Spectroscopic (FT-IR, FT-Raman) investigations and quantum chemical calculations of 1,7,8,9-tetrachloro-10,10-dimethoxy-4-{3-[4-(3-methoxyphenyl) piperazin-1-yl]propyl}-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione

Article abstract of DOI:10.1016/j.saa.2014.03.077

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

Full text of DOI:10.1016/j.saa.2014.03.077

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
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) investigations and quantum
chemical calculations of 1,7,8,9-tetrachloro-10,10-dimethoxy-
4-{3-[4-(3-methoxyphenyl)piperazin-1-yl]propyl}-4-azatricyclo
[5.2.1.02,6]dec-8-ene-3,5-dione
b
R. Renjith a, Y. Sheena Mary b, C. Yohannan Panicker a, , Hema Tresa Varghese ,
⇑
c
d
e
´
Magdalena Pakosinska-Parys , C. Van Alsenoy , Abdulaziz A. Al-Saadi
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 Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
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
ꢀ
ꢀ
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:
Received 4 January 2014
Received in revised form 28 February 2014
Accepted 15 March 2014
Available online 1 April 2014
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of
1,7,8,9-tetrachloro-10,10-dimethoxy-4-{3-[4-(3-methoxyphenyl) piperazin-1-yl]propyl}-4-azatricy-
clo[5.2.1.02,6]dec-8-ene-3,5-dione have been investigated experimentally and theoretically using Gauss-
ian09 software package. The stability of the molecule arising from hyper-conjugative interaction and
charge delocalization has been analyzed using NBO analysis. 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. Molecular Electrostatic
Potential was performed by the DFT method and the infrared and Raman intensities have also been
reported. First 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. Mulliken’s net charges
have been calculated and compared with the atomic natural charges.
Keywords:
FT-IR
FT-Raman
Azatricyclo
Hyperpolarizability
PED
Ó 2014 Elsevier B.V. All rights reserved.
⇑
Corresponding author. Tel.: +91 9895370968.
E-mail address: cyphyp@rediffmail.com (C.Y. Panicker).
http://dx.doi.org/10.1016/j.saa.2014.03.077
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
439
the large second order electric susceptibilities of organic materials.
Since the second order electric susceptibility is related to first
hyperpolarizability, the search for organic chromophores with
large first hyperpolarizability is fully justified.
Introduction
Various biologically active synthetic compounds have six mem-
bered two nitrogen containing heterocyclic rings in their structure.
Two such compounds are piperazine and pyrazine. Piperazine is an
organic compound that consists of a six-membered ring containing
two nitrogen atoms at opposite positions in the ring. Piperazine ex-
ists as small alkaline deliquescent crystals with a saline taste. The
piperazines are a broad class of chemical compounds, many with
important pharmacological properties, which contain a core piper-
azine functional group. It has been reported that some piperazine
derivatives are capable of inducing apoptosis in some cancer cells
[1]. Sharma and Ravani [2] reported the synthesis and screening
of 2-(2-(4-substituted piperazine-1-yl)-5-phenylthiazol-4-yl)-3-aryl
quinazolinone derivatives as anticancer agents. Some piperazine
derivatives possess high biological activity for multidrug resistance
in cancer and malaria [3]. Synthesis and anticancer activity of
new 1-[(5 or 6-substituted 2-alkoxyquinoxalin-3-yl)aminocar-
bonyl]-4-(hetero)arylpiperazine derivatives were reported by Lee
et al. [4]. Hatnapure et al. [5] reported synthesis and biological
evaluation of novel piperazine derivatives of flavone as potent
anti-inflammatory and antimicrobial agent. Kesan et al. [6] re-
ported the FT-IR and Raman spectroscopic and quantum chemical
investigations of some halide complexes of 1-phenylpiperazine. Liu
et al. [7] reported synthesis and cytotoxicity of novel ursolic acid
derivatives containing an aryl piperazine moiety. Studies showed
that 3-salicylidenepiperazine-2,5-dione was supposed to be the
most promising precursor for the synthesis of spiro[benzofuran-
2(3H)-20-piperazine]-30,60-dione as a main skeleton of aspirochlorine
[8,9]. The effect of 1,4-bis-(4-(1H-benzo[d]imidazol-2-yl-phenyl))
piperazine, on U937 leukemia cell viability was investigated by
Sampson et al. [10]. In the present study, IR and Raman spectra of
1,7,8,9-tetrachloro-10,10-dimethoxy-4-{3-[4-(3-methoxyphenyl)-
piperazin-1-yl]propyl}-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
(TDMPAD) are reported both experimentally and theoretically.
There has been growing interest in using organic materials for non-
linear optical devices, functioning as second harmonic generators,
frequency converters, electro-optical modulators, etc. because of
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 as previously described
[11]. 1,7,8,9-Tetrachloro-4-(3-chloropropyl)-10,10-dimethoxy-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 [12].
In order to get the title compound, 1,7,8,9-tetrachloro-10,10-dime-
thoxy-4-{3-[4-(3-methoxyphenyl)piperazin-1-yl]propyl}-4-azatri-
cyclo[5.2.1.02,6]dec-8-ene-3,5-dione (3) (Scheme 1), a mixture of
compound 2 (0.3 g, 0.0007 mol), an appropriate 1-(3-methoxy-
phenyl) piperazine 0.25 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:
CH2Cl2–CH3OH, 95:5) [12].
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
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 Gaussian09
program [13] using the B3LYP/6-31Gꢁ and B3LYP/SDD basis sets
Scheme 1. Compound synthesis.

440
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
derivatives to confirm the convergence to minima on the potential
energy surface. The DFT hybrid B3LYP functional and SDD methods
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 [14]. The Stuttgart/Dresden
effective core potential basis set (SDD) [15] was chosen particu-
larly because of its advantage of doing faster calculations with rel-
atively better accuracy and structures [16]. Then the 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 in Table S1 as sup-
porting material. The assignments of the calculated wavenumbers
are aided by the animation option of GAUSSVIEW program, which
gives a visual presentation of the vibrational modes [17]. The po-
tential energy distribution (PED) is calculated with the help of
GAR2PED software package [18]. The 1H NMR data were obtained
from the DFT method using basis set 6-31Gꢁ. Potential energy sur-
face scan studies have been carried out to understand the stability
of planar and non-planar structures of the molecule. The HOMO–
LUMO energy is calculated by B3LYP/ SDD method.
Fig. 1. FT-IR spectrum of TDMPAD.
Results and discussion
IR and Raman spectra
The observed IR, Raman bands and calculated (scaled) wave-
numbers and assignments are given in Table 1. In the following
discussion, Phenyl ring is designated as R1, piperazine ring is des-
ignated as R2, the imido fragment ring is designated as R3 and
cyclohexene ring is designated as R4.
In the spectra of methyl esters the overlap of the region in
which both anti symmetric stretching [19] tasCH3 absorb with a
weak to medium intensity (2985 25 and 2970 30 cmꢂ1) is not
large and regularly seen above 3000 cmꢂ1. For the title compound
these bands are assigned at 3074, 3065, 3057, 3056, 3047,
2984 cmꢂ1 (SDD), 3063 cmꢂ1 (IR) and at 3057 cmꢂ1 in the Raman
spectrum. The symmetrical stretching mode tsCH3 is expected in
the range 2920 80 cmꢂ1 in which all the three CH bonds extend
and contract in phase [19]. The bands at 2955, 2954, 2947 cmꢂ1
theoretically (SDD) and at 2947 cmꢂ1 in the Raman spectrum are
assigned as these modes. Two bending vibrations can occur within
a methyl group. With methyl esters the overlap of the regions in
which methyl anti symmetric deformations are active (1460 25
and 1450 15 cmꢂ1) is quite strong, which leads to many coincid-
ing wavenumbers [19]. This is obvious, not only for the anti
Fig. 2. FT-Raman spectrum of TDMPAD.
to predict the molecular structure and vibrational wavenumbers.
