Advances in Materials Physics and Chemistry, 2011, 1, 39-43

doi:10.4236/ampc.2011.12007 Published Online September 2011 (http://www.SciRP.org/journal/ampc)

Synthesis, Crystal Growth and Characterization

of Organic NLO Material: M-Nitroacetanilide
Ramesh Rajendran1, Thangammal Harris Freeda1, Udaya Lakshmi Kalasekar2, Rajesh Narayana Peruma3
1
Physics Research Center, S. T. Hindu College, Nagercoil, India
2
Department of Physics, College of Engineering and Technology, Saveetha University, Chennai, India
3
Center for Crystal Growth, SSN College of Engineering, Kalavakkam, Chennai, India
E-mail: [email protected]
Received May 3, 2011; revised June 17, 2011; accepted June 25, 2011

Abstract

Single crystals of m-Nitroacetanilide (mNAa) were successfully grown by slow evaporation method at a
constant temperature 40°C from methanol solution. The solubility studies for mNAa were estimated. The cell
dimensions were obtained by single crystal X-ray diffraction (XRD) study. The functional groups have been
confirmed using Fourier transform infrared (FTIR) analysis. The placement of protons was identified from
Nuclear Magnetic Resonance Spectroscopy (NMR) spectral analysis. UV-visible and fluorescence spectral
analyses were carried out for the grown crystals. Thermo gravimetric analysis and differential thermal analy-
sis were carried out to determine the thermal properties of the as grown crystal. The Second Harmonic Gen-
eration (SHG) efficiency of mNAa was also determined.

Keywords: Supersaturated Solution, X-Ray Diffraction, Single Crystal Growth, Organic Compounds,
Nonlinear Optic Materials

1. Introduction electron donor and acceptor groups. Hence in this class

one such acetanilide derivatives, mNAa was taken under
Nonlinear optical materials (NLO) have proven to be an study which showed efficient NLO property. Some of the
interesting candidate for a number of applications such acetanilide derivatives such as Acetoacetanilide [7,8] and
as second harmonic generation, frequency mixing, elec- p-aminoacetanilide [9] were found to exhibit NLO prop-
tro-optic modulation, etc. In recent years, organic NLO erties. mNAa is a meta substituted aromatic compound
materials are attracting a great deal of attention for possi- with molecular formula C8H8N2O3. The molecular struc-
ble use in optical devices because of their large optical ture of mNAa, given in Figure 1, shows the charge
nonlinearity, low cut-off wavelengths, short response time transfer between electron acceptor (NO2) and electron
and high laser damage thresholds [1]. Considerable work donor (NHCOR where R = CH3) groups. This compound
has been done in order to understand the microscopic crystallizes in the monoclinic system in the chiral space
origin of nonlinear behavior of organic materials [2-5]. group P21 with four independent molecules in the
The NLO properties of large organic molecules and po- asymmetric unit. In this paper, we report the material
lymers have been the subject of extensive theoretical and synthesis, solubility, crystal growth, single crystal X-ray
experimental investigations during the past two decades diffraction (XRD), Fourier Transform Infrared Spec-
and they have been investigated widely due to their high troscopy (FTIR), optical, Fluorescence, thermal and NLO
nonlinear optical properties, rapid response in electroop- studies of mNAa.
tic effect and large second- or third-order hyperpolar-
izibilities compared to inorganic NLO materials [6]. Th-
us, there is much impetus to design and understand or-
ganic compounds for SHG applications.
To possess NLO property organic materials should
contain highly conjugated  electron system affected by Figure 1. Molecular structure of mNAa.

