Temperature dependence of the Raman spectrum of 1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one

Article abstract of DOI:10.1016/j.saa.2017.02.051

The heterocyclic chalcone containing thiophene ring 1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one, C₁₃H₉ClOS was synthesized and investigated using experimental techniques such as nuclear magnetic resonance (¹H and

Full text of DOI:10.1016/j.saa.2017.02.051

Accepted Manuscript
Temperature dependence of the Raman spectrum of
1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one
T.A. de Toledo, R.C. da Costa, H.M. Al-Maqtari, J. Jamalis, P.S.
Pizani
PII:
DOI:
Reference:
S1386-1425(17)30162-2
doi: 10.1016/j.saa.2017.02.051
SAA 14973
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
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Revised date:
Accepted date:
21 September 2016
13 February 2017
22 February 2017
Please cite this article as: T.A. de Toledo, R.C. da Costa, H.M. Al-Maqtari, J. Jamalis,
P.S. Pizani Temperature dependence of the Raman spectrum of
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author was captured as affiliation for all authors. Please check if appropriate. Saa(2017),
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ACCEPTED MANUSCRIPT
Temperature dependence of the Raman spectrum of 1-(4-Chlorophenyl)-3-(2-
thienyl)prop-2-en-1-one
T. A. de Toledoa, b, *, R. C. da Costaa,c, H. M. Al-Maqtarid, J. Jamalisd, P. S. Pizania
a Universidade Federal de São Carlos, Departamento de Física, São Carlos-SP, 13565-905,
Brazil.
b Universidade de Cuiabá, Faculdade de Engenharia, Campus Barão, Cuiabá - MT, 78005-300,
Brazil.
c Universidade Federal de Campina Grande, Centro de Ciências e Tecnologia Agroalimentar,
Pombal-PB, 58840-000, Brazil.
d Universiti of Teknologi Malaysia, Department of Chemistry, Faculty of Science, Malaysia.

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Abstract
The heterocyclic chalcone containing thiophene ring 1-(4-Chlorophenyl)-3-(2-thienyl)prop-2-
en-1-one, C13H9ClOS was synthesized and investigated using experimental techniques such as
nuclear magnetic resonance (1H and 13C NMR), Fourier transform infrared spectroscopy (FTIR)
at room temperature, differential scanning calorimeter (DSC) from room temperature to 500 K
and Raman scattering at the temperature range 10-413 K in order to study its structure and
vibrational properties as well as stability and possible phase transition. Density functional
theory (DFT) calculations was performed to determine the vibrational spectrum viewing to
improve the knowledge of the material properties. A reasonable agreement was observed
between theoretical and experimental Raman spectrum taken at 10 K since anharmonic effects
of the molecular motion is reduced at low temperatures, leading to a more comprehensive
assignment of the vibrational modes. Increasing the temperature up to 393 K, was observed the
typical phonon anharmonicity behavior associated to changes in the Raman line intensities, line-
widths and red-shift, in special in the external mode region, whereas the internal modes region
remains almost unchanged due its strong chemical bonds. Furthermore, C13H9ClOS goes to
melting phase transition in the temperature range 393-403 K and then sublimates in the
temperature range 403-413 K. This is denounced by the disappearance of the external modes
and the absence of internal modes in the Raman spectra, in accordance with DSC curve. The
enthalpy (ΔH) obtained from the integration of the endothermic peak in DSC curve centered at
397 K is founded to be 121.5 J/g.
Keywords: Heterocyclic; 1-(4-Chlorophenyl)-3-(2-thienyl)prop-2-en-1-one; Spectroscopic
studies; Phase transition; Phonon Anharmonicity; DFT calculations.

Corresponding author. Phone: (55) 65 99981-3753;
E-mail address: thiagotoledo21@gmail.com
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1. Introduction
The investigation of temperature dependence of the Raman spectrum of the
organic materials, in special those with potential biological application, has attracted the
attention of many studies in the last decades because the vibrational spectrum plays a
fundamental role in material properties like thermal expansion, anharmonicity, stability
and phase transition [1-3]. For example, in the case of pharmaceuticals, any change in
the molecular structure may lead to modification in the biological properties, therefore
is essential to determine the temperature stability range in order to avoid risk to human
life [4,5]. On the other hand, in the case of electronic device applications, the
understanding of electron-phonon interaction, transport and vibrational properties due to
heating is also a relevant matter because of technological driver such as nanoparticles
for thermal medical therapies and thermal management of nanoscale electronic devices
[6, 7]. Usually, this information may be revealed by band position and line broadening
in the Raman spectrum when temperature increases.