Molecular geometry was fully optimized by Berny’s optimization
algorithm using redundant internal coordinates. Harmonic vibra-
tional wavenumbers are calculated using the analytic second
Fig. 3. Optimized geometry of TDMPAD (B3LYP/SDD).

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
441
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
3131
3119
3110
3074
3073
3065
3058
3052
3046
3022
3004
2997
2996
2976
2969
2967
2965
2963
2958
2957
2951
2946
2942
2914
2910
2879
2858
2815
2792
1709
1644
1610
1597
1576
1510
1504
1499
1493
1491
1489
1487
1482
1481
1475
1473
1472
1468
1460
1453
1441
1432
1429
1405
1387
1381
1369
1365
1358
1354
1352
1335
1332
1317
1312
1302
1296
1291
1285
1266
1256
1248
1235
1229
7.13
7.36
47.95
196.35
51.12
61.41
105.39
79.85
29.71
155.57
23.40
11.67
126.86
41.56
34.15
39.16
140.31
24.11
89.97
40.38
75.36
74.70
52.52
151.37
27.95
53.83
118.17
75.56
101.57
94.60
52.28
19.51
0.30
23.54
85.41
4.47
19.43
10.65
5.36
7.82
14.57
6.72
14.40
12.65
7.28
14.35
26.86
29.65
7.61
33.94
0.71
4.71
3124
3119
3108
3074
3071
3065
3057
3056
3047
3032
3013
3007
3002
2986
2984
2976
2966
2965
2956
2955
2954
2952
2947
2923
2905
2887
2865
2824
2801
1677
1611
1594
1589
1565
1486
1481
1478
1474
1469
1468
1467
1460
1458
1456
1454
1453
1447
1446
1437
1427
1418
1415
1392
1370
1368
1357
1354
1345
1340
1336
1326
1322
1300
1299
1286
1282
1276
1272
1256
1244
1236
1220
1219
4.00
111.28
124.68
38.22
55.85
80.69
66.26
134.44
28.19
19.99
7.43
131.73
38.01
28.93
104.38
35.43
48.77
19.66
98.94
47.36
253.78
13.83
46.82
92.20
64.04
130.33
78.06
110.46
95.42
51.19
27.013
0.58
–
–
–
–
–
3063
–
–
–
3022
–
–
–
2990
–
–
–
–
–
–
–
–
–
2923
–
–
2844
2816
2780
1699
1646
1598
1579
–
1493
–
–
–
–
–
–
–
1459
–
–
–
–
–
1440
–
–
1404
–
1375
–
–
–
–
–
1336
–
3129
–
3111
–
3069
–
3057
–
–
3038
–
–
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
t
CH(R1)(94)
CH(R1)(99)
CH(R1)(96)
asCH3(95)
CH(R1)(99)
asCH3(99)
asCH3(99)
asCH3(98)
asCH3(98)
asCH2(99)
C4AH10(56),
asCH2(97)
C4AH10(44),
14.68
20.17
14.56
21.68
18.34
36.22
16.61
26.79
19.35
3.05
17.82
9.58
22.52
12.46
9.48
26.60
17.06
11.33
1.39
10.42
0.86
t
t
C5AH12(44)
C5AH12(56)
10.14
0.69
–
48.07
16.26
39.80
30.52
35.47
27.16
23.71
10.80
50.94
8.75
37.99
41.47
54.87
64.69
76.18
61.84
28.78
431.57
47.12
331.12
90.64
2.51
21.40
11.74
20.86
53.67
12.46
1.49
109.02
30.76
2.91
38.67
57.39
41.71
58.34
19.84
48.84
56.33
13.29
1.51
34.97
35.83
54.01
60.18
78.38
92.33
64.18
32.68
500.30
38.19
416.26
105.40
7.91
2988
–
–
2968
–
–
–
–
2950
2947
2924
2898
–
2851
2816
2799
1670
1620
1598
1581
1548
–
–
–
–
–
–
1462
–
–
–
–
–
–
–
1439
–
–
1410
–
1378
–
–
–
–
–
1334
–
–
1303
–
–
–
–
–
1264
–
1228
–
–
asCH2(R2)(94)
asCH3(100)
asCH2(R2)(94)
asCH2(94)
asCH2(R2)(84)
sCH2(50),
sCH3(48),
sCH3(47),
sCH2(93)
sCH3(100)
tCH2(R2)(36)
tCH2(R2)(36)
tCH2(30)
asCH2(R2)(94)
sCH2(R2)(100)
sCH2(R2)(96)
sCH2(R2)(92)
sCH2(R2)(92)
sCH2(95)
C@O(77)
C@O(79)
C@C(78)
CAC(R1)(61), dCH(R1)(14)
CAC(R1)(65), dCH(R1)(19)
21.86
91.90
3.92
13.33
7.61
2.97
4.35
15.85
8.31
5.34
dCH2(R2)(63), dCH(R1)(12)
dCH2(R2)(63), dCH2(15),
dCH2(R2)(80), dCH2(11)
dCH2(59), dCH2(R2)(12)
dCH2(R2)(44), dCH3(17)
dasCH3(63), dCH2(R2)(19)
tCAC(R1)(64), dCH2(20)
dasCH3(98)
dasCH3(70)
dCH2(57), dCH2(R2)(21)
dasCH3(98)
27.55
12.26
21.77
113.18
1.02
2.19
26.40
88.55
33.36
12.78
4.62
20.62
7.83
45.97
5.36
9.65
6.95
2.09
8.66
77.13
3.43
25.13
4.44
79.61
112.38
226.19
4.22
3.50
3.69
4.88
6.20
4.02
5.52
11.69
22.10
17.15
3.32
30.03
0.62
3.06
6.10
9.32
8.44
4.29
3.17
3.25
3.90
6.63
18.70
4.36
11.42
14.78
9.87
7.07
10.40
3.22
3.59
6.58
14.77
5.626
2.00
2.74
9.26
4.45
9.00
10.19
16.78
44.44
4.20
5.34
5.01
1.82
dasCH3(76)
dasCH3(66)
dCH2(74)
tCAC(R1)(56), dCH3(17)
dsCH3(89)
dsCH3(93)
dsCH3(42), tCAC(R1)(18), dCH(R1)(15)
dCH2(46), dCH2(R2)(32)
dCH2(57), dCH2(R2)(14)
dCH2(R2)(46), dCH2(12)
dCH2(R2)(61)
dCH2(R2)(46), dCH2(16)
t
t
dCH2 (R2)(49), dCH2(18)
t
t
dCH(R1)(62), dCH2(19), dCH2(R2)(15)
dCH2(71), dCH2(R2)(11)
dCH2(67)
dC4AH10(64), dC5AH12(18)
dCH2(R2)(38), dCH2(18)
dC5AH12(62), dC4AH10(16)
dCH2(R2)(29), dCH2(27)
13.14
9.57
6.51
2.21
3.12
18.46
110.55
1.41
5.66
9.84
4.64
19.55
71.10
99.15
254.01
7.42
3.61
2.74
7.92
7.67
31.81
29.65
16.36
31.81
29.65
16.36
16.38
12.07
16.93
5.77
14.48
7.12
11.82
14.41
12.47
4.51
C16AN15(51), dCH(R1)(22)
C52AN47(49), dCH2(R2)(25), dCH(R1)(12)
C13AN15(57), dCH2(20)
CAC(R1)(51), dCH2(R2)(22)
–
1306
–
1291
–
–
–
1262
–
1228
–
–
6.86
28.00
27.24
16.89
45.40
0.96
10.89
14.54
6.86
10.89
14.54
3.54
tC19AN15(56), dCH2(18),
dCH2(77)
dCH2(R2)(36),
dCH2(R2)(49),
17.12
43.10
t
t
CN(R2)(23)
CH(R1)(9)
(continued on next page)

442
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
Table 1 (continued)
B3LYP/6-31Gꢁ
B3LYP/SDD
IR
Raman
Assignmentsa
t
IRI
RA
t
IRI
RA
t
t
1207
1193
1193
1178
1167
1162
1161
1157
1151
1144
1132
1129
1126
1119
1115
1105
1098
1091
1085
1079
1067
