Synthesis and characterization of semicarbazone of p-hydroxy-3-methoxy acetophenone (SPH3MA) single crystal

Article abstract of DOI:10.1016/j.physb.2010.09.010

Single crystals of semicarbazone of p-hydroxy-3-methoxy acetophenone (SPH3MA) were grown by a slow evaporation solution growth technique at room temperature. This is the first report in the literature on the crystallization of SPH3MA. The cell parameters of the grown crystals were estimated by single crystal X-ray diffraction analysis. The various planes of reflection were identified from the XRD powder pattern. The presence of functional groups was identified from FTIR and ¹H NMR. The results were found to be in accordance with the structure of the crystal. The formation of charge transfer complex was confirmed by UVvisNIR spectroscopy. The thermal stability of the grown crystal was studied by thermal analysis.

Full text of DOI:10.1016/j.physb.2010.09.010

Physica B 406 (2011) 135–138
Contents lists available at ScienceDirect
Physica B
journal homepage: www.elsevier.com/locate/physb
Synthesis and characterization of semicarbazone of p-hydroxy-3-methoxy
acetophenone (SPH3MA) single crystal
n
S. Janarthanan a, Y.C. Rajan b, P.R. Umarani a, S. Selvakumar c, S. Pandi a,
a Department of Physics, Presidency College, Chennai, Tamilnadu, India
b Department of Materials Science, National Chiao Tung University, Taiwan, ROC
c Department of Physics, L.N.G. College, Ponneri, Tamilnadu, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Single crystals of semicarbazone of p-hydroxy-3-methoxy acetophenone (SPH3MA) were grown by a
slow evaporation solution growth technique at room temperature. This is the first report in the
literature on the crystallization of SPH3MA. The cell parameters of the grown crystals were estimated
by single crystal X-ray diffraction analysis. The various planes of reflection were identified from the XRD
powder pattern. The presence of functional groups was identified from FTIR and 1H NMR. The results
were found to be in accordance with the structure of the crystal. The formation of charge transfer
complex was confirmed by UV–vis–NIR spectroscopy. The thermal stability of the grown crystal was
studied by thermal analysis.
Received 29 April 2010
Received in revised form
10 September 2010
Accepted 14 September 2010
Keywords:
Solution crystal growth
Organic compounds
UV absorption
& 2010 Elsevier B.V. All rights reserved.
X-ray diffraction
1. Introduction
we report the synthesis, growth and characterization of a new
organic crystal viz. semicarbazone of p-hydroxy-3-methoxy
acetophenone (SPH3MA) by a slow evaporation technique. The
low temperature solution growth technique can be applied
to a wide range of compounds for producing high quality crystals
[13–15].
Optical nonlinear conjugated organic systems have been
widely studied in view of their potential application as active
components in photonic and electro–optic devices [1,2]. Research
in this area is focused on finding materials exhibiting large
nonlinearity, fast response time, low transmission loss, and high
thermal stability. Research in the field of organic NLO materials
has gained momentum in the recent past on account of the
interesting applications of the materials such as optical
parametric amplifiers, optical parametric oscillators, Q-switched
optical applications, etc. [3–7]. However, most of the organic NLO
crystals are associated with poor mechanical strength and thermal
stability [8,9]. An organic molecule should have high second order
2. Experimental
Single crystals of semicarbazone of p-hydroxy-3-methoxy
acetophenone were grown by a slow evaporation method from
semicarbazide hydrochloride and p-hydroxy-3-methoxy aceto-
phenone using sodium acetate as a catalyst. Alcoholic solvents
like ethanol and methanol were used for growing semicarbazone
crystals. Semicarbazide hydrochloride, sodium acetate, and
p-hydroxy-3-methoxy acetophenone were mixed in the mole
ratio 2:4:1, respectively. The prepared solution was found to be
turbid. Hence, ethanol was added and stirred well, and the solu-
tion was gently warmed till a clear solution was obtained [16].
The obtained product was purified by repeated recrystalliza-
tion before it was used for crystal growth. The growth experiment
was performed in a constant temperature bath at 32 1C. Good
quality single crystals (Fig. 1) were harvested after 15–20 days.
The reaction and molecular structure of the grown crystal is
shown in Scheme 1. The grown crystal was subjected to powder
X-ray diffraction analysis to confirm the crystallinity and also to
estimate the lattice parameters. Powder X-ray diffraction pattern
hyperpolarizability
hyperpolarizability can be enhanced by increasing intramolecular
charge transfer interaction by extending the -conjugated system
(b) to exhibit large NLO properties. The
p
[10]. The increase in conjugation length decreases the energy
gap and narrows down the optical transparency window. Basically,
semicarbazone family crystals exhibit nonlinear optical behaviour
[11,12].
A thorough literature study on semicarbazone crystals and
their applications due to the NLO property reveals that there is no
systematic study on the synthesis and characterization of
acetophenone based semicarbazone derivatives. In this paper,
n Corresponding author. Tel.: +91 9444018924.
E-mail addresses: srijana26@gmail.com, drspandi@gmail.com (S. Pandi).
0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.09.010

