Synthesis, structure, growth and characterization of an organic crystal: 1,5-diphenylpenta-2,4-dien-1-one

Article abstract of DOI:10.1107/S0021889812030403

1,5-Diphenylpenta-2,4-dien-1-one (DDO) chalcone single crystals, synthesized by a base-catalysed aldol condensation reaction between cinnamaldehyde and acetophenone, have been grown by the slow evaporation of an ethanol solution. The crystals belong to the orthorhombic system with centrosymmetric space group Pbca. The DDO crystals are transparent in the visible region and have a lower optical cut-off at ～445 nm with a band-gap energy of 2.87 eV. Thermogravimetry/differential scanning calorimetry thermal analysis shows that the crystal is stable up to 375 K and it has a good chemical stability. The vibrational patterns of the chalcone have been investigated by Fourier transform IR and Fourier transform Raman spectroscopy. Microhardness studies were also carried out to elucidate the mechanical behaviour. Theoretical calculations were performed using the Hartree-Fock method with 6-31G(d,p) as the basis set, and the first-order hyperpolarizability is 7.077 × 10 ^-30 electrostatic units, which is >25 times that of urea. The crystalline perfection evaluated by high-resolution X-ray diffraction analysis reveals multiple peaks. The molecular packing leads to a centrosymmetric arrangement, resulting in zero second harmonic generation [χ⁽²⁾ = 0] efficiency. Interestingly, the bromo- and chloro-substituted chalcones are good nonlinear optical materials.

Full text of DOI:10.1107/S0021889812030403

research papers
Journal of
Synthesis, structure, growth and characterization
of an organic crystal: 1,5-diphenylpenta-2,4-
dien-1-one
Applied
Crystallography
ISSN 0021-8898
Received 11 April 2012
Accepted 3 July 2012
a
a
b
a
M. Rajasekar, K. Muthu, G. Bhagavannarayana and S. P. Meenakshisundaram *
a
b
Department of Chemistry, Annamalai University, Annamalainagar 608 002, India, and Crystal
Growth and X-ray Analysis Activity, CSIR-NPL, New Delhi 110 012, India. Correspondence e-mail:
aumats2009@gmail.com
1,5-Diphenylpenta-2,4-dien-1-one (DDO) chalcone single crystals, synthesized
by a base-catalysed aldol condensation reaction between cinnamaldehyde and
acetophenone, have been grown by the slow evaporation of an ethanol solution.
The crystals belong to the orthorhombic system with centrosymmetric space
group Pbca. The DDO crystals are transparent in the visible region and have a
lower optical cut-off at ꢀ445 nm with a band-gap energy of 2.87 eV.
Thermogravimetry/differential scanning calorimetry thermal analysis shows
that the crystal is stable up to 375 K and it has a good chemical stability. The
vibrational patterns of the chalcone have been investigated by Fourier transform
IR and Fourier transform Raman spectroscopy. Microhardness studies were also
carried out to elucidate the mechanical behaviour. Theoretical calculations were
performed using the Hartree–Fock method with 6-31G(d,p) as the basis set, and
ꢂ30
the first-order hyperpolarizability is 7.077 ꢁ 10
electrostatic units, which is
25 times that of urea. The crystalline perfection evaluated by high-resolution
>
X-ray diffraction analysis reveals multiple peaks. The molecular packing leads to
a centrosymmetric arrangement, resulting in zero second harmonic generation
(
2)
[
ꢀ
are good nonlinear optical materials.
= 0] efficiency. Interestingly, the bromo- and chloro-substituted chalcones
#
2012 International Union of Crystallography
Printed in Singapore – all rights reserved
1
. Introduction
abilities of 26 derivatives of 1,5-diphenylpenta-2,4-dien-1-ones
(DDOs) and 18 chalcones were systematically calculated and
studied with the ab initio molecular orbital method. It was
revealed that the DDO molecules had high hyperpolariz-
abilities; the intramolecular charge transfer from the diene
portion to the carbonyl group is the dominating contributor to
the molecular charge transfer, and in turn the main influencing
factor of hyperpolarizabilities (Wu et al., 2004). A literature
survey reveals that the growth aspect of 1,5-diphenylpenta-
2,4-dien-1-one crystals has not been reported. We have
therefore undertaken the current study of DDO. The crys-
talline perfection plays an important role in device perfor-
mance, which depends on the growth technique and conditions
(Vijayan et al., 2006). Therefore, the crystalline quality of the
grown crystals has been examined by high-resolution X-ray
diffraction (HRXRD) studies. The grown crystals are also
characterized by X-ray diffraction (XRD), Fourier transform
(FT) IR, FT–Raman, UV–Vis, thermal analysis, microhard-
ness studies and the Kurtz powder technique.
