ANALYSIS ARTICLE Vol. 14, 2018 Science DISCOVERY · It also has posses the strong nonlinear optical properties (Boyd, R. W. 2003). The most of the applications were made by using

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Crystal growth and characterization of piperazinium p-chlorobenzoate

Vallikkodi M☼, Sudhahar S

Department of Physics, Alagappa University, Karaikudi- 630 004, India

☼Corresponding author: Department of Physics, Alagappa University, Karaikudi- 630 004, India E-Mail: [email protected] Article History Received: 13 April 2018 Accepted: 22 May 2018 Published: May 2018 Citation Vallikkodi M, Sudhahar S. Crystal growth and characterization of piperazinium p-chlorobenzoate. Discovery Science, 2018, 14, 28-35 Publication License

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ABSTRACT The nonlinear optical properties of piperazinium p-chlorobenzoate (PCP) crystal were successfully grown with the help of temperature gradient method. The good quality of PCP single crystal is formed. The PCP is characterized with the help of X-ray diffraction (XRD), Fourier transform infrared (FTIR) measurement, photoluminescence (PL), Raman spectroscopy, ultra violet visible spectroscopy (UV) and finally etching analysis was done. Key words: Piperazinium p-chlorobenzoate , Non linear optical crystal , Slow evaporation method.

1. INTRODUCTION In recent years, organic materials which are used in the potential application such as frequency conversion, optical signal processing, and light modulation and optical switching etc (Sankar, G. U. (2007), Moorthy, C. G (2017). Sankar, G., (2016)) Organic compounds

ANALYSIS Vol. 14, 2018

Science ISSN 2278–5485

EISSN 2278–5477

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possess carbon – carbon bonds (Sankar, G. U., (2018)), carbon – hydrogen bonds as well as covalent bonds between carbon and oxygen and nitrogen. It also has posses the strong nonlinear optical properties (Boyd, R. W. 2003). The most of the applications were made by using the artificial crystals like Piperazinium p-chlorobenzoate. The optical industry, electronic industry and optoelectronics in their applications the crystals are obtained the important role (Boyd, R. W. 2003). In this paper, the two organic compounds are mixed with the homogeneous process. The non linear optical single crystal of PCP is formed by the slow evaporation solution growth method and characterization and results of PCP crystal is obtained by using single crystal XRD, powder XRD, FTIR, Raman, PL, Etching and UV.

2. MATERIALS AND METHODS The piperazinium p-chlorobenzoate single crystal was prepared in the room temperature by slow evaporation solution growth method using as an acetone solvent. The precursor’s materials of piperazine (98%) and p-chlorobenzoic acid (99%) were taken in the equimolar ratio of 1:1 for the synthesis process is shown in figure 1. The p-chlorobenzoic acid was first dissolved in the solvent of acetone, after complete dissolved acid material and then the base compound of piperazine was added little by little with the acid solution (Zhu, Q., 2012). The solution is allowed to get a homogenous mixture by continuously stirring for 8 hours using the temperature control magnetic stirrer in the room temperature circumstances. After attaining the homogenous saturated state the solution was filtered using the whatman filter paper which is having the fine holes in the range of 110 m and the filtered solution was covered with the perforated sheet having the fine holes for the evaporation and it was kept at the room temperature without disturbance. After 2 successive recrystallization process the good quality PCP crystal was harvested with in the span of 56 days is shown in figure 2 (Mahalingam, Vallikkodi., 2018).

NH

HN

PIPERAZINE

O

HO

Cl

P CHLOROBENZOIC ACID

NH2+

HN

PIPERAZINIUM P CHLOROBENZOATE

O

-O

Cl

Figure 1 Synthesis scheme of piperazinium p-chlorobenzoate

Figure 2 Grown crystal of piperazinium p-chlorobenzoate


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3. RESULT AND DISCUSSION XRD Analysis (i) The single crystal X-ray diffraction analysis is the powerful tool for determination of the structure of the crystal. The cell parameters of the PCP is found to be a =14.91 Å, b = 6.326 Å, c = 6.310 Å, α =90, =94.948, γ =90 and volume V = 592.99 Å3. The PCP crystal belongs to the monoclinic crystal system with P21/n space group, thus satisfying one of the basic and essential requirements for NLO materials. The structural parameters of the PCP crystal were listed in the table 1. Table 1 PCP crystal

Crystal property Piperazinium P-chlorobenzoate Empirical formula C4H11N2

+ • C7H4ClO2−

Crystal system Monoclinic Space group P21/n Unit cell parameters a = 14.91 Å, b =6.326 Å, c = 6.310 Å,

