Vibrational spectra and computational study of 3-amino-2-phenyl quinazolin-4(3H)-one

Article abstract of DOI:10.1016/j.molstruc.2009.10.026

FT-Raman and FT-IR spectra of 3-amino-2-phenyl quinazolin-4(3H)-one were recorded and analyzed. The vibrational wavenumbers of the title compound have been computed using the Hartree-Fock/6-31G* and B3LYP/6-31G* basis sets and compared with the experiment

Full text of DOI:10.1016/j.molstruc.2009.10.026

Journal of Molecular Structure 963 (2010) 137–144
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Vibrational spectra and computational study of 3-amino-2-phenyl
quinazolin-4(3H)-one
b
c
d
e
C. Yohannan Panicker a, , Hema Tresa Varghese , K.R. Ambujakshan , Samuel Mathew , Subarna Ganguli ,
*
Ashis Kumar Nanda f, Christian Van Alsenoy g, Y. Sheena Mary h
a Department of Physics, TKM College of Arts and Science, Kollam, Kerala 691005, India
b Department of Physics, Fatima Mata National College, Kollam, Kerala 691001, India
c Department of Physics, MES Ponnani College, Ponnani South, Malappuram, Kerala, India
d Department of Physics, Mar Thoma College, Thiruvalla , Kerala 689103, India
e Calcutta Institute of Pharmaceutical Technology and Allied Health Sciences, Banitabla, Uluberia, Howrah-711316, West Bengal, India
f Department of Chemistry, North Bengal University, Raja Rammohunpur, Siliguri 734013, West Bengal, India
g University of Antwerp, Chemistry Department, Universiteitsplein 1, B2610 Antwerp, Belgium
h Thushara, Neethinagar-64, Pattathanam, Kollam, Kerala, India
a r t i c l e i n f o
a b s t r a c t
Article history:
FT-Raman and FT-IR spectra of 3-amino-2-phenyl quinazolin-4(3H)-one were recorded and analyzed. The
vibrational wavenumbers of the title compound have been computed using the Hartree–Fock/6-31G* and
B3LYP/6-31G* basis sets and compared with the experimental data. The prepared compound was iden-
tified by NMR and mass spectra. The red shift of the NH stretching wavenumber indicates the weakening
of the NH bond. The simultaneous IR and Raman activation of the C@O stretching mode gives the charge
Received 8 September 2009
Received in revised form 15 October 2009
Accepted 15 October 2009
Available online 20 October 2009
transfer interaction through a
p-conjugated path. The first hyperpolarizability, Infrared intensities and
Keywords:
Quinazoline
IR
Raman
HF
Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported
values of similar derivatives and is an attractive object for future studies of non-linear optics. The assign-
ments of the normal modes are done by potential energy distribution (PED) calculations. Optimized geo-
metrical parameters of the title compound are in agreement with reported similar structures.
Ó 2009 Elsevier B.V. All rights reserved.
DFT calculations
PED
1. Introduction
Compounds possessing all three activities are not common. Quina-
zolines and quinazoline derivatives exhibit potent antimicrobial
Quinazolines are frequently used in medicine because of their
wide spectrum of biological activities [1]. Compounds containing a
fused quinazoline or isoquinoline ring belong to a broad class of
compounds that has received a considerable attention over the past
years due to their wide range of biological activities [2,3]. Some of
the aminoquinazoline derivatives were found to be inhibitors of
the tyrosine kinase [4,5] or dihydrofolate reductase enzymes [6,7]
and so they work as potent anticancer agents. They are also used
to design medicines against hypertension and malaria and to fight
infections involving acquired immune deficiency syndrome (AIDS)
[8]. Among a wide variety of nitrogen heterocycles that have been
explored for developing pharmaceutically important molecules,
the quinazolines have played an important role in the medicinal
chemistry and subsequently emerged as a pharamacophore [9]. In
normal practice, three groups of agents (chemotherapeutic, analge-
sic and anti-inflammatory) are prescribed simultaneously.
[10] and central nervous systems activities such as anti-inflamma-
tory [11] and anticonvulsant [12]. Anti-tumor activities are also re-
ported for 2,3-dihydro-2-aryl-4-quinazolines [13,14]. Several
quinazoline derivatives have been reported for their antibacterial,
antifungal, anti-Human Immunodeficiency Virus (HIV) [15,16],
anthelmintic [17], central nervous system depressant [18], antitu-
bercular[19], hypotensive [20], anticonvulsant [21], anti-fibrillatory
[22], diuretic [23] and antiviral activities [24–26]. Some reports have
suggested that 2-styrylquinazolin-4-ones [27,28] could be effective
inhibitors of tubulin polymerization. The 2,3-disubstituted quin-
azolones have been predicted to possess antiviral and antihyperten-
sive activities [29]. Synthesis of vascinone, a naturally occurring
bioactive alkaloid having a quinazolone system, has been reported
recently [30]. Quinazolines are widely used for the extraction and
analytical determination of metal ions. Nitraquazone, a quinazoline
derivative, has been found to possess potent phosphodiesterase
inhibitory activity [31] which is potentially useful in the treatment
asthma [32]. Alagarsamy et al. [33] have reported the synthesis
and analgesic, anti-inflammatory and antibacterial activities of
* Corresponding author.
E-mail address: cyphyp@rediffmail.com (C.Y. Panicker).