Chalcones and their analogues are relatively easily available,
not only by isolation from natural products but also by the
methods of classical and combinatorial synthesis. The cyto-
toxic, anticancer, chemopreventative and mutagenic proper-
ties of a number of chalcones have been reviewed (Dimmock
et al., 1999). The antibacterial, fungistatic and fungicidal
properties of these compounds have also been reviewed
(
Opletalova, 2000; Opletalova & Sedivy, 1999). With appro-
priate substituents, chalcones are a class of nonlinear optical
NLO) materials (Fichou et al., 1988; Goto et al., 1991).
(
Recently, it has been noted that among many organic
compounds reported for their second harmonic generation,
chalcone derivatives have excellent blue light transmittance
and good crystallizability (Bertl et al., 2004; Kitaoka et al.,
1990). Among the many known organic NLO materials,
chalcones exhibit extremely high and fast nonlinearity (Fichou
et al., 1988; Goto et al., 1991; Bertl et al., 2004; Uchida et al.,
1998; Zhang et al., 1990) and show a preference to crystallize
as noncentrosymmetric structures (Ravindra, Kiran, Dhar-
maprakash et al., 2008; Ravindra, Kiran, Nooji et al., 2008).
Another importance of this type of compound is its high
photosensitivity and thermal stability, which are used in
developing various crystalline electro-optical devices
2
. Experimental
2.1. Synthesis and crystal growth
The title compound was synthesized using cinnamaldehyde
(Loba Chemie) and acetophenone (E-Merck) according to the
(Williams, 1983). The first-, second- and third-order polariz-
9
14 doi:10.1107/S0021889812030403
J. Appl. Cryst. (2012). 45, 914–920

research papers
previously reported method (Furnis et al., 1989) with a yield of
80%. Acetophenone (0.01 mol) was mixed with cinnam-
To evaluate the crystalline perfection of the specimen
crystals, HRXRD analysis was carried out. A multicrystal
X-ray diffractometer developed at the National Physical
Laboratory, New Delhi (Lal & Bhagavannarayana, 1989), was
used to record high-resolution rocking or diffraction curves
(DCs). In this system, a fine focus (0.4 ꢁ 8 mm; 2 kW Mo)
X-ray source energized by a well stabilized Philips X-ray
generator (PW 1743) was employed. A well collimated and
ꢀ
aldehyde (0.01 mol) in ethanol and the mixture was treated
with 10% sodium hydroxide. The mixture was stirred well and
put aside for 24 h, and DDO was obtained as a yellow preci-
pitate. The resulting yellow solid mass was collected by
filtration and dried. The synthesized material was further
purified by repeated recrystallization from hot rectified spirit
(m.p. 375 K). The chloro- and bromo-substituted chalcones
monochromated Mo Kꢁ beam obtained from the three Si
1
were synthesized by aldol condensation using substituted
acetophenone and cinnamaldehyde.
monochromator crystals set in a dispersive (+, ꢂ, ꢂ) config-
uration was used as the exploring X-ray beam. The diffracted
intensity was measured by using a scintillation counter. The
DCs were recorded by changing the glancing angle (the angle
between the incident X-ray beam and the surface of the
specimen) around the Bragg diffraction peak position ꢃB
(taken as zero as a reference point) starting from a suitable
DDO single crystals were grown using the slow evaporation
solution growth technique at room temperature. Many organic
solvents such as ethanol, methanol, acetone and acetonitrile
were tried as a medium, and ethanol was found to be suitable
for the growth of perfect crystals. A saturated solution of
DDO in ethanol was prepared and the solution was stirred for
arbitrary glancing angle (ꢃ). The detector was kept at the same
angular position 2ꢃ with a wide opening for its slit, the so-
B
called ! scan (Bhagavannarayana & Kushwaha, 2010). Before
recording the diffraction curve, to remove the noncrystallized
solute atoms remaining on the surface of the crystal and also
to ensure the surface planarity, the specimens were first lapped
and chemically etched in a nonpreferential etchant of water
and acetone mixed in a 1:2 volume ratio.