1062
1057
1043
1036
1017
1015
1004
993
986
981
969
960
953
949
947
929
915
886
874
864
844
841
823
821
815
798
763
755
748
723
707
691
688
681
675
655
618
616
610
601
595
554
550
536
528
491
489
458
450
439
424
422
45.41
112.08
26.58
130.56
69.86
27.62
24.33
25.29
98.78
9.43
37.74
69.62
16.52
0.18
10.90
55.32
60.13
7.84
3.80
7.58
2.79
2.21
5.38
5.68
1.98
4.12
4.06
2.33
5.56
1.48
5.19
6.81
9.25
5.07
11.68
7.99
2.49
6.88
4.13
2.46
3.14
15.08
13.64
8.97
3.94
2.69
8.79
40.54
17.48
2.97
6.07
2.80
4.50
4.83
4.23
7.99
7.86
7.47
0.57
1.86
0.63
1.03
1.98
2.74
4.39
2.37
1.01
9.16
3.03
6.75
13.20
1.28
1.42
3.69
3.27
0.19
3.56
2.62
8.09
0.17
0.68
1.85
1.63
5.77
1.00
2.22
1.58
3.04
1.72
1.33
3.30
1.72
1196
1187
1181
1164
1159
1157
1153
1145
1145
1140
1127
1122
1118
1108
1104
1098
1093
1081
1071
1065
1062
1054
1049
1036
1035
1020
1012
998
994
982
967
963
962
961
947
937
924
914
877
867
855
849
836
825
809
802
788
768
750
743
713
700
682
680
675
667
646
611
609
598
590
588
542
539
524
520
483
480
452
444
432
418
414
368
54.37
20.13
145.36
108.92
24.48
62.46
6.72
46.98
38.34
22.44
56.61
56.79
7.19
2.74
1.41
9.53
2.12
2.72
4.96
4.51
5.91
3.00
2.28
1.49
6.42
6.18
8.85
7.06
6.26
15.80
9.47
3.92
5.39
3.91
3.07
1.50
28.49
5.17
8.14
8.87
5.37
11.48
1.75
37.22
9.35
9.99
12.59
4.26
8.69
2.75
8.92
9.24
7.02
2.77
0.58
0.39
0.17
3.04
2.66
5.77
0.59
1.36
9.42
2.87
6.90
1.78
1.42
14.79
4.84
23.16
0.21
3.85
3.97
7.68
0.46
0.72
1.23
2.27
5.55
0.83
1.88
1.66
3.83
2.06
0.97
3.88
1.39
1198
–
1175
–
–
–
–
1143
1143
–
–
–
–
–
–
1099
–
1197
–
1170
–
–
1157
–
–
–
–
1133
–
1116
–
–
1100
–
1084
–
–
–
1055
–
1040
–
dCH2(45), dCH2(R2)(10)
t
CAC(R4)(48), dC5AH12(15), dC4AH10(12)
dCH(R1)(55), dCH2(R2)(11)
dCH(R1)(56), CAC(R1)(9)
CN(R2)(45), CH2(R2)(11)
CAO(58), dCH3(12)
t
t
t
dCH3(75)
dCH3(51),
t
CAO(11)
t
CAO(43), dCH3(14)
dCH3(75),
t
CN(R3)(12), tCN(R2)(7)
t
t
CAC(R4)(47), dR1(14)
C31AN38(49), dCH2(R2)(15)
dCH3(75)
dCH3(61),
dCH3(95)
6.69
0.04
48.57
60.65
2.11
tCAC(R4)(17)
t
t
t
C39AN38(R2)(49), dCH2(22),
CAC(R4)(29), dCH3(12)
CAC(R4)(57), dCH2(R2)(17)
–
–
1067
–
–
3.48
148.74
1.20
34.63
37.31
5.99
7.94
dCH(R1)(41),
t
CAC(R1)(38)
CAO(43), dC3AC7(12)
CAC(R3)(32), CAC(R4)(20),
CAC(R4)(35), dCH2(R2)(13),
C19AC28(37), dCH2(R2)(17)
146.18
40.16
35.31
18.80
124.25
8.61
t
t
t
t
t
tC19AN15(21)
–
1034
1030
–
1013
–
–
985
–
–
–
–
–
–
930
–
876
–
–
–
–
–
815
–
778
765
–
–
719
–
679
–
–
–
644
–
–
–
591
–
557
–
–
–
–
–
dCH2(R2)(20),
t
C
31AN38(11),
tC45AN47(R2)(8)
7.80
2.18
t
t
t
t
t
t
C
28AC31(25),
t
t
t
CAC(R2)(14), dCH2(R2)(10)
CAC(R4)(8)
C3AC7(17), dCAO(13),
2.01
8.92
–
1013
–
993
–
967
–
CAC(R2)(58),
CAC(R1)(41),
14.52
74.15
79.45
17.70
1.29
11.32
13.89
1.57
12.23
27.67
7.43
49.49
8.63
63.74
51.39
34.50
15.34
7.78
6.54
7.95
7.85
30.55
9.57
C
63AO62(54)
CAC(R4)(33)
CAC(R2)(42), dCH3(R2)(22)
CH(R1)(17)
CH(R1)(69), R1(15)
R1(38)
R1(11)
CAC(R4)(19)
63AO62(18)
dR1(40), c
c
t
t
t
t
t
t
t
s
–
–
CACl(12),
CAO(51),
CAO(45), t
CAC(R3)(31),
CAN(R2)(35)
CAN(R2)(52),
CAC(R3)(33), s
s
s
943
–
924
905
885
–
tC
4.69
6.84
6.63
0.82
t
CAC(R4)(5)
R1(19)
CAC(R4)(12)
cCH(R1)(35)
10.83
5.57
1.95
dCH2(43),
dCH2(R2)(37),
CH(R1)(62)
dCH2(64)
CH(R1)(54),
dCH2(52), dR1(13), dCAO(10)
sR1(22), t
–
–
11.51
7.68
44.72
27.55
9.93
23.94
48.37
14.77
13.57
14.70
11.54
24.66
1.76
c
5.09
835
–
813
796
–
761
–
736
709
–
–
681
–
–
643
–
610
–
–
564
–
537
–
520
–
481
449
–
37.77
32.04
13.89
22.18
40.81
20.30
9.97
9.03
12.24
4.32
2.49
8.47
27.30
35.89
1.44
7.21
0.96
1.58
19.52
6.20
0.03
5.25
21.61
0.16
7.48
c
sR1(23)
t
CN(R2)(21), dR1(13),
t
CH(R1)(14)
C@O(10)
dCH2(R2)(40),
cCH(R1)(74),
s
s
R3(22),
R1(12)
c
dCH2(R2)(53)
dCN(R2)(35),
t
C31AN38(10)
dC@O(21), dCH2(20),dR1(12)
dC@O(16), R3(15)
R1(57), CH(R1)(21)
CACl(34), R1(26),
CACl(42), dR1(32),
CAO(19), CACl(52)
CACl(43)
CH(R1)(13), 52AN47(27),
CH(R1)(16), dCAO(32), CAO(7)
s
s
c
t
t
t
s
c
C@O(17)
2.96
sR1(10)
26.82
34.14
0.61
8.29
1.91
1.91
13.18
5.42
0.08
5.19
22.95
0.27
7.54
5.09
4.35
4.11
19.72
8.85
t
dR3(12), t
c
t
c
C
sR1(24)
t
dR2(23), dR3(19), dCH2(R2)(15)
dR3(29), dR2(19), dR1(17)
dCACl(21),
dR1(37), dCAO(26)
dCACl(15), R1(47), dC@O(12)
dR2(38), dR1(25)
cC@O(48)
s
dCH2(19), 15AC19(31), dR1(27)
c
N
c
C@O(52), tC6AC7(19)
dR2(53),
c
C
31AN38(19)
3.41
2.99
6.65
18.86
8.33
459
–
–
–
416
–
sR1(44),
c
CH(R1)(11)
sR1(26), dC52AN47(17), dCH(R1)(15)
–
–
399
379
dCH2(16), dR2(45)
dR1(29), dC31AN38(36)
dCAO(23), dC52AN47(31), dR1(6)
dC@O(20), dCAO(36), dCACl(15)
375
4.50
4.92

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
443
Table 1 (continued)
B3LYP/6-31Gꢁ
B3LYP/SDD
IR
Raman
Assignmentsa
t
IRI
RA
t
IRI
RA
t
t
366
357
336
329
325
318
314
301
282
280
270
266
261
250
224
210
206
191
189
174
172
163
159
152
149
143
136
133
128
121
115
110
102
97
0.52
7.97
1.79
0.91
3.32
13.32
4.31
8.37
1.75
17.15
5.07
4.53
0.24
2.29
3.81
0.43
10.36
1.18
1.94
0.24
1.22
0.30
0.52
1.35
3.62