In the view of mentioned facts and our concern on the investigation of the
thermal properties of organic materials, the heterocyclic chalcone containing thiophene
ring 1-(4-Chlorophenyl)-3-(2-thienyl)prop-2-en-1-one, C13H9ClOS is synthesized and
investigated using the experimental technique such as nuclear magnetic resonance (1H
and 13C NMR), Fourier transform infrared spectroscopy (FTIR) at room temperature,
differential scanning calorimeter (DSC) from room temperature to 500 K and Raman
scattering technique in the temperature range 10-413 K in order to investigate its
molecular structure, vibrational properties, stability and a possible phase transition,
which is a fundamental parameter for technological application. To improve the
knowledge of the physical properties of this material, theoretical calculation based on
density functional theory (DFT) is performed viewing to predict the most of vibrational
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modes and then correlating with the experimentally observed infrared and Raman bands,
that is, the theoretical predictions serves as a guide to understand the vibrational
spectrum. To the best of our knowledge, there is limited information available in the
literature about C13H9ClOS properties, with exception of the crystalline structure
determination at low temperature available in ref. [8], which also motivates this
investigation. According to literature [9-15], thiophene and chalcone derivatives exhibit
several biological properties, among others, antibacterial and anticancer activities as
well as shows a potential application in optical devices because of the large nonlinear
optical coefficient due its conjugated π-electrons. It is also appropriate to mention that
the presence of double bond in conjunction with carbonyl group in the molecular
structure of chalcone derivatives is responsible for their biological properties [11,12],
meanwhile the C=C-S nucleus is associated to biological activities of thiophene
derivatives [9]. Furthermore, it is supposed that the combination of chalcones with
heterocyclic thiophene ring may increases the biological activities of chalcone
derivatives [16].
2. Experimental Procedures
2.1 – Synthesis process
C13H9ClOS was synthesized according to chemical procedure described in the
literature [15], as displayed in Figure 1. A mixture of 4-chloroacetophenone (1) (0.02
mol) with thiophene-2-carbaldehyde (2) (0.02 mol) was dissolved in methanol 25 mL,
aqueous potassium hydroxide 15 mL was added drop wise. The reaction mixture was
stirred at room temperature overnight and then the solid product was separated, washed,
dried to obtain the organic compound (3). The crystal used in Raman experiment was
growth by slow evaporation of room temperature of methanol solution of (3).
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2.2 – Measurements and experimental apparatus
13
1H and C NMR spectra (400 MHz and 300 MHz respectively) were recorded
on Bruker Avance II spectrometer using deuterated chloroform (CDCl3) as solvent.
Chemical shift values were given in δ (ppm) scales. Thin layer chromatography (TLC)
alumina sheets pre-coated with silica gel 60 F254 (0.2 mm thickness) was used to
monitor and detect compounds and the spots were visualized under UV lamp at 254 nm.
All chemicals and reagents were of analytical grade and were used without further
purification. The infrared spectrum was recorded using potassium bromide (KBR) pellet
method on Shimadzu 8000 series standard spectrometer in the spectral region 650-4000
cm-1 with spectral resolution of 4 cm-1. The thermal properties of the C13H9ClOS was
characterized by differential scanning calorimetry (DSC) in Netzsch DSC 200 F3 Maia
from room temperature to 500 K, at a heating rate of 5 K/min under argon atmosphere.
The Raman scattering measurements were performed in a HR800 Evolution micro-
Raman spectrometer from Horiba-Jobin-Yvon with a charge coupled device as light
detector and the 633 nm line of a He-Ne laser as excitation source. The low-temperature
measurements were performed in cryogenic closed system in the temperature range
from 10 to 290 K. For the high temperature measurements (room temperature up to 433
K) were used a Linkan TS1500 micro furnace.
