Synthesis, crystal structure, experimental and theoretical investigations of 3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one

Article abstract of DOI:10.1016/j.molstruc.2016.08.022

A chalcone derivative namely, (E)-3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one (1v) has been synthesized and characterized on the basis of its spectral data. The solid state self-assembly studies of 1v were carried out through single crystal X-ray technique to see the major non-covalent interactions responsible for molecular alignment in the solid state. Furthermore, the optimized molecular geometry, vibrational frequencies, ¹H and ¹³C NMR chemical shift (in gas and in chloroform solvent) values and the molecular electrostatic potential (MEP) surface parameters of 1v were calculated using DFT/B3LYP/HF/M06 method with 6–311++G (d,p) basis set in ground state. All the theoretical calculations for 1v were found in good agreement with experimental data.

Full text of DOI:10.1016/j.molstruc.2016.08.022

Accepted Manuscript
Synthesis, crystal structure, experimental and theoretical investigations of 3-(4-
ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one
Faiza Anam, Asghar Abbas, Kong Mun Lo, Shahid Hameed, Ponnadurai Ramasami,
Yunusa Umar, Aman Ullah, Muhammad Moazzam Naseer
PII:
S0022-2860(16)30852-3
10.1016/j.molstruc.2016.08.022
MOLSTR 22848
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 1 February 2016
Revised Date: 9 August 2016
Accepted Date: 9 August 2016
Please cite this article as: F. Anam, A. Abbas, K.M. Lo, S. Hameed, P. Ramasami, Y. Umar, A. Ullah,
M.M. Naseer, Synthesis, crystal structure, experimental and theoretical investigations of 3-(4-ethoxy-3-
methoxyphenyl)-1-phenylprop-2-en-1-one, Journal of Molecular Structure (2016), doi: 10.1016/
j.molstruc.2016.08.022.
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GRAPHICAL ABSTRACT

ACCEPTED MANUSCRIPT
Synthesis, crystal structure, experimental and theoretical investigations of 3-
(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one
a
a
b
a
c,
Faiza Anam, Asghar Abbas, Kong Mun Lo, Shahid Hameed , Ponnadurai Ramasami *
d
e
a,
Yunusa Umar , Aman Ullah and Muhammad Moazzam Naseer *
a
Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
b
Department of Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
c
University of Mauritius, Mauritius
d
Department of Chemical and Process Engineering Technology, Jubail Industrial College
POBox 10099, Jubail Industrial City- 31961, Saudi Arabia.
e
Department of Agricultural, Food and Nutritional Science, University of Alberta, Canada.
Abstract
A chalcone derivative namely, (E)-3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one (1v)
has been synthesized and characterized on the basis of its spectral data. The solid state self-
assembly studies of 1v were carried out through single crystal X-ray technique to see the major
non-covalent interactions responsible for molecular alignment in the solid state. Furthermore, the
1
13
optimized molecular geometry, vibrational frequencies, H and C NMR chemical shift (in gas
and in chloroform solvent) values and the molecular electrostatic potential (MEP) surface
parameters of 1v were calculated using DFT/B3LYP/HF/M06 method with 6-311++G(d,p) basis
set in ground state. All the theoretical calculations for 1v were found in good agreement with
experimental data.
Keywords: Alkoxychalcone, Crystal Structure, FT-IR, NMR spectroscopy, DFT calculations.
*
9
Corresponding Authors: Email; ramchemi@intnet.mu (P. Ramasami), moazzam@qau.edu.pk; Fax: +92 51
0642241: Phone: +92 51 90642129 (M.M. Naseer)
1

