Vibrational spectroscopic and quantum chemical calculations of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-methylene)amino)benzene sulfonamide

Article abstract of DOI:10.1016/j.saa.2011.10.073

FT-IR and FT-Raman spectra of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl- methylene)amino)benzene sulfonamide were recorded and analyzed. The vibrational wavenumbers were computing at various levels of theory. The data obtained from theoretical calculations

Full text of DOI:10.1016/j.saa.2011.10.073

Spectrochimica Acta Part A 87 (2012) 29–39
Contents lists available at SciVerse ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Vibrational spectroscopic and quantum chemical calculations of
(E)-N-Carbamimidoyl-4-((naphthalen-1-yl-methylene)amino)benzene
sulfonamide
Asha Chandrana, Hema Tresa Vargheseb, Y. Sheena Maryb, C. Yohannan Panickerc,d,∗
,
T.K. Manojkumare, Christian Van Alsenoyf, G. Rajendrang
a Department of Chemistry, TKM College of Arts and Science, Kollam, Kerala, India
b Department of Physics, Fatima Mata National College, Kollam, Kerala, India
c Department of Physics, TKM College of Arts and Science, Kollam, Kerala, India
d Research Centre, Department of Physics, Mar Ivanios College, Nalanchira, Trivandrum, Kerala, India
e Indian Institute of Information Technology and Management-Kerala, Technopark, Trivandrum, Kerala, India
f
Department of Chemistry, University of Antwerp, B2610, Antwerp, Belgium
g Department of Chemistry, University College, Trivandrum, Kerala, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 September 2011
Accepted 31 October 2011
FT-IR and FT-Raman spectra of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-methylene)amino)benzene
sulfonamide were recorded and analyzed. 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 results indicate that B3LYP method is able to provide satisfactory results
for predicting vibrational frequencies and structural parameters. The calculated first hyperpolarizability
is comparable with reported values of similar derivatives and is an attractive object for future studies
of non-linear optics. The geometrical parameters of the title compound are in agreement with that of
similar derivatives.
Keywords:
Naphthalene
Sulfonamide
DFT calculations
FT-IR
© 2011 Elsevier B.V. All rights reserved.
FT-Raman
1. Introduction
form a significant class of compounds in medicinal and pharma-
ceutical chemistry with several biological applications [11–14].
The naphthalene and its derivatives are of great interest in bio-
logical activity and widely used as a parent compound to make
drugs. Srivastava has investigated the infrared and Raman spec-
trum of the condensed and liquid phase naphthalene and its cation
[1]. Extensive recent studies of vibrational spectra of substituted
naphthalene compounds have assigned [1–4] complete vibrational
mode and frequency analyses. Naphthalene is classified as a ben-
zenoid polycyclic aromatic hydrocarbon which is crystalline white
solid with the structure of two fused benzene rings and do not
contain heteroatoms or carry substituents. Like benzene, naphtha-
lene can undergo electrophilic aromatic substitution. It constitute
a group of widespread pollutants of great environmental interest
[5,6]. It is widely recognized that polycyclic aromatic hydrocar-
bons and their metabolities are among the most toxic, carcinogenic
and mutagenic atmospheric contaminants [7–10]. Sulfonamides
Many chemotherapeutically important sulfa drugs, like sulphadi-
azine, sulphathiazole, sulphamerazine and sulfonamides, posses
SO2NH moiety which is an important toxophoric function [15].
The chemistry of sulfonamides has been known as synthons in
the preparation of various valuable biologically active compounds
[16,17] used as antibacterial [18], protease inhibitor [19], diuretic
[20], anti-tumor [21], and hypoglycaemic [22]. To our knowledge,
no theoretical HF or density functional theory (DFT) calculations or
detailed vibrational spectroscopic analyses have been performed
on the title compound.
2. Experimental
All the chemicals were procured from Sigma–Aldrich, USA.
0.5 mg of sulphaguanidine and 0.3 ml of 1-napththaldehyde in
20 ml ethanol is refluxed 2 h and cooled. The light yellow precipitate
was filtered off, washed with ethanol and dried. Elemental analy-
sis: found/calculated (%): C 61.2/61.3; H 4.42/4.53; N 15.80/15.50; S
9.01/9.59; O 9.02/9.01. The FT-IR spectrum (Fig. 1) was recorded on
a DR/Jasco FT-IR 6300 spectrometer in KBr pellets, number of scans
16, resolution 2 cm−1. The FT-Raman spectrum (Fig. 2) was obtained
∗
Corresponding author at: Department of Physics, TKM College of Arts and Sci-
ence, Kollam, Kerala, India. Tel.: +91 9895370968.
E-mail addresses: cyphyp@rediffmail.com, h varghese@rediffmail.com
(C.Y. Panicker).
1386-1425/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2011.10.073

30
A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
Fig.
1. FT-IR
spectrum
of
(E)-N-Carbamimidoyl-4-((naphthalen-1-yl-
methylene)amino)benzene sulfonamide.
Fig. 4. Profile of potential energy surface scan for the torsion angle C21–N20–C18–C11
.
absence of imaginary values of wavenumbers on the calculated
vibrational spectrum confirms that the structure deduced corre-
sponds to minimum energy. Potential energy distribution is done
using GAR2PED program [25]. The assignment of the calculated
wavenumbers is aided by the animation option of MOLEKEL pro-
gram, which gives a visual presentation of the vibrational modes
[26,27]. Potential energy surface scan studies have been carried out
to understand the stability of planar and non planar structures of
the molecule. The profiles of potential energy surface for torsion
angles C21–N20–C18–C11, N34–S31–C28–C24, N37–C36–N34–S31 and
Fig. 2. FT-Raman spectrum of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-
methylene)amino)benzene sulfonamide.
N
38–C36–N34–S31 are given Figs. 4–7. The energy is minimum for
on a BRUKER RFS 100/S, Germany. For excitation of the spectrum
the emission of a Nd:YAG laser was used, excitation wavelength
1064 nm, maximal power 150 mW, measurement of solid sample.
One thousand scans were accumulated with a total registration
time of about 30 min. The spectral resolution after apodization was
−175.5 (−1463.11766 Hartree), 80.0 (−1463.11278 Hartree), 36.9
(−1463.11599 Hartree) and −146.1 (−1463.11659 Hartree) for the
above torsion angles.
2 cm−1
.
4. Results and discussion
The observed IR, Raman bands and calculated (scaled)
wavenumbers and assignments are given in Table 2.
3. Computational details
Calculations of the title compound were carried out with
Gaussin03 program [23] using the HF/6-31G*, B3PW91/6-31G*
and B3LYP/6-31G* basis sets to predict the molecular structure
and vibrational wavenumbers. The wavenumber values computed
contain known systematic errors [24] and we therefore, have
used the scaling factor values of 0.8929 and 0.9613 for HF and
DFT basis sets. Parameters corresponding to optimized geometry
(B3LYP) of the title compound (Fig. 3) are given in Table 1. The
Fig. 3. Optimized geometry (B3LYP) of (E)-N-Carbamimidoyl-4-((naphthalen-1-yl-
methylene)amino)benzene sulfonamide.
Fig. 5. Profile of potential energy surface scan for the torsion angle N34–S31–C28–C24.

A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
31
Table 1
Optimized geometrical (B3LYP) parameters, atom labeling according to Fig. 3.
