Synthesis, crystal growth and characterization of 1,5-diphenylpenta-1,4- dien-3-one: An organic crystal

Article abstract of DOI:10.1016/j.physb.2011.07.055

1,5-Diphenylpenta-1,4-dien-3-one ( dibenzalacetone, DBA) was synthesized by a base-catalyzed aldol condensation reaction between benzaldehyde and acetone. High quality single crystals have been grown by the slow evaporation of ethanol solution and the crystal belongs to monoclinic system with centrosymmetric space group C 2/c. The DBA crystals are transparent in the entire visible region and have a lower optical cutoff at ～440 nm. It is stable up to 119 °C and has a good chemical stability. The high resolution X-ray diffraction curve (DC) indicates that the specimen is free from structural grain boundaries. Molecular packing leads to a centrosymmetric arrangement resulting in zero second harmonic generation (SHG; X⁽²⁾=0) efficiency.

Full text of DOI:10.1016/j.physb.2011.07.055

Physica B 406 (2011) 4195–4199
Contents lists available at ScienceDirect
Physica B
journal homepage: www.elsevier.com/locate/physb
Synthesis, crystal growth and characterization of
1,5-diphenylpenta-1,4-dien-3-one: An organic crystal
a
b
a
a,n
K. Vanchinathan , G. Bhagavannarayana , K. Muthu , S.P. Meenakshisundaram
a
Department of Chemistry, Annamalai University, Annamalainagar 608 002, Chennai, India
b
National Physical Laboratory (CSIR), New Delhi 110 012, India
a r t i c l e i n f o
a b s t r a c t
Article history:
1,5-Diphenylpenta-1,4-dien-3-one ( dibenzalacetone, DBA) was synthesized by a base-catalyzed aldol
condensation reaction between benzaldehyde and acetone. High quality single crystals have been
grown by the slow evaporation of ethanol solution and the crystal belongs to monoclinic system with
centrosymmetric space group C 2/c. The DBA crystals are transparent in the entire visible region and
have a lower optical cutoff at ꢀ440 nm. It is stable up to 119 1C and has a good chemical stability. The
high resolution X-ray diffraction curve (DC) indicates that the specimen is free from structural grain
Received 13 March 2011
Received in revised form
1
2 May 2011
Accepted 30 July 2011
Available online 9 August 2011
Keywords:
boundaries. Molecular packing leads to a centrosymmetric arrangement resulting in zero second
Crystal growth
High resolution X-ray diffraction
FT-IR spectroscopy
Chalcone
(2)
harmonic generation (SHG;
w ¼0) efficiency.
&
2011 Elsevier B.V. All rights reserved.
Bulk crystal
1
. Introduction
Chalcones and their analogs are relatively easily available, not
as non-centrosymmetric structures [19,20]. Another importance
of this type of compound is their high photosensitivity and
thermal stability, which are used in developing various crystalline
electro-optical devices [11,21]. Literature survey reveals that the
growth and the structure of 1,5-diphenylpenta-1,4-dien-3-one
crystals were not reported. The crystalline perfection plays an
important role in device performance, which depends on the
growth technique and conditions [22] and therefore, the crystal-
line quality of the grown crystals are examined by high-resolution
X-ray diffractrometry (HRXRD) studies. The grown crystals are
also characterized by XRD, FT-IR, FT-Raman, DRS, thermal analysis
and Kurtz powder technique.
only by isolation from the natural products but also by the
methods of classical and combinatorial synthesis. The cytotoxic,
anticancer, chemopreventative and mutagenic properties of a
number of chalcones have been reviewed [1]. The antibacterial,
fungistatic and fungicidal properties of these compounds have
also been reviewed [2,3]. Chalcones and their analogs are used as
potential therapeutic agents in diseases of the cardiovascular
system [4]. Chalcones and their heterocyclic analogs exhibit
anti-inflammatory, antitumour [5–7], antibacterial, antifungal
[
8,9], antitubercular, antiviral, antiprotozal and gastroprotective
activities [3]. Chalcones present interesting biological properties,
such as cytotoxicity [10], anti-herpes acitivity [11] and antitu-
mour acivity [6] and may be useful for the chemotherapy of
leishmaniasis [12], among others. In addition, with appropriate
substituents, chalcones are a class of nonlinear optical (NLO)
materials [13,14]. Recently, it has been noted that among many
organic compounds reported for their second harmonic genera-
tion, chalcone derivatives have excellent blue light transmittance
and good crystallizability [15,16]. Among the many known
organic NLO materials, chalcones exhibit extremely high and fast
non linearity [13–15,17,18] and show a preference to crystallize
2
. Experimental
2.1. Synthesis and crystal growth
The title compound was synthesized according to the reported
method [23] with a yield of ꢀ80%. The product was purified by
repeated recrystallization from hot rectified spirit (m.p.119 1C).
n
DBA single crystals were grown using slow evaporation solu-
tion growth technique at room temperature. A saturated solution
Corresponding author. Tel.: þ91 4144 221670.