3. Computational Methods
Density functional theory (DFT) calculations were performed using B3LYP
[17,18] method with 6-311G(d, p) basis set on ORCA software package [19]. The
harmonic vibrational frequencies were calculated at optimized molecular structure and
non-negative frequency was obtained. Therefore, in our calculations we have obtained a
true minimum of potential energy. The Raman spectrum was obtained from the sum of
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the Lorentzian functions with haft-band-width (HW) of 4 cm-1. In addition, the Raman
intensity given by DFT calculations were converted to relative intensity ( ) using the
I
Si
expression derived from Raman scattering activity
(
)
theory,
1
I 1012(0 i )4i Si , where
is the wavenumber of the laser source excitation

0

and
is the wavenumber normal mode [20]. The theoretical spectrum was scaled by
i
scale factor of 0.98 and 0.978 in the spectral region below and above 1800 cm-1,
respectively, in order to best comparison with experimental Raman spectrum, because
in our calculations the anharmonicity was neglected. Finally, the experimental Raman
spectrum taken at 10 K was compared with theoretical one.
4. Results and Discussions
4.1. Molecular Structure
1
1
Figure 2 shows the H and 13C NMR spectra of C13H9ClOS. The H NMR
spectrum confirm the proposed structure due to the presence of six signals integrating
for nine protons. For example, two olefinic protons of H-α and H-β appeared as doublet
at 7.31 ppm and 7.98 ppm, respectively. In addition, trans-configuration of C13H9OSCl
is confirmed by coupling constant of vinylic protons (15.20 Hz). Moreover, the 13C
NMR spectrum revealed eleven signals for carbons in agreement with the proposed
structure and also showed the chemical shift values of α and β carbons at δ 120.12 and δ
137.73 ppm, respectively. Furthermore, the appearance of the signal at δ 188.55 ppm
corresponds to carbonyl group [21, 22]. Finally, the complementary analytical data of
NMR spectra used to identify the molecular structure of C13H9ClOS are: 1H NMR (400
MHz, CDCl3): δ 7.13 (dd, 1H, J = 3.6 Hz, J = 5.2 Hz, H-4), 7.31(d, 1H, J = 15.2 Hz, H-
α), 7.40 (d, 1H, J = 3.6 Hz, H-3), 7.47 (d, 1H, J = 5.2 Hz, H-5), 7.50 (d, 2H, J = 8.6 Hz,
H-‘3 and H-‘5), 7.96 (d, 1H, J =15.2 Hz, H-β), 7.98 (d, 2H, J =8.6 Hz, H-‘2 and H-‘6);
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13C NMR (75 MHz, CDCl3): 120.12, 128.46, 128.96, 129.13, 129.83, 132.46, 136.41,
137.73, 139.21, 140.21, 188.55.
Figure 3 shows the optimized structure of C13H9ClOS obtained with B3LYP/6-
311G(d,p) method as well as atomic numbering scheme used in this study to describe
the vibrational normal modes and the structural properties. The C13H9ClOS molecule
comprises two rings, named here as R1 and R2. R1 are formed by atoms C1 to C6,
which comes from benzene ring. R2 are formed by atoms C10 to S1, which comes from
thiophene ring. R1 and R2 are linked by enone chain (C9=C8-C7=O1). On table 1, the
comparison between experimental data available in ref. [8] and calculated geometric
parameters for C13H9ClOS is listed. From this table, it is seen that the predicted bond
distance and angle for C13H9ClOS is comparable to analogous experimental one, with
exception of the C10-C11 [1.382 Å], C11-C12 [1.415 Å], C10-S1 [1.753 Å], C13-S1
[1.723 Å], C9-C10-C11 [130.7º] and C12-C13-S1 [111.7º], since it exhibits a deviation
value of 0.315 Å, 0.272 Å, 0.315 Å, 0.087 Å, 8.9º and 11.4º in relation to experimental
data given in ref. [8], which may be explained by atomic substitution and disorder effect
in thiophene ring, as discussed in ref. [8] and [23]. Another interesting features
predicted by DFT calculations for C13H9ClOS molecule is associated to the bond
distance of carbon-carbon (C9-C8), carbonyl group (C7-O1) and carbon-chlorine (C2-
Cl1) calculated to be 1.349, 1.225 and 1.755 Å. The first one is in close agreement with
experimental and theoretical data reported in ref. [8] and [10], but present a deviation of
0.001/0.006 Å and 0.012/0.018 Å in relation to experimental data available in the
literature for (2E)-1-(4-Chlorophenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one,
C16H13ClOS [24] and C13H9ClOS [8], which is probably attributed to higher π-
conjugation effect, as indicated by ref. [12] for analogous material. Furthermore, the
bond angle of C3-C2-C1 and C4-C5-C6 in R1 calculated to be 121.2º and 118.5º
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exhibits a small deviation of 0.62/0.74º and 1.16/0.61° in relation to experimental data
available in ref. [8] and [24]. Finally, it is worth to mention that C13H9ClOS is twisted
about the C5-C7 bond with dihedral angle of -12.01º and -27.58º in relation to
thiophene ring (C8-C9-C10-C11) and benzene ring (C6-C5-C7-C8), as displayed in ref.