Bond lengths (Å)
Bond angles (◦)
Dihedral angles (◦)
C1–C2
C1–C6
C1–H8
C2–C3
C2–H9
C3–C4
C3–C10
C4–C5
C4–C11
C5–C6
C5–H12
C6–H13
1.3784
1.4171
1.0848
1.4245
1.0861
1.4414
1.4217
1.4255
1.4436
1.3816
1.0833
1.0852
1.0862
1.3820
1.3941
1.4634
1.4081
1.0839
1.0847
1.0940
1.2955
1.4056
1.4135
1.4105
1.3956
1.0844
1.3939
1.0834
1.3922
1.0840
1.3935
1.0841
1.8634
1.6355
1.6380
1.8057
1.0148
1.4283
1.2817
1.3882
1.0228
1.0089
1.0085
A(2,1,6)
A(2,1,8)
A(6,1,8)
A(1,2,3)
A(1,2,9)
A(3,2,9)
A(2,3,4)
A(2,3,10)
A(4,3,10)
A(3,4,5)
A(3,4,11)
A(5,4,11)
A(4,5,6)
A(4,5,12)
A(6,5,12)
A(1,6,5)
119.7
120.5
119.8
121.0
120.5
118.4
119.5
120.8
119.6
117.7
118.2
124.1
121.3
120.3
118.4
120.7
119.6
119.7
118.6
120.9
120.5
119.7
121.5
118.8
121.5
117.9
120.6
120.0
120.4
119.7
117.7
122.3
120.1
122.1
122.7
117.7
119.6
120.4
119.9
119.8
120.5
118.5
121.0
118.1
121.2
120.7
118.1
122.0
119.9
123.4
118.6
118.0
107.7
110.9
98.8
D(6,1,2,3)
D(6,1,2,9)
D(8,1,2,3)
D(8,1,2,9)
D(2,1,6,5)
D(2,1,6,13)
D(8,1,6,5)
D(8,1,6,13)
D(1,2,3,4)
D(1,2,3,10)
D(9,2,3,4)
D(9,2,3,10)
D(2,3,4,5)
D(2,3,4,11)
D(10,3,4,5)
D(10,3,4,11)
D(2,3,10,7)
D(2,3,10,15)
D(4,3,10,7)
D(4,3,10,15)
D(3,4,5,6)
D(3,4,5,12)
D(11,4,5,6)
D(11,4,5,12)
D(3,4,11,14)
D(3,4,11,18)
D(5,4,11,14)
D(5,4,11,18)
D(4,5,6,1)
0.1
−179.8
180.0
0.0
−0.2
179.7
180.0
−0.1
0.2
−179.7
−179.9
0.2
C
10–H7
−0.4
C10–C15
C11–C14
C11–C18
C14–C15
C14–H16
C15–H17
C18–H19
C18–N20
C21–N20
179.8
179.5
−0.3
A(1,6,13)
A(5,6,13)
A(3,10,7)
−0.1
179.8
−180.0
−0.1
A(3,10,15)
A(7,10,15)
A(4,11,14)
A(4,11,18)
A(14,11,18)
A(11,14,15)
A(11,14,16)
A(15,14,16)
A(10,15,14)
A(10,15,17)
A(14,15,17)
A(11,18,19)
A(11,18,20)
A(19,18,20)
A(18,20,21)
A(20,21,22)
A(20,21,23)
A(22,21,23)
A(21,22,24)
A(21,22,25)
A(24,22,25)
A(21,23,26)
A(21,23,27)
A(26,23,27)
A(22,24,28)
A(22,24,29)
A(28,24,29)
A(23,26,28)
A(23,26,30)
A(28,26,30)
A(24,28,26)
A(24,28,31)
A(26,28,31)
A(28,31,32)
A(28,31,33)
A(28,31,34)
A(32,31,33)
A(32,31,34)
A(33,31,34)
A(31,34,35)
A(31,34,36)
A(35,34,36)
A(34,36,37)
A(34,36,38)
A(37,36,38)
A(36,37,41)
A(36,38,39)
A(36,38,40)
A(39,38,40)
0.3
−179.4
−179.9
0.5
C21–C22
C
C
21–C23
22–C24
0.5
C22–H25
C23–C26
−179.1
−179.3
1.1
C
C
C
23–H27
24–C28
24–H29
−0.0
D(4,5,6,13)
D(12,5,6,1)
−179.9
179.6
C26–C28
26–H30
C
D(12,5,6,13)
D(3,10,15,14)
D(3,10,15,17)
D(7,10,15,14)
D(7,10,15,17)
D(4,11,14,15)
D(4,11,14,16)
D(18,11,14,15)
D(18,11,14,16)
D(4,11,18,19)
D(4,11,18,20)
D(14,11,18,19)
D(14,11,18,20)
D(11,14,15,10)
D(11,14,15,17)
D(16,14,15,10)
D(16,14,15,17)
D(11,18,20,21)
D(19,18,20,21)
D(18,20,21,22)
D(18,20,21,23)
D(20,21,22,24)
D(20,21,22,25)
D(23,21,22,24)
D(23,21,22,25)
D(20,21,23,26)
D(20,21,23,27)
D(22,21,23,26)
D(22,21,23,27)
D(21,22,24,28)
D(21,22,24,29)
D(25,22,24,28)
D(25,22,24,29)
D(21,23,26,28)
D(21,23,26,30)
D(27,23,26,28)
D(27,23,26,30)
D(22,24,28,26)
D(22,24,28,31)
D(29,24,28,26)
D(29,24,28,31)
D(23,26,28,24)
D(23,26,28,31)
D(30,26,28,24)
D(30,26,28,31)
−0.34
C28–S31
S31–O32
0.3
−179.9
−179.8
0.0
S
31–O33
S31–N34
N
C
34–H35
36–N34
−0.3
179.8
179.3
−0.7
C36–N37
C36–N38
N
N
N
37–H41
38–H39
38–H40
2.0
−177.5
−177.5
2.9
−0.1
−180.0
179.9
−0.0
−175.5
5.0
41.4
−141.1
178.4
0.1
0.9
119.4
111.8
106.3
113.5
122.3
120.5
127.2
111.2
121.6
114.7
114.9
120.4
117.1
−177.4
−179.2
1.5
−1.5
179.1
−0.4
179.6
177.9
−2.1
1.7
−178.2
−179.0
1.1
0.6
178.9
−179.4
−1.0
−1.2
−179.6
178.7
0.3

32
A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
Table 1 (Continued)
Bond lengths (Å)
Bond angles (◦)
Dihedral angles (◦)
D(24,28,31,32)
D(24,28,31,33)
D(24,28,31,34)
D(26,28,31,32)
D(26,28,31,33)
D(26,28,31,34)
D(28,31,34,35)
D(28,31,34,36)
D(32,31,34,35)
D(32,31,34,36)
D(33,31,34,35)
D(33,31,34,36)
D(31,34,36,37)
D(31,34,36,38)
D(35,34,36,37)
D(35,34,36,38)
D(34,36,37,41)
D(38,36,37,41)
D(34,36,38,39)
D(34,36,38,40)
D(37,36,38,39)
D(37,36,38,40)
−172.6
−40.2
71.1
5.9
138.3
−110.4
37.3
−164.3
−75.8
82.6
152.2
−49.4
36.9
−146.1
−166.2
10.8
3.8
−173.0
−171.1
40.0
6.1
−142.7
4.1. IR and Raman spectra
stretching vibrations. In the present study, the N34–H35 stretching
bands has split into a doublet, 3336, 3215 cm−1 in the IR spectrum
owing to the Davydov coupling between neighboring units. The
splitting of about 121 cm−1 in the IR spectrum is due to the strong
intermolecular hydrogen bonding. Furthermore the NH stretching
wavenumber is red shifted by 144 cm−1 in the IR spectrum with a
strong intensity from the computed wavenumber which indicate
the weakening of the NH bond [36]. In N-monosubstituted amides,
the in-plane bending frequency and the resonance stiffened C–N
band stretching frequency fall close together and therefore interact.