Copyright © 2011 SciRes. AMPC

40 R. RAMESH ET AL.

2. Experimental Single crystals of mNAa were grown by slow evapo-

ration growth technique using methanol as the solvent.
2.1. Material Synthesis About 250 ml of saturated solution was prepared at 40˚C
and it was carefully filtered at the same temperature us-
The title compound was synthesized from analytical re- ing Whatman filter paper of pore size 11 μm. The filtered
agent (AR) mNA and acetic anhydride following the solution was taken in a beaker and placed in a constant
procedure given by Mahalakshmi et al. [10]. Required temperature bath maintained at 40˚C having an accuracy
quantity of m-nitroaniline was dissolved in acetic anhy- of ±0.01˚C. Optically good quality seed crystal of di-
dride at room temperature. The direct reaction between mension 7 mm × 2 mm × 1 mm, obtained from slow
them as shown in the Scheme 1 immediately yielded evaporation method, was introduced into this solution.
yellow colour compound. The precipitated product was Crystal of dimension 10 mm × 4 mm ×3 mm was har-
filtered and dried using vacuum filtration. The material vested in a growth period of two days using solvent
was repurified by recrystallization processes. evaporation method. The morphology of the harvested
crystal was tetragonal bipyramid as shown in Figure 3.
2.2. Solubility and Crystal Growth
3. Results and Discussions
The solubility of mNAa was determined using methanol,
since methanol is found to be a suitable solvent to grow 3.1. Single Crystal X-Ray Diffraction
considerable size crystals. Recrystallized salt was dis-
solved in methanol and the solution was maintained at Single crystal XRD studies were carried out on the as
30˚C in a constant temperature bath and stirred continu- grown mNAa crystal using Enraf-Nonius CAD-4 single
ously to ensure homogenization of the solution. On re- crystal XRD reveals that mNAa belongs to monoclinic
aching the saturation, the amount of the salt in the solu- system. The unit cell parameters obtained are a = 9.7609
tion was analyzed gravimetrically. The same procedure Å (9.767 Å), b = 13.3084 Å (13.298 Å), c = 13.3124 Å
was repeated for the temperatures 35˚C, 40˚C, 45˚C and (13.272 Å), β = 103.15˚ (102.99˚) and cell volume is
50˚C and results are shown in Figure 2. The mNAa ex- 1683.8 Å3 (1679.8 Å3). These values are in close agree-
hibits good solubility and a positive solubility-tempera- ment with the corresponding values given in parentheses
ture gradient in methanol. From the figure we understand reported by Mahalakshmi et al. [10].
that the solubility of mNAa is going saturated at higher
temperatures. 3.2. Fourier Transform Infrared Spectroscopy

FTIR spectrum of the as grown crystals was recorded in

the range 400 cm–1 - 4000 cm–1 at room temperature us-
ing JASCO 460 plus FTIR spectrometer. The sample was
prepared following the pressed KBr pellet technique. The
Scheme 1. Reaction mechanism of m-Nitroacetanilide.
presence of functional groups of the sample, were identi-
fied from the spectrum as shown in Figure 4. The ab-
8.0 sorption at 3263 cm–1 is due to N-H stretching. The peak
at 1674.10 cm–1 corresponds to C = O stretching vibra-
7.5 tion of carbonyl group. The presence of nitro group is
confirmed by the peaks at 1556.88 cm–1 and 1599 cm–1.
Concentration (gm/CC)

7.0 The peaks at 1380 cm–1, 1472.81 cm–1 and 1426.40 cm–1
are due to C = C stretching [11-13].
6.5

3.3. Nuclear Magnetic Resonance Spectroscopy

6.0 (NMR)

5.5 NMR spectrum of mNAa was recorded using JEOL GS

× 400 model FT-NMR spectrometer. mNAa crystal was
5.0 powdered and dissolved in deuterated Dimethyl Sulfox-
30 35 40 45 50 55 60
ide (DMSO). FT-NMR spectrum recorded for mNAa is
Temperature deg C
shown in Figure 5. A triplet at 7.5 ppm is due to aro-
Figure 2. Solubility curve of mNAa. matic proton. The singlet at 2.07 ppm is assigned to

Copyright © 2011 SciRes. AMPC

 R. RAMESH ET AL. 41

was recorded in the region 200 nm - 1100 nm using

SHIMADZU 1601 UV-Vis spectrophotometer. The ma-
ximum transmittance is about 61% for mNAa crystal of 3
mm thickness. UV-Vis transmission spectrum presented
in Figure 6 shows that the crystal has good transparency
in the range 340 nm - 1100 nm, which indicates that this
crystal can be employed in the NLO applications in the
entire visible and IR region. The absence of the absorp-
tion in the visible region is the necessity for this com-
Figure 3. Photograph of as grown crystal. pound as it is to be exploited for NLO applications in the
room temperature.