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Introduction
Chalcones (benzylideneacetophenones) belong to one of the largest classes of plant
metabolites and are precursors of flavonoids and isoflavonoids that play major role in the plant
defense mechanism to protect from microorganisms, insects and animals [1-8]. Synthetically,
chalcones can easily be obtained by the Claisen-Schmidt condensation reaction between
substituted acetophenones and benzaldehydes. The possibility of having different substituents on
the two aromatic rings and their ability to act as Michael acceptors make this class of compounds
highly attractive drug scaffolds. Hence, a large variety of their derivatives have been synthesized
in recent years with interesting and diverse pharmacological activities such as anti-fungal, anti-
bacterial, anti-cancer, anti-inflammatory, anti-plasmodial, immunosuppressive, anti-oxidant, anti-
leishmanial, analgesic and anti-pyretic activities etc [9-16]. Other than their applications in
medicinal chemistry, they have also been reported to show nonlinear optical and luminescent
properties [17-20].
With the advent of various computational methods in recent years, the theoretical
investigations for solving structure and chemical reactivity related problems are getting increased
attention from computational chemistry community [21-29]. These methods are presently
emerging as an efficient tool for predicting molecular structures, harmonic force fields,
vibrational wavenumbers, IR intensities and Raman activities etc. of biologically important
molecules, and may serve as an alternative tool to various spectral techniques, that are needed for
structure elucidation, in near future. Therefore, a lot of energy and money may be saved by using
these methods.
In this context and as continuation of our recent research interests in organic synthesis,
self-assembly and theoretical spectral investigations of small organic molecules [30-44], herein,
we report the synthesis, solid state self-assembly, optimized molecular geometry, vibrational IR
analysis, Nuclear Magnetic Resonance (NMR) analysis and molecular electrostatic potential
(MEP) calculated at the B3LYP/6-311++G(d,p) level of (E)-3-(4-ethoxy-3-methoxyphenyl)-1-
phenylprop-2-en-1-one (1v), focusing on the comparison of calculated and the experimental
results.
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Experimental
General
All reagents and solvents were used as purchased from the supplier or recrystallized/redistilled as
required. Thin layer chromatography (TLC) was performed using aluminium sheets coated with
silica gel 60 F254 (Merck). The melting point of chalcone derivative (1v) was determined in open
capillary tubes by using Gallenkamp apparatus (MP-D) and was uncorrected. The FT-IR was
-1
recorded on NICOLET 6700 FT-IR Spectrometer (4000-400 cm ) using ATR (attenuated total
1
13
reflectance) method. The H and C-Nuclear Magnetic Resonance (NMR) spectra of 1v were
determined on Bruker spectrometer at 300MHz and 75MHz in CDCl , respectively, using
3
residual solvent signals as a reference.
Synthesis of a chalcone derivative (1v) [45]
In a 100 mL two neck-round bottom flask equipped with reflux condenser containing DMF
(
10 mL) was added 4-hydroxy-3-methoxybenzaldehyde (2g, 0.01 mole) and anhydrous K CO
2
3
o
(
2.07g, 0.015 mole) and heated the reaction mixture at 60-65 C for 30 minutes before the
dropwise addition of bromoethane (0.01 mole). After addition of bromoethane, the whole
o
reaction mixture was heated under N at 80 C for 4-5 hours. After the completion of the reaction,
2
monitored by TLC, the reaction mixture was poured into separating funnel containing
ethylacetate and washed several times with water. The organic layer was then dried over
anhydrous MgSO4, evaporated by using rotary evaporator to get 4-ethoxy-3-
methoxybenzaldehyde intermediate, which was used in the next step without further purification.
The 4-Alkoxy-3-methoxybenzaldehyde intermediate (0.01 mole, 1g) was dissolved in ethanol (10
mL) in a 100 mL round bottom flask and 37% ice cooled NaOH solution (10 mL) was then added
into it. After stirring the reaction mixture for 30 minutes at 0°C, the acetophenone (0.01 mole)
was added dropwise and stirred for another 4-6 hours. The precipitates thus appeared were
poured into the crushed ice, filtered and washed thoroughly with water. The obtained solid was
finally recrystallized from ethanol to get pure 1v.
1
v: Yield 94%; yellow crystals; m. p. 105-108˚C; R = 0.47 (n-hexane : ethyl acetate, 4:1), IR( ,
f
-1
1
cm ): 1652 (C=O), 1574 (C=C), 1237, 1035 (Ar-O-R); H NMR (300 MHz, CDCl ), 1.51 (3H, t,
3
J =6.9 Hz), 3.99 (3H, s), 4.17 (2H, q, J = 6.9 Hz), 6.91 (1H, d, J = 8.4 Hz), 7.18-7.28 (2H, m),
7
.40 (1H, d, J = 15.6 Hz), 7.49-7.54 (3H, m), 7.78 (1H, d, J = 15.6 Hz), 8.03 (2H, d, J = 6.9 Hz);
3

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1
3
C NMR (75 MHz, CDCl ) δ 14.07, 56.03, 64.03, 110.32, 112.16, 119.95, 123.21, 127.67,
3
1
28.45, 128.58, 132.58, 138.53, 145.17, 149.41, 150.86, 190.72; EIMS (m/z), 282.
2
.3. Crystallographic data collection and structural refinement
The single crystal X-Ray diffraction measurements for the 1v were carried out using Bruker
APEX-II CCD area-detector equipped with graphite monochromator at 296(2) K with Mo Kα
radiations (λ = 0.71073 Å). The structure is solved by direct methods [46] full-matrix least-
squares refinement on F² and 236 parameters for 4323 unique intensities (Rint = 0.011). The
crystal data and refinement details of 1v are summarized in Table 1.
Computational details
In the present work, all computations were performed with the Gaussian 09 program
package [47]. GaussView 5 molecular visualization program [48] was used for visual animation
and also for the verification of the normal modes assignment. The molecular structure and
vibrational calculations of chalcone derivative 1v were computed by using Becke-3-Lee Yang
Parr (B3LYP), HF and M06 levels of theory [49-51]. The standard 6-311++G(d,p) basis set is
used for all the calculations. The VEDA4 program [52] was used to characterize the normal
vibrational modes on the basis of Potential Energy Distribution (PED). The wavenumbers and
their intensities obtained from the computation were used to simulate infrared spectra. For the
NMR computations, the optimized molecular geometry of 1v was first obtained at the B3LYP/6-
1
13
3
11++G(d,p), HF/6-311++G(d,p) and M0/6-311++G(d,p) levels and then, the H and C NMR
chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method after the
molecular geometry optimization in gas phase. Furthermore, molecular electrostatic potential
(MEP) of 1v was computed using DFT/ B3LYP method with 6-311++G(d,p) basis set.
Results and discussion
Synthesis and spectral characterization
The synthesis of chalcone 1v was initiated by the preparation of 4-ethyloxy-3-
methoxybenzaldehyde intermediate by reacting equimolar quantities of 4-hydroxy-3-
0
methoxybenzaldehyde with ethyl bromide in DMF solvent using K CO as a base at 80 C. The
2
3
reaction proceeded smoothly providing excellent yield. The 4-ethyloxy-3-methoxybenzaldehyde
intermediate was then reacted with acetophenone under base catalyzed Claisen-Schmidt
4

