Journal of Crystal Growth 233 (2001) 863867

Growth and characterization of organic NLO crystals of semicarbazone of acetophenone

N. Vijayana, R. Ramesh Babua, R. Gopalakrishnana,*, S. Dhanuskodib, P. Ramasamyc
b a Department of Physics, Anna University, Chennai-600025, India Department of Physics, Bharathidasan University, Trichirappalli 620024, India c Crystal Growth Centre, Anna University, Chennai-600025, India

Received 26 June 2001 Communicated by M. Schieber

Abstract Semicarbazone of acetophenone is one of the potential organic NLO materials for photonic and optoelectronic applications. This crystal has been grown by slow evaporation technique. X-ray, FT-IR, melting point and UVVisible methods are used to characterize the grown crystals. r 2001 Published by Elsevier Science B.V.
Keywords: A1. Solubility; A2. Growth from solutions; B1. Organic compounds; B2. Non-linear optic materials

1. Introduction The large nonlinear optical eects found in some organic crystals make them attractive for applications in frequency conversion and optical processing [1]. NLO materials play an important role in the eld of bre optic communications and optical signal processing. In the last two decades, extensive research has shown that organic crystals can exhibit nonlinear optical eciencies which are two orders of magnitude higher than those of inorganic materials [2,3]. The important nonlinear optical materials from the device point of view are generally in the form of single crystals and must meet a wide variety of
*Corresponding author. E-mail address: krgkrishnan@annauniv.edu, krgkrishnan@hotmail.com (R. Gopalakrishnan).

ancillary material requirements for optical use. In general, they will require extraordinary stability with regard to ambient conditions and high intensity light sources [4]. Organic nonlinear optical materials are often formed by weak van der Waals and hydrogen bonds and hence possess high degree of delocalization. Organic materials are molecular materials that oer unique opportunities for fundamental research as well as for technological applications. Single crystals of semicarbazone of acetophenone are one of the potential organic NLO materials, which belong to the ketone group of compound. In the present investigation we report the growth of semicarbazone crystals by slow evaporation technique and the grown semicarbazone crystals were characterized by single crystal XRD, melting point measurement, FT-IR and UVVisible spectra analyses.

0022-0248/01/$ - see front matter r 2001 Published by Elsevier Science B.V. PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 1 6 2 8 - 1

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2. Experimental procedure Single crystals of semicarbazone of acetophenone were grown by slow evaporation method from semicarbazide hydrochloride and acetophenone using sodium acetate as catalyst. Alcoholic solvents like ethanol and methanol were used for growing semicarbazone crystals. Semicarbazide hydrochloride, sodium acetate and acetophenone were mixed in the mole ratio 2.16 : 4.40 : 1, respectively. The prepared solution was stirred well (if the solution appeared to be turbid methanol/ethanol was to be added) and gently warmed on a steam bath, until a clear solution was obtained. The solution was taken in a closed container and placed in a constant temperature bath (CTB) at 401C. After few hours, spontaneous nucleation was observed in the solution [5]. Needle-shaped good transparent single crystals of semicarbazone were obtained in 810 days (Fig. 1). The chemical reaction and molecular structure of semicarbazone of acetophenone are shown in reaction Scheme 1.

Fig. 1. Single crystals of semicarbazone of acetophenone.

From the single crystal X-ray analysis it is conrmed that the grown semicarbazone crystal is triclinic and the space group is P1 and it is established that if the crystal belongs to the space group P1, it exhibits the second harmonic generation [6,7]. 3.2. Measurement of melting point

3. Characterization 3.1. X-ray diraction The single crystal X-ray diraction data of the grown semicarbazone crystals were obtained using single crystal X-ray diractometer (Model: ENRAF NONIUS CAD4). The crystallographic data are given in Table 1.