A Hartree–Fock calculation was performed using the
GAUSSIAN03 (Frisch et al., 2004) program package on a
personal computer without any constraints on the geometry,
using 6-31G(d,p) as the basis set (Schlegel, 1982). By the use
of the GAUSSVIEW molecular visualization program (Frisch
et al., 2000) the optimized structure of the molecule has been
visualized. The second harmonic generation (SHG) test on the
crystal was performed by the Kurtz powder method (Kurtz &
Perry, 1968). An Nd:YAG laser, providing modulated radia-
tion of 1064 nm with an input radiation of 2.35 mJ per pulse,
was used as the optical source and directed onto the powdered
sample through a filter.
3
h at room temperature to obtain a homogeneous solution. A
beaker containing DDO 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. Tiny
crystals were obtained in a period of 4–5 d. Defect-free seed
crystals of DDO were used for bulk growth. Photographs of
the as-grown DDO crystals are shown in Fig. 1.
2.2. Characterization studies
The structural analysis of DDO was carried out for a
selected yellow tablet of approximately 0.20 ꢁ 0.20 ꢁ 0.30 mm
using a Bruker Kappa APEXII X-ray diffractometer. Single-
crystal XRD data were collected on a diffraction system that
employs graphite-monochromated Mo Kꢁ radiation (ꢂ =
3
. Results and discussion
˚
.71073 A). The structures were solved and refined by full-
0
matrix least squares on F with the WinGX software package
2
3.1. FT–IR and FT–Raman
(
(
Farrugia, 2012), utilizing the SHELXS97 and SHELXL97
In order to confirm the functional groups present in the
DDO molecule, an FT–IR spectrum was recorded (Fig. 2a) in
1
Sheldrick, 2008) modules. The plots for the structures were
created with the DIAMOND software (Brandenburg, 2007).
All non-H atoms were refined anisotropically. The powder
XRD pattern was recorded by a PANalytical X’pert PRO
X-ray diffractometer. FT–IR spectra were recorded using an
AVATAR 330 FT–IR spectrometer. FT–Raman spectra were
recorded using a Bruker RFS 100/S instrument. A CARY 5E
UV–Vis spectrophotometer was used for the UV–Vis studies.
Thermogravimetry/differential scanning calorimetry (TG/
DSC) curves were recorded on an SDT Q600 (TA Instru-
ments) thermal analyser. The Vickers microhardness was
evaluated for the well polished grown crystal using a Reichert
4000E ultramicrohardness tester.
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: RG5013). Services for accessing these data are described
at the back of the journal.
Figure 1
Photographs of as-grown DDO crystals.
ꢃ
J. Appl. Cryst. (2012). 45, 914–920
M. Rajasekar et al.
1,5-Diphenylpenta-2,4-dien-1-one 915

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Table 1
Observed vibrational bands of DDO crystals (cm ).
t ¼ kꢂ=ꢄ cos ꢃ;
ð1Þ
–1
where k is the Scherrer constant, ꢂ is the X-ray wavelength, ꢃ
is the peak position measured in radians and ꢄ is the integral
breadth of reflections (in radians 2ꢃ) located at 2ꢃ.
FT–IR
FT–Raman
1654
1586 and 1445 1585 and 1452
–
C
O stretching
1654
Aromatic vibration and C C bending
modes of ꢁ,ꢄ-unsaturated carbon
C—H out of plane
1650–2000
3022 and 3063 3061
1650–2000
3.3. Optical studies
C—H stretching of CH CH
The optical absorption spectrum of the DDO crystal is
shown in Fig. 4. The crystal has good transmission in the entire
visible region and the lower cut-off wavelength is ꢀ445 nm.