E-mail address: aumats2009@gmail.com (S.P. Meenakshisundaram).
0921-4526/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2011.07.055

4
196
K. Vanchinathan et al. / Physica B 406 (2011) 4195–4199
Fig. 1. Photographs of as-grown DBA crystals.
of DBA in ethanol was prepared and the solution was stirred for
h at room temperature to obtain a homogeneous solution.
Fig. 2. FT-IR spectrum of DBA crystal.
3
A small portion of the mother solution was used to get seed
crystals by slow evaporation of the solvent. Tiny crystals were
obtained in 3 days. Macroscopic defect-free seed crystals of DBA
were harvested after attaining a suitable size. One such seed was
introduced into the previously prepared mother solution.
A beaker containing DBA solution was tightly covered with a thin
polythene sheet to control the evaporation rate of the solvent and
kept undisturbed in a dust free environment. The photographs of
the as-grown DBA crystals are shown in Fig. 1.
2.2. Characterization studies
The single-crystal structure of DBA was carried out from a
3
selected yellow tablet of approximately 0.28 ꢁ 0.23 ꢁ 0.18 mm .
Crystal data were collected and integrated using an Oxford
Diffraction Xcalibur-S CCD system equipped with graphite mono-
˚
Fig. 3. FT-Raman spectrum of DBA crystal.
chromated Mo Ka(l¼0.71073 A) radiation at 150 K. The structure
was solved by direct methods (SHELXS-97) and refined by
full-matrix least squares against F2 using SHELXL-97 software
Table 1
ꢂ1
[
24]. The molecular structure was drawn using ORTEP-3. The
Observed vibrational bands of DBA in (cm ).
powder XRD pattern is recorded by PANalytical X’pert PRO X-ray
diffractometer. A multicrystal X-ray diffractometer developed at
NPL [25] has been used to record high-resolution diffraction
curves (DCs). Fourier transform infrared spectra were recorded
using AVATAR 330 FT-IR spectrometer. Fourier transform Raman
spectra were recorded using FT-RAMAN BRUKER RFS 100/S Instru-
ment. UV–vis spectra were recorded using CARY 5E UV–vis spectro-
photometer. DSC curves were recorded on a SDT Q600 (TA
instrument) thermal analyzer. DSC analysis of DBA crystal is carried
out between 50 and 300 1C in the nitrogen atmosphere. The SHG test
on the crystal was performed by the Kurtz powder method [26]. An
Nd:YAG laser with modulated radiation of 1064 nm was used as the
optical source and directed on the powdered sample through a filter.
FT-IR
FT-Raman
Conjugated –C¼C–
C¼O stretching
Aromatic vibration and C¼C bending
modes of -unsaturated carbon
1625
1626
–
1650
1651
1592 and 1493
1596 and 1449
a, b
C–H out-of-plane
1650–2000
1650–2000
C–H stretching of CH¼CH
3025 and 3052
3026 and 3060
to aromatic ring vibrations and C¼C bending modes of
a,
b
–unsaturated carbons, respectively. The absorption bands observed
ꢂ1
in the region of 1000–800 cm were the characteristic of C–H out-
of-plane bending or wagging vibrations of hydrogen atoms attached
to unsaturated carbons (alkene). The observed FT-IR and FT-Raman
(Fig. 3) vibrational bands of DBA are listed in Table 1.
3
. Results and discussion
3.2. Powder XRD analysis
3.1. FT-IR and FT-Raman
The DBA powder sample was scanned in the 2
y range of ꢀ2
In order to confirm the functional groups present in the DBA
(0 is not supposed to be correct) ꢂ801 at a scanning rate of 11/
min. The results of powder XRD pattern were shown in Fig. 4. The
XRD profiles show that all samples were of single phase without
detectable impurity. Narrow peaks indicate the good crystallinity
of the material, which is further confirmed by HRXRD.
