Synthesis, growth and characterization of a new promising organic nonlinear optical crystal: 4-Nitrophenyl hydrazone

Article abstract of DOI:10.1016/j.saa.2015.07.031

Abstract 4-Nitrophenyl hydrazone single crystals were grown by slow evaporation of solvent method using acetone as a solvent. The grown crystals were subjected to various characterizations such as X-ray diffraction studies, UV-visible studies, thermogravi

Full text of DOI:10.1016/j.saa.2015.07.031

Accepted Manuscript
Synthesis, growth and characterization of a new promising organic nonlinear
optical crystal: 4–nitrophenyl hydrazone
B.C. Hemaraju, M.A. Ahlam, N. Pushpa, K.M. Mahadevan, A.P. Gnana Prakash
PII:
S1386-1425(15)30076-7
http://dx.doi.org/10.1016/j.saa.2015.07.031
SAA 13925
DOI:
Reference:
To appear in:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
Received Date:
Revised Date:
Accepted Date:
4 July 2014
29 June 2015
6 July 2015
Please cite this article as: B.C. Hemaraju, M.A. Ahlam, N. Pushpa, K.M. Mahadevan, A.P. Gnana Prakash, Synthesis,
growth and characterization of a new promising organic nonlinear optical crystal: 4–nitrophenyl hydrazone,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2015), doi: http://dx.doi.org/10.1016/j.saa.
2
015.07.031
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Synthesis, growth and characterization of a new promising
organic nonlinear optical crystal: 4–nitrophenyl hydrazone
1
B C Hemaraju , M A Ahlam , N Pushpa , K M Mahadevan and A P Gnana Prakash *
1
2
3
1
1
Department of Studies in Physics, University of Mysore, Mysore-570 006, India
2
Department of PG Studies in Physics, JSS College, Ooty Road, Mysore-570025, India
3
Department of PG Studies in Pharmaceutical Chemistry, Kuvempu University Kadur P.G.Center, Kadur 577
548, Karnataka, India,
Corresponding author: gnanaprakash@physics.uni-mysore.ac.in
*
Abstract
4
-nitrophenyl hydrazone single crystals were grown by slow evaporation of solvent method
using acetone as a solvent. The grown crystals were subjected to various characterizations
such as X-ray diffraction studies, UV-visible studies, thermogravimetric analysis and
differential thermal analysis (TGA/DTA) and second harmonic generation (SHG). The cell
parameters were calculated by using single crystal XRD measurement and the crystal system
1
was found as orthorhombic with non-centro-symmetric space group Pca2 . The crystallinity
of the grown crystal was confirmed by powder X-ray diffraction analysis. The Fourier
transform infrared (FTIR) and nuclear magnetic resonance (NMR) studies confirmed the
presence of functional groups in the sample. The optical transmittance spectrum shows that
the crystal is transparent in the visible wavelength range. The scanning electron microscopy
(
SEM) was used to study the surface morphology of the grown crystal. The chemical
composition of the grown crystal was confirmed by energy dispersive X-ray (EDX) analysis.
The TGA/DTA results showed that the material is stable up to 146 °C. The NLO property of
the crystal was confirmed by Kurtz and Perry method and SHG conversion efficiency is
1
5.39 times when compared to KDP crystal.
Highlights
•
•
•
•
New NLO crystal is grown by slow evaporation of solvent at room temperature.
The sample crystallizes in orthorhombic space group Pca2
NMR and FTIR studies confirm the purity and functional groups of the grown crystal.
Second harmonic generation efficiency is 15.39 times higher than KDP.
1
.
Keywords
Nonlinear optical materials, X-ray diffraction, Crystal structure, Optical properties, SHG
1
. Introduction
In the recent past, growing the non-linear optical (NLO) single crystals has emerged as one of
the most attractive fields of research in view of its potential applications in the area of laser
technology, optical communication, optical data storage, optical signal processing, optical
switching, optical computing, optical bi-stability etc [1-4]. The organic nonlinear optical
materials are very interesting and promising for high-speed electro-optic applications in
future telecommunication networks. Recently, a large number of organic compounds with
nonlocalized π electron systems and a large dipole moment have been synthesized to realize
the nonlinear susceptibilities larger than the inorganic optical materials. The basic structure of
organic NLO materials is based on π bond systems and due to the overlaping of π orbital,
delocalization of electronic charge distribution leads to a high mobility of the electron
density. Functionalization of both ends of the π bond system with appropriate electron donor
1