The measurement of the absorption coefficient ꢁ as a function
of frequency ꢅ of the incident beam provides a means to
determine the band gap Eg of a material. The optical
absorption coefficient (ꢁ) was calculated using the relation
ꢂ1
the spectral range of 400–4000 cm . The absorption bands
corresponding to asymmetric and symmetric C—H stretching
vibrations of the –CH group were observed at 3022 and
ꢂ1
3063 cm , respectively. The weak absorption features at
summation bands in the range of 2000–1650 cm
ꢂ1
were
attributed to the aromatic C—H out-of-plane bending. The
ꢂ1
ꢁ
¼ ð2:303=dÞ logð1=TÞ;
ð2Þ
weak absorption band at 1654 cm corresponds to the C
stretching vibration. The relatively stronger absorption band
O
ꢂ1
ꢂ1
where T is the transmittance and d is the thickness of the
crystal. The optical band gap in most materials can be deter-
mined using the Tauc relation, which is expressed as
at 1586 cm and a weaker absorption band at 1445 cm are
due to aromatic ring vibrations and C C bending modes of
,ꢄ-unsaturated C atoms, respectively. The absorption bands
observed in the region of 1000–800 cm are characteristic of
C—H out-of-plane bending or wagging vibrations of H atoms
attached to unsaturated C atoms (alkene). The observed FT–
IR and FT–Raman (Fig. 2b) vibrational bands of DDO are
listed in Table 1.
ꢁ
ꢂ1
r
ðꢁhꢅÞ ¼ Aðhꢅ ꢂ E Þ ;
ð3Þ
g
3.2. Powder XRD analysis
The powder XRD pattern is shown in Fig. 3. The XRD
profiles show that all samples were of single phase without
detectable impurity. The well defined Bragg peaks at specific
2ꢃ angles show the high crystallinity of the DDO crystal. The
crystallite size (t) of the DDO crystal is calculated (59 nm)
using the Scherrer equation:
Figure 3
Powder XRD pattern of a DDO crystal.
Figure 2
Vibrational patterns: (a) FT–IR and (b) FT–Raman.
Figure 4
UV–Vis spectrum (the Tauc plot is given as an inset).
ꢃ
9
16 M. Rajasekar et al.
1,5-Diphenylpenta-2,4-dien-1-one
J. Appl. Cryst. (2012). 45, 914–920

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where A is a constant, h is Planck’s constant and r is an index
that depends on the nature of electronic transition responsible
for the optical absorption. The Tauc plot of the optical
absorption spectrum measured at room temperature for DDO
is given as an inset in Fig. 4. The direct optical energy gap can
be obtained from the intercept of the resulting straight lines
where P is the applied load in kilograms and d is the mean
diagonal length of the indentation impression in micrometres.
As seen in Fig. 6, the hardness of the grown crystal increases as
the load increases. Cracks started developing around the
indentation mark beyond a load of 100 g. This may be a result
of the internal stresses released during the indentation. The
work hardening index is equal to 4.4.
2
with the energy axis at (ꢁhꢅ) = 0, and the band-gap energy of
the specimen is deduced as 2.87 eV with an absorption edge at
432 nm (Fig. 4).
3.6. HRXRD
3
.4. Thermal analysis
Fig. 7 shows the high-resolution X-ray diffraction curve
recorded using Mo Kꢁ radiation for a typical DDO single-
1
TG/DSC was performed to investigate the thermal beha-
viour of the as-grown crystals (Fig. 5). In the DSC analysis, a
sharp endothermic peak was found at around 376 K, and it
was assigned to the melting point, at which no weight loss has
been noticed in the TG analysis. Below this endotherm, no
exothermic or endothermic peak is observed. In the thermo-
gravimetric analysis, the material exhibits single-stage weight
loss starting around 543 K, which may be due to the decom-
position of the DDO, and below this temperature no signifi-
cant weight loss is observed. The sharpness of the endothermic
peak observed with DSC shows the good degree of crystal-
linity of the material. No decomposition up to the melting
point ensures the stability of the material for laser applications
where the crystals are required to withstand high tempera-
tures. The sharp endotherm is indicative of a solid-state
transition for relatively pure material. The melting point was
also determined by using a Sigma Instruments melting point
apparatus (372–373 K).