molecule, FT-IR spectrum was recorded (Fig. 2) in the spectral range
ꢂ1
of 400–4000 cm . The absorption bands corresponding to asym-
metric and symmetric C–H stretching vibrations of –CH group
ꢂ1
were observed at 3025 and 3052 cm , respectively. The weak
ꢂ1
absorption at summation bands in the range of 2000–1650 cm
were attributed to the aromatic C–H out-of-plane bending. The
3.3. Diffuse reflectance spectra
ꢂ1
weak absorption band at 1650 cm
corresponds to the C¼O
stretching vibration. The relatively stronger absorption band at
UV cutoff is ꢀ440 nm and the absorbance is minimum in the
ꢂ1
ꢂ1
1592 cm and a weaker absorption band at 1493 cm were due
450–800 nm range (Fig. 5). Comparison of the cutoff l of DBA

K. Vanchinathan et al. / Physica B 406 (2011) 4195–4199
4197
Fig. 6. The sharp peak at 119 1C is due to the melting point of the
grown crystal. The sharpness of the peaks shows the good degree
of crystallinity of the material. No decomposition up to the
melting point ensures the stability of the material for application
in laser where the crystals are required to withstand high
temperatures. The sharp endotherm is indicative of solid state
transition for relatively pure material. The melting point was also
determined using Sigma instrument melting point apparatus
(
116 1C).
3.5. HRXRD
Fig. 7 shows the high-resolution rocking/diffraction curve (DC)
recorded for a typical DBA crystal using (0 1 0) diffracting planes
in symmetrical Bragg geometry by employing the multicrystal
1
X-ray diffractometer with MoKa radiation. As seen in the figure,
the DC contains a single peak and indicates that the specimen is
free from structural grain boundaries. The FWHM (full width at
half maximum) of the curve is 70 arc s, which is somewhat more
than that expected from the plane wave theory of dynamical
X-ray diffraction [27] for an ideally perfect crystal but close to
that expected for nearly perfect real life crystals. This much
broadness with good scattered intensity along both the wings of
the DC indicates that the crystal contains both vacancy and
interstitial type of defects [28]. More details about the size and
shape of the defects may be obtained from the study of high-
resolution diffuse X-ray scattering measurements [25], which is
not the main focus of the present investigation. However, such
microscopic defects may not have much effect on the device
performance, which are many times unavoidable due to thermo-
dynamical considerations and also due to impurities originated
Fig. 4. Powder XRD patterns of DBA crystal (a) single crystal structure pattern
b) experimental pattern.
(
Fig. 5. Diffuse reflectance spectrum of DBA crystal.
Table 2
Fig. 6. DSC of DBA crystal.
UV data of DBA and substituted DBA in (nm).
Name of chalcones
l
max (nm)
1
1
1
,5-diphenylpenta-1,4-dien-3-one
ꢀ440
ꢀ440
ꢀ440
a
,5-bis(4-chlorophenyl)penta-1,4-dien-3-one (CDBA)
b
,5-bis(methoxyphenyl)penta-1,4-dien-3-one (PDBA)
a
ref [19].
b
ref [20].
with that of p-chlorodibenzalacetone (CDBA) [19] or p-methoxy
dibenzalacetone (PDBA) [20] shows no significant changes
(
Table 2) due to p-chloro or p-methoxy substituents.
3.4. Thermal analysis (differential scanning calorimetry)
The DSC was performed to know the thermal behavior of the
grown crystals. The DSC of the grown DBA crystal is shown in
Fig. 7. HRXRD recorded for DBA crystal.

4
198
K. Vanchinathan et al. / Physica B 406 (2011) 4195–4199
right from the raw material and/or due to the entrapment of
vacancies and solvent molecules [29].
centrosymmetric, SHG and second order NLO responses are not
exhibited for DBA. But no crystal symmetry restrictions are there
for third order NLO responses. The optical switches and optical
limiting devices demand materials with fast and large third order
optical nonlinearity. Even though SHG is zero in DBA, it is expected
to have practical third order NLO applications. In 3-(4-methylphe-
nyl)-1-(3-thienyl)-2-propen-1-one(MTC) [30], the main contribu-
tion to SHG results from the strong hydrogen bonds, which
appear as intense IR bands of hydrogen bond vibration. No such
strong hydrogen bonds are observed in DBA using mercury soft-
ware and it could be the reason for zero SHG. Wu et al. [31]
suggested from their theoretical hyperpolarizability studies on
3.6. Single crystal XRD
Using single crystal XRD studies, the lattice parameters of DBA
are determined and the crystal data are given in Table 3 along
with those of CDBA and PDBA. The ORTEP and packing diagrams
are shown in Figs. 8 and 9. The DBA molecule is nonplanar. Taking
0
0
C4–C9 phenyl ring as plane 1 (PL1), C4 –C9 phenyl ring as plane 2
(
PL2) and the central C4–C3A¼C2A–C1 as plane 3 (PL3), the
dihedral angles between them, A12, A13 and A23 are 54.851, 19.91
and 38.261, respectively, showing that the two phenyl rings are
rotated in the opposite directions with respect to the central part,
plane 3. The C4–C3A¼C2A–C1 torsional angle is 179.2 (6)1.
