12 (8)
dCH2 (R2) (52), dCH2 (32)
dC5AH12 (66), dC4AH10 (8
dCH2 (R2) (37), dCH2 (27)
dCH2 (69)
dCH2 (72)
dCH2 (R2) (43),
dCH2 (R2) (52)
15.45
43.54
23.95
14.78
55.40
0.83
33.17
56.30
14.21
4.18
8.03
9.69
10.92
8.10
4.33
5.81
10.31
3.23
3.67
1.58
–
–
–
1259
–
–
1217
–
–
1188
–
1165
–
1264
1242
–
1226
–
1201
1186
–
1166
–
tCAN (R2) (19)
t
t
CAC (R3) (48)
CAC (R3) (48), dC5AH12 (14), dC4AH10 (23)
CAC (R1) (15)
40AN38 (R2) (31), dCH2 (10)
dCH3 (42), C7AO9 (17)
1.44
2.69
4.74
5.18
20.46
4.51
69.55
dCH (R1) (77), t
tC
7.61
5.29
62.77
58.15
t

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
505
Table 1 (continued)
B3LYP/6-31Gꢁ
B3LYP/SDD IR
Raman
Assignmentsa
t
IRI
13.28
64.05
101.24
6.28
49.46
62.31
17.39
15.24
46.15
64.25
7.81
0.50
147.09
0.75
35.74
35.84
5.16
RA
t
IRI
RA
t
t
1163
1160
1152
1143
1135
1129
1126
1116
1106
1098
1089
1087
1078
1069
1061
1057
1039
1035
1029
1016
1015
993
986
982
972
969
960
948
943
931
915
912
886
873
871
857
842
821
811
797
756
752
750
5.52
1.06
4.10
2.52
6.63
1.33
4.56
9.75
4.51
1157
1155
1145
1140
1126
1124
1118
1109
1099
1093
1081
1071
1065
1062
1054
1049
1037
1031
1020
1013
1011
995
982
980
966
962
961
959
947
926
915
903
877
872
867
850
833
814
809
789
752
750
743
712
701
699
689
681
666
646
610
7.36
8.52
4.28
4.17
4.09
2.17
2.18
5.79
5.41
9.64
5.56
–
–
1145
–
–
–
–
–
1096
–
–
–
–
–
–
–
1038
–
1019
–
–
–
981
–
–
–
–
–
–
936
–
905
–
–
868
–
825
–
–
786
754
–
–
712
–
–
–
681
–
642
620
–
–
–
–
–
–
–
–
–
–
–
–
420
–
–
–
–
–
–
–
–
–
–
–
1148
–
–
–
1118
–
1096
–
–
1069
1065
–
–
–
1042
1029
–
dCH (R1) (61)
dCH3 (68)
83.37
19.33
44.57
70.33
7.35
t
t
t
t
asCAOAC (42), dCH3 (29),
19AN15 (34), CAC (R3) (14)
CAC (R4) (41), dR4 (12)
C31AN38 (25), dCH2 (R2) (12)
tC6AC7 (10)
C
t
dCH3 (75)
dCH3 (60), tCAC (R4) (16)
8.40
44.45
64.08
2.53
t
t
t
C39AN38) (48), dCH2 (23), dCH2 (R2) (6)
CAC (R4) (40), dCH3 (10)
CAC (R3) (52), dCH2 (R2) (16)
11.42
6.15
1.49
7.14
3.87
2.36
3.89
18.78
10.03
21.70
8.84
4.62
7.07
37.08
11.22
1.01
2.85
5.55
4.92
1.69
5.12
5.38
12.56
7.55
7.49
0.11
2.42
0.51
1.17
4.64
4.46
0.76
0.51
7.17
3.60
13.58
5.32
1.00
1.33
3.48
3.29
3.51
3.47
3.27
6.92
0.16
1.91
1.61
5.63
0.31
0.88
2.86
1.36
1.42
1.60
0.46
1.49
2.66
10.61
2.48
7.40
6.54
1.43
1.27
15.77
8.46
1.28
5.60
3.78
2.76
2.38
25.07
9.76
7.31
26.86
15.60
11.30
1.20
1.47
31.24
2.80
7.79
13.16
3.85
3.83
7.74
12.27
8.83
1.93
6.51
0.84
0.33
0.54
1.82
6.72
0.36
1.11
7.31
3.17
16.20
5.01
0.02
1.27
4.58
3.07
5.19
4.30
4.82
6.02
0.66
1.26
2.56
5.27
0.14
1.07
2.35
1.63
2.00
1.28
0.56
1.25
0.54
14.78
2.63
7.64
6.27
1.65
2.09
3.22
dCH (R1) (32),
t
CAC (R1) (17)
asCAO (45), dCAO (13)
CAC (R3) (31), 19AN15 (21),
CAC (R4) (41), dCH2 (R2) (26)
140.01
48.91
23.24
26.73
5.49
t
t
t
t
C
tCAC (R4) (20)
dCH (R1) (37), dCH2 (R4) (7)
t
t
t
t
t
c
t
c
c
t
t
c
t
t
C
28AC31 (43), dCH2 (R2) (15), dCH2 (20),
CAC (R2) (41), 28AC31 (6), dCH2 (R2) (15)
19AC28 (51), 28AC31 (6)
CAC (R1) (50)
CAC (R3) (40), dCAO (12)
CH (42), CAC (R4) (13)
CAN (R2) (33), dCH2 (R2) (16)
CH (R1) (75), CACACAC (R1) (14)
CH (44), CAC (R1) (12)
8.72
10.65
1.84
15.12
76.95
11.21
2.50
9.12
1.61
6.97
tC
tC
C
–
19.40
52.75
27.57
1.10
1011
999
–
979
964
–
t
s
0.43
9.73
5.59
9.92
1.13
9.58
4.12
t
12.33
11.78
8.02
0.20
5.11
41.01
34.61
7.87
10.41
9.89
0.30
3.36
39.98
0.21
19.14
20.59
55.24
14.62
8.59
CAC (R4) (65)
sCAOAC (33), tCAC (15), sR4 (12)
CH (R1) (75), dCACAC (R1) (10)
sCAOAC (39),
CAC (R2) (33)
–
–
946
928
–
906
883
–
–
–
830
–
–
792
–
–
738
–
–
tCAC (R3) (10)
40.79
25.79
6.88
dCH2 (R2) (55),
45AN47 (R2) (34),
dCH2 (R2) (37)
CH (R1) (71)
dCH2 (47), R4 (22), t
t
CAO (18)
t
C
t
CAC (R1) (21), tCAC (R2) (12)
6.20
6.14
0.63
5.00
c
s
CACACAC (R1) (12)
CAO (10)
CH2 (R4) (16), dCH2 (R4) (15)
s
dCH2 (R2) (41),
s
dCH2 (55)
0.84
c
CH (R1) (97)
dCH2 (34), dR4 (15), dCAO (11)
dCH2 (R2) (43), R3 (22), C@O (10)
CH (R1) (58), CACACAC (R1) (29),
dCH2 (52)
R4 (13),
dC@O (21), dCH2 (19), dR4 (12)
32.08
21.26
88.15
15.37
14.86
14.13
5.17
s
s
c
c
c
C
52AN47 (19)
s
tC46AN47 (R2) (47), tC31AN38 (10)
724
715
707
0.69
s
s
s
s
t
t
t
t
CN (R2) (27), dCACAC (R1) (20)
R3 (12), C@O (12)
CACACAC (R1) (82),
R4 (20), C@O (16),
CACl (64), CAOAC (23)
CACl (54), dR3 (32)
CACl (42), dCACAC (R1) (21)
CACl (59), dCAOAC (28)
11.75
23.28
2.67
26.64
36.33
0.11
8.89
0.73
1.37
19.53
0.07
6.59
19.82
7.02
0.96
8.32
7.08
696
–
c
692
688
675
655
625
616
611
600
38.36
1.47
25.54
34.90
0.34
c
CH (R1) (28)
680
661
643
624
604
598
–
572
537
–
520
500
–
481
431
–
–
404
–
–
–
334
–
–
317
–
c
tC6AC7 (15)
t
609
8.87
1.66
1.96
598
589
588
539
523
521
510
482
481
436
427
416
412
368
362
353
333
325
321
314
307
dR2 (43), dCH2 (R2) (28), dR3 (21)
dR3 (65), dR2 (11)
595
550
12.91
0.05
dCACl (51),
CACl (56),
t
s
CACl (15)
R4 (20), dC@O (12)
c
536
528
517
491
491
443
434
422
416
375
363
356
337
329
324
318
314
6.94
dR2 (38), dCH2 (24), dCACACA (R1) (13)
dCH2 (32), 19AN15 (20)
CACACAC (R1) (40),
C@O (32), CAC (26),
dR2 (52)
20.78
14.33
0.51
cC
s
c
C
52AN47 (35)
c
t
sR4 (15)
8.95
0.32
0.85
dCAN (31), dR2 (15)
dC52AN47 (57)
14.36
15.42
0.29
5.17
0.90
7.15
1.99
0.89
5.57
13.95
14.00
1.23
s
s
CACACAC (R1) (56)
CACACAC (R1) (73)
5.27
2.49
6.09
1.83
0.71
6.48
dC@O (30), dCAO (26),
c
CACl (17)
c
t
t
t
c
C31AN38 (42), sR2 (23)
CACl (11), dCAO (31)
CACl (16), dR4 (29)
CACl (19),
sR4 (35), dCAO (13)
C19AN15 (18), dCAO (10)
11.85
2.58
11.74
3.74
dCAO (62)
sR2 (16)
(continued on next page)

506
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
Table 1 (continued)
B3LYP/6-31Gꢁ
B3LYP/SDD IR
IRI
Raman
Assignmentsa
t
IRI
RA
t
RA
t
t
303
282
278
270
269
250
207
196
192
186
179
172
160
159
157
152
147
140
131
124
119
113
106
86
8.13
1.57
1.04
2.94
4.62
2.53
3.08
1.22
1.40
1.18
1.27
0.46
0.52
1.11
1.64
3.17
0.62
0.76
0.47
2.13
0.21
0.88
0.91
0.50
0.63
0.69
1.15
4.05
2.05
1.40
1.00
2.69
2.69
4.46
1.31
1.64
299
278
269
266
256
245
203
193
188
177
175
169
156
155
154
150
143
136
129
119
117
112
109
84
8.70
2.27
15.06
3.98
3.77
2.08
6.83
6.54
1.96
0.41
0.95
0.70
0.56
0.06
1.54
0.03
0.99
3.80
3.01
0.90
1.12
0.32
1.29
4.16
1.42
0.18
0.66
0.41
0.40
0.01
0.19
0.08
0.07
0.20
0.96
3.01
4.31
3.93
1.34
1.44
1.31
1.21
1.42
0.33
0.36
1.01
1.43
3.70
0.78
0.92
0.92
1.43
0.36
0.73
0.67
0.40
0.47
0.49
2.43
2.31
1.87
0.86
0.93
2.74
1.69
3.36
1.39
1.58
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
267
–
250
–
–
–
–
–
167
–
–
–
–
–
–
–
–
–
–
–
87
–
–
–
–
–
–
–
–
–
–
dCAO (46)
dC19AN15 (43), dC@O (29)
11.61
0.88
13.77
2.43
5.51
7.39
1.34
0.76
0.64
0.97
0.66
0.02
2.10
0.07
1.61
2.22
3.19
0.95
1.19
1.02
0.10
4.34
0.72
0.61
0.44
0.13
0.31
0.01
0.14
0.09
0.08
0.18
sR2 (37)
dC19AN15 (17), dCACl (15), dR4 (13)
s
s
s
s
s
R2 (42),
CACACAC (R1) (9),
CAO (14), C19 AN15 (9)
R2 (33), CACACAC (R1) (17),
CAO (26), R3 (12)
CH3 (17)
s
CACACAC (R1) (11)
c
C31AN38 (8)
c
s
cC31AN38 (10)
s
s
dCACl (20),
s
s
CH3 (30), dCACl (20)
CAO (32)
dCACl (60)
dCACl (77)
sCAO (21),
s
s
CH3 (21)
CH3 (12), sCAO (11)
dCACl (13),
s
s
s
s
s
s
s
s
s
s
s
CAO (25), dCACl (18)