0.52
0.23
1.59
2.73
1.22
1.22
0.96
1.10
5.54
3.60
0.43
0.87
0.41
0.39
0.55
0.19
0.09
0.35
0.24
0.17
1.67
11.43
2.63
7.00
6.32
1.38
0.66
1.14
2.49
5.02
3.71
2.27
0.83
1.43
0.91
2.54
0.59
0.91
0.83
0.59
0.58
2.75
2.17
1.40
0.49
0.67
0.77
1.84
0.38
0.45
0.61
0.05
1.57
0.89
0.56
1.39
1.73
1.01
1.04
0.29
2.95
0.88
3.76
0.57
1.37
366
353
333
326
321
313
308
297
278
274
267
260
257
245
220
206
204
188
186
169
166
159
156
147
143
135
132
127
123
118
110
100
97
1.88
6.74
1.51
0.69
3.56
13.79
6.04
9.16
2.25
15.11
4.47
1.87
1.83
1.54
2.91
4.21
7.69
0.81
3.25
0.22
1.46
0.16
0.46
1.99
2.24
0.80
2.72
1.25
1.73
0.45
1.69
0.22
7.50
1.40
3.13
0.57
1.19
0.29
0.77
0.67
0.20
0.17
0.53
0.31
0.03
0.77
14.47
2.75
7.49
6.37
1.44
0.71
1.04
2.61
3.74
4.27
1.87
0.98
1.58
0.98
2.67
1.01
0.94
0.76
0.77
0.74
3.07
2.42
1.65
0.40
1.13
0.53
0.87
0.64
0.36
0.45
0.90
1.08
0.39
0.47
1.37
1.21
0.82
1.06
0.34
2.45
0.86
3.33
0.28
1.32
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
cC31AN38(41), sR2(21)
dCACl(57), dCAO(15)
dCACl(51), dR1(19)
353
339
–
–
315
–
296
–
–
266
–
–
239
222
–
–
189
–
171
–
–
–
150
–
–
–
–
–
–
113
–
98
–
–
–
–
–
–
–
–
–
–
dCACl(46),
15AC19(27),
dCAO(66)
R2(43), dCAO(16)
sR1(15), dCAO(13)
c
N
c
C
31AN38(17), sR2(16)
s
dCAO(45), dR1(15)
dN15AC19(45), dC@O(19)
s
R2(33),
sCH3(17)
dR1(19), dCACl(45), dN15AC19(13)
s
s
s
CH3(34),
s
R1(24)
R2(44), CH3(11)
R1(37), cC31AN38(18)
s
dCAO(53), dCH(R1)(17), dC52AN47(16)
s
s
s
s
R1(42),
R2(21),
CAO(31),
R1(41),
s
s
R2(18),
CH2(22),
R2(11),
CAO(11),
s
CH3(12)
15AC19(11)
R3(12), 15AC19(19)
CH3(16)
cN
s
s
s
cN
s
dCACl(15),
sR3(49)
s
s
s
s
s
CACl(40),
CACl(75)
CACl(86)
CACl(54),
CAO(50),
s
CAO(19)
s
CO(23)
s
CACl(15)
R2(45),
R3(12), CH3(10)
CH3(48), dCO(12)
R2(16)
CH3(18)
C19AN15(13)
dCACl(17),
s
s
s
sCH2(12)
CO(45),
s
s
dCO(53), s
s
s
s
s
s
s
s
s
R2(49),
s
R3(50),
c
CH2(36), dC52AN47(34)
CO(47), CH3(23), R2(13)
CH3(60),
s
s
96
84
80
69
62
58
55
33
21
11
9
7
c
CACl(18)
86
81
70
63
60
56
35
22
CO(29),
R1(40),
CAO(49),
s
R2(17), sCH3(16)
c
CACl(24)
CACl(23),
R2(24), dR1(13)
c
cC52AN47(19)
c
CACl(32), s
s
s
c
c
s
s
s
R3(52),
R3(31),
s
s
R2(19),
R1(15),
s
R1(16),
s
CO(10)
C52AN47(24)
R1(16)
CH2(32)
cC31AN38(8)
sR2(10), c
C52AN47(35),
N15AC19(34),
CH2(33),
R2(45),
CH2(42), s
s
s
CH2(26),
R2(15), s
s
11
9
7
s
R2(17),
CH2153)
R2(32)
–
–
s
a
t
– stretching; d – in-plane deformation;
c – out-of-plane deformation; s – torsion; as – antisymmetric; s – symmetric; R1 – phenyl ring; R2 – piperazine ring; R3 – imido
fragment; R4 – cyclohexene ring; IRI – IR intensity; RA – Raman activity; potential energy distribution are given in brackets in the assignment column.
symmetric deformations, but also for the symmetric deformations
[19] mostly displayed in the range 1380 15 cmꢂ1. The SDD calcu-
lation give 1468, 1460, 1458, 1454, 1453, 1447 and 1427, 1418,
1415 cmꢂ1 as anti symmetric and symmetric CH3 deformations
for the title compound. Experimentally dasCH3 vibration is ob-
served at 1459 cmꢂ1 in the IR spectrum and dsCH3 vibration is ob-
served at 1404 (IR) and 1410 cmꢂ1 (Raman). The methyl rocking
wave numbers are expected in the regions [19] 1100 95 and
1080 80 cmꢂ1. The bands calculated at 1153, 1145, 1140, 1118,
1108, 1104 cmꢂ1 (SDD), 1143 cmꢂ1 (IR) and at 1116 cmꢂ1 (Raman)
are assigned as rocking modes of the methyl groups.
980 cmꢂ1. Govindarajan et al. [22] reported
tions at 1310 and 1260 cmꢂ1 experimentally. Xuan and Zhai [23]
tCAO stretching vibra-
reported t
CAO anti symmetric vibrations at 1232 cmꢂ1 in IR and
1238 cmꢂ1 theoretically.
For bridging methylene groups [24–26] the CH2 (at C19, C28, C31
)
vibrations are observed in the region of 2800–3000, 1200–1400,
875–1150 and 600–850 cmꢂ1. The vibrations of these CH2 groups
(the anti symmetric stretch
scissoring vibration and wagging vibration) appear in the regions
of 2940–3005, 2870–2940, 1420–1480 and 1320–1380 cmꢂ1
tasCH2, symmetric stretch tsCH2, the
,
respectively [19,25,26]. These bands are observed at 3038, 2968,
2950, 2799, 1378 cmꢂ1 in the Raman spectrum, 3022, 2780,
1375 cmꢂ1 in the IR spectrum and in the ranges of 3032–2966,
2956–2801, 1474–1446, 1392–1299 cmꢂ1 theoretically (SDD) for
the title compound respectively. The twisting and rocking vibra-
tions of the CH2 group appear in the region [19] of 1200–1280
and 740–900 cmꢂ1, respectively. For the title compound the twist-
ing vibrations are observed at 1291, 1228, 1198 cmꢂ1 in the IR
spectrum, 1228, 1197 cmꢂ1 in the Raman spectrum and at 1286,
1236, 1196 cmꢂ1 theoretically (SDD). The rocking deformations
A methoxy group attached to an aromatic ring give
tasCAO C in
the range 1310–1050 cmꢂ1 and
tsCAOAC in the range [19,20]
1010–960 cmꢂ1. For the title compound the bands at 1157, 1145,
1065 cmꢂ1 and 998, 961, 947 cmꢂ1 (SDD) are assigned as anti sym-
metric and symmetric CAOAC stretching vibrations, respectively.