1,5-diphenylpenta-2,4-dien-1-one molecules that the carbonyl group
present at the middle splits of the conjugated system into two
relatively independent bonds. Chalcones are regarded as cross con-
jugated molecule that possesses two independent hyperpolar parts to
have a 2D
b
characters. Large SHG is due to unidirectional
3.7. NLO studies
Chalcones are attractive because their properties can be easily
controlled by suitable substitution in the phenyl ring. Substituting
different donor and acceptor groups on phenyl rings brings remark-
able changes in their physical properties. The p-chloro and
p-methoxy substituted DBA crystals crystallize in a non-centrosym-
metric space group leading to high SHG efficiency [19,20]. Being
Fig. 9. Packing diagram of DBA crystal.
Table 3
Crystal data of DBA and substituted DBA.
1
4
,5-diphenylpenta-1,
-dien-3-one
1,5-bis(4-chlorophenyl)
1,5-bis(4-methoxyphenyl)
a
b
penta-1,4-dien-3-one
penta-1,4-dien-3-one
Molecular formula
Molecular weight (gm/mole)
Melting point (1C)
Color
C
17
H
14
O
C
17
H
12Cl
2
O
19 18 3
C H O
234.28
303.17
193
294.33
131
116
Pale yellow
Monoclinic,C2/c
colorless
Pale yellow
Space group
Orthorhombic, P21 21 2
Orthorhombic,Aba2
Unit cell dimensions
˚
˚
˚
a¼28.4700(19) A
b¼5.8108(3) A˚
a¼24.509(3) A
b¼4.9846(5) A˚
a¼33.5830(6) A
b¼7.2756(9) A˚
c¼7.7929(5) A˚
c¼5.8103(6) A˚
c¼6.132(5) A˚
b
¼100.163(6)1
b
¼901
b¼901
Volume
˚
3
˚
3
˚
3
1
8
268.98(13) A
709.82 (13) A
2
1498.3 (12) A
4
Z
Crystal size
0.28 mm ꢁ 0.23 mm ꢁ 0.18 mm
0.38 mm ꢁ 0.36 mm ꢁ 0.28 mm
0.52 mm ꢁ 0.22 mm ꢁ 0.04 mm
a
ref [19].
b
ref [20].
Fig. 8. ORTEP diagram of DBA crystal.

K. Vanchinathan et al. / Physica B 406 (2011) 4195–4199
4199
arrangement of molecular dipoles in which
to establish a net polarization. To maximize (
have a head-to-tail alignment of molecules connected through strong
intermolecular hydrogen bond interactions. The zero SHG in DBA
could be due to anti-parallel alignment of molecular dipoles, in which
m
of each molecule adds
[6] Y. Xia, Z.Y. Yang, P. Xia, K.F. Bastow, Y. Nakanishi, K.H. Lee, Bioorg. Med.
Chem. Lett. 10 (2000) 699.
(2)
w
) it is necessary to
[
[
7] R. Agarwal, K.C. Chaudhary, V.S. Misra, Indian J. Chem. Sect. B 22 (1983) 308.
8] S. Gafner, J.L. Wolfender, S. Mavi, K. Hostettmann, Planta Med. 62 (1996) 67.
[9] M. Popova, V. Bankova, S. Spassov, I. Tsvetkova, C. Naydenski, M.V. Silva,
M. Tsartsarova, Z. Naturforsch. Teil C 56 (2001) 593.
10] N.J. Lawrence, D. Rennison, A.T. McGown, S. Ducki, L.A. Gul, J.A. Hadfield,
N. Khan, J. Comb. Chem. 3 (2001) 421.
11] A. Phrutivorapongkul, V. Lipipun, N. Ruangrungsi, K. Kirtikara, K. Nishikawa,
S. Maruyama, T. Watanabe, T. Ishikawa, Chem. Pharm. Bull. 51 (2003) 187.
12] S. Pandey, S.N. Suryawuanshi, S. Gupta, V.M.L. Srivastra, Eur. J. Med. Chem.