and acceptor groups can enhance the asymmetric electronic distribution in either or both the
ground and excited states, these leading to an increased optical nonlinearity [5-7]. Hydrazone
derivatives are an important class of organic compounds and tend to form crystals in non-
centro-symmetric space groups and motivated to investigate non-linear properties [8]. Some
of hydrazone derivatives were used in nonlinear optics for the preparation of crystals and
Langmuir–Blodgett films. Some of nitrophenyl hydrazone crystals exhibit a large
macroscopic optical nonlinearity with optimal molecular packing for electro-optics and
terahertz-wave generation [10-13]. The synthesis and structure of various phenyl hydrazone
compounds are investigated and their photochemical and photophysical properties are studied
systematically [14-19]. In the present work we emphasize the involvement and interplay of
the hydrazone moiety (–CH=N–NH–) with additional functional groups, in forming
intermolecular interactions through spectroscopic technique. Based on extensive use of
phenyl hydrazone compounds for various photophysical properties, in this paper for the first
time, we report the synthesis, characterization and NLO property of 4-nitrophenyl hydrazone.
2
. Experimental
2
.1. Synthesis of 4-nitrophenyl hydrazone
The mixture of 99 % purity of 4-nitroacetophenone (5 gm, 30 mmol) and 98 % purity of
phenyl hydrazine (3.26 ml, 30 mmol) was dissolved in 50 ml of methanol and 2-3 drops of
glacial acetic acid was added. The reaction mixture was then heated for 30 min in water bath.
After the completion of the reaction and up on cooling the reaction mixture, the product was
separated out as red crystalline solid. The product thus obtained was then filtered, washed
with ethanol and dried to get pure 4-nitrophenyl hydrazone in good yield. The chemical
reaction is shown in the following scheme:
2
.2. Single crystal growth and characterization
The dried product of 4-nitrophenyl hydrazone was dissolved in acetone and the total content
was covered by a perforated sheet to facilitate the evaporation of the solvent at room
temperature. In about 24 hours, we obtained needle shaped crystals as shown in Fig. 1. The
grown crystal was confirmed by single crystal and powder XRD analysis. The single crystal
XRD data was recorded by using Nonius CAD-4/MACH3 diffractometer, with Mo-Kα
radiation (λ=0.71073 Å). The powder XRD study was carried out to demonstrate the
crystallinity of the sample by using a Rigaku-Miniflex X-ray diffractometer with Cu-Kα
radiations (λ=1.5406 Å). The FTIR spectrum of the grown crystal was recorded in the
-1
frequency range from 400–4000 cm using FTIR-8400S spectrophotometer, Shimadzu model
-
1
under a resolution of 4 cm and with the scanning speed of 2 mm/sec following KBr pellet
1
13
technique. The H-NMR (400 MHz) and C-NMR (100 MHz) spectrums of the grown
crystals were recorded using a Bruker-AMX 400 MHz in (CH CO as solvent. The optical
3 2
)
transmittance spectrum of 4-nitrophenyl hydrazone crystal was recorded using Perkin-Elmer
2