crystal specimen. On careful observation, the curve does not
seem to be a single peak. The solid line (convoluted curve) is
well fitted with the experimental points represented by the
filled circles. On deconvolution of the diffraction curve, it is
0
0
clear that the curve contains an additional peak, which is 125
away from the higher-intensity peak. The additional peak
corresponds to an internal structural low-angle boundary. For
a better understanding, a schematic of a structural grain
boundary is given in the inset of Fig. 7. As seen in the inset,
3.5. Mechanical studies
Transparent crystals free from cracks were selected for
microhardness measurements. Before indentation, the crystals
were carefully lapped and washed to avoid surface defects.
Vickers hardness indentations were made on the as-grown
surface of the DDO crystals at room temperature with a load
ranging from 25 to 100 g, keeping the time of indentation as
10 s for all trials. The Vickers hardness number, H , was
calculated from the following equation:
v
Figure 6
A plot of Vickers hardness number (kg mm ) versus load (g).
ꢂ2
2
ꢂ2
H ¼ 1:8544 P=d kg mm ;
ð4Þ
v
Figure 5
TG/DSC of a DDO crystal.
Figure 7
HRXRD of a DDO crystal.
ꢃ
J. Appl. Cryst. (2012). 45, 914–920
M. Rajasekar et al.
1,5-Diphenylpenta-2,4-dien-1-one 917

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two regions of the crystal are misoriented by a finite angle ꢁ,
also known as the tilt angle. The tilt angle may be defined as
the misorientation angle between the two crystalline regions
on opposing sides of the structural grain boundary. The two
Table 2
SHG outputs.
Chalcone
I2! (mV)
1,5-Diphenylpenta-2,4-dien-1-one
0
0
regions may be perfect. If ꢁ ꢄ 1 , we may call it a very low
1-(4-Bromophenyl)-5-phenylpenta-2,4-dien-1-one
1-(4-Chlorophenyl)-5-phenylpenta-2,4-dien-1-one
2 times that of KDP
5 times that of KDP
0
4.5 times that of urea
15.5 times that of urea
0
ꢅ
angle boundary. If 1 < ꢁ < 1 , we call it a low-angle boundary.
More details of such structural grain boundaries, including
their affect on physical properties, are available elsewhere
a
1
1
1
,5-Diphenylpenta-1,4-dien-3-one
,5-Bis(4-chlorophenyl)penta-1,4-dien-3-one
,5-Bis(4-methoxyphenyl)penta-1,4-dien-3-one
b
c
(Bhagavannarayana et al., 2005; Bhagavannarayana & Kush-
waha, 2010). The angular separation between the two peaks
References: (a) Vanchinathan et al. (2011); (b) Ravindra, Kiran, Dharmaprakash et al.
2008); (c) Ravindra, Kiran, Nooji et al. (2008).
(
0
0
gives the tilt angle ꢁ, which is 125 for the specimen crystal as
seen in the figure. The FWHMs of the main peak and the low-
0
0
angle boundary are, respectively, 120 and 220 . These rela-
tively high values reveal the fact that both the regions of the
crystal are not perfect. These types of structural defects are
probably generated in the crystals as a result of mechanical/
thermal fluctuations that occurred during the growth process
and/or because of the fast growth (Bhagavannarayana et al.,
the orthorhombic crystal system with centrosymmetric space
group Pbca, and the obtained cell parameter values,
˚
a = 15.4307 (9), b = 10.2659 (5), c = 16.4124 (9) A, V =
3
2599.9 (2) A and Z = 8, are in good agreement with the
˚
reported values (Kashino & Haisa, 1980). The DDO molecule
is planar. Taking the C1–C6 phenyl ring as plane 1, the C12–
C17 phenyl ring as plane 2 and the central C7–C11 linkage as
plane 3, the dihedral angles between them, A , A and A23
2010). It may be mentioned here that such minute defects
could be detected with well resolved peaks in the diffraction
curve only because of the high resolution of the diffract-
ometer. The influence of such defects may not reflect much on
the NLO properties. However, a quantitative analysis of such
unavoidable defects is of great importance, particularly in the
case of phase matching applications as explained in our recent
article (Bhagavannarayana et al., 2011).
