Synthesis, characterization of (3E)-1-(6-chloro-2-methyl-4-phenyl quinolin-3-Yl)-3-aryl prop-2-en-1-ones through IR, NMR, single crystal X-ray diffraction and insights into their electronic structure using DFT calculations

Article abstract of DOI:10.1016/j.saa.2014.09.124

3E-1-(6-Chloro-2-methyl-4-phenylquinolin-3-yl)-3-arylprop-2-en-1-ones were synthesized and characterized by FTIR, ¹H NMR, ¹³C NMR, HSQC, DEPT-135. In addition the compound 3E-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2,5-dimetho

Full text of DOI:10.1016/j.saa.2014.09.124

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Synthesis, characterization of (3E)-1-(6-chloro-2-methyl-4-phenyl
quinolin-3-Yl)-3-aryl prop-2-en-1-ones through IR, NMR, single crystal
X-ray diffraction and insights into their electronic structure using DFT
calculations
a
b
a
c
S. Sarveswari a, , A. Srikanth , N. Arul Murugan , V. Vijayakumar , Jerry P. Jasinski ,
⇑
Hanna C. Beauchesne c, Ethan E. Jarvis c
a Centre for Organic and Medicinal Chemistry, VIT University, Vellore 632014, India
b Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, SE-10691 Stockholm, Sweden
c Department of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, United States
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
ꢀ
3E-1-(6-Chloro-2-methyl-4-
phenylquinolin-3-yl)-3-arylprop-2-
en-1-ones synthesized.
ꢀ
ꢀ
ꢀ
Characterized by IR, 1H NMR, 13C
NMR, HSQC, DEPT-135.
X-ray diffraction of study on
compound 3a.
DFT calculation to investigate their
electronic structure and chemical
reactivity.
a r t i c l e i n f o
a b s t r a c t
Article history:
3E-1-(6-Chloro-2-methyl-4-phenylquinolin-3-yl)-3-arylprop-2-en-1-ones were synthesized and charac-
terized by FTIR, 1H NMR, 13C NMR, HSQC, DEPT-135. In addition the compound 3E-1-(6-chloro-2-
methyl-4-phenylquinolin-3-yl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one was subjected to the single
crystal X-ray diffraction studies. Density functional theory calculations were carried out for this chalcone
and its derivatives to investigate into their electronic structure, chemical reactivity, linear and non-linear
optical properties. The structure predicted from DFT for chalcone is in good agreement with the structure
from XRD measurement.
Received 17 July 2014
Received in revised form 25 September
2014
Accepted 28 September 2014
Available online 6 October 2014
Keywords:
Chalcones
Ó 2014 Elsevier B.V. All rights reserved.
Synthesis
Spectral characterization
Single crystal X-ray studies
DFT studies
Linear and non-linear optical properties
Introduction
⇑
Corresponding author at: Centre for Organic and Medicinal Chemistry VIT
University, Vellore 632014, Tamil Nadu, India. Mobile: +91 948732178.
E-mail address: sarveswari@gmail.com (S. Sarveswari).
Chemically chalcones are open chain flavonoids in which
the two aryl rings are joined together by three carbons, in an
http://dx.doi.org/10.1016/j.saa.2014.09.124
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.

S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
1011
a
-b-unsaturated carbonyl system. Fundamentally they are consid-
General procedure for the Synthesis of 3E-1-(6-chloro-2-methyl-4-
phenylquinolin-3-yl)-3-arylprop-2-en-1-one (3a-m)
ered as derivatives of a phenyl styryl ketone. Chalcones are often
synthesized by a Claisen–Schmidt aldol condensation reaction.
Chalconoids constitute an important class of naturally occurring
A mixture of 1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)eth-
anone (1) (0.974 g, 0.0033 mol), 2,5-dimethoxy benzaldehyde
(2a) (1 g, 0.006 mol) and 1 g of KOH in 50 mL ethanol was stirred
at room temperature for about 15 h. Completion of the reaction
was monitored by TLC. Then the reaction mixture was concen-
trated and neutralized with dil. HCl. Then the crude product was
filtered, dried and purified by recrystallization from ethanol. In
order to prove the generality of the reaction the procedure was
repeated with various arylaldehydes (2b-m). The product forma-
tion was confirmed by spectral techniques.
compounds [1–3] exhibiting
a wide spectrum of biological
activities. Several potential properties of chalcones can be listed
as antimalarial, [4–7] antimicrobial [8] and anti-tuberculosis
[9] activities. Moreover, many recent reports are dealing with
the cytotoxic [10–13] as well as anti-HIV [14] properties of
hydroxychalcone derivatives. Some derivatives of the chalcone
class compounds have been described in literature as inhibitors
of ovarian cancer cell proliferation and pulmonary carcinogenesis
[15].
Other than the medical applications, in recent years, chalcones
have been used in the field of material science as non-linear
optical (NLO) response materials [16] for their applications
toward optical limiting [17], electrochemical sensing [18] and
langmuir film [19]. The chalcones with promising NLO properties
are also useful in advanced technologies like optical computing,
optical communication [20–23] and opto electronics [24–27].
The property of interest at the molecular level is hyperpolarizabil-
ity (b) of the materials which has to be optimized [20]. However,
for the macroscopic second-order non-linear susceptibility to be
larger, not only b but also the orientation and packing of mole-
cules in crystal become important. Eventually, the molecules
should assemble in a non-centrosymmetric crystal structure.