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.10.026

138
C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
some novel 2-phenyl-3-substituted quinazolin-4(3H)-ones. Costa
et al. [34] reported the synthesis of 4H-3,1-benzoxazines, quinazo-
lin-2-ones and quinoline-4-ones by palladium-catalyzed oxidative
carbonylation of 2-ethynylaniline derivatives. These nitrogen het-
erocycles can be used as valuable intermediates for the preparation
of dye stuffs [34] and pharmaceutical products [35–37] since they
exhibit a wide range of biological activities. Nanda et al. [38]
reported the antibacterial activity and QSAR studies of some 3-{ary-
lideneamino}-2-phenyl quinazoline-4(3H)-ones. The three dimen-
sional quantitative structure activity relation (QSAR) studies for
one large set of quinazoline type epidermal growth factor receptor
(EGF-R) inhibitors were conducted using two types of molecular
field analysis techniques: comparative molecular field analysis and
comparative molecular similarity indices analysis [39]. A number
of reports have shown that a broad class of 4-anilinoquinazolines
are potent and highly selective inhibitors of EGF-R phosphorylation
[4,5,42,40,41]. Chen et al. [42] reported the intramolecular imidate-
amide rearrangement of 2-substituted 4-(chloroalkoxy)quinazoline
derivatives. Quantum mechanical study of the competitive hydra-
tion between protonated quinazoline and Li+, Na+ and Ca2+ ions are
reported by Sawunyama et al. [43]. Various quinazoline derivatives
interrupted pregnancy by 40–50% and shows anti-implantation
activity and also used in contraceptive compositions [44]. The pres-
ent study is on the analysis of FT-IR and FT-Raman spectra of 3-ami-
no-2-phenyl quinazolin-4(3H)-one and using the computational
method, theoretically the wavenumbers were calculated. This work
is a part of our investigations of substituted quinazoline derivatives.
The authors have reported the spectroscopic studies of 3-{[(2-
hydroxyphenyl)methylene]amino}-2-phenylquinazolin-4(3H)-one
[45] and 3-{[(4-fluorophenyl)methylene]-2-phenylquinazolin-4(3H)-
one [46].
Fig. 1. FT-IR spectrum of 3-amino-2-phenyl quinazolin-4(3H)-one (a) experimental
(b) theoretical – B3LYP.
2. Experimental
To an ethanolic solution of 2-phenyl-3,1-benzoxazin-4(3H)-one
(1 g, 4.22 mmole) hydrazine hydrate (98%, 1.5 ml) was added and
the mixture was heated in a water bath for about 3 h. The flask
containing the reaction mixture was cooled and the solid thus
formed was filtered and washed with water. The air dried product
was re-crystallized from ethanol. Purity of the compound was
checked by thin layer chromatography, using benzene and ethyl
acetate as mobile phase in the ration 7:3. Iodine vapour was used
as detecting agent. Yield was found to be 87%. Melting point was
determined in open capillary tubes on a Thomas Hoover apparatus
and was uncorrected. m.p. 177–180 °C. Mass spectra recorded on a
FAB, JOEL SX 102 mass spectrometer and NMR spectra were re-
corded on a Bruker-Avance 300 MHz FT-NMR spectrometer, sol-
vent CDCl3, TMS internal standard, the peak assignments——
were done on the basis of TOCSY, COSY and HSQC(HETCORR) spec-
tra in addition to 13C-spectra; the assigned proton shifts d (ppm):
H8, 8.33, H10, 7.78, H7, 7.78, H9, 7.52, H15,17, 7.78, H19,20,
7.52, N–H–H bonded, 5.02, N–H free, 1.7; the assigned 13C shifts
d (ppm): C4, 126.39, C5, 129.24, C6, 134.5, C1, 130.2, C12,13,
129.25, C14,16, 129.25, C18, 127.06, C22, 161.6, C3, 120.1, C2,
146.99, C23, 154.6, C11, 134.05. Proton coupling values in Hz:
J8,9, 8.2, J8,10, 1.0, J9,10, 0.0; The other coupling values are not cal-
culated due to close super imposition of the protons. MS(m/z)
238(M + 1), 223(M-14). Anal. Calculated/found: H 4.67/4.63, C
70.87/70.91, N17.71/17.69.
Fig. 2. FT-Raman spectrum of 3-amino-2-phenyl quinazolin-4(3H)-one (a) exper-
imental (b) theoretical – B3LYP.
The FT-IR spectrum (Fig. 1) was recorded on a DR/Jasco FT-IR
spectrometer with KBr pellets. 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, resolution 2 cmꢀ1, mea-
surement on solid sample.
3. Computational details
Calculations of the title compound were carried out with Gauss-
ian03 software program [47] using the HF/6-31G* and B3LYP/6-
31G* basis sets to predict the molecular structure and vibrational

C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
139
Table 1
wavenumbers. Calculations were carried out with Becke’s three
parameter hybrid model using the Lee–Yang–Parr correlation func-
tional (B3LYP) method. Molecular geometries were fully optimized
by Berny’s optimization algorithm using redundant internal coor-
dinates. Harmonic vibrational wavenumbers were calculated using
analytic second derivatives to confirm the convergence to minima
on the potential surface. At the optimized structure (Fig. 3) of the
examined species, no imaginary wavenumber modes were ob-
tained, proving that a true minimum on the potential surface
was found. The DFT hybrid B3LYP functional tends also to overes-
timate the fundamental modes; therefore scaling factors have to be
used for obtaining a considerably better agreement with experi-
mental data. Therefore, a scaling factor of 0.9613 and 0.8929 were
uniformly applied to the B3LYP and HF calculated wavenumbers
[48]. The observed disagreement between theory and experiment
could be a consequence of the anharmonicity and of the general
tendency of the quantum chemical methods to overestimate the
force constants at the exact equilibrium geometry. The potential
energy distribution (PED) is calculated with the help of GAR2PED
software package [49]. Parameters corresponding to optimized
geometry (DFT) of the title compound are given in Table 1.