[8], in contrast to almost planar structure predicted by DFT calculations. This difference
may be explained by the absence of the atomic packing factor and disorder of thiophene
ring because DFT calculation is performed on isolated molecule of C13H9ClOS without
any constrain to potential energy surface (PES), whereas it crystalline structure belongs
to triclinic structure, space group P-1, with two molecular formulas per unit cell as well
as stabilized by intermolecular interactions (퐶 − 퐻 ⋯ 휋) involving R1 and R2 [8].
4.2. Vibrational Analysis
Figure 4 shows the theoretical and experimental Raman spectra of the
C13H9ClOS recorded at 10 K with a reasonable accordance between them, in especial
because at low temperature the anharmonic effects of the molecular motion is reduced,
leading to more comprehensive vibrational spectrum. In the experimental spectrum, it is
observed two different types of vibrational motions, since in the molecular crystal the
force between molecules, which is responsible to link between molecules in the solid
state, is weak compared to the intramolecular. Therefore, the external modes usually
arise in the vibrational spectrum in lower frequencies relationship to internal modes [26,
27]. In this context, the first spectral region (in the range 10-200 cm-1) is associated to
external modes in which molecules in the unit cell moves relatives to one another in
phase, whereas the second one (in the range ~280-3200 cm-1) is attributed to functional
group modes like stretching (ν), in-plane (δ) and out-of-plane (γ) bending vibrational
modes of C-C, C-O and C-H and skeletal torsion (τ) modes, as listed in Table 2. In
order to illustrate the normal mode description given in this study, the wave vector
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displacement for four selected vibrational normal modes from isolated molecular
structure of C13H9ClOS is presented in Figure 5.
In the phonon spectrum, it is seen 13 external modes centered at 21, 34, 43, 51,
60, 79, 93, 105, 124, 139, 147, 155 and 196 cm-1. According to DFT calculations, this
vibrational motion is described as molecular torsion modes relationship to equilibrium
position of the molecule. On the other hand, in the internal mode region, the
characteristic band associated to vibrational motion of the para-substituted benzene is
usually reported in the vibrational spectrum near 1415 and 1515 cm-1 [28]. Thus, the
Raman band centered at 1417 and 1518 cm-1 in the vibrational spectrum of C13H9ClOS
is attributed to benzene substitution pattern and assigned as C=C stretching coupling
with CH bending mode, in close agreement with theoretical description. In the infrared
spectrum of the C13H9ClOS, these vibrational mode arises at 1421 and 1510 cm-1, as it
can be observed in supplementary file. The stretching mode of C=O and C=C is seen in
vibrational spectrum of chalcone derivatives [15, 29], respectively, in the range 1850-
1600 cm-1 and 1625-1575 cm-1. For (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophe-
nyl)prop-2-en-1-one this vibrational mode is observed near 1655 and 1583 cm-1 [14, 16].
In the case of C13H9ClOS, these vibrational mode arises in the Raman spectrum at 1584,
1591 and 1653 cm-1, while in the infrared spectrum at 1565, 1582 and 1652 cm-1.
According to DFT calculations, these vibrational modes are described as mix mode
composition of ν(C=O) coupled to ν(C=C) and CH bending and is predicted at 1596 and
1675 cm-1. It is relevant to mention that the weak intensity Raman line at 1653 cm-1 is
may be associated to C=O substitution effect in benzene ring, in contrast to medium-
strong band in the infrared spectrum viewed at the 1652 cm-1. Another interesting
contribution in the vibrational spectrum of the C13H9ClOS is related to thiophene ring
vibrational motion. The semi-circle and quadrant stretching together with CH bending
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in thiophene ring is reported in ref. [28, 30] near 1357, 1408 and 1588 cm-1, respectively.