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condensation reaction conditions for 4-6 hours to get our desired chalcone derivative 1v in 94%
1
13
yields (Scheme 1). The structure of 1v was confirmed by its physical and spectral (IR, H and C
NMR) data and were found geometrically pure with E configuration (Jtrans = ~16 Hz) around
1
double bond by HNMR spectroscopy.
-1
In FT-IR spectrum, the characteristic bands at 1652 and 1574 cm were assigned to the
carbonyl group (C=O) and olefinic double bond (−CH=CH−), respectively [53-55]. Furthermore,
two bands at 1237 and 1035 were indicative of the presence of alkyl-aryl ether (Ar-O-R) moiety.
Similarly, the two prominent doublets, one at 7.40 ppm and the other at 7.78 ppm with coupling
1
constants 15.6 Hz each in the H-NMR spectrum of 1v confirmed the presence of α and β -
hydrogen atoms of the olefinic double bond in the α, β-unsaturated carbonyl system. The
coupling constant (Jtrans = ~16 Hz) also confirmed E-configuration and geometrical purity of 1v.
Furthermore, the methoxy (-OCH ) and methylene (ArO−CH −) protons appeared as a singlet
3
2
and a quartet at 3.99 ppm and 4.17 ppm, respectively. Likewise, the conclusions drawn from the
1
3
C NMR data also supported the formation of desired chalcone derivative 1v.
Solid state self-assembly
The dependence of outstanding bulk properties of solids on the molecular alignment is the main
driving force for crystal engineers to understand solid state self-assembly process and to explore
new functional solids. The solid state self-assembly studies of 1v were carried out to identify the
structural features that play major role in the molecular alignment in the solid state. For this
purpose, good-quality single crystals of 1v suitable for X-ray analysis were grown in ethanol
solvent. The crystal data and structural refinement parameters of 1v are summarized in Table 1.
The 3D-network of 1v is composed of various 1D-tapes (Figure 1). Each 1D-tape is formed
by the connection of various antiparallel/centrosymmtric-arranged molecules of 1v through
CH···O and CH···π interactions (Figure 1a). These tapes are also connected to the neighbouring
chains by CH···O interactions to form 2D-sheets which by means of CH···O and CH···π
interactions form 3D-network of 1v (Figure 1b).
Molecular geometry
The optimized molecular structure along with the numbering of atoms of 1v calculated at
B3LYP/6-311++G(d,p) level of theory is given in Fig. 2. The geometrical parameters (bond
lengths and bond angles) corresponding to the optimized geometries of the title compound are
given in Table 2 along with the X-ray experiment data. Generally, most of the optimized bond
lengths and angles are slightly different from the experimental ones. This is expected because,
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one isolated molecule is considered in theoretical gas phase calculation, whereas packed
molecules are considered in solid phase during the experimental measurement. However, the
calculated geometric parameters are in good agreement with the experimental results. To be
specific, the root mean square (RMS) errors are 0.0835 Å, 0.0780 Å and 0.0851 Å for the bond
lengths calculated at HF, B3LYP and M06 respectively; while the RMS values for the bond
angles are found to be 1.09°, 1.13° and 1.04° calculated at HF, B3LYP and M06 respectively.
Vibrational IR Spectra Analysis
The optimized structural parameters were used to compute the vibrational wavenumbers
for the title compound at HF/6-311++G(d,p), B3LYP/6-311++G(d,p) and M06/6-311++G(d,p)
levels of theory. Since, the calculated vibrational wavenumbers are generally larger than the
observed values due to the well-known systematic errors and the neglect of anharmonicity and
incomplete treatment of electron correlation and basis set truncation. The differences are
accounted for by using scaling factor. However, the high frequency region for the vibrational
modes contains the stretching vibrational modes related to functional groups of a molecule and
the lower frequency region can include the overlapped bands of the compounds, the characteristic
properties of high and low frequency regions require different scaling factors. For these reasons,
-1
the calculated vibrational wavenumbers were scaled as 0.983 for frequencies less than 1700 cm
-1
and 0.958 for frequencies higher than 1700 cm for B3LYP/6-311++G(d,p) basis set [56, 57].
Table 3 presents the calculated (scaled) vibrational wavenumbers and IR intensities along with
the assignment of vibrational modes for the 1v compound. The Table also shows the observed
infrared wavenumbers of 1v for comparison. The assignment of the fundamental vibrational
modes is proposed on the basis of Potential Energy Distribution using VEDA 4 program and the
animation option of Gauss View graphical interface of Gaussian program. A detailed description
of the normal modes based on PED is given in the last column of Table 3. The (E)-3-(4-
(pentyloxy)phenyl)-1-phenylprop-2-en-1-one molecule (1v) has 39 atoms and the number of
fundamental vibration modes is 111 which are all IR active. The absence of imaginary
wavenumbers in the calculated vibrational spectrum confirms that the optimized structure
corresponds to the minimum energy on the potential energy surface.
The vibrational wavenumbers and the corresponding intensities obtained from
calculations at the three levels of theory were used to simulate the IR spectra of the title
compound. For simulation, pure Lorentizian band shape with a bandwidth of full width and half
maximum (FWHM) of 10 cm-1 was used to plot the calculated IR and Raman spectra. The
6