α = 90, = 94.948, γ = 90

Volume of the unit cell V = 748 Å3 Radiation wavelength = 0.71073 Å

(ii) The crystalline nature of the piperazinium p-chlorobenzoate crystal was characterized by Powder x-ray diffraction analysis to reveal crystalline perfection of the compound. The x-ray diffraction spectrum of PCP was recorded using the X’pert PRO powder diffractometer with CuKα radiation having the wavelength of = 1.5406 Å. The sample was scanned from the range of 10 to 80 at the rate of 2/minute. The recorded powder x-ray diffraction spectrum is shown in Figure 3. The presence of sharp and well defined peaks confirms the good crystalline nature of Piperazinium p-chlorobenzoate crystal and the corresponding peaks were indexed. The sharp intense peak was found at 22.4°with the crystal faces of (310). The sharp intense peaks are shown in the table 2. Table 2 Peaks of XRD

Pos. [°2Th.] Height [cts] FWHM Left [°2Th.] d-spacing [Å] Rel. Int. [%] 14.7069 77.37 0.1476 6.02343 7.48 16.6224 176.25 0.1968 5.33337 17.04 18.1809 100.49 0.1476 4.87954 9.72 19.7484 80.99 0.1476 4.49565 7.83 20.1696 446.77 0.1968 4.40271 43.20 21.7896 430.82 0.1476 4.07890 41.66 22.4797 1034.23 0.1968 3.95521 100.00 25.4805 221.98 0.1476 3.49581 21.46 27.7228 123.40 0.1476 3.21795 11.93 29.2866 319.77 0.1476 3.04959 30.92 30.5905 119.80 0.2460 2.92250 11.58 31.4813 141.33 0.1968 2.84182 13.67 33.1687 115.07 0.1968 2.70100 11.13 33.5828 39.46 0.1476 2.66864 3.82 34.4488 46.07 0.1476 2.60351 4.45 35.3384 32.82 0.1476 2.53998 3.17 36.9673 132.69 0.3444 2.43171 12.83 38.6006 47.94 0.1476 2.33250 4.64 39.8114 123.66 0.1476 2.26431 11.96 43.1903 25.59 0.2952 2.09468 2.47 45.8773 23.94 0.2952 1.97806 2.31


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48.8818 32.39 0.1968 1.86327 3.13 49.8526 25.25 0.2952 1.82924 2.44 51.2820 51.57 0.1968 1.78156 4.99 53.1836 54.02 0.2460 1.72226 5.22 56.5272 17.10 0.3936 1.62807 1.65 60.3542 29.38 0.1476 1.53367 2.84 77.7309 13.80 0.5904 1.22860 1.33

Figure 3 Powder XRD pattern of PCP crystal

FTIR Analysis The FTIR spectrum was recorded to understand the chemical bonding and it provides useful information regarding the molecular structure of the compound. The KBr pellet technique was used to analyze the sample. FTIR spectrum was taken for the powdered sample in the wavelength range 4000-400 cm-1 using 380 FTIR Spectrophotometer having the resolution of 0.5 cm-1 and the spectrum of FTIR is shown in Figure 4. The observed FTIR is summarized in table 3. Table 3 FTIR frequency assignments of PCP compound

Functional groups Theoretical value FTIR Experimental

value Assignments

Water 3700 – 3100 3246.55 OH stretch

Alcohols 1200 -1000 1094.15 C-O stretch

Acid chloride 1810 – 1775 1790.95 C=O stretch

Acid chloride 730 – 550 598.87 C-CL stretch

Carboxyl 1320 – 1210 1273.76 C-O stretch

Alkanes ~1465 1469.42 CH2 bend

Alkanes ~720 723.71 CH2 bending 4 more

Aromatics 3020 - 3000 3005.72 C-H stretch


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Aromatics 1600 – 1505 1589.90 C-C stretching in ring

Amines 3500 – 3300 3442.26 N-H stretch

Amines 1200 – 1025 1094.15 C-N (stretch)Alkyl

Figure 4 FTIR spectrum of PCP Raman Analysis Laser Raman spectrum was taken for the powdered sample in the wavelength range 4000-400 cm-1 using STR 500 mm focal length laser Raman spectrometer and the Raman spectrum is shown in the figure 5. Raman bands along with their vibrational assignments are summarized in table 4. Table 4 Raman frequency assignments of PCP compound