The NH deformation band of guanidine structural motif is expected
in the region 1395 25 cm−1 [31,32]. The B3LYP calculations give
this modes at 1356 and 1408 cm−1. The out-of-plane NH defor-
mation is expected in the region 650 50 cm−1[31] and bands at
675(IR), 669(Raman) and 668, 575 cm−1 (B3LYP) are assigned as
this mode. Wang and Ma [37] reported NH stretching bands in
the region, 3365–3374 cm−1 and guanidine C N stretching bands
in the region 1598–1638 cm−1. According to Henry et al. [38] IR
spectrum exhibits typical features for Schiff base possessing sev-
eral bands of ꢀNH and ꢀCH vibration with maxima in the range of
3380–3270 cm−1 and 2950–2890 cm−1, as well as strong and broad
The C N stretching skeletal bands [28–30] are observed in the
range of 1627–1566 cm−1. B3LYP calculations give these modes at
1684 and 1611 cm−1. The C–N stretching vibration [31] is mod-
erately to strongly active in the region 1275 55 cm−1. Primary
aromatic amines with nitrogen directly on the ring absorb at
1330–1200 cm−1 because of the stretching of the phenyl C–N
bond [32]. For the title compound, the C21–N20 stretching mode
is observed at 1264 cm−1 in Raman and at 1259 cm−1 theoreti-
cally. Panicker et al. [33] reported CN stretching mode at 1219,
1237 (IR), 1222 (Raman) and at 1292, 1234, 1200 cm−1 theoreti-
cally. The CN stretching modes C36–N38 and C36–N34 are assigned
at 1071 and 918 cm−1 theoretically, which is expected in the range
of 850–1115 cm−1 [31]. The band at 2980 cm−1 in Raman and at
2970 cm−1 (B3LYP) is assigned as the C18–H19 stretching mode
and the bands at 1408 and 977 cm−1 (B3LYP) are assigned as the
in-plane and out-of-plane CH deformation bands.
The N–H stretching vibrations generally give rise to bands at
3500–3300 cm−1 [34,35]. In the present case, the bands observed at
3443, 3359 (B3LYP) and 3410, 3336 cm−1 (IR) are the assigned as NH
bands due to ꢀC N at 1635 cm−1
.
Fig. 6. Profile of potential energy surface scan for the torsion angle N37–C36–N34–S31
.
Fig. 7. Profile of potential energy surface scan for the torsion angle N38–C36–N34–S31.

Table 2
Calculated vibrational wavenumbers (scaled), measured IR and Raman bands and assignments.
HF/6-31G*
B3PW91/6-31G*
B3LYP/6-31G*
IR
Raman
Assignmentsa
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
ꢀ (cm−1
)
3548
3450
3428
3380
3051
3043
3042
3041
3037
3025
3024
3021
3007
3000
2996
2948
1713
1669
52.59
72.11
53.22
52.87
4.09
74.91
56.60
3615
3485
3480
3373
3129
3121
3119
3118
3114
3108
3104
3103
3091
3083
3081
2977
1699
1632
32.36
54.88
17.92
22.97
4.84
115.89
278.72
42.99
42.27
128.26
61.79
215.75
176.56
45.42
123.30
151.29
25.65
130.24
95.27
21.28
3587
3460
3443
3359
3120
3113
3112
3108
3106
3097
3094
3093
3080
3072
3069
2970
1684
1620
26.82
40.16
18.52
19.43
5.73
1.21
7.05
20.89
3.73
42.02
5.55
127.83
234.31
98.01
41.49
132.76
58.62
123.04
197.09
42.69 -
168.05
31.18
184.93
139.81
93.17
–
–
–
–
–
3143
3125
–
–
–
–
–
–
–
3067
3031
2980
–
ꢀasNH2(99)
ꢀsNH2(98)
ꢀNH(98)
ꢀNH(100)
ꢀCHII(98)
ꢀCHII(98)
ꢀCHI(100)
ꢀCHI(97)
ꢀCHII(99)
ꢀCHI(95)
ꢀCHII(99)
ꢀCHI(99)
ꢀCHI(93)
ꢀCHI(93)
3484
3410
3336, 3215
–
–
–
–
–
–
–
–
–
–
–
–
–
113.98
34.27
117.12
119.35
144.96
27.26
39.82
207.79
44.41
156.81
135.40
66.95
19.77
23.84
2.54
1.58
7.57
11.75
16.46
2.88
40.96
9.61
28.01
8.72
1.84
24.10
4.59
36.37
17.79
3.74
4.78
3.84
1.09
24.78
6.70
3.83
0.34
0.85
18.21
39.19
11.53
855.44
ꢀCHI(95)
ꢀCH(98)
ꢀCN(76),ıNH(15)
ꢀPhI(40),
16.51
322.11
490.02
23.98
214.05
89.86
37.75
11.34
948.59
24.07
200.59
77.17
15.52
2149.81
1624
1621
ꢀCN(15)
1639
38.52
107.68
1623
164.94
1473.63
1611
102.72
1255.17
–
–
ꢀPhI(19),
ꢀCN(62)
1626
1605
1599
100.84
4.87
141.70
5.80
13.95
304.64
1610
1593
1587
95.33
7.09
47.36
6.35
26.20
257.97
1609
1582
1574
130.15
0.92
47.69
81.10
1.73
267.56
–
–
–
–
ıNH2(83)
ꢀPhI(68)
ꢀPhII(65),
ꢀPhI(14)
1591
–
1588
1574
191.68
10.65
2153.80 1573
40.78
32.33
1569
478.68
344.85
1559
6053.08
28.07
1554
414.62
352.22
–
–
1540
–
–
ꢀPhII(67)
ꢀPhII(27),
ꢀPhI(60)
6577.19
1515
1495
1467
1446
1418
1414
1399
12.81
101.89
6.45
17.70
74.43
33.79
39.40
12.26
155.05
11.49
1523
1482
1465
1445
1409
1400
1397
12.61
52.57
26.80
8.13
13.56
2.93
117.90
100.10
270.51
53.69
205.12
527.76
460.29
1515
1478
1463
1443
1408
1396
1391
9.95
65.32
–
–
–
–
–
–
–
1510
–
1466
1438
–
ꢀPhI(70),ıCHI(20)
ꢀPhII(77),ıCHII(20)
ıCHI(68)
ꢀPhI(49),ıCHI(43)
ıNH(72)
ıCHI(65)
ꢀPhII(63),
ıCHII(27)
53.99
26.58
9.00
22.53
1.48
118.24
277.26
51.82
279.76
399.14
473.34
7.74
514.81
141.05
45.54
–
42.87
43.17
1385
1394
1342
14.35
6.33
236.59
484.65
1379
1372
1.12
692.74
250.30
78.75
1361
1356
2.08
633.44
348.27
70.51
–
–
–
–
ꢀPhI(81)
ꢀasSO2(53),
ꢀCN(44)
1322
1315
1305
63.61
4.80
135.68
366.51
51.46
1.09
1351
1335
1297
36.36
11.47
4.90
223.13
12.54
9.05
1340
1316
1300
61.84
6.74
3.71
483.88
7.69
8.02
–
–
1302
1346
–
1305
ꢀPhI(77)
ꢀPhII(83)
ꢀPhII(16),
ıCHII(72)
ꢀPhI(14),
ıCHI(49)
1267
0.82
4.70
1276
12.90
112.97
1274
7.46
79.29
–
–
1246
1219
1206
16.66
13.14
77.60
114.28
63.40
158.19
1263
1254
1230
10.89
20.14
8.10
20.29
103.79
49.19
1259
1250
1223
19.81
27.28
7.97
18.49
193.38
55.93
–
–
1229
1264
–
1226
ꢀCN(82)
ıCHI(35)
ꢀPhI(65),
ıCHI(19)
1191
1180
10.79
36.76
40.44
97.72
1202
1184
109.70
3.18
766.10
18.38