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experimental and simulated IR spectra of 1v molecule are presented in Figure 3. This figure
clearly shows the spectral characteristics of the title molecule. Generally, the aromatic C-H
-1
stretching modes appears in the region 3100 – 3000 cm [58]. In the present study, the vibrational
-1
mode at 3067 cm in the FTIR spectrum of 1v (Fig. 3) is attributed to aromatic C-H stretching
-1
vibrations. This mode was found to be 3230, 3267 and 3055 cm at B3LYP/6-311++G(d,p),
HF/6-311++G(d,p) and M06/6-311++G(d,p) respectively and this show good agreement between
experimental and theoretical vibrational wavenumbers.
Nuclear Magnetic Resonance (NMR) analysis
1
13
The H and C NMR spectroscopy is a very important analytical tool used by chemist for
the identification and characterization of organic compounds. However, since there is no simple
correlation between the measured chemical shifts and structural parameters, the interpretation of
experimental NMR spectra could be awkward. The calculation of NMR chemical shifts can
provide in many cases the necessary information for the correct interpretation of experimental
NMR spectra. Thus, the combined use of experimental and quantum mechanical calculation of
chemical shifts offers a powerful tool for the reliable interpretation and prediction of the
1
13
structures of bulky molecules. In the present work, the H and C NMR isotropic shielding for
v molecule were calculated with the Gauge Invariant Atomic Orbitals (GIAO) method using the
1
optimized geometrical parameters obtained from the HF/6-311++G(d,p), B3LYP/6-311++G(d,p)
and M06/6-311++G(d,p) levels of theory. The chemical shifts are reported in ppm relative to
1
13
TMS isotropic chemical shifts for H and C calculated at the same level of theory. The
1
13
experimental and calculated H and C NMR chemical shift values of 1v molecule are presented
1
3
in Table 4. Generally, the C NMR chemical shifts for aromatic ring are greater than 100 ppm.
1
3
As can be seen from Table 3, the C NMR chemical shift values of aromatic carbons of 1v
compound have been observed at the interval of 110 – 151 ppm. The observed and calculated
chemical shift values of C and C atoms (that are connected to the oxygen atoms O and O
11
12
10
20
respectively) are higher than those of other ring carbon atoms. The chemical shifts of methyl and
methylene carbon atoms which are shielded by their own hydrogen atoms are observed down
1
3
field. On the other hand, the C chemical shift of carbonyl group (CO) was observed at 190.72
ppm and calculated to be at 189.59, 192.02 and 186.75 ppm at HF, BELYP and MO6 methods
1
13
respectively. In general, both H and C NMR calculations are in reasonable agreement with the
1
3
1
experimental values. The correlation between the observed and calculated C ( H) chemical shift
7

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values were found to be 0.9872(0.9695), 0.9944(0.9868) and 0.9922(0.9814) for HF, B3LYP and
M06 respectively.
Molecular electrostatic potential (MEP)
Molecular Electrostatic Potential (MEP) mapping is very important in the study of molecular
interactions, prediction of relative sites for nucleophilic and electrophilic attack, molecular cluster
and predication wide range of macroscopic properties [59, 60]. To predict reactive sites for
nucleophilic and electrophilic attack for 1v molecule, the MEP at the B3LYP/6-311++G(d,p)
optimized geometry was calculated and the result is illustrated in Figure S1 (Supporting
Information). The electrostatic potentials at the surface are represented by different colors; red,
blue and green represent the regions of negative, positive and zero electrostatic potentials
respectively. In addition, the negative regions (red color) of MEP are related to electrophilic
reactivity, and the positive regions (blue color) are related to the nucleophilic reactivity. As can
be seen from Figure 4, the negative electrostatic potentials are mainly localized over the carbonyl
oxygen atom, and is a potential site for electrophilic attack. The MEP of 1v is dominated by the
green regions which correspond to electrostatic potential halfway between the red and the blue
and are potential sites for intermolecular interactions.
Conclusions
In conclusion, we have synthesized a chalcone derivative namely, (E)-3-(4-ethoxy-3-
1
methoxyphenyl)-1-phenylprop-2-en-1-one (1v), characterized on the basis of its spectral (IR, H
1
3
&
C NMR and MS) data and its solid state self-assembly studies were carried out through
single crystal X-ray technique. The CH···O and CH···π interactions were found to be the main
supramolecular forces involved in stabilization of its self-assembly in the solid state.
Furthermore, spectral and crystallographic structural data have been verified through quantum
chemical computations of 1v at HF/6-311++G(d,p), B3LYP/6-311++G(d,p) and M06/6-
1
3
11++G(d,p) levels of theory . The optimized molecular geometry, vibrational frequencies, H
1
3
and C NMR chemical shift (in gas and in chloroform solvent) values and the molecular
electrostatic potential (MEP) surface parameters of 1v showed good agreement with experimental
data. Therefore, these computational methods may be considered as powerful tools not only to
compliment the experimental results but also as a replacement to some expensive and tedious
experimental characterizations.
Acknowledgements
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We are highly grateful to the Department of Chemistry, Quaid-i-Azam University for necessary
laboratory facilities and Higher Education Commission (HEC), Govt. of Pakistan for financial
support.
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14