Besides the strong NLO response, these materials must also fulfill
the technological requirements for practical applications such as
wide transparency extending down to UV region, fast response,
thermal stability, chemical stability, mechanical stability and high
laser damage threshold [28]. The structural tuning of chalcones
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2,5-
dimethoxyphenyl)prop-2-en-1-one (3a)
IR (KBr, cmꢁ1): The characteristic frequencies are at 1645 cmꢁ1
(a
, b-unsaturated carbonyl stretching), 1573 cmꢁ1 (conjugated
alkene function), 1382 cmꢁ1 (CAN stretching), 707.88 cmꢁ1 (CACl
stretching),. 1H NMR (400 MHz, CDCl3, d (ppm)): 2.69 (s, 3H),
3.71(s, 3H), 3.72 (s, 3H), 6.62 (d, 1H, J: 16.4), 6.76 (d, 1H, J: 8.8),
6.81 (d,1H, J: 2.8), 6.90 (dd, 1H, J1: 2.8 J2 = 8.8,), 7.28–7.30 (m,
2H), 7.38–7.40 (m, 3H), 7.44 (d, 1H, J: 16.4), 7.57(d, 1H, J: 2), 7.66
(dd, 1H, J1: 2.2 J: 9.0), 8.05 (d, 1H, J: 9.2); 13CNMR (100 MHz, CDCl3,
d (ppm)) 23.00 (CH3), 55.77, 55.94 (OCH3), 112.35, 112.78, 118.33,
123.38, 125.16, 126.27, 128.14, 128.48, 128.76, 130.05, 130.53,
130.89, 132.33, 133.57, 134.60, 142.49, 144.57, 146.07, 152.95,
153.43, 155.52, 197.74 (C@O). ESI: 443.121.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2,3-
dichlorophenyl)prop-2-en-1-one (3b)
to increase the conjugation length and to yield D-
p
-A, and
IR (KBr, cmꢁ1): 3061 (@CAH), 3028 (CAH, Ar), 2922 (CAH),
D- -A- -D (where D and A refer to donor and acceptor groups)
p
p
1707 (C@O), 1620 (C@C), 707 (CACl) cmꢁ1 1H NMR (400 MHz,
;
like architectures have been shown to increase the non-linear
response in these materials [29]. The carbonyl group at the mid-
dle of the two aromatic centers acts as an acceptor and facilitates
intramolecular charge transfer. In the former case, the charge
transfer occurs from one end to another end (donor to acceptor)
and in the latter case, the charge transfer occurs from two ends
to center. Considering the usage of chalcones in various afore-
mentioned applications, it is of importance to synthesize and
characterize chalcones varying with respect to conjugation length
and substitutions with different electron withdrawing and donat-
ing groups which has been undertaken in this study to some
extent.
In view of the various biological, pharmacological and techno-
logical applications of these compounds, we have synthesized a
series of 3E-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-aryl-
prop-2-en-1-ones and characterized by IR, 1H NMR, 13C NMR,
HSQC, DEPT-135. One of these compounds was subjected to the
single crystal X-ray diffraction studies. Density functional theory
calculations were carried out for these chalcones to investigate
into their electronic structure and chemical reactivity. The linear
and non-linear optical response properties of this chalcone have
been also investigated using time dependent density functional
theory.
CDCl3, d (ppm)): 2.71 (s, 3H), 6.49 (d, 1H, J: 16.0), 7.15 (t, 1H, J:
8), 7.24 (dd, 1H, J1: 7.6 J2: 1.6 Hz), 7.31(dd, 2H, J1: 7.6 J2: 1.6),
7.41–7.46 (m, 4H), 7.51 (d, 1H, J: 16.0), 7.60 (d, 1H, J: 2.4), 7.69
(dd, 1H, J1: 9.0 J2: 2.4), 8.06 (d, 1H, J: 9.0); 13CNMR (100 MHz,
CDCl3, d (ppm)): 24.01, 125.11, 125.86, 125.97, 127.43, 128.69,
129.03, 130.23, 130.65, 130.79, 131.24, 132.06, 132.60, 132.90,
133.12, 134.08, 134.39, 134.61, 142.10, 144.79, 146.26, 155.22,
197.00 (C@O). ESI: 451.022.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(3,4-
dimethoxyphenyl)prop-2-en-1-one (3c)
IR (KBr, cmꢁ1): 3130 (@CAH), 3007 (CAH, Ar), 2964 (CAH),
1641 (C@O), 1616 (C@C), 1593 (C@C, Ar), 1141 (CAOAC), 572
(CACl) cmꢁ1 1H NMR (400 MHz, CDCl3, d (ppm)): 2.63 (s, 3H),
;
3.78 (s, 3H), 3.82 (s, 3H), 6.43 (d, 1H, J:16.2), 6.73 (d, 1H, J: 8.4),
6.77 (d, 1H, J:1.6), 6.85 (dd, 1H, J: 8.4 J: 1.6), 6.95 (d, 1H, J: 16.2),
7.21–7.24 (m, 2H), 7.32–7.36 (m, 3H), 7.51 (d, 1H, J: 2.3), 7.62
(dd, 1H, J1: 8.9 J2: 2.3), 7.99 (d, 1H, J:8.9 Hz); 13CNMR (100 MHz,
CDCl3, d (ppm)): 23.96, 55.89, 56.03, 109.69, 111.02, 123.43,
125.13, 125.75, 126.23, 126.86, 128.56, 128.83, 129.88, 130.54,
130.97, 132.43, 133.47, 134.60, 144.55, 146.12, 147.33, 149.27,
151.91, 155.46, 197.09 (C@O). ESI: 443.121.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2-
methoxyphenyl)prop-2-en-1-one (3d)
Experimental
IR (KBr, cmꢁ1): 3128 (@CAH), 2985 (CAH, Ar), 2912 (CAH),
1645 (C@O), 1624 (C@C), 711 (CACl) cmꢁ1 1H NMR (400 MHz,
;
Infrared spectra were recorded using KBr disc on a FT–IR
Perkin–Elmer spectrophotometer. NMR spectra were measured
on a BRUKER AVANCE III spectrometer at 400 MHz. All the
chemical shifts are reported in d units downfield from TMS. The
procured reagents and solvents were used as received without
any further purification.