The melting point of the grown crystals was found using melting point apparatus (model: TEMPO PT 100230 V). The micro-capillary tube containing the powder sample was inserted into the melting point apparatus with a thermometer nearby. The temperature was gradually increased and the powder started to melt into a transparent solution. The corresponding temperature was measured, indicating the melting point (1961C) of

Scheme 1. Reaction of acetophenone with semicarbazide hydrochloride.

N. Vijayan et al. / Journal of Crystal Growth 233 (2001) 863867 Table 1 Unit cell parameters of semicarbazone a ( 10.56(1) A b ( 10.96(1) A c ( 12.621(4) A a 66.88(4)1 b 75.86(4)1 g 70.77(7)1 Volume

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( 1256.4600 A3

Fig. 2. FT-IR spectrum of semicarbazone of acetophenone.

semicarbazone of acetophenone. The error in the measurement was 711C. 3.3. FT-IR spectra In order to absorb infrared radiation a molecule must undergo a net change in dipole moment, as a consequence of its vibrational motion. The FT-IR spectrum of semicarbazone of acetophenone was recorded using FTIR spectrometer (Model: BRUKER IFS 66 V FT-IR) in the region 4000 400 cm1 and the spectrum is shown in Fig. 2. Below 1400 cm1 the region is called nger print region. There is an intense sharp peak at 3479.3 cm1, assigned to the free unhydrogen bonded NH stretch. The broad envelope between 2750 and 3361.2 cm1 is due to overlapping of peaks of hydrogen bonded NH and aromatic CH stretching modes. The considerable broadening reveals that the packing of the molecules in

the crystal is largely through intermolecular hydrogen bonding of these NH groups. The symmetric and asymmetric CH stretching modes of CH3 group appear as a shoulder just below 3000 cm1 in the broad envelope. The CQO stretch of semicarbazide moiety is observed at 1740.4 cm1. The aromatic ring skeletal vibrations are observed at 1594.3 and 1476.9 cm1 [8]. The CH3 bending modes are positioned at 1432.2 and 1302.7 cm1. The stretch is seen at 1116.8 cm1. The out-of-plane aromatic CH bond is observed at 758.8 cm1. The bands at 1887.1,1954.2 and 2007.4 cm1 are overtones [8] (Table 2). 3.4. UVVisible spectra Fig. 3 shows the UVVisible spectrum of the semicarbazone of acetophenone crystals

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Fig. 3. UVVis spectrum of semicarbazone of acetophenone.

Table 2 Vibrational frequency of the semicarbazone of acetophenone Vibrational frequency (cm1) 3479.3 3052.1 1740.4 1594.3 1432.2 Assignments NH stretching CH stretching CQO stretching CQC aromatic/CQN CQC aromatic

4. Conclusion The grown crystal of semicarbazone of acetophenone has been characterized using a single crystal X-ray diractometer and it is found that the crystal belongs to a triclinic system and space group P1. The unit cell parameters are determined. The FTIR spectrum of the compound reveals both free and hydrogen bonded NH stretching modes, and the latter is found to be the major driving force for packing of molecules in the crystal. The ultraviolet spectrum proves the highly transparent nature of the material between 950 and 325 nm.

recorded using a UVVisible spectrophotometer (Model: VARIAN CARRY 5E UVVis NIR). The UV spectrum of the methanolic solution of semicarbazone was scanned between 200 and 950 nm. There is no absorption band between 325 and 950 nm, hence the crystal of semicarbazone is expected to be transparent to all the UV Visible radiations in between these two wavelengths [9]. The characteristic absorption band is observed only at 285 nm.

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N. Vijayan et al. / Journal of Crystal Growth 233 (2001) 863867 [4] P.N. Prasad, D.J. Williams, Non-linear optical eects in molecules and polymers, Wiley, USA, 1991. [5] J. Basset et al., Vogels Text Book of Practical Organic Chemistry, Fourth edition, English language book society, 1987. [6] M.P. Cifuentes, J. Driver, Mark G. Humphery, I. Asselberghs, A. Persoons, M. Samoc, B. Luther-Davies, J. Organomet. Chem. 607 (2000) 72.

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