CAO (33), dCAO (21),
CAO (27)
sCH3 (11)
CAO (29), dCAO (28)
R2 (28),
CH2 (28),
c
C
s
31AN38 (12)
R2 (32)
R3 (47), cC19AN15 (10)
CAO (36)
81
80
71
62
57
37
23
21
81
79
70
60
54
34
22
14
R3 (53),
R4 (38),
s
c
R2 (13)
CACl (14),
52AN47 (12),
R3 (16), R4 (15)
R4 (31)
s
R2 (12)
CACl (11)
CAO (16),
c
C
c
c
CACl (27),
s
s
s
s
s
s
s
s
R3 (33),
s
CH2 (24),
CH2 (27),
CH2 (37),
CH2 (53),
R2 (45)
c
C
52AN47 (23), R3 (12)
s
s
s
s
C
19AN15 (19), sR2 (18)
R2 (22)
R2 (17)
11
6
9
7
t
– Stretching; d – in-plane deformation;
c – out-of-plane deformation; s – torsion; as – asymmetric; s – symmetric; Phenyl ring – R1; piperazine ring – R2; imido fragment
ring – R3; cyclohexene ring – R4; potential energy distribution is given in brackets in the assignment column.
1350–1315 cmꢂ1 in the infrared and more distinctive in Raman
spectrum. For the title compound the SDD calculations give the
at around 284 cmꢂ1 [39,40]. Pazdera et al. [58,59] reported the
CCl stretching mode at 890 cmꢂ1. For 2-cyanophenylisocyanide
dichloride, the CCl stretching mode is reported at 870 (IR),
877 cmꢂ1 (Raman), and 882 cmꢂ1 theoretically [60]. Arslan et al.
[61] reported the CCl stretching mode at 683 (experimental)
and at 711, 736, 687, and 697 cmꢂ1 theoretically. The deforma-
tion bands of CCl are reported [60] at 431, 435, 441, and
441 cmꢂ1. For the title compound, the bands at 642, 620 cmꢂ1
in the IR, 661, 643, 624, 604 cmꢂ1 in Raman and 666, 646, 610,
609 cmꢂ1 (SDD) are assigned as CCl stretching modes. The defor-
mation bands of CCl are also identified. This is in agreement with
the literature data [39,62,63]. For 4-chlorophenylboronic acid, the
CCl stretching and deformation bands are reported at 571 (DFT),
and at 287 and 236 cmꢂ1, respectively [64].
t
CH modes at 3013 and 3002 cmꢂ1. Tarabara et al. [47] and
Kas’yan et al. [51] reported the
t
CH modes at 3080 cmꢂ1 and
3070–3050 cmꢂ1 for similar derivatives. Atroshchenko et al. [53]
reported the CH stretching vibrations at 1805, 1887, 1925,
2968 cmꢂ1 and deformations bands of CH at 1474, 1483 cmꢂ1 the-
oretically. The deformation bands of the CH are observed at 1281,
1270 cmꢂ1 theoretically for the title compound. Most of the bands
are not pure, but contains significant contributions from other
modes. For the title compound, the CAC stretching modes are
observed at 1093, 1081, 1062, 1054, 1011, 995, 966, 962 cmꢂ1
theoretically and at 1011, 999, 964 cmꢂ1 in the Raman spectrum
for the CAC bonds in R3 and R4 and these modes contain
contributions from other modes as well.
The C@C stretching mode is expected in the region [50] 1667–
1640 cmꢂ1. For the title compound, the C@C stretching mode is as-
signed at 1589 cmꢂ1 in the IR spectrum and at 1594 cmꢂ1 theoret-
ically. For a series of propenoic acid esters, Felfoldi et al. [65]
The vibrations belonging to the bond between the ring and
chlorine atoms are worth to discuss here since mixing of vibra-
tions is possible due to the lowering of the molecular symmetry
and the presence of heavy atoms on the periphery of the mole-
cule [54–56]. Mooney assigned vibrations of CACl, Br and I in
the wavenumber range of 1129–480 cmꢂ1 [55,56]. The CCl
stretching vibrations give generally strong bands in the region
reported the
El-Emam et al. [66] reported the asymmetric stretching CH2
vibrations in the piperazine ring in the range 3033–2966 cmꢂ1
t t .
C@O at 1690 cmꢂ1 and C@C at 1625 cmꢂ1
,
while the symmetric vibrations lying in the range 2874–
2834 cmꢂ1. For the title compound the bands observed at 2980,
2972, 2968, 2957 cmꢂ1 (SDD) were assigned for CH2 asymmetric
stretching modes. Bands observed at 2921, 2884, 2870, 2822 cmꢂ1
(SDD), 2873, 2831 cmꢂ1 (IR) and 2902, 2878, 2822 cmꢂ1 are as-
signed for symmetric CH2 stretching modes for the title compound.
In a study on the determination of piperazine rings in ethyleneam-
ines, poly(ethyleneamine) and polyethylenimine by infrared spec-
trometry, Spell reported that the piperazine ring was found to be
710–505 cmꢂ1
. For simple organic chlorine compounds, CCl
absorptions are in the region 750–700 cmꢂ1. Sundaraganesan
et al. [57] reported CCl stretching at 704 (IR), 705 (Raman), and
715 cmꢂ1 (DFT) and the deformation bands at 250 and
160 cmꢂ1. The aliphatic CCl bands absorb [38] at 830–560 cmꢂ1
and putting more than one chlorine on a carbon atom raises
the CCl wavenumber. The CCl2 stretching mode is reported at
around 738 cmꢂ1 for dichloromethane and scissoring mode dCCl2

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
507
associated with sharp, well-defined absorptions at 1300–
1345 cmꢂ1, 1125–1170 cmꢂ1, 1010–1025 cmꢂ1 and 915–940 cmꢂ1
regions of the IR spectrum [67]. El-Emam et al. [66] reported the
vibrations of CH2 groups in the piperazine ring (the asymmetric
C5AC4 = 1.5693 Å. Conley et al. [69] reported the corresponding
values as 1.2025, 1.3985, 1.2104, 1.4054, 1.4865, 1.5155, 1.555 Å
and 1.1974, 1.3995, 1.2004, 1.3824, 1.4866, 1.4826, 1.3436 Å for
different similar derivatives. The N15AC19 bond length (1.4729 Å)
is longer than N15AC13 (1.4037 Å) and N15AC16 (1.4021 Å) bond
stretch
tasCH2, symmetric stretch tsCH2, the scissoring vibration
and wagging vibration) in the range 3033–2966, 2874–2834,
1457–1422 and 1379–1344 cmꢂ1 respectively. A very sharp and in-
tense band was observed at 1037 cmꢂ1 by da Silva et al. and was as-
signed to the ring CH2 rocking motions. As stated by Spell, [67] this is
one of the most useful bands for detecting the presence of di-substi-
tuted piperazines. The twisting and rocking vibrations of the CH2
lengths. This indicates, as expected, a delocalized
tem along the imide part of the molecule (O18AC13AN15AC9AO17
as reported by Bartkowska et al. [72]. Bartkowska et al. [72]
reported the bond lengths, C13AO18 = 1.2032, N15AC13 = 1.3913,
p-electron sys-
)
C
13AC4 = 1.5193, C4AC5 = 1.5453,
1.388 Å and the bond angles, N15AC19AC28 = 111.3°,
AN15 = 124.3°, 18AC13AC4 = 127.8°, 15AC13AC4 = 107.8°, O17
AC16AN15 = 127.2°, 15AC16AC5 = 107.0°, 16AN15AC13 = 114.2°,
16AN15AC19 = 123.8°, C13AN15AC19 = 121.7°, whereas the corre-
C
16AO17 = 1.2073,
N
15AC16
=
O18AC13
group appear in the region [38] of 1200–1280 and 740–900 cmꢂ1
,
O
N
respectively. These modes are also assigned (Table 1). For the title
compound the twisting vibrations are observed at 1259,
1217 cmꢂ1 in the IR spectrum, 1264, 12ꢂ216 cmꢂ1 in the Raman spec-
trum and at 1274, 1255, 1220, 1213 cm theoretically. The rocking
deformations are observed at 786 cmꢂ1 in the IR spectrum, 863,
792 cmꢂ1 in the Raman spectrum and at 915, 877, 850, 789 cmꢂ1
theoretically and these modes are not pure, but contain significant
contributions from other modes also. El-Emam et al. [66] reported
the CAN stretching vibrations in the region 1154–756 cmꢂ1. For
N
C
C
sponding values in the present case are 1.2409, 1.4037, 1.5346,
1.5693, 1.2426, 1.4021 Å and 112.7°, 124.3°, 127.4°, 108.1°,
124.3°, 108.2°, 113.8°, 123.5°, 122.6°.