1196
1182
72.37
2.21
556.21
14.58
–
–
–
ꢀPhI(44),
ıCHI(31),ꢀCN(14)
ıCHI(18),
ıCHII(64)
1186

Table 2 (Continued)
HF/6-31G*
B3PW91/6-31G*
B3LYP/6-31G*
IR
Raman
Assignmentsa
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
IIR
RA
ꢀ (cm−1
)
ꢀ (cm−1
)
1178
1160
1144
12.34
33.00
75.08
5.47
79.90
7.49
1177
1170
1156
0.43
87.88
7.60
5.72
518.96
70.56
1177
1168
1154
0.54
125.64
8.40
3.11
802.97
85.46
1177
–
–
–
–
–
ıCHI(80)
ꢀsSO2(53),ıCHII(35)
ꢀPhI(33),
ıCHI(45)
1126
1108
1084
1072
15.57
0.64
29.49
2.96
1122
1108
1091
1080
84.24
3.36
5.16
0.18
83.38
5.59
1123
1109
1088
1071
84.34
3.46
3.96
1137
–
1136
–
ıNH2(78),
ꢀCN(16)
ꢀPhII(26),
ıCHII(61)
ꢀPhII(56),
ıCHI(24)
0.61
97.45
1.55
3.11
2.07
2.91
102.92
6.62
1086
–
1092
–
25.18
63.19
67.71
ıNH(40),
ꢀCN(50)
1063
1061
1055
1049
16.52
23.24
3.56
33.15
48.92
8.17
1058
1037
1018
1003
61.73
18.13
8.99
123.74
44.51
106.49
21.14
1047
1033
1014
1000
49.15
22.41
7.34
105.87
71.16
96.20
7.53
–
–
–
–
1050
ꢀCHII(68)
ꢀPhI(62)
ꢀPhI(68)
ıPhII(30),
ꢁCH(16),ꢁCHI(43)
ꢁCHI(56),
ıPHII(17)
ꢁCHI(71)
ꢁCHII(79)
ꢁCH(69),
ꢁCHI(27)
ꢁCHII(80)
ꢁCHI(89)
ꢁCHI(87)
ꢀCN(64)
–
–
–
0.75
3.74
13.57
10.50
1033
3.11
22.61
999
0.32
64.67
996
3.87
125.18
–
–
1033
1023
1016
1.16
26.34
4.89
1.56
89.63
4.82
995
988
981
3.98
1.20
14.79
67.42
0.90
208.84
990
984
977
5.23
0.52
14.50
71.10
2.25
207.18
–
–
–
–
–
–
1007
992
989
956
912
901
889
0.50
0.55
1.95
195.54
11.33
32.44
200.77
40.22
36.05
12.32
5.97
3.34
3.24
960
957
940
937
926
877
870
0.18
1.29
10.47
1.39
5.47
11.77
8.66
88.53
1.65
955
952
934
918
906
876
868
0.26
1.19
0.67
151.47
129.20
27.82
3.71
15.19
1.49
9.07
11.23
8.17
97.31
1.71
–
–
–
–
–
–
–
–
–
–
–
–
–
–
119.28
5.44
169.13
26.90
3.78
ꢀCN(67)
ıPhI(78)
ꢁCHI(63),
ꢂPhI(25)
6.78
880
863
843
836
829
3.79
26.98
21.47
32.78
2.22
862
852
843
823
816
166.02
33.13
21.70
12.94
67.07
14.53
6.25
23.90
21.82
14.75
856
850
840
819
806
129.34
44.16
18.08
17.73
41.33
14.37
6.60
24.70
28.21
1.18
–
–
–
821
–
–
–
–
818
–
ꢀSN(69)
24.29
32.39
53.90
49.11
ꢁCHII(68)
ꢁCHII(77)
ꢁCHII(72)
ꢁCHI(75),
ꢂPhI(11)
20.71
811
795
786
760
759
740
707
679
650
90.28
10.21
1.34
7.36
6.50
2.85
3.15
6.31
4.85
3.39
4.48
3.57
806
790
780
756
739
735
717
674
665
41.89
0.62
1.39
797
789
779
752
735
727
713
668
663
54.24
2.70
12.38
10.83
11.68
13.07
7.08
–
–
ıSO2(32),
ꢀSN(11),ıNH2(41)
ıPhI(64),
ꢀPhI(11)
ꢂPhI(46),
ꢁCHI(34)
ıPhII(36),
ꢀPhI(20)
ꢁCHI(67),
ꢂPhI(22)
ıCN(42),
ıNH(21)
ꢂPhII(61),
ꢁCN(14)
ꢁCN(21),
ꢁNH(42)
10.69
11.13
15.16
34.08
6.03
–
–
63.81
4.64
58.22
3.51
–
–
5.02
–
–
4.97
25.88
6.10
4.88
–
740
–
13.19
137.38
14.35
3.86
25.68
8.29
34.07
8.19
–
10.16
104.68
7.51
5.64
–
713
669
–
13.57
23.16
86.22
39.60
5.95
675
–
31.86
ıPhI(44),
ıPhII(22)

640
38.17
21.83
641
2.78
5.86
640
2.47
5.41
–
635
ꢂPhI(25),
ꢀCS(65)
634
609
0.85
86.11
8.32
6.25
627
603
1.83
129.07
8.47
11.15
629
600
1.57
116.18
8.85
8.78
–
608
622
–
ıPhII(73)
ıPhI(52),
ıPhII(21)
580
33.24
13.15
579
95.01
31.85
575
97.11
39.34
–
–
ıCN(27),
ꢁCN(12),ꢁNH(41)
ꢂPhI(55)
569
566
28.01
175.58
8.46
3.34
552
551
146.37
40.03
9.36
27.08
551
546
2.50
182.31
18.99
11.43
–
547
–
547
ꢁNH2(38),
ıCN(23),ꢁCN(15)
ꢂPhII(31),
ıPhI(24),ıCN(20)
ıPhI(69)
555
37.42
3.56
541
19.25
34.21
541
10.57
43.71
–
–
526
503
10.41
6.80
18.98
6.08
521
501
21.53
13.30
19.44
7.13
521
501
22.01
11.95
20.89
6.67
–
–
518
–
ıPhI(38),
ꢂPhII(26),ꢁCN(20)
ꢂPhI(51)
ꢂPhI(71)
ıSO2(40),
ıCN(22),ꢂPhI(10)
ꢂPhI(23),
485
474
467
1.44
35.20
48.33
2.71
12.17
4.18
477
471
464
8.03
45.12
67.13
9.76
18.89
7.69
478
471
462
4.20
21.45
109.04
7.75
15.48
16.52
–
–
–
–
–
460
433
429
29.59
9.23
2.45
5.29
430
421
45.57
22.52
4.76
2.34
426
422
40.94
17.82
3.23
3.03
–
–
–
–
ıSO2(52)
ꢂPhI(35),
ıSO2(40)
418
406
67.91
29.40
7.72
3.80
416
401
0.39
31.61
26.25
8.36
418
402
0.74
35.94
24.81
9.06
–
406
417
–
ꢂPhII(78)
ıCN(34),
ꢂPhI(32)
381
363
344
46.00
35.80
58.90
4.97
3.20
3.26
374
361
353
34.10
24.64
22.37
15.74
5.23
6.11
370
364
351
26.58
66.31
9.43
2.45
25.17
11.10
–
–
–
373
–
342
ꢂNH(66)
ꢂNH2(73)
ıSO2(58),
ꢂNH2(15)
ꢂNH(45),
ıSO2(24),ꢂPhII(23)
ıSO2(40),
ıCN(29)
333
292
276
38.66
36.75
16.90
2.68
4.30
7.68
319
297
280
81.47
10.35
13.39
15.81
8.49
7.30
319
288
277
52.86
9.96
17.98
18.84
6.13
–
–
–
–
291
–
18.76
ıSO2(44),
ıCN(32)
272
267
5.18
2.17
8.65
6.59
263
251
3.11
3.22
18.53
4.94
264
247
2.57
1.89
21.11
4.72
–
–
–
–
ꢂPhI(64)
ıSO2(56),
ıCS(10)
227
206
10.21
9.98
5.10
3.35
223
193
9.98
3.95
11.92
6.52
222
194
7.81
2.81
10.20
9.41
–
–
214
–
ıSO2(32),
ꢂPhII(40)
ıSO2(40),
ıNH(24),ꢁCS(18)
ꢂPhI(64)
178
153
5.47
4.56
1.02
8.50
180
156
6.37
10.05
6.36
44.44
181
157
6.17
10.64
5.45
39.54
–
–
–
–
ıSO2(22),
ꢂCN(36)
150
7.52
0.74
149
0.79
2.41
149
1.33
1.35
–
–
ıNH(33),
ꢂPhI(47)
142
126
5.21
0.63
14.30
3.63
146
122
0.16
0.80
21.46
2.54
146
121
0.17
0.96
25.82
2.66
–
–
–
117
ꢂPhI(64)
ꢂSO2(39),
ıCC(18),
ꢂPhII(19)
ꢂPhI(63),
91
1.13
7.74
94
0.53
15.46
95
0.62
16.03
–
–
ꢂCN(13)

36
A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
The NH2 stretching modes of guanidine are expected in the
region 3260–3390 cm−1 [31] and in the present case bands at 3587,
3460 cm−1 (B3LYP) and 3484 (IR) are assigned as NH2 stretching
modes. Topacli and Topacli [39] reported the calculated wavenum-
bers in the range of 3670–3920 cm−1 for NH2 stretching modes.