In the Raman spectrum of C13H9ClOS, the latter is associated to the band centered at
1361 and 1425 cm-1, while appears at 1358, 1410 and 1583 cm-1 in the infrared
spectrum. Moreover, many of the bands seen in the vibrational spectrum of the aromatic
rings in the spectral region 1300-620 cm-1 involve in-plane and out-of-plane CH
bending vibrations mixed with C-C stretching and C-C-C bending vibrations [16, 28].
For example, the in-plane CH bending of benzene ring is reported at 1037, 1146 and
1178 cm-1, while the out-of-plane CH bending at 673, 846 and 990 cm-1 [28]. For this
reason, the band centered around at 1078, 1092, 1109 and 1179 cm-1 in the Raman and
infrared spectrum of the C13H9ClOS is assigned as in-plane CH bending, δ(CH), while
the band located proximally at 874, 955, 970 and 979 cm-1 is attributed to out-of-plane
CH bending mode, γ(CH), in agreement with theoretical description. For thiophene ring,
the in-plane CH bending arises in the vibrational spectrum at 1036, 1083, 1085 and
1256 cm-1, while the out-of-plane CH bending appears at 683, 867 and 898 cm-1 [30].
Thus, the Raman (infrared) band near 1029 (1031), 1045 (1049), 1135 (113) and 1216
(1210) cm-1 is assigned as in-plane CH bending, whereas the band centered at 679 (673)
and 892 (889 and 912) cm-1 is attributed to out-of-plane CH bending. According to DFT
calculations, the first vibrational mode is predicted at 1014, 1046, 1080, 1128 and 1247
cm-1, while the second one at 814, 818 and 902 cm-1. Furthermore, to complete the
tentative assignment of the vibrational mode of C13H9ClOS, it is discussed the CH
stretching mode of benzene and thiophene ring common reported in the region 3000-
3200 cm-1 [25, 28, 30]. In the Raman spectrum of C13H9ClOS, it is observed six bands
with very low intensity near 3020, 3059, 3074, 3086, 3109 and 3111 cm-1, whereas in
the infrared spectrum it is seen five bands proximally at 3075, 3080, 3083, 3100 and
3200 cm-1 also with very low intensity. In particular, the band centered at 3059, 3086
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and 3111 cm-1 is described by DFT calculations as a vibrational contribution of ν(C8H5)
+ ν(C6H4) + ν(C1H1), νR1(CH) + ν(C8H5) and ν(C13H9), respectively.
4.4. Temperature dependence on Raman spectra
Figure 6 shows the Raman spectra of the C13H9ClOS in the temperature range
10-413 K, in the lattice mode region. Increasing temperature from 10 K to 393 K, it can
be observed a red-shift, change in the line-width and relative intensity of some external
modes, while the internal modes remain almost unchanged with temperature. For
organic crystals, this effect is, in general, attributed to phonon anharmonicity as well as
to the nature of the chemical bond (intra- and inter-molecular). For example, it is seen
the coalescence of the Raman band in external and internal modes region with
increasing temperature, as shown in Fig. 6 and 7, described as: (i) the band located at 46
and 53 cm-1 (at 10 K) assign as lattice modes becomes a asymmetric band centered at 42
cm-1 in the temperature range 200-300 K; (ii) the band at 80 cm-1 also attributed to
lattice mode exhibits loss in intensity and moves more faster that the intensity at 57 cm-1
which leads to the coalescence of both at 393 K; (iii) the low intensity band at 93 cm-1
presents loss in intensity as temperature increase and becomes a shoulder with a very
low intensity of the band near 96 cm-1 in the Raman spectrum taken at room
temperature; (iv) the Raman band associated to stretching of C=C coupled with CH
bending near 1416 and 1424 cm-1 (indicated by down-arrow) becomes a single band
near 1421 cm-1 at 403 K, and (v) the shoulder located at 1593 cm-1 associated to mix
mode composition of ν(C=O) + ν(C=C) + δ(CH), moves more fast than the intensity
line at 1585 cm-1 which leads to the coalescence of both at room temperature. These
thermal events are characteristic of phonon anharmonicity contribution to inter-atomic
potential. However, a great modification in the Raman spectra profile occurs in the
temperature range 393-413 K. The first change is associated to the melting of the
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molecular crystal C13H9ClOS. This phenomenon, seen proximally at 403 K, is explained