ACCEPTED MANUSCRIPT
Table 1. Crystallographic data for chalcone derivative 1v
Crystal data
CCDC
1v
983900
C H NO
3
Chemical formula
Mr
1
8
18
296.33
Crystal system, space group
Temperature (K)
a, b, c (Å)
Monoclinic, P2 /c
1
139
12.4849 (2), 14.0781 (2), 8.7868 (1)
β (°)
105.787 (1)
1486.14 (4)
4
3
V (Å )
Z
Radiation type
Mo Kα
-1
µ (mm )
0.09
Crystal size (mm)
Data collection
Diffractometer
0.30 × 0.16 × 0.10
Bruker APEX-II CCD area-detector
diffractometer
Absorption correction
Multi-scan
(
SADABS; Sheldrick, 1996)
Tmin, Tmax
0.670, 0.746
No. of measured, independent and 14019, 3415, 2783
observed [I > 2σ(I)] reflections
Rint
sin θ/λ)max (Å )
0.023
0.650
-1
(
Refinement
2
2
2
R[F > 2σ(F )], wR(F ), S
No. of reflections
0.037, 0.102, 1.02
3415
No. of parameters
192
H-atom treatment
H-atom parameters constrained
0.25, -0.18
-3
∆
〉max, ∆〉min (e Å )
1
(a)

ACCEPTED MANUSCRIPT
Table 2: The calculated and experimental molecular geometry parameters of the 1v.
Bond
Length*
Bond
Angle *
(°)
A(8-1-11)
A(1-8-4)
Calculated bond length (Å)
Calculated bond angle (°)
X-Ray
Å)
X-Ray
(°)
(
(Å)
HF
B3LYP
1.406
1.338
1.343
1.398
1.196
1.084
1.086
1.084
1.514
1.087
1.087
1.408
1.380
1.375
1.073
1.403
1.471
1.379
1.077
1.329
1.072
1.488
1.503
1.393
1.390
1.073
1.382
1.075
1.388
1.076
1.384
1.072
1.390
1.074
1.086
1.080
1.086
1.074
1.386
1.075
M06
HF
B3LYP
M06
R(1-8)
R(1-11)
R(2-12)
R(2-32)
R(3-20)
R(4-5)
R(4-6)
R(4-7)
R(4-8)
R(8-9)
R(8-10)
1.438
1.365
1.369
1.428
1.226
0.980
0.980
0.980
1.508
0.989
0.990
1.432
1.353
1.359
1.422
1.226
1.092
1.093
1.092
1.516
1.097
1.097
1.418
1.396
1.387
1.082
1.412
1.456
1.398
1.088
1.348
1.082
1.479
1.505
1.402
1.401
1.083
1.389
1.084
1.396
1.084
1.393
1.081
1.392
1.083
1.095
1.089
1.095
1.083
1.394
1.084
1.417
1.343
1.349
1.406
1.218
1.093
1.093
1.093
1.504
1.100
1.100
1.413
1.390
1.381
1.085
1.406
1.450
1.391
1.091
1.342
1.086
1.473
1.496
1.396
1.395
1.085
1.384
1.086
1.390
1.086
1.387
1.084
1.387
1.085
1.098
1.090
1.098
1.085
1.388
1.086
116.9
107.3
110.3
110.3
115.7
125.1
116.7
115.1
124.7
109.4
109.5
109.4
122.0
120.2
109.4
109.5
109.5
109.5
109.5
109.5
110.3
110.3
108.5
119.1 120.4
107.6 107.7
109.5 109.8
109.5 109.8
115.9 116.1
125.0 124.9
118.4 119.8
115.7 115.9
125.0 124.8
111.4 111.5
105.7 106.1
111.4 111.5
121.7 121.6
119.6 119.8
108.5 108.7
108.5 108.5
110.7 110.6
108.5 108.7
109.8 109.9
110.7 110.6
111.0 110.6
111.0 110.6
108.3 108.2
119.1 119.0
119.3 119.3
119.9 120.2
120.9 121.0
119.8 119.8
121.8 121.7
118.4 118.5
118.2 118.0
118.0 118.3
123.8 123.7
115.9 115.7
128.3 127.7
120.8 120.6
120.4 120.8
115.8 116.6
121.0 121.5
120.4 120.0
118.6 118.4
118.7 118.6
117.8 118.0
123.4 123.0
118.8 119.1
118.2 118.8
120.7 120.5
120.5 120.6
120.6 120.5
121.1 120.7
119.9 119.9
120.1 120.0
120.0 120.1
120.1 120.0
119.8 119.9
120.1 120.0
120.1 120.0
120.1 120.2
119.1 118.8
118.8 118.6
109.4 109.1
109.5 109.4
109.4 109.1
118.9 118.9
119.8 119.8
118.8
107.5
109.7
109.7
115.8
125.0
117.8
115.7
125.0
111.5
106.4
111.6
121.8
119.9
108.5
108.2
110.6
108.5
110.3
110.6
111.1
111.2
107.7
119.2
119.3
119.9
120.8
120.0
121.7
118.3
118.4
118.2
123.4
116.2
128.0
120.8
120.3
115.8
120.9
120.0
119.0
118.3
117.6
123.4
118.9
118.1
120.6
120.5
120.5
121.3
120.0
120.0
120.0
120.1
119.9
120.0
120.0
120.1
119.2
118.9
109.1
109.0
109.1
119.0
119.9
1.0
A(1-8-9)
A(1-8-10)
A(1-11-12)
A(1-11-28)
A(12-2-32)
A(2-12-11)
A(2-12-13)
A(2-32-33)
A(2-32-34)
A(2-32-35)
A(3-20-18)
A(3-20-21)
A(5-4-6)
A(5-4-7)
A(5-4-8)
A(6-4-7)
A(6-4-8)
A(7-4-8)
A(4-8-9)
A(4-8-10)
A(9-8-10)
A(12-11-28) 119.3
A(11-12-13) 120.2
A(11-28-29) 119.8
A(11-28-30) 120.3
A(12-13-14) 119.7
A(12-13-15) 120.6
A(14-13-15) 119.7
A(13-15-16) 118.6
A(13-15-30) 118.8
A(16-15-30) 122.6
A(15-16-17) 116.7
A(15-16-18) 126.5
A(15-30-28) 120.9
A(15-30-31) 119.6
A(17-16-18) 116.8
A(16-18-19) 119.0
A(16-18-20) 121.9
R(11-12) 1.409
R(11-28) 1.385
R(12-13) 1.380
R(13-14) 0.950
R(13-15) 1.403
R(15-16) 1.463
R(15-30) 1.391
R(16-17) 0.950
R(16-18) 1.335
R(18-19) 0.949
R(18-20) 1.475
R(20-21) 1.495
R(21-22) 1.394
R(21-36) 1.393
R(22-23) 0.950
R(22-24) 1.385
R(24-25) 0.950
R(24-26) 1.380
R(26-27) 0.950
R(26-38) 1.387
R(28-29) 0.950
R(28-30) 1.391
R(30-31) 0.950
R(32-33) 0.980
R(32-34) 0.980
R(32-35) 0.980
R(36-37) 0.950
R(36-38) 1.387
R(38-39) 0.950
RMSD
0.084 0.078
0.085 A(19-18-20) 119.0
A(18-20-21) 117.8
A(20-21-22) 119.6
A(20-21-36) 120.9
A(22-21-36) 119.4
A(21-22-23) 120.0
A(21-22-24) 120.2
A(21-36-37) 119.9
A(21-36-38) 120.1
A(23-22-24) 119.9
A(22-24-25) 120.0
A(22-24-26) 120.1
A(25-24-26) 120.0
A(24-26-27) 119.8
A(24-26-38) 120.3
A(27-26-38) 119.9
A(26-38-36) 119.9
A(26-38-39) 120.0
A(29-28-30) 119.9
A(28-30-31) 119.5
A(33-32-34) 109.5
A(33-32-35) 109.5
A(34-32-35) 109.5
A(37-36-38) 119.9
A(36-38-39) 120.1
RMSD
1.1
1.1
*Atomic number are given in Figure 3.
2