12
13
ꢅ
are 0.69, 19.91 and 19.53 , respectively, showing that the two
phenyl rings are rotated in opposite directions with respect to
the central plane 3. The C6—C7—C8—C9 and C9—C10—
ꢅ
C11—C12 torsion angles are ꢂ160.63 (18) and 178.39 (18) ,
respectively. The internal angle at the ring atom (C6) to which
ꢅ
the carbonyl C atom (C7) is bonded is 118.4 , while the
internal angle at the equivalent atom (C12) in the other ring is
3.7. Single-crystal XRD
ꢅ
slightly smaller (117.36 ).
The structural analysis of the DDO crystal was carried out
by single-crystal XRD analysis. The displacement ellipsoid
plot of DDO is given in Fig. 8(a). The compound crystallizes in
3.8. NLO studies
Chalcone properties can be easily controlled by suitable
substitution in the phenyl ring. Substituting different donor
and acceptor groups on phenyl rings can result in remarkable
changes in the physical properties. Being centrosymmetric,
DDO crystals do not exhibit SHG when they are exposed to
an Nd:YAG laser (1064 nm), but there are no crystal
symmetry restrictions for third-order NLO responses. Inter-
estingly, even though SHG is zero in DDO, the p-bromo- and
p-chloro-substituted DDO crystals exhibit a considerable
SHG efficiency and the performance of 1-(4-chlorophenyl)-5-
phenylpenta-2,4-dien-1-one is striking (Table 2). Interestingly,
in the related 1,5-diphenylpenta-1,4-dien-3-one crystals
(Vanchinathan et al., 2011), high efficiency is also exhibited by
the p-chloro (Ravindra, Kiran, Dharmaprakash et al., 2008)
and p-methoxy (Ravindra, Kiran, Nooji et al., 2008) deriva-
tives. NLO behaviour depends on structure and orientation. A
favourable molecular alignment in the case of substituted
(
2)
(2)
chalcones leads to high SHG efficiency, ꢀ . To maximize ꢀ
it is necessary to have a head-to-tail alignment of molecules
connected through strong intermolecular hydrogen-bond
interactions. The absence of SHG in DDO could be due to
antiparallel alignment of molecular dipoles, in which the
dipole moment, ꢆ, of each molecule gets cancelled. Classic
hydrogen bonds are not observed in the present study except
for some weak ꢇ interactions.
Figure 8
(a) Displacement ellipsoid plot of the title compound. (b) Optimized
molecular structure.
ꢃ
9
18 M. Rajasekar et al.
1,5-Diphenylpenta-2,4-dien-1-one
J. Appl. Cryst. (2012). 45, 914–920

research papers
Table 3
of the sample and no decomposition is observed up to the
melting point. Good transmission in the entire visible region is
observed with a band gap energy of 2.87 eV as estimated by
diffuse reflectance spectroscopy. HRXRD studies reveal a
low-angle structural grain boundary. The high first-order
hyperpolarizability with zero SHG could be attributed to
orientation factors. The halogen-substituted chalcones exhibit
a high SHG efficiency.
The calculated dipole moment (in D), ꢄ components and ꢄtot value of
DDO (in electrostatic units).
ꢄ
xxx
ꢄ
xxy
ꢄ
xyy
ꢄ
yyy
ꢄ
xxz
ꢄ
xyz
ꢄ
yyz
ꢄ
xzz
ꢄ
yzz
ꢄ
zzz
ꢄ
tot
ꢂ773.119
ꢂ452.348
60.064
17.790
ꢂ14.443
32.529
10.887
13.303
8.671
0.189
7.077 ꢁ 10
The authors thank the Department of Science and Tech-
nology (DST), New Delhi, for financial support through
research grant No. SR/S2/LOP-0025/2010, and MR is grateful
to DST for a project fellowship. KM is thankful to CSIR, New
Delhi, for the award of a senior research fellowship.