For the title compound the C4AH10, C5AH12, bond lengths are
1.0936, 1.0939 Å whereas reported values are 0.96, 0.9601 Å [69].
The cyclohexene ring fragment is a sterically strained system. Pre-
sumably, this is the reason for elongation of skeletal CAC bonds,
C1AC2, C2AC3, C3AC4, C5AC6, C6AC1. The CAC bond lengths in the
five member ring (C5AC16, C4AC13) are elongated to a lesser extent.
These may be explained by change of the substitution pattern in
the nitrogen containing five member ring as reported by Tarabara
et al. [47].
the title compound CAN stretching vibrations (C40AN38, C39AN38
C
,
45AN47, C46AN47) are found at 1165, 1096, 905 cmꢂ1 in the IR spec-
trum, 1166, 1096, 906, 738 cmꢂ1 in the Raman spectrum and at
1161, 1099, 903, 743 cmꢂ1 theoretically. Two absorptions charac-
teristic for the piperazine ring, at 1130 and 1168 cmꢂ1 and assigned
for the CAN stretching vibrational modes were observed by da Silva
et al. [68]. The shift in the wavenumber may be attributed to the
bulky groups attached to the piperazine ring. The CAC stretching
vibrations in the piperazine ring were reported at 972, 903 cmꢂ1
[66]. For the title compound these vibrations are observed at
1031, 926 cmꢂ1 theoretically, at 936 cmꢂ1 in IR and at 1021,
928 cmꢂ1 in Raman spectrum.
The methoxy groups, O14AC11AH23 24 27 and O9AC8AH20,21,22
,
,
inclined almost equally with respect to the other parts of the six
member ring. The bond angles C1AC6AC7, C5AC6AC7, C2AC3AC7,
C4AC3AC7, C6AC1AC2 and C4AC3AC2 are respectively 99.7°,
102.1°, 99.7°, 102.8°, 107.8° and 105.2°. In addition the declination
of the five member ring from the cyclohexene ring are given by the
angles C6AC5AC16 and C3AC4AC13 by 118.7° and 119.2° which are
almost equal as reported in the literature [47]. The conjugation in
the imido group is essentially disturbed; the torsion angles C13
AN15AC16AC5, C16AN15AC13AC4 are 8.2°, ꢂ6.2° and the C13AN15
and C16AN15 bond lengths are elongated to 1.4037, 1.4021 Å
relative to the average value 1.371 Å [73].
Geometrical parameters
To the best of our knowledge, no X-ray crystallographic data of this
molecule has yet been established. However, the theoretical results
obtained are almost comparable with the reported structural parame-
ters of the parent molecules. For the imido fragment of the title com-
For the cyclohexene ring, Manohar et al. [74] reported the bond
lengths
C1AC2 = 1.3194,
C1AC6 = 1.5174,
C6AC5 = 1.5523,
pound, the SDD calculations give the bond angles, C16AN15AC13
18AC13AN15, O18AC13AC4, N15AC13AC4, C13AC4AC5, C13AC4AH10
C5AC4AH10, C16AC5AH12, C4AC5AH12, O17AC16AN15, O17AC16AC5,
15AC16AC5, as 113.8°, 124.3°, 127.4°, 108.1°, 104.9°, 107.7°, 113.7°,
,
,
C6AC7 = 1.5484, C5AC4 = 1.5353, C4AC3 = 1.5543, C3AC7 = 1.5473,
C3AC2 = 1.5144 Å and the corresponding bond lengths of the title
compound are 1.3472, 1.5334, 1.5705, 1.5870, 1.5693, 1.5750,
1.5903, 1.5311 Å. The bond angles reported by Manohar et al.
[74] are C3AC4AC5 = 102.9°, C3AC2AC1 = 107.5°, C3AC7AC6 = 92.4°,
C2AC3AC4 = 107.2°, C6AC5AC4 = 103.1°, C6AC1AC2 = 107.7°, C5AC6
AC1 = 106.8°, C2AC3AC7 = 99.52°, C4AC3AC7 = 101.12°, C5AC6
AC7 = 101.1°, C1AC6AC7 = 99.4°, where as the corresponding calcu-
lated (SDD) values of the title compound are 102.8°, 107.4°, 91.3°,
105.2°, 102.9°, 107.8°, 106.1°, 99.7°, 102.8°, 102.1°, 99.7°.
O
N
107.9°, 113.6°, 124.3°, 127.4°, 108.2°, respectively, whereas the re-
ported values of similar derivatives are 114.7°, 124.0°, 128.5°, 107.4°,
105.8°, 112.3°, 113.8°, 113.3°, 113.1°, 126.3°, 129.2°, 106.5° and
111.0°, 126.1°, 128.4°, 105.5°, 109.9°, 115.0°, 136.0°, 118.0°, 118.0°,
123.7°, 131.4°, 104.9° [69]. Conley et al. [69] reported the dihedral an-
gles, C16AN15AC13AO18 = 179.5°, C16AN15AC13AC4 = ꢂ4.0°, O18AC13-
AC4AC5 = 177.5°,
N
15AC13AC4AC5 = ꢂ0.5°,
C
13AC4AC5AC16 = 1.7°,
In the present case, the oxygen atoms O17 and O18 are equally
inclined from the N15 atom given by the angles O17AC16AN15, O18
AC13AN15 (124.3°) and from C4 and C5 atoms given by the angles
C13AN15AC16AC5 = 5.1°,
C4AC5AC16AO17 = 176.7°,
C4AC5AC16
AN15 = ꢂ4.0° whereas for the title compound the corresponding val-
ues are 178.7°, ꢂ6.2°, 176.4°, 1.5°, 2.9°, 8.2°, 177.6° and ꢂ6.5° respec-
O
17AC16AC5, O18AC13AC4 (127.4°) as reported in the literature
[75].
There are four types of CC bonds involved in the title compound,
tively. Pinho
e Melo et al. [70] reported the bond lengths
N15AC16 = 1.3654,
N15AC13 = 1.4484 Å, bond angles
C16AN15
AC13 = 116.8°, C16AN15AC19 = 121.6°, C13AN15AC19 = 121.6°, C5AC16
AN15 = 121.9°, N15AC13AC4 = 107° and dihedral angles C13AN15AC16
AC5 = 177.2°, C16AN15AC13AC4 = 169.9° which are in agreement with
our calculated values.
strained CC bonds of R1, R2, R3, R4, propyl group and of the car-
bon–carbon bridge. The CC bond lengths are in the range
1.5346–1.5693, 1.5311–1.5750, 1.5415–1.5432 Å, in R3, R4, propyl
group and 1.5903, 1.5870 Å in the carbon–carbon bridge respec-
tively. The CH bond lengths are C4AH10 = 1.0936 and
C5AH12 = 1.0939 Å. The CH bond lengths are in the range 1.0958–
1.1119 Å for the bridging CH2 groups, and for the CH3 groups, CH
bond lengths are in the range of 1.0918–1.0951 Å. The optimized
carbon–carbon bridge angles C3AC7AC6 = 91.3° is similar to the
structures reported by Manohar et al. [74].
Lee and Swager [71] reported the bond lengths O17AC16
=
1.1954, O18AC13 = 1.2054, N15AC16 = 1.3776, N15AC13 = 1.3765 Å
and the bond angles C5AC16AN15 = 106.3°, C4AC13AN15 = 106.5°.