UV-visible spectrophotometer in the range of 350 – 800 nm. The SEM images and EDX
pattern of the grown crystals were recorded using Quanta 200 with Genesis eds software.
Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out
-1
using TA instruments Q600 SDT in the nitrogen atmosphere at a heating rate of 10 °C min .
The study of nonlinear optical conversion efficiency has been carried out using the modified
setup of Kurtz and Perry at Indian institute of Science (IISc), Bangalore [20].
Fig. 1. The photograph of the as-grown 4-nitrophenyl hydrazone crystals.
3
. Results and discussion
3
.1. Single crystal X-ray diffraction
Single crystal X-ray diffraction analysis of 4-nitrophenyl hydrazone crystal have been carried
out to identify the structure and to estimate the lattice parameters. The title compound
crystallizes in orthorhombic crystal system with space group Pca2 which is recognized as
1
non-centro-symmetric, thus satisfying one of the basic and essential material requirements for
the SHG activity of the crystals. The structural details of the crystal are given in table 1.
Table 1. Crystal structure details of 4-nitrophenyl hydrazone.
Crystallographic data of 4-nitrophenyl
hydrazone
Formula
Crystal structure
Space group
a (Å)
13 11 3 2
C H N O
Orthorhombic
Pca2
1
10.31(3)
9.54(2)
8.20(4)
90.00(0)
789.7753
1.428
b (Å)
c (Å)
α ˚ = β ˚ =γ ˚
Cell volume (Å )
Density (gm.cm )
Molecular weight
(
)
( )
( )
3
-3
241
3
.2. Powder X-ray diffraction
The powder X-ray diffraction analysis was carried out to confirm the crystallinity of the
sample. The grown crystal was crushed to a uniform fine powder and subjected to powder X-
ray diffraction. The XRD pattern of the grown crystal was recorded and is shown in Fig. 2.
The intensity versus 2θ was recorded by varying from 10° to 90° at a rate of 5°/min by
3

employing continuous scan mode. The sharp and well defined peaks at specific 2θ values
indicate the good crystalline nature of the sample.
1
4000
2000
0000
1
1
8
000
000
000
000
0
6
4
2
10
20
30
40
50
60
70
80
90
2θ (degree)
Fig. 2. Powder XRD pattern of 4-nitrophenyl hydrazone crystal.
3
.3. FTIR Spectral Measurement
The Fourier transform infrared spectroscopy was used to identify the functional groups
present in 4-nitrophenyl hydrazone crystal. The FTIR spectrum of the grown crystal was
-1
recorded in the frequency range of 400–4000 cm and is shown in Fig. 3, it can be seen that,
-
1
an absorption peaks at 3333.10 cm is due to the stretching frequency of N-H group. The
-
1
peak at 3022.55 cm corresponding to stretching absorption of =CH group in aromatic rings.
-
.1
The spectrum shows the absorption band at 1491.92 cm due to bending vibration of CH
3
-1
group. Further the peaks correspond to C=O group in the region 1640-1700 cm disappeared
and new peak appears at 1595.18 cm indicates the formation of C=N group. N-H and C=N
-1
-
1
-1
stretching at 3333.10 cm and 1595.18 cm confirm the sample has hydrazone derivatives
-1
-1
[
21]. Absorptions at 1548.89 cm and 1323.21 cm correspond to symmetrical and
asymmetrical vibrations for -NO group. The resultant spectrum confirms the presence of all
functional groups in the material.
2
4

-
Wavenumber (cm )
1
Fig. 3. FTIR spectrum of 4-nitrophenyl hydrazone crystal.
1 13
.4. NMR Spectral Measurement ( H and C)
3
The NMR spectroscopy is a powerful tool in terms of structural information derived from the
spectrum. It involves the change of the spin state of a nuclear magnetic moment when the
nuclear magnetic field is changed. Thus, NMR techniques are used to detect the presence of
1
particular nuclei in a compound for a given nuclear species [22]. The H-NMR (400 MHz)
1
3
and C-NMR (100 MHz) spectrums of the grown crystal are shown in fig. 4 and fig.5
1
respectively. The H-NMR spectrum (Fig. 4) indicates four kinds of proton signals related to
the main functional groups. The singlet at δ = 2.349 ppm is corresponds to the methyl protons
1
(
-CH
3
). Also the H-NMR spectrum shows that the singlet as a broad signal at δ = 9.077 ppm
strongly assignable to amino proton (-NH). The protons of unsubstituted phenyl appear as
two multiplets signals in the region of δ = 6.845 to 7.338 ppm. However, the protons of 4-
nitrophenyl appear as two doublets. The doublet of the protons adjusted to the nitro group
appear in down field at 8.219 ppm with coupling constant J=7.6 Hz and the other doublet
appear at 8.075 ppm with coupling constant J=7.6 Hz as shown in Fig. 4.
5