Optimized geometrical parameters (DFT) of 3-amino-2-phenyl quinazolin-4(3H)-one,
atom labeling is according to Fig. 3.
Bond lengths (Å)
Bond angles (°)
Dihedral angles (°)
C1–C2 1.4115
C1–C6 1.3882
C1–H7 1.0836
C2–C3 1.4164
C2–N24 1.3892
C3–C4 1.4081
C3–C22 1.4513
C4–C5 1.3887
C4–H8 1.0841
C5–C6 1.4126
C5–H9 1.0847
C6–H10 1.0853
C11–C12 1.4103
C11–C13 1.4092
A(2,1,6) 120.0
A(2,1,7) 118.0
A(6,1,7) 122.0
A(1,2,3) 119.1
A(1,2,24) 119.0
A(3,2,24) 121.9
A(2,3,4) 120.4
A(2,3,22) 118.7
A(4,3,22) 120.8
A(3,4,5) 119.7
A(3,4,8) 118.6
A(5,4,8) 121.7
A(4,5,6) 120.1
A(4,5,9) 120.1
A(6,5,9) 119.8
A(1,6,5) 120.7
A(1,6,10) 119.7
A(5,6,10) 119.6
A(12,11,13) 118.9
A(12,11,23) 116.9
A(13,11,23) 124.1
A(11,12,14) 120.7
A(11,12,15) 118.5
A(14,12,15) 120.8
A(11,13,16) 120.1
A(11,13,17) 119.5
A(16,13,17) 120.3
A(12,14,18) 120.1
A(12,14,19) 119.7
A(18,14,19) 120.2
A(13,16,18) 120.6
A(13,16,20) 119.4
A(18,16,20) 120.0
A(14,18,16) 119.6
A(14,18,21) 120.2
A(16,18,21) 120.2
A(3,22,25) 115.0
A(3,22,26) 126.0
A(25,22,26) 119.0
A(11,23,24) 117.5
A(11,23,25) 121.8
A(24,23,25) 120.7
A(2,24,23) 120.3
A(22,25,23) 123.2
A(22,25,27) 115.2
A(23,25,27) 121.5
A(25,27,28) 110.0
A(25,27,29) 106.17
A(28,27,29) 111.1
D(6,1,2,3) ꢀ0.0
D(6,1,2,24) ꢀ179.2
D(7,1,2,3) 179.7
D(7,1,2,24) 0.6
D(2,1,6,5) 0.1
D(2,1,6,10) 179.9
D(7,1,6,5) ꢀ179.7
D(7,1,6,10) 0.2
D(1,2,3,4) ꢀ0.1
D(1,2,3,22) 178.6
D(24,2,3,4) 179.1
D(24,2,3,22) ꢀ2.3
D(1,2,24,23) 179.7
D(3,2,24,23) 0.6
C11–C23 1.4873
D(2,3,4,5) 0.1
D(2,3,4,8) 179.9
C12–C14 1.3949
C12–H15 1.0829
C13–C16 1.3983
C13–H17 1.0805
C14–C18 1.4006
C14–H19 1.0853
C16–C18 1.3990
D(22,3,4,5) ꢀ178.5
D(22,3,4,8) 1.3
D(2,3,22,25) 0.8
D(2,3,22,26) ꢀ179.5
D(4,3,22,25) 179.4
D(4,3,22,26) -0.9
C16–H20 1.0854
D(3,4,5,6) 0.0
4. Results and discussion
C18–H21 1.0855
C22–N25 1.4172
C22–O26 1.2565
C23–N24 1.3155
C23–N25 1.3996
N25–N27 1.4254
N27–H28 1.0201
D(3,4,5,9) ꢀ179.9
D(8,4,5,6) ꢀ179.8
D(8,4,5,9) 0.2
The observed IR and Raman bands with their relative intensities
and calculated (scaled) wavenumbers and assignments are given in
Table 2.
D(4,5,6,1) ꢀ0.1
D(4,5,6,10) ꢀ179.9
D(9,5,6,1) 179.9
D(9,5,6,10) ꢀ0.0
4.1. IR and Raman spectra
N27–H29 1.0214
D(13,11,12,14) 1.2
D(13,11,12,15) ꢀ178.0
D(23,11,12,14) 177.1
D(23,11,12,15) ꢀ2.2
D(12,11,13,16) ꢀ0.5
D(12,11,13,17) ꢀ179.9
D(23,11,13,16) ꢀ176.0
D(23,11,13,17) 4.6
D(12,11,23,24) ꢀ28.09
D(12,11,23,25) 150.1
D(13,11,23,24) 147.5
D(13,11,23,25) ꢀ34.3
D(11,12,14,18) ꢀ1.0
D(11,12,14,19) 179.3
D(15,12,14,18) 178.3
D(15,12,14,19) ꢀ1.5
D(11,13,16,18) ꢀ0.5
D(11,13,16,20) 179.4
D(17,13,16,18) 178.9
D(17,13,16,20) ꢀ1.1
D(12,14,18,16) ꢀ0.0
D(12,14,18,21) ꢀ179.8
D(19,14,18,16) 179.7
D(19,14,18,21) ꢀ0.1
D(13,16,18,14) 0.8
D(13,16,18,21) ꢀ179.4
D(20,16,18,14) ꢀ179.2
D(20,16,18,21) 0.6
D(3,22,25,23) 2.4
D(3,22,25,27) ꢀ178.8
D(26,22,25,23) ꢀ177.3
D(26,22,25,27) 1.5
D(11,23,24,2) ꢀ179.2
D(25,23,24,2) 2.7
D(11,23,25,22) 177.6
D(11,23,25,27) ꢀ1.1
D(24,23,25,22) ꢀ4.3
D(24,23,25,27) 177.0
D(22,25,27,28) 102.4
D(22,25,27,29) ꢀ17.9
D(23,25,27,28) ꢀ78.8
D(23,25,27,29) 160.9
In N- or S-bonded NH2, the asymmetric NH2 stretching vibra-
tion is observed at 3350 40 cmꢀ1 as in hydrazine [50–52], thiose-
micarbazides [53,54], N-aminoheretocyclic aromatic compounds
[55] and sulfonamides [56–59] and the NH2 symmetric stretching
vibration [60] in the region 3250 70 cmꢀ1. In the present case the
DFT calculations give values 3414 and 3306 cmꢀ1 as asymmetric
and symmetric NH2 stretching modes. The NH2 scissoring vibration
give rise to a band in the region 1620 20 cmꢀ1 and the rocking
vibration [60] in the range 1195 90 cmꢀ1. The NH2 scissoring
vibrations are observed at 1647 cmꢀ1 in IR spectrum, 1636 cmꢀ1
Fig. 3. Optimized geometry of 3-amino-2-phenyl quinazolin-4(3H)-one.