CDCl3, d (ppm)): 2.69 (s, 3H), 3.77 (s, 3H), 6.67 (d, 1H, J: 16.6),
6.85 (t, 1H, J: 8.6), 6.90 (d,1H, J: 7.2), 7.28–7.35 (m, 4H), 7.21–
7.38 (m, 3H), 7.46 (d, 1H, J: 16.6), 7.57 (d, 1H, J: 2.0), 7.67 (dd,
1H, J1 = 8.8 J2: 2.0 Hz), 8.06 (d, 1H, J: 8.8); 13CNMR (100 MHz,
CDCl3, d (ppm)): 23.99, 55.44, 111.12, 120.74, 122.95, 125.17,
126.29, 128.12, 128.46, 128.61, 128.74, 128.79, 128.97, 130.04,

1012
S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
Table 2
130.54, 130.86, 132.31, 132.41, 133.63, 134.60, 142.83, 144.54,
Selected crystal bond lengths (Å), bond angles (°), and torsion angles (°) for
C27H22NO3Cl.
146.07, 155.53, 158.43, 197.87 (C@O); ESI: 413.11.
O1–C16
O2–C25
O3–C26
N1–C3
1.2218(15)
1.4205(19)
1.4138(18)
1.3690(16)
O2–C20
O3–C23
N1–C2
C1–C9
1.3671(18)
1.3671(17)
1.3191(16)
1.3725(16)
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(4-
chlorophenyl)prop-2-en-1-one (3e)
IR (KBr, cmꢁ1): 3441 (CAN), 3059 (@CAH), 2999 (CAH, Ar),
2927 (CAH), 1670 (C@O), 1629 (C@C), 709 (CACl) cmꢁ1 1H NMR
;
C20–O2–C25
C2–N1–C3
N1–C3–C4
O1–C16–C1
O3–C23–C22
117.96(13)
118.43(10)
118.20(11)
119.40(11)
125.96(12)
C23–O3–C26
N1–C2–C1
N1–C3–C8
O1–C16–C17
O3–C23–C24
118.32(13)
122.59(11)
122.86(10)
120.82(11)
114.80(12)
(400 MHz, CDCl3, d (ppm)): 2.66 (s, 3H), 6.50 (d,1H, J: 16.4), 7.02
(d, 1H, J: 16.4), 7.19–7.27 (m, 6H), 7.37–7.39 (m, 3H), 7.57 (d, 1H,
J:1.8), 7.66 (dd, 1H, J1: 8.8 J2: 1.8), 8.03 (d, 1H, J: 8.8);
13CNMR (100 MHz, CDCl3, d (ppm)): 23.99, 125.08, 126.06,
127.85, 128.66, 129.00, 129.49, 129.92, 130.60, 131.13, 132.43,
132.54, 133.21, 134.52, 137.04, 144.64, 145.07, 146.20, 155.32,
196.91 (C@O); ESI: 417.07.
O1–C16–C17–C18
N1–C3–C4–C5
C1–C9–C10–C11
C2–N1–C3–C4
C9–C1–C16–O1
ꢁ172.69(14)
178.83(12)
110.36(14)
ꢁ179.68(11)
99.27(15)
O2–C20–C21–C22
N1–C3–C8–C7
C1–C9–C10–C15
C2–N1–C3–C8
178.13(15)
ꢁ178.17(11)
ꢁ73.08(15)
0.16(18)
C9–C1–C16–C17
ꢁ83.20(15)
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(3,4,5-
trimethoxyphenyl)prop-2-en-1-one (3f)
IR (KBr, cmꢁ1): 3100 (@CAH), 2976 (CAH, Ar), 2941 (CAH),
Table 3
Weak intermolecular interactions for C27H22NO3Cl, [Å and °].
1651 (C@O), 1618 (C@C), 704 (CACl) cmꢁ1 1H NMR (400 MHz,
;
CDCl3, d (ppm)): 2.69 (s, 3H), 3.83 (s, 9H), 6.53 (d,1H, J = 15.8 Hz),
6.54 (s, 1H), 6.98 (d, 1H, J: 15.8), 7.29 (dd, 2H, J1: 6.1 J2: 2.3), 7.42
(dd, 3H, J1: 6.1 J2: 2.3), 7.58 (d, 1H, J: 2.3), 7.69 (dd, 1H, J1: 8.9 J2:
2.3), 8.07 (d, 1H, J: 8.9); 13CNMR (100 MHz, CDCl3, d (ppm):
23.95, 56.16, 61.00, 76.73, 105.57, 125.15, 126.22, 127.08, 128.62,
128.92, 129.30, 129.90, 130.50, 131.10, 132.54, 133.32, 134.50,
140.83, 144.71, 146.10, 147.20, 153.44, 155.37, 197.01 (C@O);
ESI: 473.133.
D-Hꢃ ꢃ ꢃA
C12---H12ꢃ ꢃ ꢃN1 #1
C15---H15ꢃ ꢃ ꢃO1 #2
d (D–H)
d (Hꢃ ꢃ ꢃA)
2.54
2.48
d (Dꢃ ꢃ ꢃA)
3.3217(8)
<(DHA)
0.95
0.95
139.3
132.9
3.2060(17)
Symmetry transformations used to generate equivalent atoms: #1 1ꢁx, 1/2 + y,
3/2ꢁz; 2 2ꢁx, 1ꢁy, 2ꢁz.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2,3-
dimethoxyphenyl)prop-2-en-1-one (3h)
IR (KBr, cmꢁ1): 3130 (@CAH), 3031 (CAH, Ar), 2964 (CAH),
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-phenylprop-2-
en-1-one (3g)
1647 (C@O), 1624 (C@C), 709 (CACl) cmꢁ1 1H NMR (400 MHz,
;
IR (KBr, cmꢁ1): 3444 (CAN), 2985 (@CAH), 2912 (CAH, Ar),
CDCl3, d (ppm)): 2.69 (s, 3H), 3.68 (s, 3H), 3.83 (s, 3H), 6.64 (d,
1H, J: 16.4), 6.92 (d, 2H, J: 8.2), 6.99 (t, 1H, J: 8.2), 7.29 (dd, 2H,
J1: 7.4 J2:1.8), 7.41–7.38 (m, 3H), 7.44 (d, 1H, J: 16.4), 7.57 (d, 1H,
J: 2.4), 7.67 (dd, 1H, J1: 9.0 J2 = 2.4), 8.06 (d, 1H, J: 9.0);
13CNMR (100 MHz, CDCl3, d (ppm)): 23.94, 55.88, 61.22, 114.71,
119.40, 124.18, 125.10, 126.15, 128.10, 128.55, 128.70, 128.83,
128.86, 130.04, 130.26, 130.58, 130.96, 132.40, 133.53, 134.55,
141.86, 144.50,146.11, 148.64, 153.02, 155.32, 197.66 (C@O); ESI:
443.121.