1
Fig. 4. The H-NMR spectrum of 4-nitrophenyl hydrazone crystal.
1
3
The C-NMR spectrum of the grown crystal (Fig. 5) is in accordance with the
proposed structure. The spectrum shows that the singlet at δ = 12.12 ppm corresponds to the
carbon atom of methyl group. The aromatic carbon atoms appear in the region at δ = 113.51
to 146.64 ppm. The singlet at δ = 147.58 ppm was assignable to carbon atom of (C=N). The
signals which appear at 30.38 ppm and 206.07 ppm are known to the carbon atoms of acetone
solvent.
1
3
Fig. 5. The C-NMR spectrum of 4-nitro phenyl hydrazone crystal.
6

3
.5. UV-visible spectral measurement
The UV-visible spectral study is a useful tool to determine the transparency, which is an
important requirement for a material to be optically active. The UV–visible spectrum of the
grown crystal was recorded in the range between 350–800 nm. The optical transmittance
spectrum of 4-nitrophenyl hydrazone crystal is shown in Fig. 6. The short wavelength cut-off
occurs at 488 nm and there is no appreciable absorption of light in the entire visible region.
The colored compounds absorb UV visible light generally with a strong absorbence in the
*
visible range. The absorption band obtained in the visible region is assigned to n→π
electronic transition of hydrazone (–CH=N–NH–) group present in the 4-nitrophenyl
hydrazone molecules [23,24] The good transmittance property of the crystal in the entire
visible region ensures its suitability for second harmonic generation application [25].
Fig. 6. UV-visible spectrum of 4-nitrophenyl hydrazone crystal.
The optical energy gap of the grown crystal is determined from the transmittance
spectrum using the equation;
ꢀ
ℎꢁ = ꢂ(ℎꢁ − ꢃꢄ)ꢅ
(1)
where A is a constant which varies with transitions, ꢆꢃ is the band gap of the material and ꢇ
ꢄ
is an index which can have the values 1/2, 3/2, 2, or 3 depending on the nature of the
electronic transitions. Here, the value of n is assigned as 1/2 for an allowed direct transition
and ꢀ is the absorption coefficient, which is calculated from the equation;
Abs
α =
(2)
t
where ꢂꢈꢉ is the absorbance of the material and ꢊꢆis the thickness of the sample. From the
ꢋ
transmittance spectrum, a graph is drawn between ℎꢁ and (ꢀℎꢁ) ꢆand is shown in Fig. 7. The
band gap energy of the grown crystal is evaluated by extrapolation a straight line in the linear
ꢋ
region of the graph at (ꢀℎꢁ) = 0. The band gap energy calculated was found to be 2.45 eV
for the grown crystal.
7