140
C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
Table 2
Calculated vibrational wavenumbers (scaled), measured infrared and Raman band positions and assignments for 3-amino-2-phenyl quinazolin-4(3H)-one.
t(HF)
IR
Raman
activity
t(DFT)
IR
Raman
activity
t(IR)
t(Raman)
Assignments of normal modes with PED (%)a
(cmꢀ1
)
intensity
(cmꢀ1
)
intensity
(cmꢀ1
)
(cmꢀ1
)
3457
3363
3047
3036
3034
3027
3021
3017
3006
3005
2998
1772
1669
1640
1621
1615
1589
1550
1493
1474
1455
1438
1346
1314
1313
1288
1276
1238
1208
1193
9.47
1.85
8.07
11.94
10.18
30.07
24.74
22.12
1.53
45.85
94.55
131.70
114.60
203.45
123.94
160.91
92.79
87.92
77.36
30.43
23.87
246.26
166.49
83.76
64.74
8.21
124.40
0.99
32.61
0.71
2.85
66.83
8.00
3414
3306
3150
3121
3115
3110
3096
3094
3081
3079
3070
1675
1614
1605
1594
1571
1551
1515
1489
1463
1462
1443
1351
1343
1333
1318
1306
1285
1245
1220
18.55
10.87
5.30
5.37
15.32
8.89
39.88
16.86
22.33
5.78
55.31
152.98
54.52
58.06
241.82
63.87
268.10
162.01
133.04
78.46
60.32
24.15
13.21
40.96
499.47
88.81
72.31
1521.11
71.56
78.60
113.38
121.33
190.58
90.18
31.85
6.91
105.78
92.41
10.27
t
t
t
t
t
t
t
t
t
t
t
t
asNH2 (99)
sNH2 (100)
C13H17 (98)
C12H15 (93)
3318 vs
3143 w
3125 w
3318 w
C1H7 (57),
C4H8 (58),
t
t
C4H8 (20),
C1H7 (31),
t
t
C6H10 (12),
C5H9 (10)
tC16H20 (21)
tC5H9 (10)
C18H21 (54),
C5H9 (48), C6H10 (25),
C14H19 (50), C16H20 (46)
C5H9 (31)
C16H20 (31), tC14H19 (22)
tC14H19 (21),
t
t
C4H8 (18)
t
t
t
7.89
6.03
C6H10 (61),
C18H21 (45),
C22O26 (63)
0.34
3050 w
1658 s
1647 sh
1603 vs
3070 s
553.04
302.99
138.16
131.56
25.56
8.35
48.82
26.35
91.49
12.13
12.33
95.32
8.32
13.19
25.40
100.54
6.69
29.08
2.85
42.48
271.22
73.24
2.03
14.66
1.27
360.95
14.03
55.58
21.86
22.24
66.03
32.39
21.95
4.42
1660 vs
1636 w
1601 vvs
1584 h
dNH (82),
tC3C22 (13)
t
t
t
t
t
Ph I (55), dCCC I (11)
Ph II (54), dCCC II (10), dCH II (16)
Ph II (61), dCH II (11)
Ph I (67), dCCC I (10), dCH I (15)
C23N24 (64)
1534 vvs
1490 sh
1466 m
1538 m
1449 s
dCH II (59),
dCH I (44),
dCH I (43),
dCH II (50),
tPh II (30)
t
t
Ph I (29)
Ph I (19)
1449 vvs
t
Ph II (22)
t
t
C23N25 (28),
Ph I (68)
cN25H28H29N27 (24), dC22N27N25 (12)
24.04
9.82
17.30
77.38
16.80
0.79
dCH II (38),
tPh II (66)
dNH (64)
dNH (22),
tPh II (12), tPh I (11)
1315 s
1307 s
1284 m
1258 m
11.59
4.97
4.40
1304 vvs
tC23N25 (11), dCH I (10),
t
Ph II (11)
1258 m
1239 m
t
t
t
C2N24 (28),
t
Ph I (14), C11C23 (25)
t
36.76
10.79
C3C22 (13), dCCC I (10), dCH I (15), tC23N24 (10),
C22N25 (10)
1182
1163
1131
1098
1088
1083
1056
1013
1011
1010
1009
988
988
976
971
949
930
891
861
852
0.96
2.00
12.68
24.96
6.63
4.01
1.32
1.37
1.79
0.20
2.01
0.75
1.84
17.83
3.93
42.12
2.57
7.21
12.30
0.32
20.29
2.95
0.69
0.90
0.17
0.09
3.96
54.99
1.75
2.22
3.20
4.18
2.38
2.28
1.22
0.22
0.59
2.94
1193
1188
1176
1163
1111
1099
1084
1030
1020
1000
999
998
983
975
971
940
891
888
875
15.62
60.94
0.21
8.96
16.05
1.93
7.41
4.77
12.55
3.17
0.01
0.26
3.80
2.89
2.08
3.49
19.37
1.76
128.07
5.17
3.51
8.42
152.90
11.70
29.07
44.06
56.93
0.62
19.02
13.10
44.79
0.51
1.54
76.45
3.71
0.25
2.56
5.401
3.65
1.92
7.38
6.81
1.68
0.12
0.75
2.90
dCH II (75),
tN25N27 (39), dCH I (28)
dCH II (86)
dCH I (70)
tPh II (14)
1180 w
1166 w
1140 m
1110 w
1080 w
1029 w
1015 w
1165 s
t
t
t
t
t
C22N25 (15), tPh I (16), dCH I (24)
1108 w
1079 w