ACCEPTED MANUSCRIPT
-1
Table 3: The experimental and calculated wavenumbers (cm ) and their assignment of 1v.
HF
Intensity
B3LYP
MO6
Intensity
Expt.
Assignment (PED ≥ 10%)
a
b
a
b
a
b
IR
234
3230
IR
Intensity
IR
3
19.45
1.09
3075
3067
3066
3065
3056
3051
3048
3039
3030
3012
3004
2984
2975
2935
2911
2909
2879
2873
1683
1619
1608
1593
1585
1576
1523
1494
1493
1479
1475
1467
1458
1456
1450
1419
1403
1378
1346
1338
1323
1316
1305
1292
1283
1264
1242
1206
1196
1180
1176
1162
1157
1149
1141
1114
1088
12.17
11.52
1.91
3057
3055
3053
3052
3043
3040
3036
3031
3022
3006
2999
2994
2990
2932
2909
2901
2866
2859
1728
1646
1622
1614
1600
1596
1531
1489
1466
1454
1446
1444
1441
1431
1427
1414
1391
1356
1354
1330
1327
1313
1289
1278
1275
1272
1250
1198
1183
1172
1165
1145
1142
1136
1123
1117
1088
9.73
υCH(99)
υCH(96)
υCH(88)
υCH(78)
υCH(78)
υCH(69)
υCH(90)
υCH(90)
υCH(86)
υC=CH(83)
3
067 w
10.43
10.43
12.79
14.93
17.29
3.02
3
3
3
3
3
3
3
3
228
225
215
206
204
193
189
181
6.40
6.73
13.49
2.52
6.57
31.76
12.26
11.77
0.42
28.71
4.46
10.68
0.48
10.39
0.07
0.08
1.14
21.49
2.17
2
2
2
976 w
973 w
972 w
3146
3116
3101
42.21
46.72
40.12
47.25
29.74
37.39
46.30
35.25
236.08
418.40
11.19
200.89
70.12
6.50
23.59
25.14
22.20
34.59
25.37
26.95
45.99
36.88
149.36
144.85
11.86
280.89
163.97
288.76
358.94
0.38
υCH
υCH
υCH
υCH
υCH
υCH
υCH
υCH
3
3
3
3
2
3
3
2
(99)
(86)
(97)
(100)
(99)
(99)
(99)
(100)
20.48
17.47
32.45
22.91
28.37
46.93
40.05
155.04
318.34
20.46
424.18
21.64
142.97
553.01
3.71
3
3
3
085
061
040
2
2
1
880 w
839 w
707 w
3028
3025
1839
υCO(77)
1
735
υCC(73) + υC=C(10)
υC=C(66) + δHCC(13) + δCCC(11)
υCC(66)
1
652 s
1756
1
1
751
734
υCC(49)
1
1
1
1
576 sh
574 s
515 w
512 s
1730
1659
1621
1620
υCC(55) + δHCC(11)
δHCH(75) +τHCCO(12)
δHCC(73)
468.16
61.18
2.51
81.09
52.34
8.16
44.48
42.51
49.49
10.16
7.48
δHCH(77)
1
1
1
602
594
590
32.23
8.06
δHCH(79)
δHCH(79)
4.62
9.36
δHCH(26)
1
1
1
448 w
1584
1572
1564
26.29
5.74
7.58
υCC(15) + δHCC(59) + δCCC(10)
δHCH(92)
446 s
27.92
5.02
15.60
8.45
444 w
16.81
62.93
81.71
8.42
δHCH(78)
1
1
1
539
531
495
32.94
71.36
10.19
271.86
26.48
4.51
7.84
υCC(29) + δHCC(46)
υCC(56)
88.46
94.90
215.84
6.93
δHCH(10)
1
336 w
335 s
1446
1427
9.54
υCO(56) + δHCC(15)
δHCC(68)
1
485.03
65.86
165.96
51.68
1.57
1
1
1
1
1
420
410
405
396
360
1.49
δHCC(65)
3.97
34.79
82.12
185.04
365.57
248.73
219.14
129.31
21.27
52.00
66.74
4.42
υCO(13) + δHCC(51)
υCC(19) + δHCC(53)
δHCC(80)
5.60
30.31
0.76
278.60
238.11
56.80
28.14
63.63
16.71
4.51
δHCC(44)
1
240 w
238 s
1318
1308
691.14
232.92
187.60
40.64
45.97
61.03
4.75
υCC(32) + δHCC(35)
υCC(15) + υC-O(10) +δ HCC(29)
δHCC(67) + δCCO(10)
δHCC(24) + τHCOC(31)
δHCC(12)
1
1
1
1
1
1
297
289
266
264
257
δHCC(65)
2.53
δHCC(20)
1
1
1
142 w
140 w
137 s
1241
1216
1206
265.93
8.04
3.59
1.63
δHCH(28)
0.93
0.39
δHCH(20)
24.20
7.93
242.06
1.68
135.28
6.89
υCC(25) + δHCC(22)
υCC(43) + δHCC(11)
υCO(25) + υCC(19) + δCCC(15)
1
1
193
153
19.08
1.90
2.75
3