The bands corresponding to the ıNH2 vibrations are expected in
the region 1610 30 cm−1 [31]. In the IR and Raman spectrum
ıNH2 is not observed. The calculated value is 1609 cm−1. The rock-
ing/twisting mode of NH2 is expected in the region 1195 90 cm−1
and the B3LYP calculations give this mode at 1123 cm−1. Exper-
imentally bands are observed at 1137 in the IR spectrum and at
1136 cm−1 in the Raman spectrum. The wagging mode of NH2 is
expected in the range 840 55 cm−1 [31]. The B3LYP calculations
give this mode at 797 cm−1. The torsion NH2 mode is expected in
the range 355 65 cm−1 [31] and the band at 364 (B3LYP) cm−1 is
assigned as this mode. For sulfonamide derivatives, the NH2 modes
are reported at 3390, 3395, 3399 cm−1 and NH modes at 3253, 3230,
3255 cm−1 [40].
The antisymmetric and symmetric stretching modes of SO2
group appear in the region 1360–1310 and 1165–1135 cm−1
,
respectively [31]. The B3LYP calculations give the antisymmetric
and symmetric stretching modes at 1356 and 1168 cm−1. The SO2
stretching mode is not pure, but contains contributions from other
modes also. Although the region of the SO2 scissors (560 40 cm−1
)
and that of SO2 wagging vibration (500 55 cm−1) partly overlap,
the two vibrations appear separately [31]. The B3LYP calculations
give these modes at 462 and 426 cm−1. Hangen et al. [41] reported
the SO2 stretching vibrations at 1314, 1308, 1274, 1157, 1147,
1133 cm−1 and SN stretching modes at 917, 920, 932, 948 cm−1 for
sulfonamide derivatives. Chohan et al. [40] reported SO2 stretch-
ing modes at 1345, 1110 cm−1 and SN and CS stretching modes
at 833 cm−1 for sulfonamide derivatives. The twisting SO2 mode
is expected in the region 440 50 cm−1 and the rocking mode at
around 350 cm−1 [31]. The B3LYP calculations give these modes
at 422 and 351 cm−1. The SN stretching vibration [31] is expected
in the region 905 30 cm−1. The band calculated at 856 cm−1
is assigned as SN stretching mode. The C–S stretching mode is
observed at 635 (Raman) cm−1 and the band at 640 cm−1 (B3LYP)
is assigned as this mode [31].
In the following discussion, naphthalene ring and para sub-
stituted phenyl ring are designated as PhI and PhII, respectively.
The naphthalene ring modes are influenced more C–C bands.
The ring stretching vibrations are expected within the region
1620–1390 cm−1 [42]. Most of the ring modes are altered and
missing by the substitutions to aromatic ring of naphthalene.
Generally the C–C stretching vibrations in aromatic compounds
form the strong bands. Govindarajan et al. [43] reported the C–C
stretching vibrations at 1564, 1490, 1417, 1340, 1261, 1212 and
1114 cm−1 experimentally and at 1570, 1496, 1424, 1354, 1269,
1213, 1120 cm−1 theoretically for the naphthalene ring. Naphtha-
lene CH stretching vibrations are reported in the IR spectrum at
3259, 3171, 3067, 3057 and 3046 cm−1 as weak bands and the
corresponding Raman band is observed at 3058 cm−1 as strong
band as expected [44,45]. Krishnakumar et al. [46] reported 1055,
1037, 778, 742, 690, 675, 538, 488, 458, 355, 298, 257 cm−1 as in-
plane and out-of-plane ring deformation bands of naphthalene ring.
Ravikumar et al. [47] reported Raman bands at 1440, 1420 and
1141 cm−1 and the IR bands at 1440, 1424, 1238, 1187, 1147 and
1140 cm−1 correspond to the naphthalene C–H in-plane bending
modes, which are mixed with other vibrational modes. In 1-
substituted naphthalene derivatives, the CH out-of-plane bending
vibrations occur at 810–785 cm−1 due to three adjacent hydrogen
atoms on the ring, and at 780–760 cm−1 for four adjacent hydrogen
atoms [44]. In 1-substitued naphthalenes, the ring C–C stretch-
ing vibrations normally appear in the region 1580–1300 cm−1
[44,45,48]. Arivazhagan et al. [42] reported the naphthalene ring

A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
37
stretching modes at 1684, 1605, 1590, 1532, 1519, 1490, 1420,
1297, 1286, 1256, 1231 and 1208 cm−1. Sellers et al. [49] reported
354, 505, 512, 626, 757, 792, 940, 1003, 1023, 1137, 1156, 1158,
1170, 1204, 1255, 1272, 1341, 1385, 1391, 1458, 1515, 1590, 1595,
1644 cm−1 as the in-plane modes and 172, 188, 387, 471, 480,
622, 705, 773, 777, 825, 879, 952, 969, 981, 987 cm−1 as out-of-
plane modes of the naphthalene ring. For the title compound, the
naphthalene ring stretching modes are assigned at 1624, 1540,
1229 cm−1 in the IR spectrum, 1621, 1591, 1510, 1346, 1226 cm−1
in the Raman spectrum and at 1620, 1582, 1554, 1515, 1361, 1340,
1223, 1196, 1033, 1014 cm−1 theoretically (B3LYP). The CH in-plane
deformations of the naphthalene ring are observed at 1177 cm−1
in the IR spectrum and at 1438, 1466 cm−1 in the Raman spec-
trum, whereas the B3LYP calculations give these modes at 1154,
1177, 1250, 1274, 1396, 1443 and 1463 cm−1. The out-of-plane CH
deformations of the naphthalene ring are assigned in the range of
735–1000 cm−1 theoretically (B3LYP). The ring stretching modes of
the naphthalene ring for the title compound are in good agreement
with the literature [44,50].
the bonds C1–C2, C11–C14, C5–C6, C14–C15 and C10–C15 are double
in two of the structures, the other are double in only one [51]. Jas
et al. [52] showed that the C14–C11, C4–C3, C11–C4 and C2–C3 bond
˚
lengths were 1.409, 1.358, 1.421, 1.417 A, respectively and also
the geometrical parameters reported in the literature [1,53,54] are
very close to our calculated data.