1050 m
1029 s
C22N25 (52), dCCC I (22)
Ph II (48), dCH II (31)
Ph II (51), dCCC II (11)
Ph I (55), dCH I (21)
1002 vs
dCCC II (61)
c
c
t
c
c
c
CH I (85),
CH II (79), s
C22N25 (12),
CH II (86)
CH I (90)
s
CCCC I (13)
CCCC II (18)
Ph II (22), dCN27N25 (16)
995 w
t
1.53
19.36
88.94
121.68
4.67
11.33
62.02
33.59
5.42
943 m
903 m
CH II (83)
904 s
dCCC I (39), dQRing (10), dNC11C23 (16)
c
c
c
t
s
s
c
s
CH I (79)
N25H28H29N27 (57),
CH II(98)
N25N27 (10),
QRing (29),
CCCC II (20),
CH I (52),
CCCC I (15),
853 w
tN25N27 (14)
850
831
794
782
775
698
811
799
783
774
826 w
792 w
826 w
798 w
t
c
c
Ph I (20), dCCC I (14)
O26C3N25C22 (22), CCCC I (19)
CH II (15), C23C12C13C11 (14)
QRing (12)
1.63
3.91
82.29
75.01
s
48.47
78.01
10.85
c
755 s
702 vs
758 w
s
CCCC I (15),
s
716
c
C11N25N24C23 (13),
c
CH II (27),
s
CCCC
II (11)
698
696
686
40.96
17.49
2.88
3.23
1.92
6.49
692
687
680
8.53
11.13
0.97
2.58
12.66
4.81
s
s
c
CCCC II (35),
CCCC II (19),
O26C3N25C22 (23),
QRing (13)
dCCC II (40), dCCC I (18), dQRing (18)
s
CCCC I (17),
c
CH II (11)
688 w
666 m
t
N25N27 (14), dCCC I (19), dQRing (16)
C11N25N24C23 (17), CCCC II
c
s
(14),
s
659
635
6.14
17.41
7.73
0.45
673
649
3.58
3.82
9.36
0.27
666 m
638 m
dCCC I (17), dC3O26C22 (15), dN25O26C22 (15),
dNC11C23 (14), dCN27N25 (10)
dCCC II (81)
604
568
540
503
485
438
419
406
385
338
298
0.11
2.53
5.55
4.95
6.04
0.03
2.29
0.29
4.94
2.48
5.14
6.03
2.41
0.47
6.09
0.51
0.20
7.71
1.96
1.83
3.03
0.91
626
583
543
512
473
445
430
410
390
334
301
0.13
1.51
6.68
3.67
1.72
0.23
2.64
3.86
17.51
4.23
0.13
6.88
7.75
1.31
6.42
1.07
0.42
11.95
4.29
2.62
2.35
1.06
618 w
587 w
569 w
531 w
511 w
470 w
440 w
425 w
419 w
dCCC I (44), dQRing (19), dCCC II (12)
sCCCC I (41),
sQRing (15), cCH I (15)
511 w
480 w
dQRing (54), dCCC I (10)
s
s
CCCC II (35),
CCCC I (54),
c
C23C12C13C11 (20),
sCCCC I (10)
s
C4C3C2N24 (16),
sC22C3C2C1 (16)
dQRing (51) ,
CCCC II (78)
dCN27N25 (35), dC3O26C22 (22),
dCC23C11 (28), CCCC I (17), dCN27N25 (20)
CCCC II (15), CCCC I (16), dQRing (32)
tC3C22 (13)
s
396 w
333 w
sCCCC II (18)
s
s
s

C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
141
Table 2 (continued)
t(HF)
IR
Raman
activity
t(DFT)
IR
Raman
activity
t(IR)
t(Raman)
Assignments of normal modes with PED (%)a
(cmꢀ1
)
intensity
(cmꢀ1
)
intensity
(cmꢀ1
)
(cmꢀ1
)
267
250
236
201
2.09
3.66
0.55
7.31
4.34
1.44
2.28
3.89
284
282
262
197
1.49
0.89
1.41
1.10
4.29
4.36
0.47
7.64
s
c
CCCC II (20), dCC23C11 (36), dQRing (30)
N27C22C23N25 (63), QRing (20)
s
270 w
191 s
dCCC I (25), dCC23C11 (20), dCCC II (16)
s
s
s
s
C4C3C2N24 (19),
QRing (19), dCC23C11 (12)
NH(47),
NH(29),
sC22C3C2C1 (19), sCCCC II (16),
181
130
37.44
0.77
2.01
1.23
147
133
30.82
24.67
2.85
4.34
s
c
CCCC I (10)
N27C22C23N25 (15), sQRing (20), sCCCC I
(18)
95
4.71
5.11
110
2.00
11.20
sNH (19), sQRing (19), dNC11C23 (16), dCN27N25
(12)
71
52
31
2.04
0.09
0.14
2.83
2.80
11.99
90
51
38
10.33
0.04
0.12
1.71
1.33
8.16
90 vs
s
s
s
QRing (41), dNC11C23 (13),
QRing (42), C11N25N24C23 (18),
CCC23N (65), dNC11C23 (16), dCC23C11 (14)
s
NH2 (10)
c
cC23C12C13C11 (13)
t, stretching; d, in-plane bending;
c, out-of-plane bending; s, torsion; s, strong; m, medium; w, weak; v, very; br, broad; ortho and mono substituted phenyl rings are
designated as PhI and PhII; QRing, quinazoline ring.