3.5. Fluorescence Studies

Fluorescence may be expected generally in molecules

that are aromatic or contain multiple conjugated double
bonds with a high degree of resonance stability [14].
Fluorescence finds wide application in the branches of
biochemistry and medicine. It is also used as lighting in
fluorescent lamps, Light Emitting Diode (LED) lamps
etc. The excitation and emission spectra for mNAa re-
corded using FP-6500 Spectrofluorometer shown in Fig-
ure 7. The emission spectrum was measured in the range
350 nm - 600 nm. It is observed that the compound was
excited at 340 nm and the corresponding emission was
Figure 4. FTIR spectrum of mNAa.
observed at 409 nm. The compound mNAa fluoresces
due to the carbonyl chromophore [15].

3.6. NLo Studies

A preliminary study of the powder SHG conversion effi-

ciency was carried using Kurtz and Perry powder tech-
nique [16]. Q-switched Nd:YAG laser (QUANTA RAY
ICR 11) of wavelength 1064 nm with an input power of
5 mJ and pulses of 8 ns with the repetition rate of 10 Hz
was used. The crystalline sample of mNAa was pow-

Figure 5. NMR spectrum of mNAa.

CH3 proton. Singlet at 3.37 ppm is due to NH. A singlet

at 10.39 ppm is due to NH proton [12].

3.4. UV-Vis Studies

Optical transmittance spectrum of mNAa single crystal Figure 6. UV-Vis spectrum of mNAa.

Copyright © 2011 SciRes. AMPC

42 R. RAMESH ET AL.

Figure 8. TGA-DTA curves of mNAa.

Figure 7. Emission spectrum of mNAa. the position of protons. The optical properties such as
UV-Vis in transmittance mode and second harmonic
dered to a particle size of  125 m. When the powder generation (SHG) conversion efficiency were investi-
sample of mNAa was illuminated with this laser source gated to explore the nonlinear optical characteristics of
emission of green light was observed. In order to deter- the above crystal. In addition, the thermal properties of
mine the efficiency of mNAa, a sample of parent com- the mNAa crystal were studied with TG analysis.
pound mNA, which is also found to be an important ma-
terial in the research field of nonlinear optics [17] was 5. Acknowledgements
powdered to the same particle size and hence was used
as reference material. The SHG conversion efficiency of This work supported by the Department of Science and
mNAa is found to be 0.1 times that of mNA. Technology, New Delhi, India under the grant of project
ref-SR/FTP/PS-20/2005, is hereby gratefully acknowl-
3.7. Thermo Gravimetric Analysis edged. The authors thank Prof. K. Panchanatheswaran,
School of Chemistry, Bharathidasan University, Tiru-
Thermo Gravimetric Analysis (TGA) and Differential chirappalli for fruitful discussions. The authors also
Thermal Analysis (DTA) were carried out for mNAa and thank Regional Sophisticated Instrumentation Centre, IIT,
spectra are shown in Figure 8. They were recorded using Chennai for recording NMR, FTIR and single crystal
a simultaneous thermal analyzer PL-STA 1500 in nitro- data collection. The authors acknowledge Prof. P. K. Das
gen atmosphere for temperature range 20˚C to 800˚C at a and Sampa Ghosh, IISc, Bangalore for having extended
heating rate of 20˚C/min. The sharp endothermic peak in the laser facilities for SHG measurements and Centre for
DTA at 148˚C indicates the melting point of the crystal. Electrochemical Research Institute (CECRI) for having
The melting point measured directly using TEMPO extended the TGA-DTA measurements.
melting point apparatus was 149˚C. There is no exother-
mic or endothermic peak below this endotherm. This 6. References
illustrates the absence of any absorbed water in the crys-
tal sample. It also shows the absence of any isomorphic [1] M. Narayan Bhat and S. M. Dharmaprakash, J. Cryst
transition. The material exhibits single sharp weight loss Growth, Vol. 236, 2002, pp. 376-380.
starting at 215˚C and below this temperature no signifi- doi:10.1016/S0022-0248(01)02094-2
cant weight loss is observed. The sharpness of the peaks [2] T. Suthan and N. P. Rajesh, J. Cryst. Growth, Vol. 312,
indicates a good degree of crystallinity of the sample. 2010, pp. 3156-3160. doi:10.1016/j.jcrysgro.2010.08.002
[3] Huaihong Zhang, Yu Sun, Xiaodan Chen, Xin Yan and
4. Conclusions Baiwang Sun, J. Cryst. Growth, Vol. 324, 2011, pp.
196-200. doi:10.1016/j.jcrysgro.2011.03.044
A single crystal of mNAa, an organic NLO material, was [4] Natalia Zaitseva, Leslie Carman, Andrew Glenn, Jason
grown by solvent evaporation method from methanol Newby, Michelle Faust, Sebastien Hamel, Nerine
solution. The single crystal X-ray analysis revealed that Cherepy and Stephen Payne, J. Cryst. Growth, Vol. 314,
the crystal belongs to monoclinic system. The functional 2011, pp. 163-170. doi:10.1016/j.jcrysgro.2010.10.139
groups were identified using FT-IR spectroscopic tech- [5] D. S. Chemla and J. Zyss, “NonlinearOptical Properties
nique. NMR spectral analysis were carried out to identify of Organic Molecule and Crystals,” Academic press, New