8
1
1
1
8
6
4
2
.4x10
8
.2x10
8
.0x10
7
.0x10
7
.0x10
7
.0x10
7
.0x10
0.0
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
hν (eV)
2
Fig. 7. The plot of (αhv) vs photon energy hv.
3
.6. Scanning electron microscopy (SEM) measurement
The SEM micrographs of the grown crystals were taken at different magnification values are
shown in Fig. 8. It gives information about surface morphology and the presence of
imperfections in the crystals. Fig. 8 clearly shows the grain distribution over the surface and a
few microcrystals present on the surface of the grown crystal.
Fig. 8. SEM micrograph of 4-nitrophenyl hydrazone crystal.
3
.7. Energy dispersive X-ray (EDX) measurement
An elemental analysis was carried out for 4-nitrophenyl hydrazone by employing the energy
dispersive X-ray (EDX) in order to confirm the composition of carbon (C), nitrogen (N) and
oxygen (O) in the crystal. Fig. 9 illustrates the EDX spectrum of the grown crystal. The
weight percentages (wt %) of C, N and O as obtained from EDX analysis is listed in table 2.
8

Fig. 9. EDX spectrum of 4-nitrophenyl hydrazone crystal.
Table 2. EDX quantification of 4-nitrophenyl hydrazone crystal.
Element
Wt (%)
At%
Carbon
Nitrogen
Oxygen
76.31
12.51
11.18
79.97
11.24
8.79
Total
100.00
100.00
3
.8. Thermal measurements
The thermo gravimetric (TG) and differential thermal analysis (DTA) are important as far as
the fabrication technology is concerned, as they provide thermal stability since considerable
amount of heat is generated during the cutting process. Thermo gravimetric analysis (TGA)
o
and differential thermal analysis (DTA) of the grown crystals were carried out between 30 C
to 987 °C. Fig. 10 shows the thermograms illustrating simultaneously recorded TGA and
DTA. The DTA curve shows a major endothermic peak, which corresponds to the melting
point of the material at 146 °C. The sharpness of the peak at 146 °C indicates the high purity
of the grown crystal. Another important observation is, there is no phase transition until the
material melts and this enhances the temperature range for the utility of crystal for NLO
applications. The absence of water in the molecular structure is indicated by the absence of
weight loss around 100 °C. There are two peaks detected at 327.2 °C and 486.7 °C, may be
due to the decomposition stage of the compound. From the TGA curve, it can be seen that
there are three stages of weight loss. The first weight loss (stage I) is a sharp one starting at
about 135.8 °C, which indicates the beginning of the melting. This is followed by a weight
loss (stage II) occurring between 296.7 °C and 557.4 °C. The weight loss (stage III) above
5
57.4 °C is assigned to the decomposition of the compound.
9

TGA93.5% at 135.8
°
C
486.7°C
20
100
327.2°C
0
80
60
40
20
DTA
1
46°C
-20
-40
-60
-80
20.3% at 966.4°C
39.7% at 296.7°C
2
2.98% at 557.4°C
0
200
400
600
C)
800
1000
Temperature (
°
Fig. 10. TGA/DTA curves of 4-nitrophenyl hydrazone crystal
.9. Powder SHG measurement
3
The study of nonlinear optical conversion efficiency has been carried out using the modified
setup of Kurtz and Perry method. A Q-switched Nd:YAG laser beam of wavelength 1064 nm
with an input power of 3.25 mJ/pulse and pulse width of 10 ns with a repetition rate of 10 Hz
were used. The grown crystals of 4-nitrophenyl hydrazone were powdered and then packed in
a micro capillary of uniform bore and exposed to laser radiations. The second harmonic
radiation generated by the randomly oriented microcrystals were focused by a lens and
detected by a photo multiplier tube. The emission of green radiation of wavelength 532 nm
from the crystal confirmed the second harmonic signal generation. A sample of potassium
dihydrogen phosphate (KDP) was used as a reference material for the present measurement.
The signal amplitude in mV on the oscilloscope indicates the SHG efficiency of the grown
crystal. A second harmonic signal of 1000 mV was obtained from 4-nitrophenyl hydrazone,
with reference material KDP (65 mV). The SHG conversion efficiency of 4-nitrophenyl
hydrazone was found to be 15.39 times when compared to that of KDP.
4
. Conclusions
The needle shaped crystals of 4-nitrophenyl hydrazone were grown by slow evaporation
technique using acetone as a solvent. The single crystal X-ray crystallographic data indicates
that the crystal belongs to orthorhombic crystal system with non-centro-symmetric space
1
group Pca2 . The powder X-ray diffraction pattern confirmed the crystallinity of the sample.
1
13
The FTIR, H NMR and C NMR spectrums show the presence of different functional
groups in the grown crystal. The UV-visible spectrum revealed that the grown crystal was
moderately transparent in the entire visible region. Therefore grown crystals were suitable for
second harmonic generation applications. The chemical composition of the grown crystal was
ascertained by EDX measurement. The SEM shows that a few microcrystals were randomly
distributed on the surface of the crystal. Thermal analysis revealed that the title compound is
stable up to 146 °C and hence the grown crystal can be used for SHG applications up to 146
°C. The SHG property of the grown crystal was tested and found to be 15.39 times when
1
0