a
PED, potential energy distribution, only contribution larger than 10% were given.
in Raman spectrum and at 1614 cmꢀ1 theoretically. The band ob-
served at 1307 cmꢀ1 in the IR spectrum and 1304 cmꢀ1 in the Ra-
man spectrum is assigned as the rocking mode of NH2 group. The
DFT calculation gives this mode at 1306 cmꢀ1. The wagging vibra-
tion is expected in the region 830 50 cmꢀ1 and torsion [60] in the
region 280 70 cmꢀ1. The DFT calculations give the wagging mode
of NH2 at 875 cmꢀ1. For the title compound the torsional modes of
NH2 are below 400 cmꢀ1. Sundaraganesan et al. [61] reported NH2
vibrations at 1632, 1284, 1223 cmꢀ1 (IR) and 1280, 987 cmꢀ1
(Raman).
et al. [70], at 1121 cmꢀ1 by Bezerra et al. [71] and at 1130 cmꢀ1 by
El-Behery and El-Twigry [72]. Sundaraganesan et al. [61] reported
the
culations give this
t
N–N stretching mode at 1083 cmꢀ1 theoretically. The DFT cal-
t
N–N mode at 1188 cmꢀ1 in the present case
and a weak band is observed at 1180 cmꢀ1 in the IR spectrum.
The existence of one or more aromatic ring in a structure is nor-
mally readily determined from the C–H and C@C–C related vibra-
tions. The C–H stretching occurs above 3000 cmꢀ1 and is
typically exhibited as a multiplicity of weak to moderate bands,
compared with the aliphatic C–H stretch [73] . In the present case,
The carbonyl group is contained in a large number of different
classes of compounds, for which a strong absorption band due to
the C@O stretching vibration is observed in the region [62]
1850–1550 cmꢀ1. If a carbonyl group is part of a conjugated sys-
tem, then the wavenumber of the carbonyl stretching vibration de-
creases, the reason being that the double bond character of the
the DFT calculations give the tCH modes in the range 3150–
3070 cmꢀ1. The bands observed at 3143, 3125, 3050 cmꢀ1 in the
IR spectrum and at 3070 cmꢀ1 in the Raman spectrum were as-
signed as tCH modes of the benzene rings.
The benzene ring possesses six ring stretching vibrations, of
which the four with the highest wavenumbers (occurring near
1600, 1580, 1490 and 1440 cmꢀ1) are good group vibrations. In
the absence of ring conjugation, the band near 1580 cmꢀ1 is usu-
ally weaker than that at 1600 cmꢀ1. The fifth ring stretching vibra-
tion which is active near 1335 35 cmꢀ1 a region which overlaps
strongly with that of the CH in-plane deformation and the intensity
is in general, low or medium high [60]. The sixth ring stretching
vibration or ring breathing mode appears as a weak band near
1000 cmꢀ1 in mono, 1,3-di and 1,3,5-trisubstituted benzenes. In
the other wise substituted benzene, however, this vibration is sub-
stituent sensitive and difficult to distinguish from the ring in-plane
deformation.
In the following discussion, the mono and ortho substituted
phenyl rings are designated as rings II and I, respectively. The
modes in the two phenyl rings will differ in wavenumber and
the magnitude of splitting will depend on the strength of interac-
tions between different parts (internal coordinates) of the two
rings. For some modes, this splitting is so small that they may be
considered as quasi-degenerate and for the other modes a signifi-
cant amount of splitting is observed. Such observations have al-
ready been reported [74–77].
C@O group is less due to the
ized. For the title compound, the
p
-electron conjugation being local-
C@O mode is seen as a strong
t
band at 1658 cmꢀ1 in the IR and at 1660 cmꢀ1 in the Raman spec-
trum. The DFT calculations give this mode at 1675 cmꢀ1. But the
electron-releasing effect in the C@O double bond causes a polariz-
ability change during vibration, making the Raman band intensity
comparable to that of the IR band. Also, here the intra molecular
charge transfer takes place via a conjugated phenyl ring path
which makes the phenyl ring stretching mode at 1603 (IR),
1601 cmꢀ1 (Raman) simultaneously active in the IR and Raman
spectra [63]. The deformation bands of C@O group are also identi-
fied (Table 2).