136
S. Janarthanan et al. / Physica B 406 (2011) 135–138
was recorded using a Rich Seifert diffractometer with CuK
˚
free N–H stretch. The broad envelope between 2780 and
3368 cmꢀ1 was due to overlapping of peaks of hydrogen bonded
N–H and aromatic C–H stretching modes. The considerable
a
(
l¼1.5418 A) radiation by crushing the SPH3MA crystal into a
fine powder. FTIR spectrum was recorded for SPH3MA on a
BRUKER 66 V FTIR spectrometer by the KBr pellet technique in the
range 400–4000 cmꢀ1 for the identification of the functional
groups. 1H NMR spectrum was recorded in a BRUCKER spectro-
meter of frequency 300 MHz using DMSO-d6 as a solvent (Aldrich)
and TMS (0.03%) as an internal standard. The optical absorption
spectrum of SPH3MA was recorded in a VARIAN CARY 5E
spectrophotometer. Thermal analyses were carried out simulta-
neously in a NETZSCH STA 409C thermal analyser from 28 to
1200 1C at a heating rate of 20 1C per min in nitrogen atmosphere.
The results of these analyses are presented in detail in the
following sections.
3. Results and discussion
The inner arrangement of atoms or molecules in a crystalline
material was revealed using the X-ray diffraction technique. The
powder X-ray diffraction analysis (Fig. 2) carried out confirmed
the crystallinity and provided the lattice parameters (Table 1). The
sample was scanned over the range 10–70 1C at a heating rate of
1 1C per min. The lattice parameters and the cell volume were
calculated using the PROSZKI software package. The peak
obtained corresponds to (0 2 0), having a maximum count of
268 cps. This was the strongest diffraction peak for the SPH3MA
crystal. The SPH3MA crystal was found to be a monoclinic crystal
system.
Fig. 2. PXRD data of SPH3MA crystal.
Table 1
The phenolic OH stretching in the FTIR spectrum (Fig. 3) gave
sharp as well as broad peaks illustrating the presence of free OH
grouping without intermolecular bonding and intensely hydrogen
bonded OH groupings. The broad peak due to hydrogen bonded
Crystallographic data of SPAS crystal.
3
a
b
c
Crystal system
˚
˚
˚
˚
a (A)
b (A)
c (A)
V (A)
15.30
6.91
14.17
901
92.281
901
1497.67
Monoclinic
OH groupings had the peak maximum at 3210 and 3350 cmꢀ1
.
There was an intense sharp peak at 3461 cmꢀ1, assigned to the
Fig. 1. Grown SPH3MA crystal.
Fig. 3. FTIR spectrum of SPH3MA crystal.
O
H
H
N
NH2
CH3COONa
N
N
NH
2 .HCl
H2N
+
O
HO
O
MeO
OMe
OH
semicarbazide.HCl
p-hydroxy-3-methoxy
SPH3MA
acetophenone
Scheme 1. Synthesis of SPH3MA.