2848 (CAH), 1645 (C@O), 1624 (C@C), 711 (CACl) cmꢁ1 1H NMR
;
(400 MHz, CDCl3, d (ppm)): 2.69 (s, 3H), 6.59 (d, 1H, J:16.2), 7.09
(d, 1H, J: 16.2), 7.27–7.35 (m, 6H), 7.36–7.43 (m, 4H), 7.58 (d, 1H,
J: 2.2), 7.68 (dd, 1H, J1: 9.0 J2: 2.2), 8.06 (d, 1H, J: 9.0);
13CNMR (100 MHz, CDCl3, d (ppm)): 23.96, 125.11, 126.15,
127.60, 128.42, 128.62, 128.92, 128.99, 129.91, 130.57, 131.06,
131.07, 132.49, 133.36, 133.94, 134.51, 144.63, 146.16, 146.99,
155.35, 197.26 (C@O); ESI: 383.20.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(3-
methoxyphenyl)prop-2-en-1-one (3i)
Table 1
Crystal data and structure refinement for 3a.
IR (KBr, cmꢁ1): 3082 (@CAH), 3005 (CAH, Ar), 2929 (CAH),
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C27H22NO3Cl
443.90
173(2)
monoclinic
P21/c
10.0436(3)
15.7864(4)
14.7023(5)
1645 (C@O), 1622 (C@C), 671 (CACl) cmꢁ1 1H NMR (400 MHz,
;
CDCl3, d (ppm)): 2.69 (s, 3H), 3.77 (s, 3H), 6.57 (d, 1H, J: 16.0),
6.82 (t, 1H, J: 2.0), 6.91(dd, 2H, J1: 8.6 J2 = 2.8), 7.05(d, 1H, J:
16.0), 7.29 (dd, 2H, J1: 7.4 J2:2.2), 7.23 (d, 1H, J:7.6),7.39–7.44 (m,
3H), 7.59 (d, 1H, J:2.4), 7.69 (dd, 1H, J1: 9.2 J2:2.4), 8.06 (d, 1H, J:
9.2); 13CNMR (100 MHz, CDCl3, d (ppm)): 23.97, 55.32, 113.05,
117.05, 121.15, 125.11, 126.15, 127.87, 128.63, 128.93, 129.92,
129.97, 130.59, 131.06, 132.49, 133.33, 134.51, 135.30, 144.63,
146.18, 146.89, 155.35, 159.91, 197.22 (C@O); ESI: 413.11.
b (Å)
c (Å)
a
(°)
90
b (°)
106.953(3)
90
2229.78(11)
c
(°)
Volume (Å3)
Z
q
4
calcmg/mm3
1.322
0.201
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(4-
methoxyphenyl)prop-2-en-1-one (3j)
m/mmꢁ1
F (000)
928.0
IR (KBr, cmꢁ1): 3005 (@CAH), 2972 (CAH, Ar), 2916 (CAH),
Crystal size (mm3)
0.28 ꢂ 0.16 ꢂ 0.12
1639 (C@O), 1618, 765 (CACl) cmꢁ1 1H NMR (400 MHz, CDCl3,
;
2H range for data collection
6.102–65.81°
Index ranges
ꢁ14 6 h 6 14, ꢁ23 6 k 6 23, ꢁ21 6 l 6 19
30,619
7659[R(int) = 0.0336]
7659/0/292
d (ppm)): 2.69 (s, 3H), 3.81(s, 3H), 6.48 (d, 1H, J:16.2), 6.84 (d,
2H, J: 8.8), 7.04 (d, 1H, J:16.2),7.29–7.27(m, 4H), 7.43–7.38 (m,
3H),7.57 (d, 1H, J: 2.3), 7.68 (dd, 1H, J1: 9.0 J2: 2.3), 8.06 (d, 1H, J:
8.8); 13CNMR (100 MHz, CDCl3, d (ppm)): 23.95, 55.44, 114.48,
125.12, 125.50, 126.22, 126.61, 128.54, 128.81, 129.87, 130.28,
130.55, 130.93, 132.39, 133.56, 134.60, 144.49, 146.11, 147.03,
155.46, 162.12, 197.14 (C@O); ESI: 413.11.
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
1.029
Final R indexes [I> = 2
r
(I)]
R1 = 0.0456, wR2 = 0.1109
R1 = 0.0690, wR2 = 0.1252
0.40/ꢁ0.29
Final R indexes (all data)
Largest diff. peak/hole (e Åꢁ3
)

S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
1013
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2-
X-ray crystallography
chlorophenyl)prop-2-en-1-one (3k)
IR (KBr, cmꢁ1): 3053 (@CAH), 2922 (CAH, Ar), 2870 (CAH),
Single crystals of (E)-1-(6-chloro-2-methyl-4-phenylquinolin-
3-yl)-3-(2,5-dimethoxy phenyl)prop-2-en-1-one 27H22NO3Cl
1678 (C@O), 1654 (C@C), 798 (CACl) cmꢁ1
;
1H NMR (400 MHz,
C
CDCl3, d (ppm)): 2.70 (s, 3H), 6.54 (d,1H, J:16.0), 7.21(dt, 1H, J1
0.93 J:7.4), 7.39 (m, 8H), 7.51 (d, 1H, J:16.0), 7.59 (d, 1H, J: 2.4),
7.68 (dd, 1H, J1: 9.2 J2: 2.4), 8.06 (d, 1H, J: 8.8); 13CNMR (100 MHz,
CDCl3, d (ppm)): 24.00, 125.12, 126.04, 127.15, 127.73, 128.61,
128.93, 129.81, 130.18, 130.22, 130.63, 131.12, 131.69, 132.23,
132.51, 133.04, 134.43, 135.19, 142.60, 144.73, 146.21, 155.28,
197.31(C@O). ESI: 416.061.