ACCEPTED MANUSCRIPT
1
1
1
039 s
036 s
034 s
1151
1133
1108
0.13
77.72
42.93
54.46
4.67
4.58
182.75
5.84
4.76
3.55
4.01
12.49
0.27
33.16
0.53
5.33
27.94
5.28
36.34
16.75
2.95
6.27
68.43
10.51
22.16
1.01
9.35
6.19
75.90
6.29
2.24
1.78
6.09
0.35
0.06
2.25
2.62
3.10
5.77
0.34
0.38
0.74
0.19
0.92
0.18
0.21
2.97
0.80
0.10
1044
1037
1036
1018
1007
999
992
975
948
931
918
911
875
865
849
844
825
798
784
783
739
738
698
686
665
621
606
594
573
522
503
467
438
408
404
375
351
341
305
285
246
241
225
189
181
166
133
117
107
60.06
44.17
97.91
223.74
26.59
1.88
0.11
0.76
1.60
1.52
21.36
1.11
1.15
1.74
23.11
2.29
0.94
14.35
25.72
27.56
8.43
3.39
52.50
5.53
18.63
1.29
4.83
10.65
78.01
6.05
2.86
1.51
5.46
1.89
0.00
1.82
2.38
3.83
6.30
0.14
0.27
0.87
0.16
0.92
0.05
0.19
3.27
0.75
1079
1059
1035
1019
997
991
989
975
953
928
925
904
869
866
844
843
815
792
791
778
741
735
696
683
660
611
607
588
569
521
501
466
435
410
400
376
360
344
311
285
250
245
218
192
183
168
137
122
106
20.77
72.22
12.73
178.14
24.05
12.17
2.42
0.62
5.54
2.54
12.72
1.54
3.43
2.80
25.15
1.30
2.95
7.89
9.97
41.97
9.81
4.07
46.52
9.28
19.48
1.79
5.61
8.82
65.88
6.64
2.60
0.93
5.36
1.05
0.17
1.89
2.89
3.22
6.55
0.56
0.48
0.31
0.16
0.96
0.08
0.17
3.02
0.65
0.24
υC-C(32) + υC-O(10)
υC-C(28) + υC-O(11)
τHCCC(63)
1
1
1
1
105
100
089
083
τHCCC(70) + τCCCC(11)
τHCCC(79) + τCCCC(15)
δCCC(74)
υCC(72)
971 vs
1063
δCCC(55)
1
1
1
039
029
014
τHCCC(83)
τHCCC(80)
υCC(36) + τHCCC(19)
υCC(17) + δCCC(10)
τHCCC(78)
9
88
77
53
9
9
τHCCC(97)
851 vs
935
τHCCC(68)
9
9
29
05
δCOC(10) + τHCCC(39)
τHCCC(40)
8
7
7
01s
877
858
846
τHCOC(68)
77 vs
75 s
τHCCC(53) + τCCCC(24)
υCO(36) + δCCO(12) + δCCC(15)
τCCCC(13) + τOCCC(66)
υCC(16) + δCCC(27)
τHCCC(25) + τCCCC(47)
τCCCC(11) + τOCCC(43)
δCCC(31)
8
7
13
87
7
12 vs
55 vs
770
42
711
7
6
6
6
6
62
54
43
δCCC(81)
δCCO(64)
τCCCC(42)
565 s
612
δCCC(39)
5
5
5
4
4
4
4
3
3
3
3
2
2
2
2
1
1
1
1
1
57
43
11
72
44
32
12
73
64
24
09
70
57
46
05
93
81
42
26
08
δCCO(18)
-
τCCCC(59)
δCCO(10) + τCCCC(26)
τHCCC(17) + τCCCC(77)
δCOC(34) + τCCCC(11)
τOCCC(68) + τCCCC(10)
δCCO(12) + δCOC(38)
δCCO(60)
τHCOC(44) + τCCCC(29)
δCOC(46)
τHCCO(28)
τHCOC(12) + τCCCC(19)
τHCCO(92)
δCCO(11) + τCCCC(27)
υCC(28) + δCCC(22)
τCCCC(34) + τCCOC(11)
δCCO(41) + τCCCC(16)
δCCO(54) + τCCCC(11)
τHCCO(10) + τCOCC(58)
0.10
-1
a
-1
Scaled vibrational IR wavenumbers (cm ); 0.983 scaling factor for the vibrational wavenumbers below 1800 cm
-
1
b
-1
and 0.958 for the vibrational wavenumbers above 1800 cm . Calculated infrared intensities in km mol .
4