by fact the that the external mode region becomes similar to Rayleigh line tail. At the
same time, in the internal mode region, several of the weaker bands could not be
resolved from their background or their position could not be determined reliable, with
exception of the vibrational modes attributed to C=C stretching coupling with CH
bending mode of benzene and thiophene rings, which arise in the spectral region 1350-
1700 cm-1. The latter may be associated with the phase transition induced by
temperature, in concordance with DSC curve, as illustrated in Fig. 8. In addition, a
discontinuity in dω/dt strongly suggest a possible phase transition, as indicated in the
literature [1] for the Salophen crystals. Moreover, near the temperature of 413 K, a
second change occurs in the Raman spectrum associated to crystal sublimation. This
thermal event is supported by the endothermic peak in the DSC curve centered at 397 K
whose enthalpy energy is founded to be 121.5 J/g. Furthermore, after cooling to room
temperature (*300 K), it was observed the crystallization of the organic substance in the
optic window of the furnace. In this sense, a new Raman spectrum was taken in order to
compare to initial one. As expected, no significant modification is observed the internal
modes region, therefore no change occurs in the molecular structure of the 1-(4-
Chlorophenyl)-3-(2-thienyl)prop-2-en-1-one, C13H9ClOS as displayed in figure 7 (a-d).
However, in the external mode region, the downshift and different intensity of the band
centered at 17, 29, 45 and 61 cm-1 (marked with down arrow) relationship to initial
spectrum taken at room temperature suggests a change of the atomic force constant, as
can be seen in the figure 6 (b).
Conclusions
In this study, the structural and vibrational properties of the 1-(4-Chlorophenyl)-
3-(2-thienyl)prop-2-en-1-one, C13H9ClOS were investigated combining experimental
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techniques such as nuclear magnetic resonance (1H NMR and 13C NMR), Fourier
transform infrared (FTIR) spectroscopy at room temperature, differential scanning
calorimeter (DSC) from room temperature to 500 K and Raman scattering in the
temperature 10-413 K with theoretical calculation based on density functional theory in
order to describe the vibrational spectrum, to determine the temperature stability and a
possible phase transition. A detailed description of vibrational normal modes is given
for C13H9ClOS in terms of experimental results of analogous compounds and DFT
calculation. The phonon anharmonicity contribution to inter-atomic potential is
observed in the Raman spectrum in all temperature range 10-393 K and is related to
change in Raman line (broadening and shift). The phase transition from solid to liquid,
attributed to disappearance of all external modes, was observed around at 403 K,
followed by sublimation of the molecular crystal in the temperature range 403-413 K, as
also indicated by the endothermic peak in DSC curve centered at 397 K with thermal
energy for the sublimation temperature of the 121.5 J/g. Furthermore, the line intensity
and shift in the Raman spectra taken after cooling (*300 K) indicates a possible change
of the atomic force constant of the material. Finally, this study provides a fundamental
support to understand origin of lattice instability and improves the knowledge of the
physical properties of the investigated material.
Acknowledgments
The Brazilian authors would like to acknowledge the agencies CNPQ and FAPESP
(grant 2013/07793-6) for financial support. Joazaizulfazli Jamalis wish to thank the
Ministry of Higher Education (MOHE) for funding this research under the Research
University Grant (RUP) with vote No. 07J48, and the Fundamental Research Grant
Scheme (FRGS) with vote No. 4F448.
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Figure Captions
Fig. 1: Chemical procedure used to synthetize the organic compound (E)-1-(4-
Chlorophenyl)-3-(thiophen-2-yl)prop-2-en-1-one, C13H9OSCl.
Fig. 2: 1H and 13C NMR spectra of the C13H9OSCl.
Fig. 3: Optimized structure of C13H9OSCl molecule obtained with B3LYP/6-311G(d,p)
method.
Fig. 4: Theoretical and experimental Raman spectra of the C13H9OSCl taken at 10 K.