The B3LYP calculations give the bond lengths within the imido
fragment as
C16AO17 = 1.2426,
N
15AC16 = 1.4021,
C13AO18 =
1.2409, 13AN15 = 1.4037,
C
C13AC4 = 1.5346,
C16AC5 = 1.5391,

508
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
The propyl group is tilted from the R2, as is evident from torsion
package at the DFT/B3LYP level in order to understand various sec-
ond-order interactions between the filled orbital of one subsystem
and vacant orbital of another subsystem, which is a measure of the
intermolecular delocalization or hyper conjugation. NBO analysis
provides the most accurate possible ‘natural Lewis structure’ pic-
ture of ‘j’ because all orbital details are mathematically chosen to
include the highest possible percentage of the electron density. A
useful aspect of the NBO method is that it gives information about
interactions of both filled and virtual orbital spaces that could en-
hance the analysis of intra and inter molecular interactions. The
second-order Fock-matrix was carried out to evaluate the donor–
acceptor interactions in the NBO basis. The interactions result in
a loss of occupancy from the localized NBO of the idealized Lewis
structure into an empty non-Lewis orbital. For each donor (i) and
acceptor (j) the stabilization energy (E2) associated with the delo-
calization i ? j is determined as
angles, C5AC16AN15AC19 (ꢂ176.4°), C16AN15AC19AC28 (ꢂ92.8°),
C4AC13AN15AC19 (178.4°) and C13AN15AC19AC28 (82.2°). The dou-
ble bonds C16AO17 and C13AO18 are conjugated with the p-system
of the R3, with the torsion angles O17AC16AN15AC13, C16AN15AC13
AC4 being ꢂ175.8°, ꢂ6.2° and O18AC13AN15AC16, C13AN15AC16AC5
being 178.7, 8.2° respectively as reported by Kasyan et al. [76]. At
N15 position, the bond angles C16AN15AC19 = 123.5°, C13AN15
AC19 = 122.6° and C16AN15AC13 = 113.8° and this asymmetry of
angles reveal the steric repulsion of the atoms H26, H25 and O17
,
O18 [76].
For the piperazine ring, El-Emam et al. [66] reported the bond
lengths 38AC40 = 1.465, 38AC39 = 1.463, 39AC46 = 1.514,
47AC45 = 1.458, N47AC46 = 1.471, C40AC45 = 1.511 and the corre-
N
N
C
N
sponding bond lengths of the title compound are 1.4887, 1.4799,
1.5362, 1.4722, 1.4742, 1.5453 Å respectively. The B3LYP calcula-
tions give the bond angles within the piperazine ring N38AC39
AC46 = 111.2, N38AC40AC45A = 113.6, N47AC45AC40 = 110.3, N47-
AC46AC39 = 110.4, C45AN47AC46 = 116.8. El-Emam et al. [66] re-
ported the corresponding values as 110.0°, 109.7°, 109.7°, 110.0°
and 110.0° for different similar derivatives. Karczmarzyk et al.
[77] reported the dihedral angles C40AN38AC39AC46 = 61.1, C45
2
ðFi;jÞ
Eð2Þ ¼ Eij ¼ qi
D
ðEj ꢂ EiÞ
where qi is the donor orbital occupancy, Ei, Ej the diagonal elements,
and Fij is the off diagonal NBO Fock matrix element.
AN47AC46AC39 = 60.1,
N
38AC39AC46AN47 = ꢂ61.5,
C
46AN47AC45
In NBO analysis large E(2) value shows the intensive interaction
between electron donors and electron-acceptors, and greater the
extent of conjugation of the whole system, the possible intensive
interaction are given in Table S2 as Supporting material. The sec-
ond order perturbation theory analysis of Fock-matrix in NBO basis
shows strong intermolecular hyper conjugative interactions are
formed by orbital overlap between n(O) and rꢁ(CAO), rꢁ(CAC),
rꢁ(CAN), n(N) and pꢁ(CAO), pꢁ(CAC) and between n(Cl) and
pꢁ(CAC) bond orbitals which result in ICT causing stabilization of
the system. These interactions are observed as an increase in elec-
tron density (ED) in CAO, CAC and CAN anti bonding orbital that
weakens the respective bonds. There occurs a strong inter molecu-
lar hyper conjugative interaction of C7AO14 from O9 of n2(O9) ?
rꢁ(C7AO14) which increases ED (0.07306 e) that weakens the
respective bonds C7AO14 (1.4229 Å) leading to stabilization of
12.60 kJ/mol and also the hyper conjugative interaction of
AC40 = ꢂ58.2,
C
39AN38AC40AC45 = ꢂ58.9,
N
47AC45AC40AN38 =
57.5°, which are in agreement with our calculated values.
First hyperpolarizability
Non-linear optics deals with the interaction of applied electro-
magnetic fields in various materials to generate new electromag-
netic fields, altered in wavenumber, phase, or other physical
properties [78]. Organic molecules able to manipulate photonic
signals efficiently are of importance in technologies such as optical
communication, optical computing, and dynamic image processing
[79,80]. In this context, the dynamic first hyperpolarizability of the
title compound is also calculated in the present study. The first
hyperpolarizability (b0) of this novel molecular system is calcu-
lated using SDD method, based on the finite field approach. In
the presence of an applied electric field, the energy of a system is
a function of the electric field. First hyperpolarizability is a third
rank tensor that can be described by a 3 ꢃ 3 ꢃ 3 matrix. The 27
components of the 3D matrix can be reduced to 10 components
due to the Kleinman symmetry [81]. The components of b are de-
fined as the coefficients in the Taylor series expansion of the en-
ergy in the external electric field. When the electric field is weak
and homogeneous, this expansion becomes
N
15AC16 from O17 of n2(O17) ? rꢁ(N15AC16) which increases ED
(0.08760 e) that weakens the respective bonds 15AC16
N
(1.4021 Å) leading to stabilization of 26.17 kJ/mol. Also the hyper
conjugative interaction of C13AN15 from O18 of n2(O18) ? rꢁ(C13
AN15) which increases ED (0.08859 e) that weakens the respective
bonds C13AN15 (1.4037 Å) leading to stabilization of 26.17 kJ/mol.
An another hyper conjugative interaction observed in C16AO17
from N15 of n1(N15) ? pꢁ(C16AO17
)
which increases ED
(0.24591 e) that weakens the respective bond C16AO17 (1.2426 Å)
leading to a stabilization of 55.22 kJ/mol. An another hyper
conjugative interaction observed in C3AC7 from Cl34 of n3(Cl34) ?
rꢁ(C3AC7) which increases ED (0.08303 e) that weakens the
respective bond C3AC7 (1.5903 Å) leading to a stabilization of
5.10 kJ/mol. Another hyper conjugative interaction is observed
C1AC2 from Cl35 of n3(Cl35) ? pꢁ(C1AC2) which increases ED
(0.19679 e) that weakens the respective bonds C1AC2 (1.3472 Å)
leading to stabilization of 14.59 kJ/mol. There occurs another
strong intermolecular hyper conjugative interaction of C1AC2 from
Cl36 of n3(Cl36) ? pꢁ(C1AC2) which increases ED (0.19679 e) that
weakens the respective bonds C1AC2 (1.3472 Å) leading to stabil-
ization of 14.89 kJ/mol. Another hyper conjugative interaction of
C6AC7 from Cl37 of n3(Cl37) ? rꢁ(C6AC7) which increases ED
(0.08183 e) that weakens the respective bond C6AC7(1.5870 Å)
leading to a stabilization of 4.54 kJ/mol. Also the hyper conjugative
interaction of C40AC45 from N38 of n1(N38) ? rꢁ(C40AC45) which
increases ED (0.02217 e) that weakens the respective bonds
X
X
X
X
1
2
1
6
1
24
E¼E0 ꢂ
l
iFi ꢂ
a
ijFiFj ꢂ
bijkFiFjFk ꢂ
c
ijklFiFjFkFl þꢄꢄꢄ
i
ij
ijk
ijkl
where E0 is the energy of the unperturbed molecule, Fi is the field at
the origin, lij ij, bijk and ijkl are the components of dipole moment,
,
a
c
polarizability, the first hyperpolarizabilities, and second hyperpolar-
izabilities, respectively. The calculated first hyperpolarizability of
the title compound is 4.49 ꢃ 10ꢂ30 esu, which comparable with the
reported values of similar derivatives [82] and which is 34.54 times
that of the standard NLO material urea (0.13 ꢃ 10ꢂ30 esu) [83].
Panicker et al. [26] and Varghese et al. [27] reported the first hyper-
polarizability of similar azatricyclo derivatives as 0.55 ꢃ 10ꢂ30 and
0.89 ꢃ 10ꢂ30 esu. We conclude that the title compound is an attrac-
tive object for future studies of non-linear optical properties.
NBO analysis
The natural bond orbital (NBO) calculations were performed
using NBO 3.1 program [84] as implemented in the Gaussian09
C
40AC45 (1.5453 Å) leading to stabilization of 4.29 kJ/mol.
There occurs another strong intermolecular hyper conjugative

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
509
interaction of C52AC54 from N47 of n1(N47) ? pꢁ(C52AC54) which in-
creases ED (0.43183 e) that weakens the respective bonds C52AC54
(1.4251 Å) leading to stabilization of 41.0 kJ/mol. These interactions
are observed as an increase in electron density (ED) in CAO, CAC
and CAN anti bonding orbital that weakens the respective bonds.
The increased electron density at the oxygen atoms leads to the
elongation of respective bond length and a lowering of the corre-
sponding stretching wavenumber. The electron density (ED) is trans-
ferred from the n(O) to the anti-bonding pꢁ orbital of the CAO, CAC
and CAN bonds, explaining both the elongation and the red shift
[85]. The hyper conjugative interaction energy was deduced from
the second-order perturbation approach. Delocalization of electron
density between occupied Lewis-type (bond or lone pair) NBO orbi-
tal and formally unoccupied (anti bond or Rydberg) non-Lewis NBO
orbital corresponds to a stabilizing donor–acceptor interaction. The
OCH3 and C@O, CACl stretching modes can be used as a good probe
for evaluating the bonding configuration around the ring. Hence the
title compound is stabilized by these orbital interactions.
charge distributions calculated by the Mulliken [86] and NBO
methods for the equilibrium geometry of TDPPAD are given in
Table S3 as Supporting material. The charge distribution on the
molecule has an important influence on the vibrational spectra.