The bands observed at 1143, 1067 cmꢂ1 (IR) and 1157, 943 cmꢂ1
(Raman) are assigned as CAOAC stretching vibrations. Klimentova
et al. [21] reported the anti symmetric and symmetric CAOAC
stretching vibrations in the range, 1214–1096 cmꢂ1 and 1030–

444
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
are observed at 815 cmꢂ1 in the IR spectrum, 813 cmꢂ1 in the Ra-
man spectrum and at 867, 836, 809 cmꢂ1 theoretically (SDD) and
these modes are not pure, but contain significant contributions
from other modes also. In the bridging methylene group, the
CAC stretching modes are found at 1049 and 1035 cmꢂ1 (SDD)
for C19AC28 and C28AC31 respectively.
3000 cmꢂ1 and is typically exhibited as a multiplicity of weak to
moderate bands, compared to the aliphatic CAH stretching. For
the title compound tCH vibrations of the phenyl ring are observed
at 3129, 3111, 3069 cmꢂ1 in the Raman spectrum and 3124, 3119,
3108, 3071 cmꢂ1 theoretically (SDD). The ring breathing mode ap-
pears as a weak band near 1000 cmꢂ1 in mono, 1,3-di and 1,3,5-tri-
substituted benzenes [19]. In the otherwise substituted benzene,
however, this vibration is substituent sensitive and difficult to dis-
tinguish from the ring in-plane deformation [19]. Panicker et al.
[42,43] reported the ring breathing modes of 1,3-disubstituted
benzenes at 1013 and 1058 cmꢂ1 theoretically and at 1058 cmꢂ1
experimentally. The band at 1013 cmꢂ1 both in the IR and Raman
spectrum and at 1012 cmꢂ1 (SDD) are assigned as the ring breath-
ing mode of the phenyl ring. For di-substituted benzene CC ring
stretching modes are seen in the range [19] 1615–1270 cmꢂ1. For
the title compound ring stretching modes of phenyl rings are ob-
served at 1579, 1440 cmꢂ1 (IR), 1581, 1548, 1462, 1439 cmꢂ1 (Ra-
man) and 1589, 1565, 1467, 1437, 1322 cmꢂ1 theoretically (SDD).
Normally CAH stretching mode is expected in the region 2850–
3000 cmꢂ1 [27]. For the title compound
tC4AH10 and tC5AH12 are
assigned at 3013, 3002 cmꢂ1 theoretically (SDD). The CH deforma-
tion vibrations appear around 1297 and 1199 cmꢂ1 [28]. For the ti-
tle compound deformation bands of C4AH10 and C5AH12 are
observed at 1282, 1272 cmꢂ1 theoretically (SDD).
The CACl stretching vibrations give generally strong bands in
the region 730–580 cmꢂ1 [29]. However, vibrational coupling with
other groups may result in a shift in the absorption band as high as
840 cmꢂ1. For simple chlorine containing organic compounds,
CACl absorptions are in the region 750–700 cmꢂ1, whereas for
the trans and gauche forms [30] they are near 650 cmꢂ1. For the ti-
tle compound, CACl stretching vibrations are assigned at 680, 675,
667, 646 (SDD), 644 (IR) and 681, 643 cmꢂ1 in the Raman spec-
trum. This result is in agreement with the reported values given
by Varghese et al. [31] and Palafox et al. [32]. The CACl stretching
modes are reported at around 738 cmꢂ1 for dichloromethane
[25,33] whereas Pazdera et al. [34] reported the CACl stretching
mode at 890 cmꢂ1. Most of the aromatic chloro compounds had
the strong to medium intensity in the region 385–265 cmꢂ1 due
to CACl in-plane bending vibration [35]. Balachandran and Pari-
mala [36] reported CACl in-plane deformation vibrational band is
at 296 cmꢂ1 (B3LYP); 300 cmꢂ1 (B3PW91) methods, respectively.
For the title compound the deformation bands of CACl are assigned
at 353, 339, 266, 150 cmꢂ1 in the Raman spectrum and below
400 cmꢂ1 theoretically (SDD).
The ring C@C stretching vibrations occur in the region 1625–
1430 cmꢂ1 [26,37]. Alasalvar et al. [37] reported the C@C stretch-
ing vibrations at 1668 cmꢂ1 theoretically. The C@C stretching is
observed at 1495, 1567, 1598 and 1686 cmꢂ1 for 2-dicyanovinyl-
5-(4-methoxyphenyl)thiophene in the IR spectrum [38]. For the ti-
tle compound, the C@C stretching mode is observed at 1598 cmꢂ1
both in the IR and Raman spectra and at 1594 cmꢂ1 theoretically
(SDD).
Normally carbonyl group vibrations occur in the region 1780–
1680 cmꢂ1 [39]. The carbonyl groups in the imide fragment give
rise to bands [24,40] in the region of 1720–1790 cmꢂ1. For the title
compound, the C@O stretching bands are observed at 1699,
1646 cmꢂ1 in the IR spectrum, 1670, 1620 cmꢂ1 in the Raman spec-
trum and at 1677, 1611 cmꢂ1 theoretically (SDD). The C@O in-
plane bending vibration is usually found at 700 cmꢂ1 [19]. For
the title compound these vibrations are assigned at 719 cmꢂ1 in
the IR spectrum, 709 cmꢂ1 in the Raman spectrum and at 713,
700 cmꢂ1 theoretically (SDD). The C@O out-of-plane bending
vibration is observed in the region 540 80 cmꢂ1 [19]. For the title
compound these bands are observed at 564 cmꢂ1 (Raman) and at
588, 483 cmꢂ1 theoretically (SDD).
The in-plane bending dCH and the out-of-plane bending
cCH of
the phenyl ring are expected above 1000 cmꢂ1 and below
1000 cmꢂ1, respectively [19]. For the present case the CH deforma-
tion bands in the phenyl ring are observed at 1306, 1175 cmꢂ1 (IR),
1303, 1170 cmꢂ1 (Raman) and at 1300, 1181, 1164, 1071 cmꢂ1 the-
oretically (SDD). The out-of-plane bending vibrations of CH in the
phenyl ring is observed at 765 cmꢂ1 (IR), 761 cmꢂ1 (Raman) and
at 963, 849, 825, 768 cmꢂ1 theoretically. The 1,3-disubstitution
pattern resembles that of mono substitution, with the CH out-
of-plane deformation at 765 cmꢂ1 in the IR spectrum and the
out-of-plane ring deformation at 679 cmꢂ1 in the IR spectrum
absorbing with equal intensity [19].