[3a] were obtained through the slow evaporation of its ethyl ace-
tate solution. A suitable crystal was selected and placed on a Nylon
Loop on an Xcalibur, Eos, Gemini X-ray diffractometer. The crystal
was kept at 173(2) K during data collection. Using Olex2 [30], the
structure was solved with the Superflip [31] structure solution pro-
gram using Charge Flipping and refined with the ShelXL [32]
refinement package using Least Squares minimization.
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(2,4-
dimethoxyphenyl)prop-2-en-1-one (3l)
Crystal structure refinement
All of the H atoms were placed in their calculated positions and
then refined using the riding model with Atom---H lengths of
0.95/%A (CH), or 0.98/%A (CHꢄ3ꢄ). Isotropic displacement param-
eters for these atoms were set to 1.2 (CH) or 1.5 (CHꢄ3ꢄ) time-
s < i > U</i > ꢄeqꢄ of the parent atom. Idealized methyl was
refined as rotating groups. Crystallographic data and details of
the data collection, structure solution and refinement are listed
in Table 1.
IR (KBr, cmꢁ1): 3047 (@CAH), 2983 (CAH), 2900 (CAH), 1625
(C@O), 1600 (C@C), 758 (CACl) cmꢁ1 1H NMR (400 MHz, CDCl3,
;
d (ppm)): 2.60 (s, 3H), 3.66 (s, 3H), 3.72 (s, 3H), 6.27 (d, 1H, J:
2.4), 6.35 (dd, 1H, J1: 8.6 J2:1.8), 6.51 (d, 1H, J:16.4), 7.20–7.16
(m, 5H), 7.29 (dd, 3H, J1: 4.6 J2:1.6), 7.47 (d, 1H, J: 2.4), 7.57 (dd,
1H, J1: 8.8 J2: 2.4), 7.96 (d, 1H, J: 9.2); 13CNMR (100 MHz, CDCl3,
d (ppm)): 23.99, 55.46, 55.53, 98.29, 105.53, 116.11, 125.18,
125.85, 126.35, 128.40, 128.64, 129.98, 130.47, 130.51, 130.74,
132.21, 133.84, 134.70, 143.05, 144.41, 146.01, 155.66, 160.08,
163.61, 197.77 (C@O); ESI: 443.121.
Crystal structure determination of compound (E)-1-(6-chloro-2-
methyl-4-phenylquinolin-3-yl)-3-(2,5-dimethoxy phenyl)prop-2-en-
1-one C27H22NO3Cl (3a)
Important bond lengths and bond angles were given in Table 2
and data on weak intermolecular interactions are presented in
Table 3. Crystal Data for C27H22NO3Cl (M = 443.90): monoclinic,
(E)-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-(thiphene)prop-
2-en-1-one (3m)
IR (KBr,cmꢁ1): 1657 (C@O), 1571 (C@C); 1H NMR (400 MHz,
CDCl3): d (ppm) 2.69 (s, 3H), 6.39 (d, 1H, J: 16.0),7.02 (dd, 1H,
J1 = 4.8 J2 = 3.6) 7.13 (d, 1H, J: 3.6), 7.22 (d, 1H, J:15.6), 7.28–
7.30(m, 2H), 7.39–7.45 (m, 4H), 7.58 (d, 1H, J:2.0), 7.68 (dd, 1H,
J1: 8.8 J2: 2.4), 8.01(d, 1H, J = 9.2); 13CNMR (100 MHz, CDCl3,
d (ppm)): 23.97, 125.11, 126.17, 126.31, 128.44, 128.64, 128.93,
129.87, 130.05, 130.57, 131.04, 132.17, 132.46, 133.32, 134.48,
139.30, 144.66, 146.15, 155.40, 196.46; ESI: 389.12.
P21/c,
b = 106.953(3)°, V = 2229.78(11) Å3, Z = 4, T = 173(2) K,
) = 0.201 mmꢁ1, Dcalc = 1.322 g/mm3, 30,619 reflections mea-
a = 10.0436(3) Å,
b = 15.7864(4) Å,
c = 14.7023(5) Å,
l
(Mo
Ka
sured (6.102 6 2
H 6 65.81), 7659 unique (Rint = 0.0336) which
were used in all calculations. The final R1 was 0.0456 (I > 2
r(I))
and wR2 was 0.1252 (all data).
Scheme 1
Synthesis of 3E-1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3-arylprop-2-en-1-ones (3a-m).
Entry
Ar
Yield (%)
M Pt (°C)
Entry
Ar
Yield (%)
M Pt (°C)
3a
3b
3c
3d
3e
3f
2, 5-Dimethoxyphenyl
2, 3-Dichlorophenyl
3, 4-Dimethoxyphenyl
2-Methoxyphenyl
4-Chlorophenyl
96
87
95
98
81
89
92
160–163
158–160
186–188
160–161
136–138
140–142
160–162
3 h
3i
3j
3 k
3 l
3 m
2, 3-Dimethoxyphenyl
3-Methoxyphenyl
4-Methoxyphenyl
2-Chlorophenyl
2, 4-Dimethoxyphenyl
Thiophene-2-yl
82
80
94
78
90
82
130–132
178–180
198–200
150–152
188–190
200–202
3, 4, 5-Trimethoxyphenyl
Phenyl
3g
Fig. 1. Molecular Structure of C16H12N2OF2 showing the atom labeling scheme and 30% probability ellipsoids.