In TDPPAD, the Mulliken atomic charge of the carbon atoms in
the neighborhood of C7, C13, C16 and C52 become more positive,
shows the direction of delocalization and shows that the natural
atomic charges are more sensitive to the changes in the molecular
structure than Mulliken’s net charges. The results are shown in
Fig. S1 as Supporting material.
Also we done a comparison of Mulliken charges obtained by dif-
ferent basis sets and tabulated in Table S4 as Supporting material
in order to assess the sensitivity of the calculated charges to
changes in (i) the choice of the basis set and (ii) the choice of the
quantum mechanical method. The results can, however, better be
represented in graphical form as shown in Fig. S2 as supporting
material. We have observed a change in the charge distribution
by changing different basis sets.
The NBO analysis also describes the bonding in terms of the nat-
ural hybrid orbital n2(O9), which occupy a higher energy orbital
(ꢂ0.32194 a.u.) with considerable p-character (99.80%) and low
occupation number (1.90187) and the other n1(O9), which occupy
a lower energy orbital (ꢂ0.57322 a.u.) with considerable p-charac-
ter (56.05%) and high occupation number (1.95769). Also n2(O14),
which occupy a higher energy orbital (ꢂ0.32774 a.u.) with consid-
erable p-character (100.0%) and low occupation number (1.90180)
and the other n1(O14), which occupy a lower energy orbital
(ꢂ0.58495 a.u.) with considerable p-character (55.98%) and high
occupation number (1.95485). Again n2(O17), which occupy a high-
er energy orbital (ꢂ0.27654 a.u.) with considerable p-character
(99.99%) and low occupation number (1.86035) and the other
n1(O17), which occupy a lower energy orbital (ꢂ0.70945 a.u.) with
considerable p-character (38.34%) and high occupation number
(1.97607). Again n2(O18), which occupy a higher energy orbital
(ꢂ0.27433 a.u.) with considerable p-character (99.99%) and low
occupation number (1.85991) and the other n1(O18), which occupy
a lower energy orbital (ꢂ0.70651) with considerable p-character
(38.43%) and high occupation number (1.97646). Again n3(Cl34),
which occupy a high energy orbital (ꢂ0.32748 a.u.) with consider-
able p-character (100.0%) and low occupation number (1.96154)
1H NMR spectrum
The experimental spectrum data of TDPPAD in DMSO with TMS as
internal standard is obtained at 400 MHz. The absolute isotropic
chemical shielding of TDPPAD was calculated by B3LYP/GIAO model
[87]. Relative chemical shifts were then estimated by using the cor-
responding TMS shielding: rcalc ꢄ (TMS) calculated in advance at the
same theoretical level as this paper. Numerical values of chemical
shift dcalc
=
rcalc ꢄ (TMS) ꢂ rcalc together with calculated values of
rcalc ꢄ (TMS), are given in Table 3. It could be seen from Table 3 that
chemical shift was in agreement with the experimental 1H NMR data.
Thus, the results showed that the predicted proton chemical shifts
were in good agreement with the experimental data for TDPPAD.
PES scan studies
A detailed potential energy surface (PES) scan on dihedral an-
gles C31AC28AC19AN15 and N38AC31AC28AC19 have been per-
formed at B3LYP/6-31G(d) level to reveal all possible
conformations of TDPPAD. The PES scan was carried out by mini-
mizing the potential energy in all geometrical parameters by
changing the torsion angle at every 20° for a 180° rotation around
the bond. The results obtained in PES scan study by varying the tor-
sion perturbation around the methyl bonds (CH2) are plotted and
given in Figs. 4 and 5. For the C31AC28AC19AN15 rotation, the min-
imum energy was obtained at ꢂ175.5° in the potential energy
curve of energy ꢂ3209.19188 Hartrees. For the N38AC31AC28AC19
rotation, the minimum energy occurs at 178.3° in the potential en-
ergy curve of energy ꢂ3209.19257 Hartrees.
and the other n2(Cl34
) which occupy a low energy orbital
(ꢂ0.32931 a.u.) with considerable p-character (99.99%) and high
occupation number (1.96588). Another n3(Cl35), which occupy a
high energy orbital (ꢂ0.34372 a.u.) with considerable p-character
(100.0%) and low occupation number (1.91960) and the other
n2(Cl35), which occupies a low energy orbital (ꢂ0.34463 a.u.) with
considerable p-character (99.87%) and high occupation number
(1.96363). Another n3(Cl36), which occupy
a energy orbital
(ꢂ0.34164 a.u.) with considerable p-character (100.0%) and low
occupation number (1.91712) and the other n2(Cl36), which occupy
a low energy orbital (ꢂ0.34301 a.u.) with considerable p-character
(99.86%) and high occupation number (1.96325). Another n3(Cl37),
which occupy a high energy orbital (ꢂ0.32349 a.u.) with consider-
able p-character (100.0%) and low occupation number (1.96083)
Molecular electrostatic potential
MEP is related to the ED and is a very useful descriptor in under-
standing sites for electrophilic and nucleophilic reactions as well as
hydrogen bonding interactions [88,89]. The electrostatic potential
V(r) is also well suited for analyzing processes based on the ‘‘recog-
nition’’ of one molecule by another, as in drug-receptor, and en-
zyme–substrate interactions, because it is through their
potentials that the two species first ‘‘see’’ each other [90,91]. To
predict reactive sites of electrophilic and nucleophilic attacks for
the investigated molecule, MEP at the B3LYP/6-31G(d,p) optimized
geometry was calculated. The negative (red and yellow) regions of
MEP were related to electrophilic reactivity and the positive (blue)
regions to nucleophilic reactivity (Fig. S3 Supporting material).
From the MEP it is evident that the negative charge covers the car-
bonyl, benzene and piperazine rings and the positive region is over
the methyl group. The more electro negativity in the carbonyl,
and the other n2(Cl37
) which occupy a low energy orbital
(ꢂ0.32654 a.u.) with considerable p-character (99.97%) and high
occupation number (1.96571). Thus, a very close to pure p-type
lone pair orbital participates in the electron donation to the
rꢁ(CAO), rꢁ(NAC) and rꢁ(CAC) orbital for n3(O9) ? rꢁ(CAO),
n3(O18) ? rꢁ 15AC13 and n1(N47) ? rꢁ
N C52AC54 interactions
respectively in the compound. The results are tabulated in Table 2.
Mulliken charges
Mulliken charges are calculated by determining the electron
population of each atom as defined in the basis functions. The

510
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
Table 2
NBO results showing the formation of Lewis and non-Lewis orbitals.