Krishnakumar and Seshadri [44] have reported the CH2 stretch-
ing modes of 2-methylpiperazine at 3078 and 2532 cmꢂ1. The CH2
scissoring vibrations of piperazine molecule were reported at
1452 cmꢂ1 for 1-phenylpiperazine [45] and at 1406 and
1293 cmꢂ1 for 2-methylpiperazine [44]. El-Emam et al. [46] re-
ported the anti symmetric stretching CH2 vibrations in the pipera-
zine ring in the range 3033–2966 cmꢂ1, while the symmetric
vibrations lying in the range 2874–2834 cmꢂ1. For the title com-
pound the bands at 2986, 2976, 2965, 2923 cmꢂ1 (SDD), 2990,
2923 cmꢂ1 (IR) and 2988, 2924 cmꢂ1 in the Raman spectrum are
assigned for CH2 anti symmetric stretching modes of the pipera-
zine ring. Bands at 2905, 2887, 2865, 2824 cmꢂ1 (SDD), 2844,
2816 cmꢂ1 (IR) and 2898, 2851, 2816 cmꢂ1 are assigned for sym-
metric CH2 stretching modes of the piperazine ring for the title
compound. The piperazine ring stretching modes are highly char-
acteristic and in a study on the determination of piperazine rings
in ethyleneamines, poly(ethyleneamine) and polyethylenimine by
Infrared spectroscopy, Spell reported that the piperazine ring was
found to be associated with sharp, well define absorptions at
1380–1345 cmꢂ1, 1125–1170 cmꢂ1 and 1010–1025 cmꢂ1 regions
of IR spectrum [47]. In accordance with Spell [47], we have also ob-
served a very strong peak in the IR spectrum at 1336 cmꢂ1 corre-
sponding to CH2 wagging mode of the piperazine ring. The
theoretically calculated corresponding wavenumber for the mode
is 1336 cmꢂ1 with a calculated IR intensity of 112.38. For the title
compound a very sharp and intense band was observed at
1034 cmꢂ1 in the IR spectrum as reported by da Silva et al. [48]
and was assigned to the ring CH2 rocking vibrations. As stated by
Spell [47], this is one of the most useful bands for detecting the
presence of di-substituted piperazines.
The identification of CAN vibrations are very difficult task, since
the mixing of several bands are possible in the region. Silverstein
et al. [26] assigned the CAN stretching absorption in the region
1382–1226 cmꢂ1 for aromatic amines. Tasal et al. [41] reported
the CAN stretching mode at 1086 cmꢂ1 for 5-chloro-6-(4-chloro-
benzoyl)-2-benzothiazolinone molecule. In the present case, the
t
C
CN stretching modes (C16AN15, C52AN47, C13AN15, C19AN15 and
31AN38) are assigned at 1345, 1340, 1326, 1244, 1122 cmꢂ1 theo-
For the title compound, the piperazine ring stretching modes
are observed at 1099, 985, 930 cmꢂ1 in the IR spectrum and at
1100, 924, 905 cmꢂ1 in the Raman spectrum. The calculated values
(SDD) corresponding to these modes are 1159, 1098, 1020, 982,
924 and 914 cmꢂ1. The CA stretching vibrations in the piperazine
ring were reported at 972, 903 cmꢂ1 [46]. El-Emam et al. [46]
retically (SDD).
The
t
CAH vibrations of the phenyl rings are expected in the re-
gion 3000–3110 cmꢂ1 [19]. The existence of one or more aromatic
rings in a structure is normally determined from the CAH and C-
ACAC ring related vibrations. The CAH stretching occurs above

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
445
reported the CAN stretching vibrations of the piperazine ring in the
region 1154–756 cmꢂ1. Piperazine ring stretching modes are re-
ported at 1240, 1155, 1134, 1043, 1032, 1018, 1002, 974,
880 cmꢂ1 theoretically and at 1238, 1143, 1045, 1004, 874 cmꢂ1
experimentally [49]. Gunasekaran and Anita [50] reported the
piperazine ring stretching modes at 1055, 1173, 1199, 1218,
1268, 1323 cmꢂ1 in the IR spectrum and at 1049, 1120, 1186,
1294 cmꢂ1 in the Raman spectrum. The substituent sensitive
modes and other deformation modes are also identified and as-
signed (Table 1).
In order to investigate the performance of vibrational wave-
numbers of the title compound, the root mean square (RMS) value
between the calculated and observed wavenumbers were calcu-
lated. The RMS values of wavenumbers were calculated using the
following expression [51].
In the present case, the oxygen atoms O17 and O18 are equally
inclined from the N15 atom given by the angles O17AC16AN15
18AC13AN15 (124.3°) and from C4 and C5 atoms given by the
,
O
angles O17AC16AC5, O18AC13AC4 (127.4°) as reported in literature
[56]. 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 R3 from the R4 are given by the angles C6AC5AC16 and
C3AC4AC13 by 118.6° and 119.3° which are almost equal as
reported in literature [24]. The conjugation in the imido group is
essentially disturbed; the torsion angles
C13AN15AC16AC5,
C
16AN15AC13AC4 are 8.5°, ꢂ6.3° and the C13AN15 and C16AN15
bond lengths are elongated to 1.4037, 1.4025 Å relative to the
average value 1.371 Å [57].
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
X
À
Á
1
n
i
For the cyclohexene ring, Manohar et al. [58] reported the bond
2
RMS ¼
tci alc
ꢂ
tei xp
:
lengths
C1AC2 = 1.3194,
C1AC6 = 1.5174,
C6AC5 = 1.5523,
n ꢂ 1
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 1.3471, 1.5334, 1.5702, 1.5866, 1.5697, 1.5757,
1.5901, 1.5309 Å. The bond angles reported by Manohar et al.
[58] are C3AC4AC5 = 102.9°, C3AC2AC1 = 107.5°, C3AC7AC6 = 92.4°,
C2AC3AC4 = 107.2°, C6AC5AC4 = 103.1°, C6AC1AC2 = 107.7°, C5A
C6AC1 = 106.8°, C2AC3AC7 = 99.5°, C4AC3AC7 = 101.12°, C5A
C6AC7 = 101.1°, C1AC6AC7 = 99.4°, where as the corresponding
calculated (SDD) values of the title compound are 102.8°, 107.3°,
91.3°, 105.2°, 102.9°, 107.8°, 106.2°, 99.7°, 102.8°, 102.1°, 99.7°.
The propyl group is tilted from the R3, as is evident from torsion
angles, C5AC16AN15AC19 (ꢂ176.2°), C16AN15AC19AC28 (ꢂ93.8°),
C4AC13AN15AC19 (178.3°) and C13AN15AC19AC28 (81.1°). The dou-
The RMS error of the observed IR and Raman bands are found to
be 11.64 (B3LYP/6-31Gꢁ), 9.63 (B3LYP/SDD) and 12.38 (B3LYP/
6-31Gꢁ), 6.25(B3LYP/SDD), respectively. The small differences
between experimental and calculated vibrational modes are
observed. This is due to the fact that experimental results belong
to solid phase and theoretical calculations belong to gaseous phase.
Geometrical parameters
To the best of their knowledge, no X-ray crystallographic data of
this molecule has yet been established. However, the theoretical
results obtained are almost comparable with the reported struc-
tural parameters of the parent molecules. For the imido fragment
of the title compound, the SDD calculations give the bond angles,
ble bonds C16AO17 and C13AO18 are conjugated with the
p-system
of the R3, with the torsion angles O17AC16AN15AC13, C16AN15A
C
16AN15AC13, O18AC13AN15, O18AC13AC4, N15AC13AC4, C13AC4-
C
C
13AC4 being ꢂ175.4°, -6.3° and O18AC13AN15AC16, C13AN15A
16AC5 being 178.6°, 8.5° respectively as reported by Kasyan
AC5, O17AC16AN15, O17AC16AC5, N15AC16AC5, as 113.7°, 124.3°
127.4°, 108.1°, 104.9°, 124.3°, 127.4°, 108.2°, respectively, whereas
the reported values of similar derivatives are 112.1°, 126.3°, 125.9°,
107.9°, 103.7°, 126.3°, 126.6°, 106.9° [52]. Conley et al. [53]
et al. [59]. The asymmetry of the bond angles C16AN15AC19
=
123.5°, C13AN15AC19 = 122.6° and C16AN15AC13 = 113.7° at N15 posi-
tion reveal the steric repulsion of the atoms H26, H25 and O17, O18 [59].