Fig. 5: Selected Raman modes for 1-(4-Chloro-phenyl)-3-thiophen-2-yl-propenone
molecule calculated with B3LYP/6-311G(d,p) method: (a) C-H bending in benzene ring
at 1201 cm-1, (b) δ(C13H9) + δ(C12H8) + δ(C11H7) at 1272 cm-1, (c) ν(C=C) +
δ(CH)at 1390 cm-1 and (d) ν(C=O) + ν(C=C) + δ(CH)at 1629 cm-1.
Fig. 6: Raman spectra of C13H9OSCl in the external mode region (a) in the temperature
range 10-300 K (b) in the temperature range 313-403 K.
Fig. 7: Raman spectra of C13H9OSCl in the temperature range 10-433 K and spectral
region (a) 300-650 cm-1, (b) 650-1250 cm-1, (c) 1250-1675 cm-1 and (d) 2900-3200 cm-1.
The dash is only for guide the eye.
Fig. 8: DSC thermogram for C13H9OSCl in the temperature range 350-420 K.
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Table Captions
Table 1: Experimental [8] and calculated geometric parameters for 1-(4-Chloro-phenyl)-
3-thiophen-2-yl-propenone, C13H9ClOS: bond distance, bond angle and dihedral angle
(Å, º).
Table 2: Experimental and theoretical Raman modes for 1-(4-Chloro-phenyl)-3-
thiophen-2-yl-propenone along with their description.
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Figure 1
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Figure 2
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Figure 3
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Figure 4
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Figure 5
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Figure 6
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Figure 7
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Figure 8
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Table 1: Experimental1 and calculated geometric parameters for 1-(4-Chloro-phenyl)-3-
thiophen-2-yl-propenone, C13H9ClOS: bond distance, bond angle and dihedral angle (Å,
º).
Bond distance (Å)
Calculated Experimental
Bond distance (Å)
Calculated Experimental
Atom name
Atom name
C1-C2
C1-C6
C1-H1
C2-C3
C2-Cl1
C3-C4
C3-H2
C4-C5
C4-H3
C5-C6
C5-C7
C6-H4
C7-O1
1.391
1.392
1.082
1.394
1.755
1.388
1.083
1.402
1.083
1.401
1.503
1.082
1.225
1.393
1.369
0.930
1.389
1.737
1.394
0.930
1.400
0.930
1.402
1.495
0.930
1.231
C7-C8
C8-C9
1.479
1.349
1.082
1.442
1.087
1.382
1.753
1.415
1.082
1.372
1.082
1.723
1.079
1.476
1.349
0.930
1.444
0.930
1.649
1.438
1.687
0.931
1.371
0.930
1.636
0.931
C8-H5
C9-C10
C9-H6
C10-C11
C10-S1
C11-C12
C11-H7
C12-C13
C12-H8
C13-S1
C13-H9
Bond angle (°)
Bond angle (°)
Atom name
Atom name
Calculated
119.1
Experimental
118.67
Calculated
109.9
Experimental
114.01
94.45
C2-C1-C6
C1-C2-C3
C1-C2-Cl1
C1-C6-C5
C3-C2-Cl1
C2-C3-C4
O1-C7-C8
C11-C10-S1
C10-C11-C12
C3-C4-C5
C4-C5-C6
C4-C5-C7
C6-C5-C7
C5-C7-O1
121.2
121.82
113.6
119.4
119.15
121.2
119.10
119.66
122.26
118.07
119.68
121.0
120.66
118.5
119.4
119.04
117.7
119.0
119.10
123.8
121.5
122.03
119.6
1 The experimental data presented here is taken from ref. [8].
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C7-C8-C9
120.2
126.6
120
C5-C7-C8
118.9
92.0
118.29
96.92
C8-C9-C10
125.46
C10-S1-C13
C11- C12-
C13
C9-C10-C11
C9-C10-S1
130.7
119.4
121.83
124.08
112.8
111.7
111.34
123.1
C12-C13-S1
Dihedral angle (°)
Calculated Experimental
Dihedral angle (°)
Calculated Experimental
Atom name
Atom name
C8-C9-C10-
C11
C6-C5-C7-C8
C4-C5-C7-C8
C6-C5-C7-O1
-13.45
167.8
167.2
-27.58
155.39
152.83
-1.05
-12.01
171.40
171.41
C8-C9-C10-S1
178.97
178.87
H6-C9-C10-
C11
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Table 2: Calculated vibrational wavenumbers (in cm-1), scaled values by the dual scale factor
0.98 (below 1800 cm-1) and 0.987 (above 1800 cm-1), experimental Raman for the wavenumber
of bands in units of cm-1, and mode description.