Bond (A–B)
ED (ea)
EDA%
EDB%
NBO
s%
p%
r
–
C1AC2
1.97964
ꢂ0.80470
1.94592
49.95
–
49.58
–
49.21
–
47.58
–
49.24
–
47.53
–
51.20
–
52.04
–
47.43
–
49.96
–
52.50
–
48.97
–
52.34
–
52.03
–
47.64
–
33.71
–
33.17
–
31.41
–
30.96
–
36.38
–
35.28
–
32.94
–
63.50
–
64.15
–
35.31
–
32.75
–
50.98
–
50.11
–
39.74
–
60.29
–
60.27
–
49.82
–
50.05
–
50.42
–
50.79
–
52.42
–
50.76
–
52.47
–
48.80
–
47.96
–
52.57
–
50.04
–
47.50
–
51.03
–
47.66
–
47.97
–
52.36
–
66.29
–
66.83
–
68.59
–
69.04
–
63.62
–
64.72
–
67.06
–
36.50
–
35.85
–
64.69
–
67.25
–
49.02
–
49.89
–
60.26
–
39.71
–
39.73
–
50.18
–
0.7067 (sp1.53)C
+0.7075 (sp1.52)C
0.7041 (sp94.85)C
+0.7101 (sp99.99)C
0.7015 (sp1.96)C
+0.7126 (sp2.66)C
0.6898 (sp2.93)C
+0.7240 (sp5.55)Cl
0.7017 (sp1.96)C
+0.7124 (sp2.66)C
0.6894 (sp2.93)C
+0.7244 (sp5.56)Cl
0.7156 (sp2.64)C
+0.6986 (sp2.95)C
0.7214 (sp2.86)C
+0.6925 (sp2.74)C
0.6887 (sp4.27)C
+0.7251 (sp6.10)Cl
0.7068 (sp3.17)C
+0.7074 (sp3.17)C
0.7246 (sp2.93)C
+0.6892 (sp1.77)C
0.6998 (sp2.91)C
+0.7143 (sp2.64)C
0.7235 (sp2.98)C
+0.6904 (sp1.77)C
0.7213 (sp2.89)C
+0.6926 (sp2.77)C
0.6902 (sp4.23)C
+0.7236 (sp6.09)Cl
39.56
39.62
1.04
60.44
60.38
98.96
99.03
66.20
72.65
74.57
84.73
66.20
72.71
74.57
84.75
72.50
74.68
74.09
73.27
81.03
85.91
76.05
76.05
74.53
63.89
74.41
72.53
74.85
63.91
74.28
73.47
80.88
85.89
76.34
69.44
77.18
69.45
81.11
74.72
81.55
74.57
69.64
67.11
66.71
61.63
99.99
99.94
66.81
69.48
66.26
78.80
66.91
61.83
99.91
99.82
71.18
74.26
73.33
72.09
76.02
69.62
70.34
76.58
70.59
76.85
72.77
72.53
72.66
72.72
77.18
68.23
77.24
68.39
63.38
71.31
64.34
65.96
pC1AC2
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
ꢂ0.36201
0.97
C1AC6
1.96243
33.80
27.35
25.43
15.27
33.80
27.29
25.43
15.25
27.50
25.32
25.91
26.73
18.97
14.09
23.95
23.95
25.47
36.11
25.59
27.47
25.15
36.09
25.72
26.53
19.12
14.11
23.66
30.56
22.82
30.55
18.89
25.28
18.45
25.43
30.36
32.89
33.29
38.37
0.01
ꢂ0.69163
1.98987
C1ACl36
C2AC3
ꢂ0.74647
1.96329
ꢂ0.69347
1.98986
C2ACl35
C3AC4
ꢂ0.74685
1.95846
ꢂ0.65078
1.95153
C3AC7
ꢂ0.65147
C3ACl34
C4AC5
1.98597
ꢂ0.69288
1.95374
ꢂ0.62402
C4AC13
C5AC6
1.97494
ꢂ0.67254
1.96075
ꢂ0.65358
C5AC16
C6AC7
1.97465
ꢂ0.67160
1.94980
ꢂ0.65073
C6ACl37
C7AO9
1.98578
ꢂ0.69161
1.99160
0.5806 (sp3.23
C
ꢂ0.89957
+0.8142 (sp2.27)O
0.5760 (sp3.38)C
+0.8175 (sp2.27)O
0.5605 (sp4.29)C
+0.8282 (sp2.96)O
0.5564 (sp4.42)C
+0.8309 (sp2.93)O
0.6032 (sp2.29)C
+0.7976 (sp2.04)N
0.5940 (sp2.00)C
+0.8045 (sp1.61)O
0.5739 (sp99.99)C
+0.8189 (sp99.99)O
0.7969 (sp2.01)N
+0.6041 (sp2.28)C
0.8009 (sp1.96)N
+0.5988 (sp3.72)C
0.5942 (sp2.02)C
+0.8043 (sp1.62)O
0.5723 (sp99.99)C
+0.8201 (sp99.99)O
0.7140 (sp2.47)C
+0.7002 (sp2.88)C
0.7079 (sp2.75)C
+0.7063 (sp2.58)C
0.6304 (sp3.17)C
C7AO14
C8AO9
1.99140
ꢂ0.89458
1.98904
r
–
r
–
r
–
r
–
ꢂ0.78548
C11AO14
C13AN15
C13AO18
1.98839
ꢂ0.78449
1.98547
ꢂ0.83157
1.99552
ꢂ1.08580
1.98592
pC13AO18
–
r
–
r
–
r
–
ꢂ0.39079
0.06
N15AC16
N15AC19
C16AO17
1.98586
33.19
30.52
33.74
21.20
33.09
38.17
0.09
ꢂ0.83572
1.98438
ꢂ0.75820
1.99554
ꢂ1.08481
1.98594
pC16AO17
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
r
–
ꢂ0.39565
0.18
C19AC28
C28AC31
C31AN38
N38AC39
N38AC40
C39AC46
C40AC45
C45AN47
C46AN47
N47AC52
C52AC53
1.97889
29.82
25.74
26.67
27.91
23.98
30.38
29.66
23.42
29.41
23.15
27.23
27.47
27.34
27.28
22.82
31.77
22.76
31.61
36.62
28.69
35.66
34.04
ꢂ0.60792
1.98119
ꢂ0.59944
1.98472
ꢂ0.69946
1.98587
+0.7763 (sp2.29)
N
0.7765 (sp2.37)N
+0.6302 (sp3.27)C
0.7763 (sp2.40)N
+0.6304 (sp3.32)C
0.7058 (sp2.67)C
+0.7084 (sp2.64)C
0.7028 (sp2.66)C
+0.7114 (sp2.67)C
0.6197 (sp3.38)C
+0.7848 (sp2.15)N
0.6196 (sp3.39)C
+0.7849 (sp2.16)N
0.7827 (sp1.73)N
+0.6224 (sp2.49)C
0.7153 (sp1.80)C
+0.6988 (sp1.94)C
ꢂ0.69495
1.98566
ꢂ0.68933
1.98375
ꢂ0.61073
1.98673
49.39
–
38.41
–
38.39
–
61.26
–
50.61
–
61.59
–
61.61
–
38.74
–
ꢂ0.60617
1.98604
ꢂ0.71137
1.98583
ꢂ0.70934
1.98642
ꢂ0.78136
1.97354
51.17
–
48.83
–
ꢂ0.67150

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
511
Table 2 (continued)
Bond (A–B)
ED (ea)
EDA%
EDB%
NBO
s%
p%
r
–
C52AC54
1.97348
ꢂ0.67112
1.63395
51.16
–
45.79
–
50.39
–
53.44
–
50.39
–
50.27
–
50.27
–
47.52
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
48.84
–
54.21
–
49.61
–
46.56
–
49.61
–
49.73
–
49.73
–
52.48
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
0.7153 (sp1.81)C
35.59
34.03
0.00
0.00
36.04
35.18
0.00
0.00
36.04
35.19
35.34
34.73
35.34
34.73
0.00
0.00
43.95
–
0.20
–
44.02
–
0.00
–
0.17
–
61.66
–
0.01
–
61.57
–
0.01
–
86.08
–
0.01
–
0.00
–
84.82
–
64.41
65.97
100.0
100.0
63.96
64.82
100.0
100.0
63.96
64.81
64.66
65.27
64.66
65.27
100.0
100.0
56.05
–
99.80
–
55.98
–
100.0
–
99.83
–
38.34
–
99.99
–
38.43
–
99.99
–
13.92
–
99.99
–
100.0
–
15.18
–
+0.6988 (sp1.94)C
pC52AC54
0.6767 (sp1.00)C
–
r
–
ꢂ0.23294
+0.7363 (sp1.00)C
C53AC55
1.97867
0.7099 (sp1.77)C
ꢂ0.67364
1.72012
+0.7043 (sp1.84)C
pC53AC55
0.7310 (sp1.00)C
–
r
–
r
–
r
–
ꢂ0.23368
+0.6824 (sp1.00)C
C54AC57
C55AC59
C57AC59
1.97870
0.7098 (sp1.77)C
ꢂ0.67373
1.98074
+0.7044 (sp1.84)C
0.7090 (sp1.83)C
ꢂ0.66703
+0.7052 (sp1.88)C
1.98075
0.7090 (sp1.83)C
ꢂ0.66702
1.67792
+0.7052 (sp1.88)C
pC57AC59
0.6893 (sp1.00)C
–
ꢂ0.22776
+0.7244 (sp1.00)C
n1O9
–
n2O9
–
n1O14
–
n2 O14
–
n1 N15
–
n1 O17
–
n2 O17
–
n1 O18
–
n2 O18
–
n1Cl34
–
n2 Cl34
–
n3 Cl34
–
n1 Cl35
–
n2 Cl35
–
n3 Cl35
–
n1 Cl36
–
n2 Cl36
–
n3 Cl36
–
n1 Cl37
–
n2 Cl37
–
n3 Cl37
–
n1 N38
–
n1 N47
–
1.95769
sp 1.28
–
sp 99.99
–
sp 1.27
–
sp 1.00
–
sp 99.99
–
sp 0.62
–
sp 99.99
–
sp 0.62
–
sp 1.00
–
sp 0.16
–
sp1.00
–
sp 1.00
–
sp 0.18
–
sp 99.99
–
sp1.00
–
sp 0.18
–
sp 99.99
–
sp 1.00
–
sp 0.16
–
sp 99.99
–
sp 1.00
–
sp 8.50
–
sp 1.00
–
ꢂ0.57322
1.90187
ꢂ0.32194
1.95485
ꢂ0.58495
1.90180
ꢂ0.32774
1.58084
ꢂ0.28378
1.97607
ꢂ0.70945
1.86035
ꢂ0.27654
1.97646
ꢂ0.70651
1.85991
ꢂ0.27433
1.99303
ꢂ0.96695
1.96588
ꢂ0.32931
1.96154
ꢂ0.32748
1.99269
ꢂ0.96823
1.96363
0.13
–
0.00
–
84.80
–
0.14
–
0.00
–
86.04
–
0.03
–
0.00
–
99.87
–
100.0
–
15.20
–
99.86
–
100.0
–
13.96
–
99.97
–
100.0
–
ꢂ0.34463
1.91960
ꢂ0.34372
1.99259
ꢂ0.96679
1.96325
ꢂ0.34301
1.91712
ꢂ0.34164
1.99308
ꢂ0.96347
1.96571
ꢂ0.32654
1.96083
ꢂ0.32349
1.89110
10.53
–
0.00
–
89.47
–
100.0
–
ꢂ0.24811
1.74920
ꢂ0.22627
a
ED/e is expressed in a.u.
benzene, and piperazine groups makes it the most reactive part in
the molecule.
significant degree of ICT from the end-capping electron-donor
groups to the efficient electron-acceptor groups through -conju-
gated path. The strong charge transfer interaction through -con-
p
p
HOMO–LUMO band gap
jugated bridge results in substantial ground state donor–acceptor
mixing and the appearance of a charge transfer band in the elec-
tronic absorption spectrum. Therefore, an ED transfer occurs from
the more aromatic part of the p-conjugated system in the electron
donor side to its electron-withdrawing part. The atomic orbital
HOMO and LUMO are the very important parameters for
quantum chemistry. The conjugated molecules are characterized
by a highest occupied molecular orbital–lowest unoccupied molec-
ular orbital (HOMO–LUMO) separation, which is the result of a
components of the frontier molecular orbital are given in Figs. S4

512
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
Table 3
Conclusion
Experimental and calculated 1H NMR parameters (with respect to TMS).