For the piperazine ring, Gao et al. [60] reported the bond
lengths
N
reported the dihedral angles,
15AC13AC4 = A4.0, 18AC13AC4AC5 = 177.5,
1.5, 13AC4AC5AC16 = 1.7, 13AN15AC16AC5 = 5.1, C4AC5AC16
C
16AN15AC13AO18 = 179.5,
C16A
N
O
N15AC13AC4AC5 =
N38AC40 = 1.4796, N38AC39 = 1.4927, C39-AC46 = 1.4997,
47AC45 = 1.4807, N47AC46 = 1.4837, C40AC45 = 1.4937 Å and the
C
C
AO17 = 176.7, C4AC5AC16AN15 = ꢂ4.0° whereas for the title com-
pound the corresponding values are 178.6, ꢂ6.3, 176.3, 1.4, 3.3,
8.5, 177.1, and ꢂ6.9° respectively. Lee and Swager [54] reported
corresponding bond lengths of the title compound are 1.4887,
1.4811, 1.5364, 1.4721, 1.4746, 1.5456 Å respectively. The SDD cal-
culations give the bond angles within the piperazine ring N38AC39-
the
bond
lengths
O17AC16 = 1.1954,
O
18AC13 = 1.2054,
AC46 = 111.2°,
N
38A40AC45 = 113.6°,
N47AC45AC40 = 110.1°,
N
C
15AC16 = 1.3776, N15AC13 = 1.3765 Å and the bond angles C5A
16AN15 = 106.3°, C4AC13AN15 = 106.5°. Naz et al. [52] reported
the bond lengths in the imido fragment as C16AO17 = 1.2023,
15AC16 = 1.3996, 13AO18 = 1.2000, 13AN15 = 1.3971,
13AC4 = 1.5196, C16AC5 = 1.5252, C5AC4 = 1.5136, whereas the
N
47AC46AC39 = 110.4°, C45AN47AC46 = 116.7°. El-Emam et al. [46]
reported the corresponding values as 110.0°, 109.7°, 109.7°,
110.0° and 110.0° for different similar derivatives. Gao et al. [60]
reported the dihedral angles C40AN38AC39AC46 = 56.9, C45AN47
N
C
C
C
AC46AC39 = 58.8, N38AC39AC46AN47 = ꢂ56.7, C46AN47AC45AC40
=
SDD calculations give the corresponding bond lengths within the
imido fragment as 1.2426, 1.4025, 1.2412, 1.4037, 1.5344,
1.5387, 1.5697 Å. The N15AC19 bond length (1.4729 Å) is longer
than N15AC13 (1.4037 Å) and N15AC16 (1.4025 Å) bond lengths.
ꢂ58.9,
C39AN38AC40AC45 = ꢂ57.7,
N
47AC45AC40AN38 = 57.7°,
which are in agreement with our calculated values.
First hyperpolarizability
This indicates, as expected, a delocalized p-electron system along
the imide part of the molecule (O18AC13AN15AC9AO17) as reported
by Bartkowska et al. [55].
Nonlinear 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 [61]. Organic molecules able to manipulate photonic
signals efficiently are of importance in technologies such as optical
communication, optical computing, and dynamic image processing
[62,63]. 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
For the title compound the C4AH10, C5AH12, bond lengths are
1.0936, 1.0939 Å whereas reported values are 0.96, 0.9601 Å [53].
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 and C6AC1. The CAC bond lengths in
the five member ring (C5AC16, C4AC13) are elongated to a lesser ex-
tent. These may be explained by change of the substitution pattern
in the nitrogen containing five member ring as reported by Tara-
bara et al. [24].

446
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
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 [64]. 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
(1.4025 Å) leading to stabilization of 26.42 kJ/mol. Also the hyper
conjugative interaction of C13AN15 from O18 of n2(O18) ? rꢁ(C13-
AN15) which increases ED (0.08843 e) that weakens the respective
bonds C13AN15 (1.4037 Å) leading to stabilization of 26.88 kJ/mol.
An another hyper conjugative interaction observed in C16AO17
from N15 of n1(N15) ? pꢁ(C16AO17) which increases ED (0.24853
e) that weakens the respective bond C16AO17 (1.2426 Å) leading
to a stabilization of 56.45 kJ/mol. An another hyper conjugative
interaction observed in C3AC7 from Cl34 of n3(Cl34) ? rꢁ(C3AC7)
which increases ED (0.08376 e) that weakens the respective bond
C3AC7 (1.5901 Å) leading to a stabilization of 5.21 kJ/mol. Another
hyper conjugative interaction is observed C1AC2 from Cl35 of
n3(Cl35) ? pꢁ(C1-C2) which increases ED (0.20073 e) that weakens
the respective bonds C1AC2 (1.3471 Å) leading to stabilization of
15.08 kJ/mol. There occurs another strong intermolecular hyper
conjugative interaction of C1AC2 from Cl36 of n3(Cl36) ? pꢁ(C1AC2)
which increases ED (0.20073 e) that weakens the respective bonds
C1AC2 (1.3471 Å) leading to stabilization of 15.36 kJ/mol. Another
hyper conjugative interaction of C6AC7 from Cl37 of n3(Cl37) ?
rꢁ(C6AC7) which increases ED (0.08282 e) that weakens the
respective bond C6AC7 (1.5866 Å) leading to a stabilization of
4.77 kJ/mol. Also the hyper conjugative interaction of C40AC45 from
N38 of n1(N38) ? rꢁ(C40AC45) which increases ED (0.02259 e) that
weakens the respective bonds C40AC45 (1.5456 Å) leading to stabil-
ization of 4.56 kJ/mol. There occurs another strong intermolecular
hyper conjugative interaction of C52AC54 from N47 of n1(N47) ?
pꢁ(C52AC54) which increases ED (0.43667 e) that weakens the
respective bonds C52AC54 (1.4217 Å) leading to stabilization of
41.79 kJ/mol. Another hyperconjugative interaction of C53AC55
from O62 of n2(O62) ? pꢁ(C53AC55) which increases ED (0.41502
e) that weakens the respective bond C53AC55 (1.4063 Å) leading
to stabilization of 29.85 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 wave number. The electron density (ED) is
transferred 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 [70]. The hyper conjugative interaction energy was
deduced from the second-order perturbation approach. Delocaliza-
tion of electron density between occupied Lewis-type (bond or
lone pair) NBO orbital and formally unoccupied (anti bond or Ryd-
berg) 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 configura-
tion around the ring. Hence the title compound is stabilized by
these orbital interactions.
X
X
X
X
1
2
1
6
1
24
E ¼ E0 ꢂ
l
iFi ꢂ
a
ijFiFj ꢂ
bijkFiFjFk ꢂ
c
ijklFiFjFkFl
i
ij
ijk
ijkl
þ ꢄ ꢄ ꢄ
where E0 is the energy of the unperturbed molecule, Fi is the field at
the origin, li ij, bijk and ijkl are the components of dipole moment,
,
a
c
polarizability, the first hyperpolarizabilities, and second hyperpo-
larizabilities, respectively. The calculated first hyperpolarizability
of the title compound is 1.38 ꢃ 10ꢂ30 esu, which comparable with
the reported values of similar derivatives [65–67] and which is
10.62 times that of the standard NLO material urea (0.13 ꢃ 10ꢂ30
esu) [68]. We conclude that the title compound is an attractive
object for future studies of nonlinear optical properties.
NBO analysis
The natural bond orbital (NBO) calculations were performed
using NBO 3.1 program [69] as implemented in the Gaussian09
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
2
ðFi;jÞ
Eð2Þ ¼ Eij ¼ qi
D
ðEj ꢂ EiÞ
qi is the donor orbital occupancy, Ei, Ej is diagonal elements, and Fij
is the off diagonal NBO Fock matrix element.