1014
S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
Results and discussions
The compound 1-(6-chloro-2-methyl-4-phenylquinolin-3-
yl)ethanone (1) was prepared using the report available in the lit-
erature [33], which in turn converted into the 3E-1-(6-chloro-2-
methyl-4-phenylquinolin-3-yl)-3-arylprop-2-en-1-ones
(3a-m)
by reacting it with various arylaldehydes, at room temperature
for 15 h (Scheme 1). Completion of the reaction was monitored
by TLC. Then the reaction mixture was concentrated and neutral-
ized with dil. HCl, filtered, dried and recrystallized from ethanol.
The formations of the desired compounds were characterized by
spectral techniques IR, NMR and mass spectral data. The com-
pound 3a has been considered as a representative compound and
its spectral characterization was described below.
The proton NMR spectrum (given in Supplementary data) of 3a
displayed the following peaks, methyl protons at C2 appeared as a
singlet at d 2.69 ppm. The two methyl of two methoxyl groups of
aryl substituent appeared as singlets at d 3.71 ppm and 3.72 ppm
(merged with each other in the spectrum). The careful examination
of the H, H-COSY (given in Supplementary data) spectrum of the
sample clearly revealed that the extreme down filed signals at d
7.57 ppm, 7.66 ppm and 8.05 ppm are due to the protons of the
quinoline ring. The doublet at d 7.57 ppm with coupling constant
of 2.1 Hz integrating for one proton is due to the proton at C-5 of
quinoline ring. The doublet of doublet appeared at d 7.66 ppm
(dd, 1H, J1: 9.1 J2: 2.1) integrating for one proton is due to the pro-
ton at C-7 of the quinoline ring. The other doublet at d 8.05 ppm (d,
1H, J = 9.1 Hz) is due to the proton at C-8 of the quinoline ring. The
doublet at d 7.44 ppm (J: 16.4 Hz) is coupled with the doublet at d
6.62 ppm (J: 16.4 Hz) is due to the alkenic protons at C-50 and C-60.
The relatively downfield signal was assigned to the proton at C-50
and the relatively upfield signal assigned to the proton at C-60 since
the C-50 is attached with the carbonyl. The coupling constant indi-
cates the presence of trans isomer (E isomer). The muliplets
between d 7.28 and 7.30 ppm (m, 2H, ortho), 7.38–7.40 ppm (m,
3H, meta and para) are due to the phenyl ring at C-4 of the quino-
line ring. The doublets at 6.76 ppm (d, 1H, J: 8.8) and 6.81 ppm (d,
1H J: 2.8) which integrating for one each are due to the protons at
C-120 and C-90 respectively. The remaining signal at d 6.90
appeared as doublet of doublet (dd, 1H, J1: 2.8 J2: 8.8) is assigned
to the proton at C-110. All these chemical shift assignment was
summarized in the Fig. 3. In a similar way, proton chemical shift
values of other members in the series are assigned and included
in the experimental section.
The carbon chemical shift values for the each carbon in the
molecule were assigned as using the HSQC. The extreme downfield
signal at d ppm was assigned to the carbonyl carbon. The extreme
upfield signal at d 23.00 ppm was assigned to methyl carbon at C-2.
The two methoxyl carbons of aryl substituent appeared at d 55.77
(C-100), 55.94 (C-80) ppm. The carbons not bearing protons (ipso
and quaternary carbons) were identified by their absence in the
DEPT-135 and HSQC spectra. Other proton bearing carbons were
assigned using HSQC. All the carbons were assigned and pictorially
represented in Fig. 4. Similarly all other compounds of the series
were assigned and included in the experimental section. One of
these compounds 3E-1-(6-chloro-2-methyl-4-phenylquinolin-3-
yl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (3a) was subjected
to the single crystal X-ray diffraction studies; density functional
theory calculations were carried out for these chalcones to investi-
gate into their electronic structure and chemical reactivity.
Fig. 2. Packing diagram of C16H12N2OF2 viewed along the b axis. Dashed lines
indicate weak C12---H12ꢃ ꢃ ꢃN1 and C15---H15ꢃ ꢃ ꢃO1 intermolecular interactions. H
atoms not involved in these weak intermolecular interactions have been deleted for
clarity.
13
7.38-7.40
12
14
15
7.28-7.30
11
3.72
OCH3
6.78
6'
O
7.57
4
8'
6.81
5
Cl
9
9'
3
4'
5'
6
7'
12'
7.44
7.66
7
10
10'
OCH3
N
1
2
11'
8
6.76
8.05
6.90
2.39
Fig. 3. Summary of proton chemical shift values of (E)-1-(6-chloro-2-methyl-4-
phenylquinolin-3-yl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (3a).
123.38
126.38
128.48
134.60
128.76
144.57
55.94
130.05
128.14
125.16
155.51
112.78
O
197.74
OCH3
133.33
Cl
112.35
142.49
N
OCH3
130.89
153.43
23.00
118.33
55.77
130.53
132.57
146.07
126.27
Fig. 4. Summary of carbon chemical shift values of (E)-1-(6-chloro-2-methyl-4-
phenylquinolin-3-yl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (3a).