Proton
rTMS
B3LYP/6-31G rcalc
dcalc ꢄ (rTMS
ꢂ
rcalc
)
Exp. dppm
FT-IR and FT-Raman spectra of TDPPAD were recorded and ana-
lyzed. The vibrational wavenumbers were computing at various
levels of theory. The data obtained from theoretical calculations
are used to assign vibrational bands obtained experimentally.
The geometrical parameters of the title compound are in agree-
ment with that of similar derivatives. In addition, the calculated
1H NMR is all in good agreement with the experimental data.
The lowering of HOMO–LUMO band gap supports bioactive prop-
erty of the molecule. MEP predicts the most reactive part in the
molecule. The calculated first hyperpolarizability is comparable
with the reported values of similar derivatives and is an attractive
object for future studies of non-linear optics.
H10
H12
H20
H21
H22
H23
H24
H25
H26
H27
H29
H30
H32
H33
H41
H42
H43
H44
H48
H49
H50
H51
H56
H58
H60
H61
H62
32.7711
29.1949
29.3181
29.0239
28.8704
29.0295
29.1431
29.1318
29.0616
29.1606
29.0454
30.7268
30.6984
30.0619
29.2889
29.2599
29.2081
29.0796
29.0874
28.8471
29.0241
28.9501
28.8454
25.7521
25.7518
25.3483
25.9348
25.3925
3.5762
3.4530
3.7472
3.9007
3.7416
3.6208
3.6393
3.7095
3.6105
3.7257
2.0443
2.0727
2.7092
3.4822
3.5112
3.5630
3.6915
3.6837
3.9240
3.747
3.65
3.65
3.65
3.65
3.65
3.65
3.65
3.59
3.59
3.65
2.16
2.18
2.45
3.50
3.54
3.55
3.72
3.72
3.74
3.73
3.74
3.74
7.01
7.00
7.33
6.99
7.29
Acknowledgements
The authors are thankful to University of Antwerp for access to
the university’s CalcUA Supercomputer Cluster. RR thanks Univer-
sity Grants Commission, India, for a research fellowship.
3.8270
3.9257
7.019
7.0193
7.4228
6.8363
7.3786
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.01.045.
References
[1] L.H. Atherden, Bentley and Driver’s Text Book of Pharmaceutical Chemistry,
eighth ed., Oxford Medicinal Publication, 2004. pp. 372–377, 204–205.
[2] A.H. Beckett, J.B. Stenlake, Practical Pharmaceutical Chemistry, fourth ed., CBS
Publishers and Distributors, 2003.
[3] R.S. Upadhayaya, N. Sinha, S. Jain, N. Kishore, R. Chandra, S.K. Arora, Bioorg.
Med. Chem. 12 (2004) 2225–2238.
[4] W.O. Foye, T.L. Lemke, D.A. William, Principles of Medicinal Chemistry, fourth
ed., Williams and Wilkins, London, 1995.
[5] L.L. Gan, Y.H. Lu, C.H. Zhou, Chin. J. Biochem. Pharm. 30 (2009) 127–131.
[6] J.L. Cai, Y.H. Lu, L.L. Gan, C.H. Zhou, Chin. J. Antibiotics 34 (2009) 454–462.
[7] L.L. Gan, J.L. Cai, C.H. Zhou, Chin. Pharm. J. 44 (2009) 1361–1368.
[8] O.A. Phillips, E.E. Udo, S.M. Samuel, Eur. J. Med. Chem. 43 (2008) 1095–1104.
[9] A. Foroumadi, S. Emami, S. Mansouri, A. Javidnia, N. Saeid-Adeli, F.H. Shirazi, A.
Shafiee, Eur. J. Med. Chem. 42 (2007) 985–992.
[10] B.B. Lohray, V.B. Lohray, B.K. Srivastava, S. Gupta, M. Solanki, P. Pandya, P.
Kapadnis, Bioorg. Med. Chem. Lett. 16 (2006) 1557–1561.
[11] A. Foroumadi, S. Ghodsi, S. Emami, S. Najjari, N. Samadi, M.A. Faramarzi, L.
Beikmohammadi, F.H. Shirazi, A. Shafiee, Bioorg. Med. Chem. Lett. 16 (2006)
3499–3503.
[12] W.J. Watkins, L. Chong, A. Cho, R. Hilgenkamp, M. Ludwikow, N. Garizi, N.
Iqbal, J. Barnard, R. Singh, D. Madsen, K. Lolans, O. Lomovskaya, U. Oza, P.
Kumaraswamy, A. Blecken, S. Bai, D.J. Loury, D.C. Griffith, M.N. Dudley, Bioorg.
Med. Chem. Lett. 17 (2007) 2802–2806.
Fig. 4. Profile of potential energy scan for the torsion angle C31AC28AC19AN15.
[13] L.L. Rokosz, C.Y. Huang, J.C. Reader, T.M. Stauffer, D. Chelsky, N.H. Sigal, A.K.
Ganguly, J. Baldwin, J. Bioorg, Med. Chem. Lett. 15 (2005) 5537–5543.
[14] J.J. Chen, M. Lu, Y.K. Jing, J.H. Dong, Bioorg. Med. Chem. 14 (2006) 6539–6547.
[15] P.J. Shami, J.E. Saavedra, C.L. Bonifant, J.X. Chu, V. Udupi, S. Malaviya, B.I. Carr,
S. Kar, M.F. Wang, L. Jia, X.H. Ji, L.K. Keefer, J. Med. Chem. 49 (2006) 4356–4366.
[16] A. Mayence, J.J.V. Eynde, L. LeCour Jr., L.A. Walker, B.L. Tekwani, T.L. Huang, Eur.
J. Med. Chem. 39 (2004) 547–553.
[17] W. Cunico, C.R.B. Gomes, M. Moreth, D.P. Manhanini, I.H. Figueiredo, I.C.
Penido, M.G.M.O. Henriques, F.P. Varotti, A.U. Krettli, Eur. J. Med. Chem. 44
(2009) 1363–1368.
[18] R.A. Smits, H.D. Lim, A. Hanzer, O.P. Zuiderveld, E. Guaita, M. Adami, G. Coruzzi,
R. Leurs, I.J.P. Esch, J. Med. Chem. 51 (2008) 2457–2467.
´
´
´
´
ˇ ´
´
´
[19] J. Penjiševic, V. Šukalovic, D. Andric, S. Kostic-Rajacic, V. Šoškic, G. Roglic, Arch.
Pharm. Chem. Life Sci. 340 (2007) 456–465.
[20] O.M. Becker, D.S. Dhanoa, Y. Marantz, D. Chen, S. Shacham, S. Cheruku, A.
Heifetz, P. Mohanty, M. Fichman, A. Sharadendu, R. Nudelman, M. Kauffman, S.
Noiman, J. Med. Chem. 49 (2006) 3116–3135.
[21] D.C. Bean, D.W. Wareham, J. Antimicrob. Chemother. 63 (2009) 349–352.
[22] A.Y. Coban, Z. Bayram, F.M. Sezgin, B. Durupinar, Bull. Microbiol. 43 (2009)
457–461.
Fig. 5. Profile of potential energy scan for the torsion angle N38AC31AC28AC19.
[23] P. Chaudhary, R. Kumar, A.K. Verma, D. Singh, V. Yadav, A.K. Chhillar, G.L.
Sharmab, R. Chandraa, Bioorg. Med. Chem. 14 (2006) 1819–1826.
[24] V.M. Farzaliev, M.T. Abbasova, A.A. Ashurova, G.B. Babaeva, N.P. Ladokhina,
Y.M. Kerimova, Russ. J. Appl. Chem. 82 (2009) 928–930.
and S5 as Supporting material. The HOMO–LUMO energy gap value
is found to be 3.182 eV, which is responsible for the bioactive prop-
erty of the compound TDPPAD, as reported in the literature [92–
94].
´
[25] J. Stefanska, A. Bielenica, M. Struga, S. Tyski, J. Kossakowski, P.L. Colla, E.
Tamburini, R. Loddo, Ann. Micribiol. 60 (2010) 151–155.

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 500–513
513
[26] C.Y. Panicker, H.T. Varghese, K.M. Pillai, Y.S. Mary, K. Raju, T.K. Manojkumar, A.
[54] C. Lee, W. Yang, R.G. Parr, Phys. Rev. 37B (1988) 785–789.
[55] E.F. Mooney, Spectrochim. Acta 20 (1964) 1021–1032.
[56] E.F. Mooney, Spectrochim. Acta 19 (1963) 877–887.
[57] N. Sundaraganesan, C. Meganathan, B.D. Joshua, P. Mani, A. Jayaprakash,
Spectrochim. Acta 71A (2008) 1134–1139.
[58] P. Pazdera, H. Divisova, H. Havilsova, P. Borek, Molecules 5 (2000) 189–194.
[59] P. Pazdera, H. Divisova, H. Havilsova, P. Borek, Molecules 566 (2000) 1166–
1174.
[60] H.T. Varghese, C.Y. Panicker, D. Philip, P. Pazdera, Spectrochim. Acta 67A
(2007) 1055–1059.