Functional groups Theoretical value Laser Ramam Experimental value

Assignments

Water 3700 – 3100 ---- OH stretch

Alcohols 1200 -1000 ---- C-O stretch

Acid chloride 1810 – 1775 1781 C=O stretch

Acid chloride 730 – 550 ---- C-CL stretch

Carboxyl 1320 – 1210 ---- C-O stretch

Alkanes ~1465 1464 CH2 bend

Alkanes ~720 ---- CH2 bending 4 more

Aromatics 3020 - 3000 ---- C-H stretch

Aromatics 1600 – 1505 1597 C-C stretching in ring


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Amines 3500 – 3300 3355 N-H stretch

Amines 1200 – 1025 1090 C-N (stretch)Alkyl

Figure 5 Laser Raman spectrum of PCP

UV-Visible optical Absorption spectral analysis The optical absorption spectral analysis of the grown PCP crystal was carried out using Perkin Elmer Lambda35 spectrometer between 250 and 800 nm. The absorption & transmittance spectrum of the as grown PCP crystal is shown in the Figure 6. The UV cut off wavelength of the crystal was found to be at 280 nm. The absence of absorption in the visible region suggests that the crystal possess the good nonlinear optical property.

Figure 6 UV-Visible absorption & transmittance spectrum of PCP Photoluminescence studies Photo luminescence spectroscopy is a non destructive method for finding out the electronic structure and optical behavior. The Photoluminescence spectrum of the grown PCP was recorded in the wavelength region between 300 nm and 550 nm using RF-5301 spectrophotometer. The PL spectrum (Figure 7) of PCP grown crystal is excited at 538 nm. From the PL spectrum, one high and one


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medium intensities green emission peaks and one medium intensity yellow emission peak was observed at 491 nm, 538 nm and 594 nm respectively. The sharp high intensity caused because of the similar transition occurring at the various energy levels within the band gap.

Figure 7 Photoluminescence spectrum of PCP Etching Studies

4. CONCLUSION The piperazinium p-chlorobenzoate crystal was successfully grown and characterized. The XRD pattern confirms the properties of NLO and the Raman and FTIR confirm all the functional groups. The UV and PL show the Optical properties. Thus, a good NLO crystal was successfully formed for LASER applications.

RREEFFEERREENNCCEE 1. Sankar, G. U. (2007). A Survey on Wavelength Based

Application of Ultraviolet LED. Computing. 2. Moorthy, C. G., Sankar, G. U., & RajKumar, G. (2017). A

Design for Charging Section of Electrostatic Precipitators by

Applying a Law for Electric Field Waves. Imperial Journal of Interdisciplinary Research, 3(6).

3. Sankar, G. Udhaya. (2016). Climate change challenge – photosynthesis vs. hydro-electrolysis principle. Climate Change. 3. 128-131.


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4. Boyd, R. W. (2003). Nonlinear optics. Academic press. 5. Zhu, Q., Oganov, A. R., Glass, C. W., & Stokes, H. T. (2012).

Constrained evolutionary algorithm for structure prediction of molecular crystals: methodology and applications. Acta Crystallographica Section B: Structural Science, 68(3), 215-226.

6. Sankar, G. U., Moorthy, C. G., & RajKumar, G. (2018). Synthesizing graphene from waste mosquito repellent graphite rod by using electrochemical exfoliation for Battery/Supercapacitor Applications. Energy Sources, Part A: Recovery, Utilization, and Environmental. DOI:10.1080/15567036.2018.1476609

7. Mahalingam, Vallikkodi & Sudhahar, S. (2018). Synthesis, growth and characterization of 2-amino 6-methylpyridinium 6-aminocaproate nonlinear optical single crystal. International Journal of Advance Engineering and Research Development. 5. DOI: 10.21090/IJAERD.ICMNRE27.

8. Mahalingam, Vallikkodi & Sudhahar, S. (2018). Synthesis, Growth and characterization of Piperazinium salicylate Nonlinear Optical Single Crystal. DOI: 10.13140/RG.2.2.20605.67046.

9. Mahalingam, Vallikkodi. (2018). Synthesis, growth and characterization of piperazinium p-aminobenzoate and piperazinium p-chlorobenzoate nonlinear optical single crystals. DOI: 10.13140/RG.2.2.16046.82243.

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ANALYSIS ARTICLE Vol. 14, 2018 Science DISCOVERY · It also has posses the strong nonlinear optical properties (Boyd, R. W. 2003). The most of the applications were made by using