The C@N stretching skeletal bands [64–66] are observed in the
range 1650–1500 cmꢀ1. For conjugated azines, the
tC@N mode is
reported [67] at 1553 cmꢀ1. For the title compound the band ob-
served at 1534 cmꢀ1 in the IR spectrum and at 1538 cmꢀ1 in the
Raman spectrum is assigned as
t
C@N mode. The B3LYP calcula-
.
tions give this mode at 1515 cmꢀ1
Corresponding to @C–N stretching vibration [62], two bands are
observed in the regions 1360–1250 and 1280–1180 cmꢀ1 for aro-
matic and unsaturated amines. Primary and secondary aromatic
amines absorb strongly in the first region. Primary aromatic
amines with nitrogen directly on the ring absorb at 1330–
1260 cmꢀ1 because of the stretching of the phenyl C–N bond
[68]. The C@N stretching bands are reported in the range [69]
For mono substituted benzene, the tPh modes are expected in
the range of 1285–1610 cmꢀ1 and for the ortho disubstituted ben-
zene [60] these modes are seen in the region 1620–1260 cmꢀ1. The
t
Ph modes are observed at 1603, 1534, 1466 cmꢀ1 in the IR spec-
trum, 1601 cmꢀ1 in the Raman spectrum, 1605, 1551, 1463,
1462, 1343 cmꢀ1 theoretically for ring Ph I and at 1490, 1449,
1315 cmꢀ1 in the IR spectrum, 1584 cmꢀ1 in the Raman spectrum,
1594, 1571, 1489, 1443, 1318 cmꢀ1 theoretically for ring Ph II. Due
to aromatic ring vibrations, quinazolines [62] absorb strongly at
1635–1610, 1580–1565, and 1520–1475 cmꢀ1. In ortho disubstitu-
1100–1300 cmꢀ1. In the present case, the
served at 1258 (IR), 1258 (Raman), 1245 (DFT),
1351 (DFT) and
C22–N25 mode at 1108 (IR), 1110 cmꢀ1 (Raman).
These modes are not pure but contain significant contributions
from other modes.
N–N has been reported at 1115 cmꢀ1 by Crane
t
C2–N24 mode is ob-
C23–N25 mode at
t
t
t

142
C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
tion, the ring breathing mode has three wavenumber intervals
depending on whether both substituents are heavy; or one of them
is heavy, while the other is light; or both of them are light. In the
first case, the interval is 1100–1130 cmꢀ1; in the second case
1020–1070 cmꢀ1; while in the third case it is between [56] 630
and 780 cmꢀ1. The ring breathing modes of the phenyl rings are as-
signed at 1020 cmꢀ1 for ring Ph I and at 983 cmꢀ1 for ring Ph II by
PED calculations.
and C1–C2–N24–C23 = 179.7°) and is more twisted from the phenyl
ring II (N24–C23–C11–C13 = 147.5° and N24–C23–C11–C12 = ꢀ28.1°) as
is evident from the torsion angles.
For a quinazoline derivative, Krishnakumar and Muthunatesan
[85] reported the bond lengths N24–C23, C23–N25, C22–C3, C3–C4,
C4–C5, C5–C6, C6–C1, C1–C2 as 1.311, 1.362, 1.427, 1.414, 1.380,
0
1.415, 1.380, 1.416 ÅA . In the present study the corresponding val-
ues are0 1.3155, 1.3996, 1.4513, 1.4081, 1.3887, 1.4126, 1.3882,
The in-plane CH vibrations are expected in the range of 1015–
1300, 1010–1300 cmꢀ1 for mono and ortho substituted benzenes,
respectively [60]. Generally, the CH out-of-plane deformations
with the highest wavenumbers have a smaller intensity than those
absorbing at lower wavenumbers. Most of the deformation bands
of the CH vibrations of the phenyl rings are not pure but contain
significant contributions for other modes (Table 2). The out-of-
plane CH deformation at 702 cmꢀ1 and the in-plane ring deforma-
tion at 666 cmꢀ1 form a pair of strong bands characteristics of
mono substituted benzene derivatives [78]. In the case of 1,2-di
substitution only one strong absorption in the region
1.4115 ÅA. The DFT calculations give the bond angles N24–C23–N25,
C23–N25–C22, N25–C22–C3, C22–C3–C4, C3–C4–C5, C4–C5–C6, C5–C6–
C1, C6–C1–C2 as 120.7°, 123.2°, 115.0°, 120.8°, 119.7°, 120.1°,
120.7°, 120.0°, respectively, where as the corresponding reported
values are 127.7°, 123.4°, 116.2°, 124.4°, 119.5°, 120.3°, 120.9°
and 120.1°, respectively [85]. Sundaraganesan et al. [61] reported
the bond lengths N25–N27 = 1.403, N27–H28 = 1.018, N27
–
0
H29 = 1.018 ÅA and bond angles N25–N27–H29 = 109.2, N25–N27
–
H28 = 109.2, H29–N27–H28 = 108.4. For the title0compound, the cor-
responding values are 1.4254, 1.0201, 1.0214 ÅA and 106.2°, 110.0°,
111.1°.
The three bond angles around C22 atom are not equal to 120
each. It is seen that the C3–C22–O26 (126°) is considerably greater
than the angle N25–C22–C3 (115°). This observation is similar to
that in the structures of hydrazones reported earlier [86] which
is explained as due to a decrease in the repulsion between the lone
pairs present in N25 and O26 atoms. The central part of the molecule
755 35 cmꢀ1 is observed and is due to
cCH. This band is observed
at 755 cmꢀ1 in the IR spectrum as a strong band for the title com-
pound. The IR bands in the 1750–2839 cmꢀ1 region and their large
broadening support the intramolecular hydrogen bonding [46].