Bielenica, C. Van Alsenoy, Spectrochim. Acta 75 (2010) 1559–1565.
[27] H.T. Varghese, C.Y. Panicker, K.M. Pillai, Y.S. Mary, K. Raju, T.K. Manojkumar, A.
Bielenica, C. Van Alsenoy, Spectrochim. Acta 76 (2010) 513–522.
[28] J. Kossakowski, A. Bielenica, B. Mirosław, A.E. Kozioł, I. Dybała, M. Struga,
Molecules 13 (2008) 1570–1583.
[29] R. Filosa, A. Peduto, P. de Capraris, C. Saturnino, M. Festa, A. Petrella, A. Pau,
G.A. Pinna, P.L. Colla, B. Busonera, R. Loddo, Eur. J. Med. Chem. 42 (2007) 293–
306.
[30] C.A. Peri, Gazz. Chim. Ital. 85 (1955) 1118–1140.
[31] J. Kossakowski, M. Pakosinska-Parys, M. Struga, I. Dybala, A.E. Koziol, P.
LaColla, L.E. Marongiu, C. Ibba, D. Collu, R. Loddo, Molecules 14 (2009) 5189–
5202.
[61] H. Arslan, U. Florke, N. Kulcu, G. Binzet, Spectrochim. Acta 68A (2007) 1347–
1355.
[62] W.O. George, P.S. Mcintyre, Infrared Spectroscopy, first ed., John Wiley and
Sons, Chichester, 1987.
[63] M.A. Palafox, V.K. Rastogi, L. Mittal, Int. J. Quantum Chem. 94 (2003) 189–204.
[64] M. Kurt, J. Raman Spectrosc. 40 (1) (2009) 67–75.
[65] K. Felfoldi, M. Sutyinszky, N. Nagy, I. Palinko, Synth. Commun. 30 (2000) 1543–
1553.
[66] A.A. El-Emam, A.S. Al-Tamimi, K.A. Al-Rashood, H.N. Misra, V. Narayan, O.
Prasad, L. Sinha, J. Mol. Struct. 1022 (2012) 49–60.
[32] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro,
M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken,
C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R.
Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B.
Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision B.01,
Gaussian Inc., Wallingford CT, 2010.
[33] J.B. Foresman, in: E. Frisch (Ed.), Exploring Chemistry with Electronic Structure
Methods: A Guide to Using Gaussian, Gaussian Inc., Pittsburg, PA, 1996.
[34] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 270–283.
[35] J.Y. Zhao, Y. Zhang, L.G. Zhu, J. Mol. Struct. Theochem. 671 (2004) 179–187.
[36] R. Dennington, T. Keith, J. Millam, GaussView, Version 5, Semichem Inc.,
Shawnee Mission KS, 2009.
[67] H.L. Spell, Anal. Chem. 41 (1969) 902–905.
[68] M.A.S. da Silva, S. Pinheiro, T. Francisco, F.O.N. da Silva, A.A. Batista, J. Ellena,
I.M.M. Carvalho, J.R. de Sousa, F.A. Dias- Filho, E. Longhinotti, I.C.N. Diógenes, J.
Braz. Chem. Soc. 21 (2010) 1754–1759.
[69] N.R. Conley, R.J. Hung, C.G. Willson, J. Org. Chem. 70 (2005) 4553–4555.
[70] T.M.V.D. Pinho e Melo, A.M.T.D.P. Cabral, A.M.R. Gonsalves, A.M. Beja, J.A.
Paixao, M.R. Silva, L.A. daVeiga, J. Org. Chem. 64 (1999) 7229–7232.
[71] D. Lee, T.M. Swager, Chem. Mater. 17 (2005) 4622–4629.
[72] B. Bartkowska, F.M. Bohnen, C. Kruger, W.F. Maier, Acta Crystallogr. C53 (1997)
521–522.
[73] H.B. Burgi, J.D. Dunitz, Structure Correlation, vol. 2, VCH, Weinheim, 1994. pp.
741–784.
[37] J.M.L. Martin, C.V. Alsenoy, GAR2PED, A Program to Obtain a Potential Energy
Distribution from a Gaussian Archive Record, University of Antwerp, Belgium,
2007.
[38] N.P.G. Roeges, A Guide to the Complete Interpretation of Infrared Spectra of
Organic Structures, Wiley, New York, 1994.
[39] G. Varsyani, Assignments of Vibrational Spectra of Seven Hundred Benzene
Derivatives, Wiley, New York, 1974.
[40] N.B. Colthup, L.H. Daly, S.E. Wiberly, Introduction to Infrared and Raman
Spectroscopy, Academic Press, New York, 1990.
[74] R. Manohar, M. Harikrishna, C.R. Ramanathan, M.S. Kumar, K. Gunasekaran,
Acta Crystallogr. E67 (2011) 1708.
[75] L.I. Kas’yan, V.A. Palchikov, A.V. Turov, S.A. Pridma, A.V. Tokar, Russ. J. Org.
Chem. 45 (2009) 1007–1017.
[76] L.I. Kasyan, S.V. Sereda, K.A. Poteknin, A.O. Kasyan, Heteroatom Chem. 8 (1997)
177–184.
[77] Z. Karczmarzyk, W. Malinka, X-ray Struct. Anal. 23 (2007) 151–152.
[78] Y.R. Shen, The Principles of Nonlinear Optics, Wiley, New York, 1984.
[79] P.V. Kolinsky, Opt. Eng. 31 (1992) 11676–11684.
[41] A. Kuwae, K. Machida, Spectrochim. Acta A 34A (1978) 785–791.
[42] S. Higuchi, H. Tsuyama, S. Tanaka, H. Kamada, Spectrochim. Acta A 30A (1974)
463–467.
[43] J. Klimentova, P. Vojtisek, M. Sklenarova, J. Mol. Struct. 871 (2007) 33–41.
[44] I.C.H. Castaneda, J.L. Jios, O.E. Piro, G.E. Tobon, C.O.D. Vedova, J. Mol. Struct. 842
(2007) 46–54.
[45] R. Zhang, X. Li, X. Zhang, Front. Chem. China 6 (2011) 358–366.
[46] G. Socrates, Infrared Characteristic Group Frequencies, John Wiley and Sons,
New York, 1981.
[47] I.N. Tarabara, Y.S. Bondarenko, A.A. Zhurakovskii, L.I. Kas’yan, Russ. J. Org.
Chem. 43 (2007) 1297–1304.
[80] D.F. Eaton, Science 25 (1991) 281–287.
[81] D.A. Kleinman, Phys. Rev. 126 (1962) 1977–1979.
[82] L.N. Kuleshova, M.Y. Antipin, V.N. Khrustalev, D.V. Gusev, E.S. Bobrikova,
Kristallografiya 48 (2003) 594–601.
[83] M. Adant, L. Dupuis, L. Bredas, Int. J. Quantum Chem. 56 (2004) 497–507.
[84] E.D. Glendening, A.E. Reed, J.E. Carpenter, F. Weinhold, NBO Version 3.1,
Gaussian Inc., Pittsburgh, PA, 2003.
[85] J. Choo, S. Kim, H. Joo, Y. Kwon, J. Mol. Struct. (Theochem.) 587 (1) (2002) 1–8.
[86] R.S. Mulliken, J. Chem. Phys. 23 (1955) 1833–1840.
[87] K. Wolinski, J.F. Hinton, P. Pulay, J. Am. Chem. Soc. 112 (1990) 8251–8260.
[88] E. Scrocco, J. Tomasi, Adv. Quantum Chem. 103 (1978) 115–121.
[89] F.J. Luque, J.M. Lopez, M. Orozco, Theor. Chem. Acc. 103 (2000) 343–345.
[90] P. Politzer, J.S. Murray, in: D.L. Beveridge, R. Lavery (Eds.), Theoretical
Biochemistry and Molecular Biophysics: A Comprehensive Survey, Protein,
vol. 2, Adenine Press, Schenectady, New York, 1991.
[48] K. Nakanishi, Infrared Absorption Spectroscopy Practical, Holden-Day, San
Francisco, 1962.
[49] S. Kundoo, A.N. Banerjee, P. Saha, K.K. Chattophyay, Mater. Lett. 57 (2003)
2193–2197.
[50] M. Silverstein, G.C. Basseler, C. Morill, Spectrometric Identification of Organic
Compounds, Wiley, New York, 1981.
[51] L.I. Kas’yan, A.V. Serbin, A.O. Kas’yan, D.V. Karpenko, E.A. Golodaeva, Russ. J.
Org. Chem. 44 (2008) 340–347.
[91] E. Scrocco, J. Tomasi, Curr. Chem. 7 (1973) 95–170.
[92] Y. Li, Y. Liu, H. Wang, X. Xiong, P. Wei, F. Li, Molecules 18 (2013) 877–893.
[93] H. Marouani, N. Raouafi, S. ToumiAkriche, S.S. Al-Deyab, M. Rzaigu, E-J. Chem.
9 (2012) 772–779.
[52] L.H. Daly, S.E. Wiberly, Introduction to Infrared and Raman Spectroscopy, third
ed., Academic Press, Boston, 1990.
[94] B.A. Saeed, R.S. Elias, S.M.H. Ismael, K.A. Hussain, Am. J. Appl. Sci. 8 (2011) 773–
776.
[53] Y.M. Atroshchenko, I.V. Shakhkeldyan, O.V. Leonova, A.N. Shumskii, N.A.
Troitskii, I.E. Yakunina, A.N. Shchukin, Y.A. Efremov, Russ. J. Org. Chem. 41
(2005) 1212–1218.