Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143–147

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synthesis, crystal growth and spectroscopic investigation of second order organic nonlinear optical single crystal: 2-Chloro-N-[4(dimethylamino)benzylidene]aniline
R.K. Balachandar, S. Kalainathan ⇑
Centre for Crystal Growth, SAS, VIT University, Vellore 632 014, Tamil Nadu, India

h i g h l i g h t s 
First time single crystal of 2Cl4DBA

g r a p h i c a l a b s t r a c t

was grown by slow evaporation technique from synthesized compound.  NMR, FTIR spectral analysis and XRD technique were used to confirm the product formation.  Good thermal stability of the grown crystal is up to 135 °C.  SHG efficiency of title crystal was more than that of standard KDP and urea material.

a r t i c l e

i n f o

a b s t r a c t
Organic nonlinear optical (NLO) crystal 2-chloro-N-[4-(dimethylamino)benzylidene]aniline (2Cl4DBA) was synthesized and grown by restricted slow evaporation technique at room temperature using acetone as solvent with good degree of transparency. The lattice parameters were determined and found to be noncentrosymmetric orthorhombic system by single crystal X-ray diffraction. The crystalline nature of the synthesized material was recorded by the powder X-ray diffraction pattern. Molecular structure of the grown crystal was investigated by 1H and 13C NMR and functional groups were identified by FTIR spectrum analysis. The optical absorbance of the grown crystal was ascertained by recording UV–Visible spectrum. Thermal and physiochemical stability of the grown material was investigated by TG/DTA analysis. SHG efficiency was determined by Kurtz–Perry Powder SHG technique and found to be 4.2 and 1.54 times greater that of standard KDP and urea crystals respectively. Ó 2013 Elsevier B.V. All rights reserved.

Article history: Received 12 February 2013 Received in revised form 28 June 2013 Accepted 16 July 2013 Available online 24 July 2013 Keywords: Slow evaporation technique Nonlinear optics X-ray diffraction NMR Organic compounds

Introduction Organic nonlinear optical materials (NLO) play a major role in nonlinear optics for the fast processing of information and for data storage applications. Organic NLO materials have been investigated due to their potentially large nonlinearities and rapid response in electro-optic effect compared to inorganic NLO materials, large numbers of molecules were available for investigation. The optical
⇑ Corresponding author. Tel.: +91 416 2202350; fax: +91 416 2243092.
E-mail address: kalainathan@yahoo.com (S. Kalainathan). 1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.saa.2013.07.021

nonlinearity of the aromatic organic molecules were enhanced when the molecule has one donor at the one end and one acceptor group bonded at the other end of the conjugated system of the molecule. An organic crystal with delocalized p-electrons usually displays a large NLO response which makes it attractive for applications in integrated optics [1–3]. Most of the organic crystals are composed of aromatic molecules that are substituted with electron donors and acceptors which exhibit intramolecular charge transfer. In the present investigation, the synthesis of the Schiff base compound, for the first time we report crystal growth of the title compound and its detailed molecular and structural confirma-