The calculated dihedral angles C15–C10–C3–C2 (179.8◦),
C1–C2–C3–C10
(−179.7◦),
C14–C11–C4–C5
(−179.3◦)
and
C6–C5–C4–C11 (−179.9◦) show that the naphthalene ring
is coplanar. For the naphthalene ring, the bond angles
are
C2–C3–C10 = 120.8,
15–C14–C11 = 121.5,
C5–C6–C1 = 120.7,
C6–C1–C2 = 119.7,
C3–C10–C15 = 120.9,
C14–C11–C4 = 119.7,
C1–C2–C3 = 121.0,
C10–C15–C14 = 120.0,
C11–C4–C3 = 118.2,
C
C3–C4–C5 = 117.7, C5–C4–C11 = 124.1◦ where as the corresponding
reported values are 120.4, 120.4, 120.3, 121.6, 120.4, 120.3, 120.3,
121.3, 119.3, 119.0, 121.6 [46]. Loughrey et al. [55] reported the
bond lengths, S31–O32 = 1.4337, S31–O33 = 1.4256, S31–N34 = 1.6051,
˚
S31–C28 = 1.7737, C21–N20 = 1.4212, C18–N20 = 1.2712 A, whereas
the corresponding values for the title compound are, 1.6355,
˚
The benzene ring possesses six ring stretching vibrations of
which the four with the highest wavenumbers occurring near 1600,
1580, 1490 and 1440 cm−1 are good group vibrations [31]. With
heavy substituents, the bands tend to shift to some what lower
wavenumbers, and the greater the number of substituents on the
ring, the broader the absorption regions [31]. In the case of C O sub-
stitution, the band near 1490 cm−1 can be very weak [31]. The fifth
ring stretching vibration is active near 1315 65 cm−1, a region
that overlaps strongly with that of the CH in-plane deformatin
[31]. The sixth ring stretching vibration, the ring breathing mode,
appears as a weak band near 1000 cm−1 in mono, 1,3-di and 1,3,5-
trisubstituted benzenes. In the otherwise substituted benzenes,
however, this vibration is substituent sensitive and difficult to dis-
tinguish from the other modes. The ring stretching modes of the
phenyl ring are assigned at 1316, 1391, 1478, 1559, 1574 cm−1
theoretically (B3LYP). According to literature [33] for para substi-
tuted benzenes, the ring breathing mode is expected in the interval
1050–1100 cm−1, and in the present case the band at 1086 in the
IR, 1092 in Raman and 1088 cm−1 (B3LYP) is assigned as the ring
breathing mode of the para substituted phenyl ring PhII. Panicker
et al. [33] reported 1062 (IR) and 1061 cm−1 (DFT) as ring breathing
mode of para substituted phenyl rings. The in-plane and out-of-
plane CH deformations are assigned theoretically (B3LYP) at 1300,
1182, 1109, 1047 cm−1 and 984, 955, 840, 819 cm−1, respectively.
For the title compound, these bands are observed at 1302, 821 in
the IR and 1305, 1186, 1050, 818 cm−1 in the Raman spectrum. The
CH stretching modes of the phenyl ring are observed at 3143 and
3125 cm−1 in the Raman spectrum and the theoretical values are
3120, 3113, 3106 and 3094 cm−1 (B3LYP).
1.6380, 1.8057, 1.8634, 1.4056 and 1.2955 A.
Petrov et al. [56] reported the molecular structure and
conformations of benzenesulfonamide by gas electron diffrac-
tion and quantum chemical calculations and according to their
results, the bond lengths, CS, SN, SO vary in the range of
˚
1.7756–1.7930, 1.6630–1.6925, 1.4284–1.4450 A and the bond
angles, CSN, CSO, NSO, HNS, HNH vary in the range, 103.9–107.1,
107.6–107.8, 105.5–107.7, 111.0–113.7, 112.6–113.6◦. These val-
ues are in agreement with the corresponding values for the
title compound. Lasibal et al. [57] reported the bond lengths
SO = 1.4269–1.4291, SN = 1.6202, SC = 1.7582, N38–C36 = 1.4103,
˚
N37–C36 = 1.2723, N34–C36 = 1.3483 A, whereas the corresponding
values in the present case are 1.6355–1.6380, 1.8057, 1.8634,
˚
1.3882, 1.2817, 1.4283 A.
At C11 position, the bond angles C4–C11–C14, C4–C11–C18 and
C
14–C11–C18 are 119.7, 121.5 and 118.8◦, respectively. This asym-
metry in angles reveals the interaction between azomethane
and the phenyl groups. At C21 position, the exocyclic angles
C
22–C21–N20 is increased by 2.7◦ and C23–C21–N20 is reduced
by 2.3◦ from 120◦ which reveals the interaction between
N20 and H25 atoms. At C28 position C26–C28–S31 = 118.0 and
C24–C28–C26 = 123.4◦, which shows the interaction between SO2
group with H30 atom. At N34 position, S31–N34–H35 is reduced by
6.5◦ and S31–N34–C36 is increased by 2.3◦ from 120◦ which shows
the interaction between H35 and O32
.
The C18–N20 moiety is slightly tilted from the naphthalene ring
as is evident from the torsion angles, C3–C4–C11–C18 = −179.1,
C4–C11–C18–N20 = −177.5,
C15–C14–C11–C18 = 179.3,
C
14–C11–C18–N20 = 2.9◦ and is more tilted from the para
substituted phenyl ring PhII as is evident from the tor-
sion angles, C24–C22–C21–N20 = 178.4, C22–C21–N20–C18 = 41.4,
4.2. Geometrical parameters and first hyperpolarizability
C
26–C23–C21–N20 = −179.2
and
C23–C21–N20–C18 = −141.1◦.
No X-ray crystallographic data of the title compound
have yet been reported to best of our knowledge. However,
the theoretical results (B3LYP) obtained are almost com-
parable with the reported structural parameters of similar
derivatives. Govindarajan et al. [43] reported C1–C2 = 1.3792,
C1–C6 = 1.4123, C2–C3 = 1.4238, C3–C4 = 1.4388, C3–C10 = 1.4467,
C4–C5 = 1.4207, C4–C11 = 1.4190, C5–C6 = 1.3746, C10–C15 = 1.3897,
The torsion angles
S31–N34–C36–N38 = −146.1
and
S31–N34–C36–N37 = 36.9◦, which shows that the N38 and N37
atoms are in different planes.
For the title compound, the DFT calculations give the
bond
angles,
C28–S31–O33 = 110.9,
C28–S31–O32 = 107.7,
S31–N34–H35 = 113.5, O33–S31–O32 = 119.4, O33–S31–N34 = 106.3,
O32–S31–N34 = 111.8, N34–S31–C28 = 98.8, C21–N20–C18 = 122.1,
S31–C28–C26 = 118.0, S31–C28–C24 = 118.6, C28–C26–C23 = 118.1,
˚
C11–C14 = 1.3739, C14–C15 = 1.4090 A for naphthalene derivatives.