ꢂ30
ꢆ
x
ꢆ
y
ꢆ
z
ꢆ
0.8562
2.8658
ꢂ0.5319
3.0379
3.9. Theoretical studies
References
Quantum mechanical calculations are used for predicting
the molecular NLO properties of molecules. Hyperpolariz-
Bertl, E., Becker, H., Eicher, T., Herhaus, C., Kapadia, G., Bartsch, H.
Gerh a¨ user, C. (2004). Biochem. Biophys. Res. Commun. 325,
&
287–295.
ability is a third-rank tensor that can be described by a 3 ꢁ 3 ꢁ
Bhagavannarayana, G., Ananthamurthy, R. V., Budakoti, G. C.,
Kumar, B. & Bartwal, K. S. (2005). J. Appl. Cryst. 38, 768–771.
Bhagavannarayana, G. & Kushwaha, S. K. (2010). J. Appl. Cryst. 43,
3
matrix. The 27 components of the three-dimensional matrix
can be reduced to ten components because of the Kleinman
symmetry (Kleinman, 1962; Frisch et al., 2000). It can be given
in the lower tetrahedral format,
154–162.
Bhagavannarayana, G., Rajesh, P. & Ramasamy, P. (2010). J. Appl.
Cryst. 43, 1372–1376.
Bhagavannarayana, G., Riscob, B. & Shakir, M. (2011). Mater. Chem.
Phys. 126, 20–23.
Brandenburg, K. (2007). DIAMOND. Crystal Impact GbR, Bonn,
Germany.
Dimmock, J. R., Elias, D. W., Beazely, M. A. & Kandepu, N. M.
0
1
2
1
6
E ¼ E ꢂ ꢆ F ꢂ ꢁ F F ꢂ ꢄ F F F þ ꢆ ꢆ ꢆ ð5Þ
ꢁ
ꢁ
ꢁꢄ
ꢁ
ꢄ
ꢁꢄꢈ
ꢁ
ꢄ
ꢈ
0
where E is the energy of the unperturbed molecule, F is the
ꢁ
field at the origin of ꢆ , and ꢆ , ꢁ and ꢄꢁꢄꢈ are the
ꢁ
ꢁ
ꢁꢄ
components of dipole moment, polarizability and first-order
hyperpolarizability, respectively.
(1999). Curr. Med. Chem. 6, 1125–1149.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
2
x
2
y
2 1=2
z
Fichou, D., Watanabe, T., Takeda, T., Miyata, S., Goto, Y. &
Nakayama, M. (1988). Jpn. J. Appl. Phys. 27, L429–L430.
Frisch, M. J., Nielson, A. B. & Holder, A. J. (2000). GAUSSVIEW
User Manual. Gaussian Inc., Pittsburgh, PA, USA.
Frisch, M. J., Trucks, G. W. et al. (2004). Gaussion03. Gaussian Inc.,
Wallingford, CT, USA.
ꢄ ¼ ðꢄ þ ꢄ þ ꢄ Þ
;
and
0
ꢄx ¼ ꢄxxx þ ꢄxyy þ ꢄxzz
ꢄy ¼ ꢄyyy þ ꢄxxy þ ꢄyzz
ꢄx ¼ ꢄzzz þ ꢄxxz þ ꢄyyz
;
;
:
ð6Þ
Goto, Y., Hayashi, A., Kimura, Y. & Nakayam, M. (1991). J. Cryst.
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The calculated first-order hyperpolarizability (ꢄ) and dipole
ꢂ30
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(
Table 3). The high value of ꢄ is a result of the behaviour of
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4
. Conclusions
Transparent crystals of 1,5-diphenylpenta-2,4-dien-1-one were
grown in ethanol by the slow evaporation solution growth
technique at room temperature. The product formation was
confirmed by FT–IR, FT–Raman and single-crystal XRD
analyses. The powder X-ray diffraction study shows the good
crystallinity of the material. TG/DSC studies reveal the purity
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ꢃ
J. Appl. Cryst. (2012). 45, 914–920
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20 M. Rajasekar et al.
1,5-Diphenylpenta-2,4-dien-1-one
J. Appl. Cryst. (2012). 45, 914–920