Copyright © 2011 SciRes. AMPC

 R. RAMESH ET AL. 43

York, 1987. [12] R. M. Silverstein, G. Clayton Bassler and T. C. Morrill,

“Spectroscopic Identification of Organic Compounds,”
[6] N. Bloembergen and J. Nonlinear, Opt. Phys. Mater, Vol. 4th edition, John Wiley & Sons, New York, 1981.
15, 1996, pp. 1-8. doi:10.1142/S0218863596000027
[13] Hobart H. Willard, Lynne L. Merritt jr., John A. Dean
[7] S. G. Prabhu and P. Mohan Rao, J. Cryst Growth, Vol. and Frank A. Settle jr., “Instrumental Methods of Analy-
210, 2000, pp. 824-827. sis, Sixth Edition,” Wadsworth Publishing Company,
doi:10.1016/S0022-0248(99)00843-X Florence, 1986, p. 609.
[8] N. Vijayan, R. Ramesh Babu, R. Gopalakrishnan and P. [14] N. J. Turro, “Molecular Photochemistry,” Benjamin, New
Ramasamy, J. Cryst. Growth, Vol. 267, 2004, pp. York, 1965.
646-653. doi:10.1016/j.jcrysgro.2004.04.008
[15] K. Biemann, “Tables of Spectral Data for Structure De-
[9] D. Sajan, I. Hubert Joe and V. S. Jayakumar, J. Physics: termination of Organic Compounds,” Springer-Verlag,
Conference Series, Vol. 28, 2006, pp. 123-126. Berlin Heidelberg, 1989.
[10] L. Mahalakshmi, V. Upadhyaya and T. N. Guru Row, [16] S. K. Kurtz and T. T. Perry, J. Appl. Phys., Vol. 39, 1968,
Acta Cryst, Vol. E58, 2002, pp. 983-984. pp. 3798-3813. doi:10.1063/1.1656857
[11] J. R. Dyer, “Applications of Absorption Spectroscopy of [17] H. -X. Cang, W. -D. Huang and Y. -H. Zhou, J. Cryst.
Organic Compounds,” Prentice-Hall of India, New Delhi, Growth, Vol. 192, 1998, pp. 236-242.
1994. doi:10.1016/S0022-0248(98)00408-4

Copyright © 2011 SciRes. AMPC