Mode Ycalc
ωscal
16
ωRaman
ωIR
Mode description
τ(structural)
1
16
2
23
23
21
τ(structural)
3
49
48
34/43/51
τ(structural)
77
4
79
60/79
τ(structural)
5
6
7
8
96
94
93/105
124/139
147/155
196
τ(structural)
τ(structural)
τ(structural)
τ(structural)
τ(structural)
τ(structural)
τ(structural)
124
160
195
257
275
297
326
367
417
477
487
497
534
572
588
643
690
702
712
745
753
768
831
122
157
191
252
270
291
319
360
409
467
477
487
523
561
576
630
676
688
698
730
738
753
814
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
287
323
361/376
396/417
464
480
485/500
542
τ(R1) + δ(C8C7O1)
τ(R1) + δ(S1C10C9)
γ(C1H1) + γ(C3H2) + γ(C4H3) + γ(C6H4)
τ(R1) + τ(R2) + γ(C8C7C5)
τ(R1) + τ(R2) + δ(C9C8H5)
τ(R1) + τ(R2) + δ(C9C8H5)
τ(R1-Cl) + τ(H5C8C7O1)
570
γ(C12H8) + γ(C11H7) + γ(C8H5)
579/592
622/628
679
697
716
724
741/748
756
Ring breath (R2)
Ring breath (R1)
γ(C1H1) + γ(C3H2) + γ(C8H5) + γ(C13H9) + γ(C8C7C5)
δ(S1C10C11) + δ(C8C7O1) + δ(R1)
γ(C11H7) + γ(C12H8) + γ(C13H9)
τ(R2)
673
706
737
754
818
τ(C8-C7-C5) + γ(C8H5) + γ(C6H4) + γ(C4H3)
Ring breath (R1 + R2)
γ(C6H4) + γ(C4H3) + γ(C11H7) + γ(C8H5)
γ(C13H9) + γ(C12H8) + γ(C11H7) + γ(C4H3) + γ(C3H2)
+ γ(C6H4) + γ(C1H1)
818
29
835
836
857
30
31
32
33
34
35
36
37
38
39
40
41
42
43
850
864
885
901
920
966
999
833
847
867
883
902
947
979
γ(C4H3) + γ(C3H2) + γ(C8H5)
δ(R2)
874
892
873
γ(C3H2) + γ(C8H5)
δ(C9C8C7) + δ(C11H7) + δ(C5C4C3)
γ(C13H9) + γ(C12H8) + γ(C11H7)
γ(C6H4) + γ(C1H1) + γ(C4H3)
γ(C4H3) + γ(C3H2)
889/912
955
970
1006
1031
979
1009 989
1023 1003
1035 1014
1067 1046
1100 1078
1102 1080
1013
1029
1036
1045
1078
γ(C9H6) + γ(C8H5)
δ(C6C5C4) + δ(C1C2C3) + δ(H5C8C7) + δ(C12H8)
δ(C6C5C4) + ν(C8C7) + δ(C12H8) + δ(C11H7)
δ(C12H8) + δ(C11H7)
δ(C4H3) + δ(C3H2) + δ(C1H1) + δ(C6H4) + ν(C2Cl1)
δ(C13H9) + δ(C12H8)
δ(C4H3) + δ(C3H2) + δ(C1H1) + δ(C6H4)
δ(C10C11H7) + δ(C12H8) + δ(C9H6) + δ(C8H5) +
δ(C13H9) + δ(C4H3)
1049
1076
1108
1131
1092
1135
1109
1130
44
1151 1128
45
46
47
48
1201 1177
1227 1202
1272 1247
1317 1291
1179
1194
1216
1222
1179
1194
1210
1236
δ(C4H3) + δ(C3H2) + δ(C1H1) + δ(C6H4)
δ(C9H6) + δ(C8H5) + δ(C6H4) + δ(C3H2) + ν(C7C5)
δ(C13H9) + δ(C12H8) + δ(C11H7)
δ(C9H6) + δ(C8H5) + δ(C6H4) + δ(C3H2)
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