6. 1 Experimental procedure Material synthesis The 2Cl4DBA was synthesized by the condensation reaction between p-aminobenzaldehyde (10 mmol. satisfying one of the basic and essential requirements for the SHG activity of the material. The protons in the aldehyde rings can see each other as aligned (parallel) or opposed (anti-parallel) and come to resonance twice. The powder XRD Prominent peaks of title crystal (h kl) values were indexed using POWDER X software program and are shown in Fig. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143–147 tion by spectroscopic techniques. 1. proton in the aldehyde ring appears as doublet because their signals are indistinguishable.054 ml. which is in good agreement with those of reported values [4]. D8 Advance model. Powder X-ray diffraction Powder X-ray diffraction patterns of finely crushed powder of 2Cl4DBA crystal was scanned in the 2h values ranging from 10° to 80° and the powder X-ray diffraction pattern were recorded with Bruker. NMR. 7. The prepared material was taken in a round bottom flask and refluxed for 8 h.K. Balachandar. The yield material was Schiff base compounds containing imine groups (AHC@NA).138 Å.831) ppm and d (6. 1H and 13C NMR spectrum of the purified 2C4DBA sample was recorded using Bruker 400 MHz instrument in deuterated chloroform with tetramethylsilane (TMS) as the internal standard.491 g. primary amine) in an equimolar amount (1:1) dissolving in ethanol.774. Grown crystals were subjected to various characterization studies like XRD. H and 13 C NMR spectral analyses Crystal growth The purified material was dissolved in the solvent acetone and stirred continuously for 5 h using magnetic stirrer and the prepared saturated solution was filtered and covered tightly with aluminum foil kept undisturbed at room temperature for controlled slow evaporation.6864 Å. b = 12.1654 Å. d (7. The structure of 2Cl4DBA containing different types of protons show different peaks as expected at different chemical shift positions from the different environment of the proton [5]. The single crystal XRD study reveals that the crystal belongs to non-centrosymmetric orthorhombic system.853. Using thin layer chromatography (TLC) the product was confirmed as a single compound and the solid product was separated using Whatman filter paper by filtering the solution and kept for dryness (yield about 77%). c = 13. Purity of the synthesized compound was further increased by three times recrystallization in the solvent acetone and the reaction mechanism is shown in scheme below (see Scheme 1). Natural evaporation of the acetone induces the spontaneous nucleation in the solution and tiny single crystals of optically transparent good quality have been harvested after 7 days. S. Reaction mechanism of 2Cl4DBA. Then the reaction mixture was allowed to cool to room temperature and salt formation occurred at the bottom of the flask as light yellow microcrystalline powder. . UV Visible. FTIR. The imine protons (AHC@NA) have no neighbor proton and it should Cl NH 2 H 3C N H 3C C O H Add 3drops of Glacial acetic acid and reflux for 8hours H 3C N H 3C C H H 2O N Cl Scheme 1. the space group ‘‘P212121’’ with the lattice parameter a = 7.5406 Å).9688 Å and V = 1306. TG/DTA and SHG. aldehyde) and 2-chloroaniline (10 mmol. (Supplementary Fig. Thus. In the present investigation.752) ppm gives two doublets respectively. The proton pairs are chemically equivalent by virtue of the symmetry within the molecule and have same electronic environment. 1.144 R. Results and discussion Single crystal X-ray diffraction Single crystal data collection analysis was performed by using diffractometer-MACH3 from Enraf–Nonius and CCD detector based-SMART APEX from Bruker-Nonius Axs. Three drops of glacial acetic acid were added as catalyst. S1) is shown the grown crystal of 2Cl4DBA. Thermal and second harmonic generation efficiency of 2-chloro-N-[4-(dimethylamino)benzylidene]aniline single crystals have been studied. Cu Ka radiation (k = 1. 1.

it appears as a triplet because of an interaction with the deuterium atom. The singlet signal at d 8. From the above observations the presence of the specific groups are confirmed. An out-of-plane CAH deformation band is a characteristic of aromatic ring with ortho-di-substitution. UV–visible spectral analysis The optical absorption spectrum of the grown crystal was recorded using Elico SL218 Double beam UV–visible spectropho- Fig.170) is due to the methyl carbon atom and the Fig. .082 ppm. FTIR spectrum does not show any signal corresponding to aldehyde group present in the reactants.056. The singlet signal at d 3. Powder XRD pattern of the grown crystal. The spectra were recorded by KBr pellet technique between the range 400 cmÀ1 and 4000 cmÀ1 shown in Fig.261 ppm corresponds to the proton of imine group which confirms the formation of the Schiff base compound [6]. Thus the molecular structure of the title compound is confirmed from the proton NMR and carbon NMR spectrum. 2.082 ppm denotes protons of methyl group. 13C NMR spectrum of title material is shown in (Supplementary Fig. 7. Benzylidene anilines display their C@N stretching as a band at 1600 cmÀ1. Balachandar. In the present case. C-H stretching absorptions are weak absorptions expected around 2924 cmÀ1. The expected bending vibrations of CAX bond are strong for CACl stretching is 600–800 cmÀ1.035–152.591) is due to the imine group carbon atom which confirms the formation of the Schiff base compound. S3).125. Each carbon atom at different positions produces a different signal. appear as a singlet. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143–147 145 three-line signal (d 76–77) from the CDCl3 solvent corresponds to the single carbon atom. S2). C@C stretching absorption is confirmed from the band at 1502 cmÀ1. Absence of characteristic aldehyde bands at 2720 cmÀ1 and 2820 cmÀ1 indicates that there is no aldehyde group in the final product. The band obtained at 1598 cmÀ1 is a proof for the formation of imine group (C = N) as a result of the condensation reaction between aldehyde and amine [7]. The d values for the protons of (ACH3)2 group attached to-N-Aromatic radicals are expected at 3. FTIR spectrum of the grown crystal.283 ppm) and the remaining two proton forms a doublets with each one H atom as neighbor (d 7. It is confirmed from the band at 750 cmÀ1.K. FTIR spectral analysis FTIR spectrum was recorded for the crushed powder of the crystal using Shimadzu FTIR spectrophotometer. 1. 7. The signal (d 40. the assignment of the each signal to a unique carbon environment in the molecule is also identified. Aniline ring had four protons. the absorption is noticed at 759 cmÀ1. out of the four protons two of hydrogen atoms were neighbors to two H-atoms thus it forms a two triplets (d 7. Rest of all the peaks corresponds to the aromatic carbons which fall on the aromatic region from (d 111. 2.R. From 13C NMR of the title compound.452 ppm) this is due to the chlorine atom is attached to the ortho position of the aromatic aniline ring. 1H NMR spectrum of the grown material is shown in (Supplementary Fig.814). The shift (d 161. S. It is evidenced from the CAH deformation vibration at 750 cmÀ1 [8].