10-membered quinoline ring are twisted by 73.3(2)° and 81.3(4)°
from its mean plane (Fig. 1). The dihedral between the mean planes
of the two phenyl rings (C10—C15 & C19—C24) is 82.7(1)°. The
dimethoxy groups para to each other in the 2,5-dimethoxyphenyl
ring are essentially in planar positions with O1/C20/C21/C22 and
O2/C23/C24/C19 torsion angles of 178.13(15)° and 179.89(12)°,
respectively. Bond lengths are in normal ranges [34] (Table 2). In
X-ray crystal structure analysis of 3E-1-(6-chloro-2-methyl-4-
phenylquinolin-3-yl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (3a)
In C27H22NO3Cl, the mean planes of the phenyl ring (C10—C15)
and prop-2-en-1-one group (C1/C16/C17/O1) attached to the

S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
1015
the crystal, weak C---Hꢃ ꢃ ꢃN and C---Hꢃ ꢃ ꢃO intermolecular interac-
tions (Table 3) are observed along with weak ring interactions
between the adjacent 5 and 6-membered rings of the quinoline
group [Cg1---Cg2 = 3.730(4) Å and Cg2---Cg2 = 3.708(5) Å where
Cg1 = N1/C2/C1/C9/C8/C3 and Cg2 = C3---C8] (Fig. 2).
the set of atoms, C9–C12–C14–C15 and C14–C15–C16–C17 which
partly define conformation geometry of the spacer group between
the phenyl quinoline and phenyl aromatic moieties. The experi-
mental spacer group geometry is significantly deviated from planar
conformation while the theoretically predicted one has near planar
conformation which is stabilized by the conjugation effect. Signif-
icant differences seen around the spacer group geometry has to be
attributed to the condensed phase effect which is not incorporated
in the DFT calculations which mimic only the vacuum environment
in this study. In the gas phase, the molecular conformation is dic-
tated by intra molecular interactions such as steric and conjugation
effect. However, in the molecular crystal the intermolecular inter-
actions between the molecules also play key role in dictating the
intra molecular structure and may led to significant changes in
the individual molecular geometry as it has been reported in the
case of number of organic molecules [41,42]. So, we attribute the
intermolecular interactions between the chalcones molecules to
be responsible for the structural differences between the theoreti-
cal and experimental XRD based models.
Further we have computed the energy, frontier molecular orbi-
tal energies, HOMO–LUMO gap and molecular dipole moment for
un-substituted chalcone (3g) and various substituted chalcones
and the results are presented in Table 5. As can be seen from the
tabulated values, the molecular dipole moment (and so their solu-
bility) can be tuned by substituting with electron donating and
electron withdrawing groups and by altering their position in the
aromatic moieties. The unsubstituted chalcone has intermediate
dipole moment and the substitution of the methoxy groups in
the phenyl ring increases the molecular dipole moment while the
substitution with chloride groups decreases the value. The
HOMO–LUMO gap is related to kinetic stability or chemical
p–p
Density functional theory calculations
The density functional theory calculations are carried out to
characterise the electronic structure of these compounds. In partic-
ular, the molecular geometry of chalcone has been optimized using
gaussian09 software [35]. We have used B3LYP exchange correla-
tion functional [36,37] and 6–31 + G(d) basis set for the calculation.
Further the time dependent density functional theory (TD-DFT)
calculations at B3LYP level of theory TZVP [38] basis set were
performed to investigate the absorption spectra of the molecule.
The molecular orbitals involved in the most intense excitations
were analysed. The first hyperpolarizabilities of the chalcones (for
3a and 3g only) were also computed from quadratic response
TD-DFT at B3LYP/TZVP level using Dalton software [39,40].
The optimized molecular geometry of chalcone has been com-
pared to structure obtained from XRD. The frequencies for the opti-
mized structure were computed to make sure that it corresponds
to minimum in energy. Important structural parameters such as
bond lengths, bond angles and dihedral angles corresponding to
the optimized structure and the structure from XRD are listed in
Table 4. Overall, the agreement between the crystal structure and
DFT optimized structure is very good. The experimental and
computed bond lengths and bond angle parameters values are
comparable over the entire molecular structure. Significant differ-
ences are seen for the dihedral angle parameters defined between
Table 4
Comparison of the important structural parameters of 3a from XRD and DFT calculations.
Bond length
Bond angle
Dihedral angle
Cl1–C2
C5–N6
C7–C8
C7–C9
1.739 (1.760)
1.369 (1.364)
1.504 (1.509)
1.431 (1.439)
1.373 (1.388)
1.487 (1.494)
1.508 (1.514)
1.222 (1.231)
1.463 (1.477)
1.335 (1.353)
1.465 (1.462)
1.408 (1.422)
1.367 (1.368)
1.420 (1.422)
Cl–C–C
C5–N6–C7
N6–C7–C8
N6–C7–C9
118.6 (118.5)
118.4 (119.1)
117.5 (117.0)
122.6 (122.2)
120.1 (120.0)
122.7 (121.2)
118.6 (118.5)
119.4 (119.0)
119.7 (120.3)
125.0 (124.1)
124.0 (127.2)
120.8 (119.4)
115.5 (116.4)
104.0 (119.0)
C3–C2–Cl–C20
C4–C5–N6–C7
C5–N6–C7–C8
C5–N6–C7–C9
179.5 (179.7)
179.7 (178.6)
178.8 (179.2)
0.5 (-1.8)
C9–C10
C10–C11
C9–C12
C12–O13
C12–C14
C14–C15
C15–C16
C16–C17
C17–O18
O18–C19
C7–C9–C10
C9–C10–C11
C7–C9–C12
C9–C12–O13
C9–C12–C14
C12–C14–C15
C14–C15–C16
C15–C16–C17
C16–C17–O18
C17–O18–C19
N6–C7–C9–C10
C7–C9–C10–C11
N6–C7–C9–C12
C7–C9–C12–O13
C7–C9–C12–C14
C9–C12–C14–C15
C12–C14–C15–C16
C14–C15–C16–C17
C15-C16-C17-O18
C16–C17–O18–C19
ꢁ1.1 (1.5)
179.4 (179.7)
176.6 (179.2)
ꢁ78.4 (ꢁ75.6)
99.0 (102.4)
9.8 (-3.9)
ꢁ178.5 (ꢁ179.0)
ꢁ148.7 (175.8)
1.7 (ꢁ0.1)
ꢁ167.5 (ꢁ178.5)
Table 5
Dipole moments and energies and molecular orbital energies of (3a-m).