Unlike benzene, the C–C bonds in the naphthalene are not of the
C
N
26–C23–C21 = 120.5, C23–C21–C22 = 119.6, N20–C21–C22 = 122.7,
same length. For the title compound, the bonds C1–C2, C11–C14
C5–C6, C10–C15, and C14–C15 are 1.3784, 1.3941, 1.3816, 1.3820,
,
20–C21–C23 = 117.7, C21–C22–C24 = 120.4, N20–C18–C11 = 122.3◦,
whereas the corresponding reported values are, 106.5, 107.4, 110.0,
119.5, 106.1, 107.7, 109.3, 118.8, 120.5, 119.1, 120.4, 119.9, 120.3,
119.3, 122.4, 118.2, 120.4, 124.4◦ [55]. The values of the bond angles
˚
1.4081 A in length, whereas the other C–C bonds lie in the range of
˚
1.4171–1.4436 A. This difference, which was established by X-ray
diffraction, in consistent with the valence bond modes of bonding
in naphthalene that involves three resonance structures where as
O
33–S31–O32 = 118.6, O32–S31–N34 = 108.9, O33–S31–N34 = 104.9,
O33,32–S31–C28 = 107.9–108.3, N34–S31–C28 = 107.9, C36–N34–S31

38
A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
= 123.0◦ reported by Lasibal et al. [57] are in agreement
with our values. Loughrey et al. [55] reported the torsion
5. Conclusion
angles,
O33–S31–C28–C26 = −142.0,
O33–S31–C28–C24 = 38.5,
The FT-IR and FT-Raman spectrum of the title compound were
recorded and analyzed. The molecular geometry and vibrational
wavenumbers were calculated using HF and DFT methods and the
optimized geometrical parameters (B3LYP) are in agreement with
that of reported similar derivatives. Potential energy surface scan
studies have been carried out to understand the stability of pla-
nar and non planar structures of the molecule. The calculated first
hyperpolarizability is comparable with the reported value of sim-
ilar derivative and may be an attractive object for further studies
of non linear optics. The predicted infrared intensities and Raman
activities are reported.
O32–S31–C28–C26 = −12.8, O32–S31–C28–C24 = 167.7, N34–S31–C28
–C26 = 103.8, N34–S31–C28–C24 = −75.7, C18–N20–C21–C23 = 143.9,
C
18–N20–C21–C22 = −39.2, C21–N20–C18–C11 = 117.6, S31–C28–C26
–C23 = −179.9, C24–C28–C26–C23 = −0.4, S31–C28–C24–C22 = 179.2,
C
26–C23–C21–N20 = 178.1, N20–C21–C22–C24 = −178.6, N20–C18–C11
–C14 = 8.1, N20–C18–C11–C4 = −172.6◦. For the title compound, the
corresponding torsion angles are 138.3, −40.2, 5.9, −172.6, −110.4,
71.1, −141.1, 41.4, −175.5, −179.6, −1.2, 178.9, −179.2, 178.4, 2.9,
−177.5◦.
There has been growing interest in using organic materials for
nonlinear optical (NLO) devices, functioning as second harmonic
generators, frequency converters, electro-optical modulators, etc.
because of 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. The organic com-
pound showing high hyperpolarizability are those containing an
electron-donating group and an electron withdrawing group inter-
acting through a system of conjugated double bonds. In the case
of sulfonamides, the electron withdrawing group is the sulfonyl
group [58,59]. Nonlinear optics deals with the interaction of applied
electromagnetic fields in various materials to generate new elec-
tromagnetic fields, altered in wavenumber, phase, or other physical
properties [60]. Organic molecules able to manipulate photonic sig-
nals efficiently are of importance in technologies such as optical
communication, optical computing, and dynamic image process-
ing [61,62]. In this context, the dynamic first hyperpolarizability of
the title compound is also calculated in the present study. The first
hyperpolarizability (ˇ0) of this novel molecular system is calculated
using B3LYP/6-31G(d) 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 × 3 × 3 matrix. The 27 compo-
nents of the 3D matrix can be reduced to 10 components due to the
Kleinman symmetry [63]. The components of ˇ are defined as the
coefficients in the Taylor series expansion of the energy in the exter-
nal electric field. When the electric field is weak and homogeneous,
this expansion becomes,
Acknowledgment
One of the authors TKM thanks KSCSTE for a research grant.
References
[1] A. Srivastava, V.B. Singh, Indian J. Pure Appl. Phys. 45 (2007) 714–720.
[2] Y. Guo, Y. Xue, X. De Zhu, Y. Guo Sen, J. Mol. Struct. Theochem. 820 (2007)
40–47.
[3] M.R. Jalilian, M. Zahedi-Tabrizi, Spectrochim. Acta 69A (2008) 278–281.
[4] M.Z. Tabrizi, S.F. Tayyari, F. Tayyari, M. Behforouz, Spectrochim. Acta 60A (2004)
111–120.
[5] V. Librando, D.S. Fazzino, Chemosphere 27 (1993) 1649–1654.
[6] F. Castelli, V. Librando, M.G.A. Sarpietro, Environ. Sci. Technol. 36 (2002)
2717–2723.
[7] D. Hoffmann, E.L. Wynder, A.C. Stern (Eds.), Air Pollution, vol. 2, Academic Press,
New York, 1977, pp. 361–455.
[8] M. Nordquist, D.R. Thakker, H. Yagi, R.E. Lehr, A.W. Wood, W. Levin, A.H.
Connery, D.M. Jerina, R.S. Bhatnagar (Eds.), Molecular Basis of Environmental
Toxicity, Ann Arbor Science Publisher, Ann Arbor, MI, 1980, pp. 329–357.
[9] R.G. Harvey, Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenic-
ity, Cambridge University Press, Cambridge, UK, 1991.
[10] S. Motta, C. Federico, S. Saccone, V. Librando, P. Mossesso, Mutat. Res. 561 (2004)
45–52.
[11] S.A. Tilles, Southern Med. J. 94 (2001) 817–824.
[12] C.G. Slatore, S. Tilles, Immun. Allerg. Clin. N. Am. 24 (2004) 477–490.
[13] C.C. Brackett, H. Singh, J.H. Block, Pharmacotherapy 24 (2004) 856–870.
[14] E. Eroglu, Int. J. Mol. Sci. 9 (2008) 181–197.
[15] A.M. Badawi, H. El-Sharkawy Ali, D.A. Ismail, Aust. J. Basic Appl. Sci. 2 (2008)
301–309.
[16] Z. Guo, P.J. Sadler, Angew Chem. Int. Ed. Engl. 38 (1999) 1512–1531.
[17] R.X. Yuan, R.G. Xiong, Z.F. Chen, P. Zhang, H.X. Ju, Z. Dai, Z.J. Guo, H.K. Fun, X.Z.
You, J. Chem. Soc., Dalton Trans. 6 (2001) 774–776.
[18] T.H. Maren, Annu. Rev. Pharmacol. Toxicol. 16 (1976) 309–327.
[19] C.T. Supuran, A. Scozzafava, A. Mastrolorenzo, Exp. Opin. Ther. Pat. 111 (2000)
221–259.
ꢀ
ꢀ
ꢀ
1
2
1
6
E = E0
−
ꢃiFi −
˛ijFiFj −
ˇijkFiFjFk
−
[20] A.E. Boyd, Diabetes 37 (1988) 847–850.
[21] T. Owa, T. Nagasu, Exp. Opin. Ther. Pat. 10 (2000) 1725–1740.
[22] C.W. Thornber, Chem. Soc. Rev. 8 (1979) 563–580.
i
ij
ijk
ꢀ
1
24
[23] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson,
H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian,
J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J.
Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A.
Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels,
M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman,
J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A.
Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham,
C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen,
M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03 Revision C.02, Gaussian, Inc.,
Wallingford, CT, 2004.
[24] J.B. Foresman, in: E. Frisch (Ed.), Exploring Chemistry with Electronic Structure
Methods: A Guide to Using Gaussian, Gaussian, Pittsburg, PA, 1995.
[25] J.M.L. Martin, C. Van Alsenoy, GAR2PED, in: A Program to obtain a Potential
Energy Distribution from a Gaussian archive record, University of Antwerp,
Belgium, 2007.
[26] P. Flukiger, H.P. Luthi, S. Portmann, J. Weber, MOLEKEL 4. 3, Swiss Centre for
Scientific Computing, Manno, Switzerland, 2000–2002.
[27] S. Portmann, H.P. Luthi, Chimia 54 (2000) 766–770.
ꢁijklFiFjFkFl + · · ·
ijkl
where E0 is the energy of the unperturbed molecule, Fi is the field
at the origin, ꢃi, ˛ij, ˇijk and ꢁijkl are the components of dipole
moment, polarizability, the first hyperpolarizabilities, and second
hyperpolarizibilites, respectively. The calculated first hyperpolariz-
ability of the title compound is 31.1 × 10−30 esu, which comparable
with the reported values of similar derivatives, but experimen-
tal evaluation of this data is not readily available. Kucharski et al.
[64] reported the first hyperpolarizability of certain sulfonamide
amphiphiles by calculation and hyper-Rayleigh scattering in the
range 0.2156–0.189 × 10−30 esu. The C36–N34 and C36–N38 bond
lengths in the calculated molecular structures vary from 1.4283
˚
to 1.3882 A which are intermediate between those of a C–N single
bond (1.48) and a C N double bond (1.28). Therefore, the calcu-
lated data suggest an extended ␲-electron delocalization over the
sulfaguanidine moiety which is responsible for the nonlinearity of
the molecule [65,66]. We conclude that the title compound is an
attractive object for future studies of nonlinear optical properties.
[28] I. Yalcin, E. Sener, O. Ozden, A. Aking, Eur. J. Med. Chem. 25 (1990) 705–708.
[29] R. Saxena, L.D. Kaudpal, G.N. Mathur, J. Polym. Sci. A: Polym. Chem. 40 (2002)
3959–3966.
[30] R.M. Silverstein, F.X. Webster, Spectrometric Identification of Organic Com-
pounds, 6th ed., Wiley, Singapore, 2003.

A. Chandran et al. / Spectrochimica Acta Part A 87 (2012) 29–39
39
[31] N.P.G. Roges, A Guide to the Complete Interpretation of the Infrared Spectra of
Organic Structures, Wiley, New York, 1994.
[48] F.R. Dollish, W.G. Fateley, F.F. Bentley, Characteristic Raman Frequencies of
Organic Compounds, Wiley, New York, 1974.
[32] N.B. Colthup, L.H. Daly, S.E. Wiberly, Introduction to Infrared and Raman Spec-
troscopy, Academic Press, New York, 1990.
[33] C.Y. Panicker, H.T. Varghese, K.C. Mariamma, K. John, S. Mathew, J. Vinsova, C.
Van Alsenoy, Y.S. Mary, J. Raman Spectrosc. 41 (2010) 707–716.
[34] L.J. Bellamy, The IR spectra of Complex Molecules, John Wiley and Sons, New
York, 1975.
[35] A. Spire, M. Barthes, H. Kallouai, G. De Nunzio, Physics D 137 (2000) 392–401.
[36] M. Barthes, G. DeNunzio, G. Ribet, Synth. Met. 76 (1996) 337–340.
[37] B. Wang, H.Z. Ma, Inorg. Chem. Commun. 4 (2001) 248–251.
[38] N. Henry, M. Lagrenee, F. Abraham, Inorg. Chem. Commun. 11 (2008)
1071–1074.
[39] C. Topacli, A. Topacli, J. Mol. Struct. 644 (2003) 145–150.
[40] Z.H. Chohan, M.H. Youssoufi, A. Jarrahpour, T.B. Hadda, Eur. J. Med. Chem. 45
(2010) 1189–1199.
[41] A. Hangen, A. Bodoki, L. Opren, G. Alznet, M. Liu-Gonzalez, J. Borras, Polyhedron
29 (2010) 1305–1313.
[42] M. Arivazhagan, V. Krishnakumar, R.J. Xavier, V. Ilango, K. Balachandran, Spec-
trochim. Acta 72A (2009) 941–946.
[43] M. Govindaraja, K. Gansan, S. Periandy, S. Mohan, Spectrochim. Acta 76A (2010)
12–21.
[44] G. Socrates, Infrared and Raman Characteristic Group Freuencies Tables and
Charts, 3rd ed., Wiley, Chichester, 2001.
[49] H. Sellers, P. Pulay, J.E. Boggs, J. Am. Chem. Soc. 107 (1985) 6487–6494.
[50] R.L. Peesole, L.D. Shield, I.C. McWilliam, Modern Methods of Chemical Analysis,
Wiley, New York, 1976.
[51] http://en.wikipedia.org/wiki/naphthalene.
[52] G.S. Jas, K. Kuczera, Chem. Phys. 214 (1997) 229–241.
[53] V. Krishnakumar, N. Prabavathi, S. Muthunatesan, Spectrochim. Acta 69A
(2008) 528–533.
[54] V. Krishnakumar, R. Mathammal, S. Muthunatesan, Spectrochim. Acta 70A
(2008) 201–209.
[55] B.T. Loughrey, M.L. Williams, P.C. Healy, Acta Cryst. E65 (2009) o2087–o2096.
[56] V. Petrov, V. Petrova, G.V. Girichev, H. Oberhammer, N.I. Giricheva, S. Ivanor, J.
Org. Chem. 71 (2006) 2952–2956.
[57] E. Lasibal, L. Rodriguez, A. Sousa-Pedrares, M. Alonso, A. Vizoso, J.
Romero, J.A. Garcia-Vazquez, A. Sousa, J. Organomet. Chem. 691 (2006)
1321–1332.
[58] X. Liu, L. Liu, X. Lu, J. Zheng, W. Wang, Y. Fang, Thin Solid Films 217 (1992)
174–177.
[59] Y. Miyamoto, K. Kaifu, T. Koyano, M. Saito, M. Kato, Thin Solid Films 210–211
(1992) 178–181.
[60] Y.R. Shen, The Principles of Nonlinear Optics, Wiley, New York, 1984.
[61] P.V. Kolinsky, Opt. Eng. 31 (1992) 1676–1684.
[62] D.F. Eaton, Science 253 (1991) 281–287.
[45] D.L. Vein, N.B. Colthup, W.G. Fateley, JG.grasselli The Handbook of Infrared and
Raman Characteristic Frequencies of Organic Molecules, Academic Press, New
York, 1991.
[46] V. Krishnakumar, R. Mathemmal, S. Muthunatesan, Spectrochim. Acta 70 (2008)
210–216.
[63] D.A. Kleinman, Phys. Rev. 126 (1962) 1977–1979.
[64] S. Kucharski, R. Janik, P. Kaatz, J. Mater. Chem. 9 (1999) 395–401.
[65] Y.P. Tian, W.T. Yu, C.Y. Zhao, M.H. Jiang, Z.H. Cai, H.K. Fun, Polyhedron 21 (2002)
1217–1222.
[66] E. Koscien, J. Sanetra, E. Gondek, B. Jaroz, I.V. Kityk, J. Ebothe, A.V. Kityk, Spec-
trochim. Acta 61 (2005) 1933–1938.
[47] C. Ravikumar, L. Padmaja, I.H. Joe, spectrochim. Acta 75A (2010) 859–866.