Acknowledgements The authors express thank to R. S.021. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143–147 observed that the material is stable up to 234 °C and weight loss of the material starts on further heating the sample.2013. sharpness indicates the good crystalline nature and purity of the synthesized material and the second is corresponds to the complete decomposition of title compound which may release volatile gases present in the material [9]. Sri Ramachandra University for helping in the NMR spectral analysis. The relative SHG efficiency of the title crystal (42 mV) is nearly 4. From TG analysis it is Conclusion The organic NLO material 2-chloro-N-[4-(dimethylamino)benzylidene]aniline was successfully synthesized and grown the single crystal from the acetone by restricted slow evaporation technique.saa. at http://dx. The grown single crystal was powdered with a uniform particle size and tightly packed in a micro-capillary of uniform bore and exposed to the laser radiation. SHG conversion efficiency measurement was carried out using Kurtz and Perry technique [10]. The crystal has low absorption starts in the visible and completely in the NIR region.54 times that of KDP (10 mV) and urea (27. The low absorbance in the region from 434 nm to 1100 nm enables very good optical transmission of the second harmonic frequencies of Nd:YAG laser. 4. Thermal analysis The thermal stability of the grown crystal was measured by thermo gravimetric analysis (TGA) and Differential thermal analysis (DTA) simultaneously from room temperature to 500 °C at the heating rate of 10 K/min. Thus the characterization confirms the suitability of the grown crystal for NLO applications.1016/j. no other phase transformations are noticed in the DTA curve.146 R. UV visible spectrum of the grown crystal shows low absorbance with cutoff 434 nm in the near visible region and entire near IR region. 85% of huge weight loss is observed between the temperature 234oC and 317oC due to the decomposition of the imine molecule and remaining 15% as carbon residue which is present in the material. 4. Other than the solid–liquid transformation from the melting point onwards. 3.8 mJ/pulse and pulse width 10 ns with a repetition rate of 10 Hz was used.2 times and 1. TG/DTA curve of the grown crystal. It is observed that cut off wavelength is at 434 nm. it is clear that there is no weight loss between 100 °C and 200 °C which attributes that there is no inclusion of water molecules present in the crystal lattice and also no weight loss before the melting point. The recorded UV–visible spectrum is shown in Fig. 3.7 mm thickness was used for measurement without polishing the crystal surface. the first one corresponds to the melting point of the material. UV–visible absorbance spectrum of the grown crystal. Confirmation of the molecular and structural was done by FTIR and NMR spectral analysis. A Q-switched Nd:YAG laser beam of wavelength 1064 nm with input beam energy 3. Supplementary material Supplementary data associated with this article can be found. in the online version. A thermal property of the grown material studied by TG/DTA analysis and melting point of the material was found to be 135 °C and the materials was stable up to 235 °C. Single crystal X-ray diffraction has been carried out to find the unit cell parameter and the crystalline nature of the synthesized material was analyzed by powder XRD pattern. The authors also express thanks to VIT University for their constant encouragement and financial support. Second harmonic generation measurement Fig. From the above observation. Lakshmi sundaram. Balachandar.07. which indicates that the material is moisture-free and stable up to 234 °C.doi. The bright green light emission (k = 532 nm) was observed which indicates the SHG behavior of the title material. . The SHG relative efficiency was found to be more efficiency 4.org/10.2 mV) respectively.K. A sample of 1.2 and 1. From the DTA analysis the two sharp endothermic peaks were observed at 135 °C and 321 °C. Fig. tometer in the wavelength range of 190–1100 nm at room temperature. Appendix A. under nitrogen atmosphere using Netzsch STA 409 PL Luxx as shown in Fig.5 times than that of standard KDP and urea as a reference material.

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