Molecule
Dipole moment, Debye
Energy, au
HOMO
LUMO
Energy gap
CH-07
CH-01
CH-02
CH-03
CH-04
CH-05
CH-06
CH-08
CH-09
CH-10
CH-11
CH-12
CH-22
5.00
7.72
4.62
5.94
6.44
3.10
6.42
7.23
4.39
6.64
5.43
8.26
4.72
–1553.719
ꢁ1782.770
ꢁ2472.901
ꢁ1782.769
ꢁ1668.246
ꢁ2013.314
ꢁ1897.284
ꢁ1782.765
ꢁ1668.246
ꢁ1668.247
ꢁ2013.312
ꢁ1782.774
ꢁ1874.472
ꢁ0.240
ꢁ0.222
ꢁ0.242
ꢁ0.221
ꢁ0.236
ꢁ0.242
ꢁ0.231
ꢁ0.236
ꢁ0.239
ꢁ0.232
ꢁ0.240
ꢁ0.229
ꢁ0.240
ꢁ0.093
ꢁ0.088
ꢁ0.103
ꢁ0.085
ꢁ0.089
ꢁ0.099
ꢁ0.088
ꢁ0.088
ꢁ0.093
ꢁ0.086
ꢁ0.099
ꢁ0.081
ꢁ0.092
0.147
0.134
0.139
0.136
0.147
0.143
0.143
0.148
0.146
0.146
0.141
0.142
0.148

1016
S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
Fig. 6. The absorption spectra computed for 3a using time dependent density
functional theory.
reactivity [43]. A larger value of HOMO–LUMO gap refers to chem-
ically stable molecules and in vice versa the chemically reactive
molecules are often associated with smaller HOMO–LUMO gap.
Here, the results on HOMO–LUMO gaps for chalcone 3g and its
substituted compounds show that the reactivity of chalcones can
be controlled through chemical substitution. Due to the limited
number of molecules studied in this work, it was not possible for
us to deduce any correlation between the electron withdrawing
and donating nature of chemical substitution and reactivity. The
frontier molecular orbitals for all the chalcones are shown in
Fig. 5. The frontier molecular orbitals in most of the cases are found
to be localized on either of the aromatic moiety. Depending upon
the chemical substitution, the frontier molecular orbitals are found
to be localized on one or another aromatic moiety. Interestingly, in
the case of chalcones, 3b, 3e, 3g, 3h, 3k and 3l the HOMO and
LUMO molecular orbitals are localized on different aromatic moie-
ties and so HOMO–LUMO type excitation will exhibit a long range
charge transfer which is something useful in the design of novel
materials with larger non-linear response and two photon absorp-
tion cross sections. Moreover, we have computed the absorption
spectra for 3g, chalcone which is shown in Fig. 6. It has two bands
in the UV region with absorption wavelengths corresponding to
391 and 318 nm. The second band is the most intense than the first
one. The molecular orbitals involved in these two intense excita-
tions were analysed. The first intense band has HOMO ) LUMO
character and these frontier molecular orbitals are shown in
Fig. 5. As can be seen this excitation has
p
)
p⁄ character and
has some charge transfer from methoxy phenyl to carbonyl group.
The second band has contributions from HOMO-3 ) LUMO and
HOMO-2 ) LUMO + 1 type excitations. The use of chalcones as
UV-absorption filter has been discussed in literature [44] and the
current study shows that the molecule 3g in fact can be used for
such application.
We have in some detail discussed about the promising
non-linear optical response properties of chalcones in the introduc-
tion section. In order to report on the non-linear optical response
properties of the chalcones studied here, we have computed the
total static first hyperpolarizability (btotal) and hyperpolarizabilility
along the molecular dipole axis (bvec) [45] for 3g and 3a compounds
(these two molecules differ with respect to substitution of two
methoxy groups in the phenyl aromatic group). The values of btotal
and bvec for 3g are respectively, 12.0 and 7.1 ꢃ 10ꢁ30 esu while for 3a
the values are respectively, 16.9 and 10.1 ꢃ 10ꢁ30 esu. The larger
first hyperpolarizability for 3g when compared to 3a is due to
presence of additional electron donating groups in the former
compound and increased molecular dipole moment. The computed
Fig. 5. The optimized molecular structure and frontier molecular orbitals picture
for chalcone (3g) and its substituted compounds (in the order 3a-m).

S. Sarveswari et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 136 (2015) 1010–1017
1017
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The single crystal X-ray structure of a new chalcone-like, com-
pound, C27H22NO3Cl, is reported and supported by 1H and 13C NMR
data. The compound crystallizes in the monoclinic, P21/c space
group. Structural features of the molecule in the asymmetric unit
are described. In addition, molecular packing includes both weak
C---Hꢃ ꢃ ꢃN and C---Hꢃ ꢃ ꢃO intermolecular interactions observed
along with weak
p–p ring interactions between adjacent 5 and
6-membered rings of the quinolone group. The molecular structure
for this chalcones optimized from density functional theory calcu-
lations is in agreement with experimental XRD structure. Further
the calculations on substituted chalcones suggest that the molecu-
lar dipole moment and reactivity and charge transfer character can
be controlled by substituting with electron withdrawing and
donating groups in the appropriate ring positions. The calculations
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Acknowledgements
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JPJ acknowledges the NSF MRI program (Grant No.
CHE-1039027) for funds to purchase the X-ray diffractometer.
S. Sarveswari and V. Vijayakumar acknowledge VIT University for
providing the grant through RGEMS and seed fund to pursue
research in health sciences related area. Authors thank the
SIF-Chemistry for providing the NMR facilities.
Appendix A. Supplementary material
CCDC 966485 contains the supplementary crystallographic
data for C27 H22 Cl1 N1 O3. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223 336 033; or email:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.saa.2014.09.124.
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