4.2. Geometrical parameters and first hyper polarizability
adopts a completely extended double bond conformation. It can be
0
To best of our knowledge, no X-ray crystallographic data of this
moleculehaveyet been established. However, thetheoreticalresults
(DFT) obtained are almost comparable with the reported structural
parameters of the parent quinazoline molecules. The experimental
N–N bond length of hydrazine [79] is reported at 1.449 Å and the
electron diffraction N–N bond length of tetramethylhydrazine [80]
isreportedat1.401 Å. Kostavaet al. [81]calculatedtheN25–N27 bond
length in the range 1.318–1.357 Å for different molecules. In the
present case the N25–N27 bond length is 1.4254 Å which is some
where between the length of an N–N single bond (1.45 Å) and an
N@N double bond (1.25 Å). For th0e title compound, the bonds
C23–N24@1.3155, C22–O26 = 1.2565 ÅA show typical double bond
characteristics. However, C2–N24 = 1.3892 Å, C22–N25 = 1.4172 Å,
C23–N25 = 1.3996 ÅbondlengthareshorterthanthenormalC–Nsin-
gle bond length of about 1.48 Å. The shortening of the C–N bonds re-
veal the effects of resonance in this part of the molecule [82]. The
difference between the lengths of C–N bonds is similar to the values
of reported quinazoline derivatives [83] and this situation can be
attributed to the difference in hybridization of the different carbon
atoms. For a quinazoline derivative, Costa et al. [34] reported C2–
N24 = 1.3954, C23–N25 = 1.3904 and C22–N25 = 1.4174 Å . Gai et al.
[87] reported C22–N25, C23–N25, C2–N24, C3–C22 and C2–C3 as
1.3703, 1.4623, 1.4043, 1.4823 and 1.3903 Å, respectively for a qui-
nazolinederivative. In thepresent case, thecorrespondingvaluesare
1.4172, 1.3996, 1.3892, 1.4519 and 1.4164 Å, respectively. For the ti-
confirmed by the C22–O26 bond length (1.2565 ÅA) which is consid-
erably longer than the standard C@O bond length 1.21 and N25–C22
0
bond length (1.4172 ÅA)0 which is shorter than the standard N–C sin-
gle bond length (1.47 ÅA) [86].
Non-linear optics deals with the interaction of applied electro-
magnetic fields in various materials to generate new electromag-
netic fields, altered in wavenumber, phase or other physical
properties [87]. Organic molecules able to manipulate photonic
signals efficiently are of importance in technologies such as optical
communication, optical computing and dynamic image processing
[88,89]. Phenyl substituents can increase molecular hyperpolariz-
ability, a result that has been described as surprising [90,91]. Anal-
ysis of organic molecules having conjugated
p-electron systems
and large hyperpolarizability using infrared and Raman spectros-
copy has evolved as a subject of research [92]. The potential appli-
cation of the title compound in the field of non-linear optics
demands the investigation of its structural and bonding features
contributing to the hyperpolarizability enhancement, by analyzing
the vibrational modes using the IR and Raman spectrum.
The first hyperpolarizability (b0) of this novel molecular system
is calculated using B3LYP/6-31G* 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 components of the 3D matrix can be reduced to 10 compo-
nents due to the Kleinman symmetry [93]. The components of b
are defined as the coefficients in the Taylor series expansion of
the energy in the external electric field. When the electric field is
weak and homogeneous, this expansion becomes
tle compound, the DFT calculations give the bond angles C22–N25
–
N27 = 115.2, C22–N25–C23 = 123.2, N27–N25–C23 = 121.5, O26–C22
–N25 = 119.0, O26–C22–C3 = 126.0, N25–C22–C3 = 115.0, C2–C3–
C4 = 120.4, C2–C3–C22 = 118.7, C4–C3–C22 = 120.8, C3–C2–C1 = 119.1,
C3–C2–N24 = 121.9, C1–C2–N24 = 119.0° where as the corresponding
reported values [84] are 120.3, 121.0, 118.0, 121.8, 122.7, 115.5,
119.7, 120.6, 119.6, 120.0, 121.2 and 118.6.
X
X
X
1
2
1
6
E ¼ E0 ꢀ
l
iFi ꢀ
a
ijFiFj ꢀ
bijkFiFjFk
i
ij
ijk
X
For the title compound, the dihedral angles C4–C3–C22
–
1
ꢀ
c
ijklFiFjFkFl þ ꢂ ꢂ ꢂ
N25 = 179.4° and C22–N25–C23–C11 = 177.6°. This indicates that the
phenyl ring I and the quinazoline moiety of the title compound
24
ijkl
are in tilted positions. Also the dihedral angles C16–C13–C11–C23
,
where E0 is the energy of the unperturbed molecule, Fi is the field at
C11–C23–N24–C2, and C11–C23–N25–C22 are ꢀ176.0°, ꢀ179.2° and
177.6°, respectively, which shows the phenyl ring II and the qui-
nazoline moiety are in different planes. The N24–C23 ring moiety
is slightly twisted from the phenyl ring I (C3–C2–N24–C23 = 0.6°
the origin, li, aij, bijk and cijkl are the components of dipole moment,
polarizability, the first hyper polarizabilities, and second hyperpo-
larizibilites, respectively. The calculated first hyperpolarizability of
the title compound is 5.05 ꢁ 10ꢀ30 esu, which is comparable with

C.Y. Panicker et al. / Journal of Molecular Structure 963 (2010) 137–144
143
Fig. 4. Correlation graph.
the reported values of similar quinazoline derivatives [94] and
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vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
n
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u
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1
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t
RMS ¼
ð
tci alc
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tei xp
Þ
n ꢀ 1
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144
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