ACCEPTED MANUSCRIPT
1
13
Table 4: The calculated and experimental H and C NMR chemical shifts (ppm) of 1v.
Calculated Chemical Shifts TMS
-311++G(d,p) GIAO (ppm)
Calculated Chemical Shifts TMS
6-311++G(d,p) GIAO (ppm)
Experiment
Chemical Shifts
Experiment
Chemical Shifts in
6
Nucleus
Nucleus
in CHCl
3
-d
3
CHCl -d
HF
B3LYP
M06
HF
B3LYP
M06
C4
C8
14.70
64.41
17.48
16.82
15.67
H5
1.51
1.51
1.76
1.30
1.79
4.02
4.01
7.01
8.15
7.77
8.60
7.61
7.77
6.90
7.89
3.69
4.14
3.73
8.27
7.66
1.36
1.48
1.03
1.50
3.69
3.69
6.73
7.81
7.40
8.34
7.37
7.51
6.63
7.51
3.40
3.92
3.43
7.87
7.50
0.38
1.19
0.82
1.15
3.39
3.38
6.90
8.23
7.38
8.21
7.60
7.64
6.45
7.62
3.38
4.04
3.57
7.76
7.49
0.53
57.65
68.68
61.28
H6
C11
C12
C13
C15
C16
C18
C20
C21
C22
C24
C26
C28
C30
C32
C36
C38
RMSD
150.86
149.41
110.32
127.67
145.17
119.5
156.05
153.40
120.20
131.56
156.41
119.26
189.59
144.73
139.70
134.38
140.32
114.92
125.00
49.69
159.34
157.36
119.86
134.12
151.17
118.76
192.02
146.99
136.61
135.26
138.15
114.95
123.22
56.76
156.78
154.95
118.08
132.50
151.57
118.23
186.75
143.89
135.71
134.27
138.33
114.75
121.99
55.60
H7
1.51
H9
4.17
H10
H14
H19
H17
H23
H25
H27
H29
H31
H33
H34
H35
H37
H39
4.17
7.18-7.28
7.40
7.78
190.72
138.53
128.45
128.58
132.58
112.16
123.21
56.03
8.03
7.49-7.54
7.49-7.54
6.91
7.18-7.28
3.99
3.99
3.99
128.45
128.58
136.53
132.61
6.34
133.81
133.44
5.79
133.38
133.32
4.83
8.03
7.49-7.54
5

ACCEPTED MANUSCRIPT
(a)
(b)
Figure 1: Solid state self-assembly of 1v: a) 1D-supramolecular tapes; b) 3D-network
1

ACCEPTED MANUSCRIPT
Figure 2: Optimized structure and atom numbering for (E)-(4-Ethoxy-3-methoxyphyl)-1-
phenylprop-2-en-1-one (1v)
2

ACCEPTED MANUSCRIPT
Figure 3. IR spectra (a) experimental and simulated at (b) B3LYP/6-311++G(d,p), (c) HF/6-
3
11++G(d,p) and (d) M06/6-311++G(d,p) of 1v.
3

ACCEPTED MANUSCRIPT
O
O
O
O
K CO , DMF
2
3
HO
CHO
O
CHO
o
8
0 C
NaOH/H
O/EtOH
2
O
RT, 4-6 hrs
O
Scheme 1. Synthesis of new chalcone derivative 1v
1

ACCEPTED MANUSCRIPT
Research Highlights:
•
•
•
•
Chalcones are attractive organic molecules with diverse applications.
Synthesis of (E)-3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one.
Spectral characterization and theoretical calculations.
B3LYP/6-311++G(d,p), HF/6-311++G(d,p) and M06/6-311++G(d,p).