40 (2005) 751.
13] D. Fichou, T. Watanabe, T. Takeda, S. Miyata, Y. Goto, M. Nakayama, Jpn. J.
Appl. Phys. 27 (1988) L429.
[
[
[
[
[
the
m
of each molecule gets canceled. Classic hydrogen bonds are not
interactions.
observed in the present study except for some weak
p
4
. Conclusions
,5-Diphenylpenta-1,4-dien-3-one (DBA) crystals were grown
1
14] Y. Goto, A. Hayashi, Y. Kimura, M. Nakayam, J. Cryst. Growth 108 (1991) 688.
in ethanol and the structure was solved by single crystal X-ray
analysis. Interestingly, the unsubstitued DBA crystallizes in a
centrosymmetry space group in contrast to the noncentrosym-
metry exhibited by para-substituted DBA crystals. The specimen
is free from structural grain boundaries as observed by HRXRD
studies. We have also used XRD, FT-IR, FT-Raman, DRS, thermal
analysis and Kurtz powder technique to characterize the grown
organic crystal.
[15] E. Bertl, H. Becker, T. Eicher, C. Herhaus, G. Kapadia, H. Bartsch, C. Gerhauser,
Biochem. Biophys. Res. Commun. 325 (2004) 287.
[
[
[
[
[
16] Y. Kitaoka, T. Sasaki, S. Nakai, A. Yokotani, Y. Goto, M. Nakayama, Appl. Phys.
Lett. 56 (1990) 2074.
17] T. Uchida, K. Kozawa, T. Sakai, M. Aoki, H. Yoguchi, A. Abdureyam,
Y. Watanebe, Mol. Cryst. Liq. Cryst. 315 (1998) 135.
18] G. Zhang, T. Kinoshita, K. Sasaki, Y. Goto, M. Nakayam, J. Cryst. Growth 100
(1990) 411.
19] H.J. Ravindra, A.J. Kiran, S.R. Nooji, S.M. Dharmaprakash, K. Chandrasekharan,
B. Kalluraya, F. Rotermund, J. Cryst. Growth 310 (2008) 2543.
20] H.J. Ravindra, A. John Kiran, S.M. Dharmaprakash, N. Satheesh Rai,
K. Chandrasekharan, B. Kalluraya, F. Roter mund, J. Cryst. Growth 310
(
2008) 4169.
Acknowledgements
[
21] D. Williams, Nonlinear Optical Properties of Organic and Polymeric Materials,
Am. Chem. Soi, Washington, DC, 1983.
The authors thank Dr. P.K. Das, Indian Institute of Science,
Bangalore for NLO measurement. One of the authors, K. Muthu is
thankful to CSIR, New Delhi, for the award of a Senior Research
Fellowship.
[22] N. Vijayan, G. Bhagavannarayana, T. Kanagasekaran, G. Ramesh Babu,
R. Gopalakrishanan, P. Ramasamy, Cryst. Res. Technol. 41 (2006) 784.
[
[
23] A.I. Vogel, Practical Organic Chemistry (1989) 1033 fifth ed.
24] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure Solution and
Refinement, Release 97-2, University of Gottingen, Gottingen Germany, 1997.
25] K. Lal, G. Bhagavannarayana, J. Appl. Crystallogr. 22 (1989) 209.
26] S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798.
27] B.W. Batterman, H. Cole, Rev. Mod. Phys. 36 (1964) 681.
28] G. Bhagavannarayana, S. Parthiban, Subbiah Meenakshisundaram, Cryst.
Growth Des. 8 (2008) 446.
[
[
[
[
References
[
1] J.R. Dimmock, D.W. Elias, M.A. Beazely, N.M. Kandepu, Curr. Med. Chem. 6
1999) 1125.
(
[29] G. Bhagavannarayana, P. Rajesh, P. Ramasamy, J. Appl. Crystallogr. 43 (2010)
[
[
[
[
2] V. Opletalova, Cesk. Farm. 49 (2000) 278.
1372.
3] V. Opletalova, D. Sedivy, Cesk. Farm 48 (1999) 252.
4] V. Opletalova, L. Jahodar, D. Jun, L. Opletal, Cesk. Farm 52 (2003) 12.
5] S. Shibata, Stem Cells 12 (1994) 44.
[30] S. Genbo, H. Youping, L. Zhengdong, J. Rihong, Cryst. Res. Tecnol 31 (1996)
935.
[31] D. Wu, B. Zhao, Z. Zhou, J. Mol. Struct. 682 (2004) 83.