compared to KDP crystal. Therefore, the aforesaid results make 4-nitrophenyl hydrazone
crystal is a good candidate for NLO applications.
Acknowledgements
This work is carried out under the research project sanctioned by UGC, Govt. of India
[
Project no. 41-911/2012 (SR)].
Reference
[
1] H.O. Marcy, L.F. Warren, M.S. Webb, C.A. Ebbers, S.P. elsko, G.C. Kennedy,
G.C.Catella, Appl. Opt. 31 (1992) 5051.
2] D.S. Chemla, J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals,
Academic Press, New York, 1987.
3] J. Zyss, Molecular Nonlinear Optics: Materials, Physics and Devices, Academic Press,
Boston, 1994.
4] R.W. Munn, C.N. Ironside, Principles and Applications of Nonlinear Optical Materials,
Chapman & Hall, London, 1993.
5] R. Rai, K. Varma, Growth and characterization of single crystal of pentachloropyridine,
Journal of Crystal Growth, 285 (2005) 111-116.
6] V. Crasta, V. Ravindrachary, S. Lakshmi, S. Pramod, M. Shridar, J.S. Prasad, Growth,
[
[
[
[
[
characterization and crystal structure analysis of 1-(4-chlorophenyl)-3-(4-chlorophenyl)-2-
propen-1-one, Journal of Crystal Growth, 275 (2005) e329-e335.
[
7] N. Vijayan, R.R. Babu, M. Gunasekaran, R. Gopalakrishnan, R. Kumaresan, P.
Ramasamy, C. Lan, Studies on the growth and characterization of p-hydroxyacetophenone
single crystals, Journal of Crystal Growth, 249 (2003) 309-315.
[
8] C. Serbutoviez, C. Bosshard, G. Knoepfle, P. Wyss, P. Pretre, P. Guenter, K. Schenk, E.
Solari, G. Chapuis, Hydrazone Derivatives, an Efficient Class of Crystalline Materials for
Nonlinear Optics, Chemistry of Materials, 7 (1995) 1198-1206.
[
9] D. Lupo, A. Laschewsky, I. Ledoux, H. Ringsdorf, W. Prass, U. Scheunemann, Second-
harmonic generation in Langmuir–Blodgett monolayers of stilbazium salt and
phenylhydrazone dyes, JOSA B, 5 (1988) 300-308.
[
10] F. Pan, C. Bosshard, M.S. Wong, C. Serbutoviez, S. Follonier, P. Günter, K. Schenk,
Polymorphism, growth and characterization of a new organic nonlinear optical crystal: 4-
dimethylaminobenzaldehyde-4-nitrophenylhydrazone (DANPH), Journal of Crystal Growth,
1
65 (1996) 273-283.
[
11] S. Follonier, C. Bosshard, U. Meier, G. Knöpfle, C. Serbutoviez, F. Pan, P. Günter, New
nonlinear-optical organic crystal: 4-dimethyl-aminobenzaldehyde-4-nitrophenyl-hydrazone,
JOSA B, 14 (1997) 593-601.
[
12] M.S. Wong, V. Gramlich, C. Bosshard, P. Günter, Hydrogen bonded lambda-shaped
packing motif based on 4-nitrophenylhydrazones: a promising design tool for engineering
acentric crystals, Journal of Materials Chemistry, 7 (1997) 2021-2026.
[
13] G.M. de Lima, S.M. Wardell, J.L. Wardell, E.R. Tiekink, A Doubly Interpenetrated
Layer Structure: 4-Acetamidobenzaldehyde 4-Nitrophenylhydrazone, Journal of Chemical
Crystallography, 40 (2010) 1159-1162.
[
14] J. Owen, E.A. White, Second harmonic generation in organic crystals, Journal of
Materials Science, 11 (1976) 2165-2169.
15] J. Owen, E. White, Preparation and electro-optic properties of 1-formyl 2 (4-nitrophenyl)
hydrazine, Journal of Materials Science, 12 (1977) 743-746.
16] D.M. Burland, R.D. Miller, C.A. Walsh, Second-order nonlinearity in poled-polymer
systems, Chemical Reviews, 94 (1994) 31-75.
[
[
1
1