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(C7-O14) which increases ED (0.07277 e) that weakens the
respective bonds C7AO14 (1.4228 Å) leading to stabilization of
12.92 kJ/mol and also the hyper conjugative interaction of
The NBO analysis also describes the bonding in terms of the nat-
ural hybrid orbital lone pair atoms. The atom n2(O9), which occupy
a higher energy orbital (ꢂ0.32402 a.u.) with considerable p-char-
acter (99.81%) and low occupation number (1.90058) and the other
n1(O9), which occupy a lower energy orbital (ꢂ0.56629 a.u.) with
considerable p-character (57.39%) and high occupation number
(1.95693). Also n2(O14), which occupy a higher energy orbital
(ꢂ0.33054 a.u.) with considerable p-character (100.0%) and low
occupation number (1.89979) and the other n1(O14), which occupy
a lower energy orbital (ꢂ0.57925 a.u.) with considerable p-charac-
ter (57.26%) and high occupation number (1.95416). Again n2(O17),
which occupy a higher energy orbital (ꢂ0.27703 a.u.) with consid-
erable p-character (99.99%) and low occupation number (1.86069)
and the other n1(O17), which occupy a lower energy orbital
(ꢂ0.70467 a.u.) with considerable p-character (39.15%) and high
occupation number (1.97567). Again n2(O18), which occupy a high-
er energy orbital (ꢂ0.27452 a.u.) with considerable p-character
(99.99%) and low occupation number (1.86057) and the other
N
15AC16 from O17 of n2(O17) ? rꢁ(N15AC16) which increases ED
(0.08746 e) that weakens the respective bonds 15AC16
N

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
447
n1(O18), which occupy a lower energy orbital (ꢂ0.70147) with con-
siderable p-character (39.22%) and high occupation number
(1.97630). Again n3(Cl34), which occupy a high energy orbital
(ꢂ0.32775 a.u.) with considerable p-character (100.0%) and low
occupation number (1.96062) and the other n2(Cl34) which occupy
a low energy orbital (ꢂ0.32964 a.u.) with considerable p-character
(99.99%) and high occupation number (1.96514). Another n3(Cl35),
which occupy a high energy orbital (ꢂ0.34411 a.u.) with consider-
able p-character (100.0%) and low occupation number (1.91754)
and the other n2(Cl35), which occupies a low energy orbital
(ꢂ0.34497 a.u.) with considerable p-character (99.87%) and high
occupation number (1.96300). Another n3(Cl36), which occupy a
high energy orbital (ꢂ0.34191 a.u.) with considerable p-character
(100.0%) and low occupation number (1.91508) and the other
n2(Cl36), which occupy a low energy orbital (ꢂ0.34326 a.u.) with
considerable p-character (99.86%) and high occupation number
(1.96263). Another n3(Cl37), which occupy a high energy orbital
(ꢂ0.32338 a.u.) with considerable p-character (100.0%) and low
occupation number (1.96067) and the other n2(Cl37) which occupy
a low energy orbital (ꢂ0.32657 a.u.) with considerable p-character
(99.97%) and high occupation number (1.96506). Another n2(O62),
which occupy a high energy orbital (ꢂ0.29109 a.u.) with consider-
able p-character (100.0%) and low occupation number (1.85158)
Fig. 4. Profile of potential energy scan for the torsion angle C19AC28AC31AN38
.
systems. Mulliken charges are calculated by determining the
electron population of each atom as defined in the basis functions.
The charge distributions calculated by the Mulliken [71] and NBO
methods for the equilibrium geometry of TDMPAD are given in
Table S4 as supporting material. The charge distribution on the
molecule has an important influence on the vibrational spectra.
In TDMPAD, the Mulliken atomic charge of the carbon atoms in
the neighbourhood of C7, C13 and C16 become more positive, shows
the direction of delocalization and shows that the natural atomic
charges are more sensitive to the changes in the molecular struc-
ture than Mulliken’s net charges. The results are represented in
Fig. S1 as supporting material. Also we done a comparison of Mul-
liken charges obtained by different basic sets and tabulated in
Table S5 (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 re-
sults 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.
and the other n1(O62), which occupy
a low energy orbital
(ꢂ0.52726 a.u.) with considerable p-character (58.77%) and high
occupation number (1.96686). 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 S3 as supporting material.
Mulliken charges
The calculation of atomic charges plays an important role in the
application of quantum mechanical calculations to molecular
Table 2
Experimental and calculated 1H NMR parameters (with respect to TMS).
1H NMR spectrum
Proton
rTMS
B3LYP/6-31G rcalc.
dcalc.
(rTMS
ꢂ
rcalc.
)
Exp. dppm
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
H64
H65
H66
32.7711
29.4169
29.3381
29.0158
28.8518
29.0223
29.1749
29.1338
29.0729
29.1842
29.0499
30.6968
30.7255
30.0863
29.8747
29.3101
29.8331
29.5502
29.0775
28.8622
29.4579
29.6395
28.8295
27.0672
26.5091
25.5122
26.3931
28.5789
28.8546
28.8816
3.3542
3.4330
3.7553
3.9193
3.7488
3.5962
3.6373
3.6982
3.5869
3.7212
2.0743
2.0456
2.6848
2.8964
3.4610
2.9380
3.2209
3.6936
3.9089
3.3132
3.1316
3.9416
5.7039
6.2620
7.2589
6.3780
4.1922
3.9165
3.8895
3.65
3.65
3.65
3.65
3.65
3.58
3.58
3.74
3.57
3.58
2.17
2.14
3.10
3.10
3.57
3.10
3.57
3.74
3.89
3.57
3.13
3.89
6.68
6.59
7.23
6.59
3.9
The experimental spectrum data of TDMPAD in DMSO with
TMS as internal standard is obtained at 400 MHz and is displayed
in Table 2. The absolute isotropic chemical shielding of TDMPAD
3.9
3.9
Fig. 5. Profile of potential energy scan for the torsion angle C31AN38AC40AC45
.

448
R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
was calculated by B3LYP/GIAO model [72]. Relative chemical
shifts were then estimated by using the corresponding TMS
PES scan studies
shielding:
theoretical level as this paper. Numerical values of chemical shift
dcalc.
calc.(TMS) ꢂ rcalc. together with calculated values of
r
calc.(TMS) calculated in advance at the same
A detailed potential energy surface (PES) scan on dihedral
angles C19AC28AC31AN38, and C31AN38AC40AC45 have been per-
formed at B3LYP/6-31G(d) level to reveal all possible conforma-
tions of TDMPAD. The PES scan was carried out by minimizing
the potential energy in all geometrical parameters by changing
the torsion angle at every 10° for a 180° rotation around the bond.
The results obtained in PES scan study by varying the torsion per-
turbation around the methyl bonds (CH2) are plotted in Figs. 4 and
=
r
r
calc.(TMS), are reported in Table 2. It could be seen from Table 2
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 TDMPAD.
Fig. 6. Molecular Electrostatic Potential map calculated at B3LYP/SDD level.
Fig. 7. HOMO, LUMO plots of TDMPAD.

R. Renjith et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 438–450
449
5. For the C19AC28AC31AN38 rotation, the minimum energy was
obtained at 177.3° in the potential energy curve of energy
ꢂ3351.19344 Hartrees. For the C31AN38AC40AC45 rotation, the
minimum energy occurs at ꢂ110.5° in the potential energy curve
of energy -3351.18569 Hartrees. (A view of the title compound is
given in Fig. S3 as supporting information).
(0.13 ꢃ 10ꢂ30 esu). We conclude that the title compound is an
attractive object for future studies of nonlinear optical properties.
Acknowledgement
RR thanks University Grants Commission, India, for a research
fellowship.
Molecular Electrostatic Potential
Appendix A. Supplementary material
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 [73,74]. 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 [75,76]. 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. 6). From the MEP it is evi-
dent that the negative charge covers the carbonyl, benzene and
piperazine rings and the positive region is over the methyl group.
The more electro negativity in the carbonyl, benzene, and pipera-
zine groups makes it the most reactive part in the molecule.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.03.077.
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