S. Janarthanan et al. / Physica B 406 (2011) 135–138
137
Fig. 4. 1H NMR spectrum of SPH3MA crystal.
broadening revealed that the packing of the molecules in the
crystal was largely through intermolecular hydrogen bonding of
these N–H groups. The symmetric and asymmetric C–H stretching
modes of –CH3 group appear as a shoulder just below 3000 cmꢀ1
in the broad envelope. The C¼O stretch of the semicarbazide
moiety was observed at 1663 cmꢀ1. The aromatic ring skeletal
vibrations were observed at 1593 and 1476 cmꢀ1. The –CH3
bending modes were positioned at 1423 and 1312 cmꢀ1. The
–HN–C¼O stretch was seen at 1124 cmꢀ1. The out-of-plane
aromatic C–H bond was observed at 761 cmꢀ1. The peak at
1571 cmꢀ1 was assigned to the C¼N stretching vibration. The
N–H bending vibration gave a peak at 1521 cmꢀ1. The CH2
bending modes were observed at 1448 cmꢀ1. The bands obtained
between 1170 and 1258 cmꢀ1 were due to ether stretching
vibration [17]. From the FTIR spectrum it was well understood
that the coupling between carbonyl group of substituted
acetophenone and amine group of semicarbazide had well gone
through without leaving any trace of starting materials.
Fig. 5. UV–vis–NIR spectrum of SPH3MA crystal.
The typical 1H NMR spectrum (Fig. 4) of SPH3MA had a sharp
singlet at 2.11 ppm due to the presence of the OCH3 group
attached to the aromatic group. The peak observed at 3.80 ppm
could be attributed to the H3C– group attached to the
semicarbazone group. The NH2 and NH groups of the
semicarbazone moieties were observed at 9.1 and 6.4 ppm,
respectively. The appearance of two sharp doublets at 6.7 and
7.1 ppm corresponded to two protons present at ortho and meta
to the phenolic –OH attached to the aromatic rings. However the
sharp singlet at 7.3 ppm was due to the presence of single proton
ortho to the –OCH3 group in the aromatic ring.
Fig. 6. TGA/DTA curve of SPH3MA crystal.
4. Conclusion
Optical absorption measurements were carried out to char-
acterize the optical properties of SPH3MA. A crystal of 2 mm
thickness was used to record the spectrum. Wavelength versus
absorbance was plotted for the sample (Fig. 5). The absorbance
was found to be very low in the entire visible and near IR region,
which was the most desired property for NLO materials. The large
transmission window in the visible region enabled it to be a
potential candidate for optoelectronic applications [18]. From
the obtained spectrum, the UV cut-off wavelength was found to
be 250 nm.
The thermograms provide information about decomposition
pattern of materials and weight loss. Hence, the thermogravi-
metric methods are limited to decomposition and oxidation
reactions. The thermal stability of SPH3MA was identified by
thermogravimetric (TG) and differential thermal analyses (DTA)
(Fig. 6). The SPH3MA sample weighing 6.978 mg was taken for the
analysis. The material was found to be stable upto 230 1C and
decomposed slightly at this temperature. The DTA revealed
exactly the same changes shown by TGA. The major weight loss
that occurred in the low temperature region began at 230 1C and
ended at around 260 1C.
The SPH3MA single crystal was grown by the slow evaporation
method. Powder XRD, FTIR, 1H NMR, and UV absorption studies
were carried out for characterization of the synthesized crystal.
Powder XRD confirmed the crystal structure. The spectral study
revealed the C¼O stretch, which in turn confirmed the structure
of SPH3MA. Optical studies showed that the crystal had a wide
transparency window in the entire visible region, making it an
ideal candidate for NLO device applications. The decomposition
temperature and percentage weight loss of the material were
found out from the TG/DTA analysis. The degree of crystallinity
and purity was also confirmed from a sharp endothermic peak in
the DTA.
Acknowledgements
It is a pleasure to acknowledge Dr. D. Jayaraman, Department
of Physics, Presidency College, Chennai, Dr. M. Vanjinathan,
Department of Chemistry, D.G. Vaishnav College, Chennai, and
Dr. V. Manivannan, Scientist, PRIST University, Tanjour, for their
constant help, support, and encouragement.