[
17] I. Kminek, D. Diskočilová, J. Straka, S. Nešpůrek, 4-Nitrophenylhydrazone of poly (4-
formylstyrene), Polymer Bulletin, 35 (1995) 315-321.
18] C. Glidewell, J.N. Low, J.M. Skakle, J.L. Wardell, Glyoxal 4-nitrophenylhydrazone:
[
triple helices linked into a three-dimensional channel structure, Acta Crystallographica
Section C: Crystal Structure Communications, 61 (2005) o493-o495.
[
19] G. de Lima, S.S.V. Wardell, J. Wardell, E.T. Tiekink, A Doubly Interpenetrated Layer
Structure: 4-Acetamidobenzaldehyde 4-Nitrophenylhydrazone, Journal of Chemical
Crystallography, 40 (2010) 1159-1162.
[
20] F. Pan, C. Bosshard, M.S. Wong, C. Serbutoviez, K. Schenk, V. Gramlich, P. Günter,
Selective Growth of Polymorphs:ꢀ An Investigation of the Organic Nonlinear Optical Crystal
-Nitro-2-thiophenecarboxaldehyde-4-methylphenylhydrazone, Chemistry of Materials, 9
5
(
1997) 1328-1334.
[
21] S.K. Kurtz, T.T. Perry, A Powder Technique for the Evaluation of Nonlinear Optical
Materials, Journal of Applied Physics, 39 (1968) 3798-3813.
[
22] R. Gandhimathi, R. Dhanasekaran, Synthesis, growth and characterization of 4-
dimethylaminobenzaldehyde-4-nitrophenylhydrazone single crystals, Optik-International
Journal for Light and Electron Optics, 125 (2014) 2912-2917.
[
23] N. Vijayan, R. Ramesh Babu, R. Gopalakrishnan, P. Ramasamy, Some studies on the
growth and characterization of organic nonlinear optical acetoacetanilide single crystals,
Journal of Crystal Growth, 267 (2004) 646-653.
[
24] S. Rajaei, S. Ghammamy, K. Mehrani, H. Sahebalzamani, Synthesis, characterization
and thermal analysis of new Cu (II) complexes with hydrazide ligands, Journal of Chemistry,
(2010) S278-S282.
25] S. Dhanuskodi, K. Vasantha, P.A.A. Mary, Structural and thermal characterization of a
7
[
semiorganic NLO material: l-alanine cadmium chloride, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy, 66 (2007) 637-642.
1
2

1
3

Highlights
•
•
•
•
New NLO crystal is grown by slow evaporation of solvent at room temperature.
The sample crystallizes in orthorhombic space group Pca2
NMR and FTIR studies confirm the purity and functional groups of the grown crystal.
Second harmonic generation efficiency is 15.39 times higher than KDP.
1
.
1
4