138
S. Janarthanan et al. / Physica B 406 (2011) 135–138
References
[10] R.A. Kuijts, G.L.J. Hesselink, Chem. Phys. Lett. 156 (1989) 209.
[11] C.C. Frazier, M.P. Cockerham, E.A. Chauchard, Chi H. Lee, J. Opt. Soc. Am. B 4
(1987) 1899.
[12] N. Vijayan, R. Ramesh Babu, R. Gopalakrishnan, S. Dhanuskodi, P. Ramasamy,
J. Cryst. Growth 236 (2002) 407.
[13] R. Ramesh Babu, S. Kumaresan, N. Vijayan, M. Gunasekaran, R. Gopalakrishnan,
P. Kannan, P. Ramasamy, J. Cryst. Growth 256 (2003) 387.
[14] R. Ramesh Babu, N. Vijayan, M. Gunasekaran, R. Gopalakrishnan, P. Ramasamy,
J. Cryst. Growth 265 (2004) 290.
[15] R. Ramesh Babu, N. Vijayan, R. Gopalakrishnan, P. Ramasamy, J. Cryst. Growth
240 (2002) 545.
[16] B.S. Furniss, A.J. Hannaford, P.W.G. Smith, A.R. Tatachell, Vogel’s Text Book
of Practical Organic Chemistry, 5th ed., English Language Book Society, 1996.
[17] R.M. Silverstein, F.X. Webster, in: Spectrometric Identification of Organic
Compounds, 6th ed., Wiley Inc., New York, 1998.
[1] S.R. Marder, J.E. Sohn, G.D. Stucky, in: Materials for Nonlinear Optics, ACS
Symposium Series 455, American Chemical Society, Washington, DC, 1991.
[2] R.G. Denning, J. Mater. Chem. 11 (2001) 19.
[3] Y. Mori, Y.K. Yap, T. Kamimura, M. Yoshimura, T. Sasaki, Opt. Commun. 1
(2002) 19.
[4] M. Ushasree, R. Muralidharan, R. Jayavel, P. Ramasamy, J. Cryst. Growth 218
(2000) 365.
[5] Z. Li, K. Wu, G. Su, Y. He, Opt. Mater. 20 (2002) 295.
[6] A.M. Petrosyan, R.P. Sukiasyan, H.A. Karapetyan, S.S. Terzyan, R.S. Feigelson, J.
Cryst. Growth 213 (2000) 103.
[7] H. Reyes, B.M. Munoz, N.F.R. Santillan, S. Rojas-Lima, P.G. Lacroix, K. Nakatani,
Mater. Chem. 12 (2002) 2898.
[8] H.O. Marcy, M.J. Rosker, L.F. Warren, P.H. Cunningham, C.A. Thomas, L.A. Deloach,
S. Pvelsko, C.A. Ebbers, J.H. Liao, M.G. Konatzidis, Opt. Lett. 20 (1995) 252.
[9] T. Tsunekawa, T. Gotoh, M. Iwamoto, Chem. Phys. Lett. 166 (1990) 353.
[18] K.V. Rajendran, D. Jayaraman, R. Jayavel, R. Mohan Kumar, P. Ramasamy,
J. Cryst. Growth 224 (2001) 122.