ANALYSIS ANALYSIS
Vol. 14, 2018 ARTICLE
Science DISCOVERY
ISSN 2278–5485 EISSN 2278–5477
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 This work is licensed under a Creative Commons Attribution 4.0 International License. General Note Article is recommended to print as color version in recycled paper. Save Trees, Save Nature.
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.
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 © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org
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Key words: Piperazinium p-chlorobenzoate , Non linear optical crystal , Slow evaporation method.
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ANALYSIS
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).
O
O
HN
HN Cl
Cl NH2+
NH HO
PIPERAZINE
P CHLOROBENZOIC ACID
-O
PIPERAZINIUM P CHLOROBENZOATE
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Figure 1 Synthesis scheme of piperazinium p-chlorobenzoate
Figure 2 Grown crystal of piperazinium p-chlorobenzoate © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org
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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 3
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 Å . 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 3
Volume of the unit cell
V = 748 Å
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 FWHM Left [°2Th.]
d-spacing [Å]
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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Rel. Int. [%]
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Height [cts]
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Pos. [°2Th.]
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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 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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Theoretical value
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Functional groups
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ANALYSIS 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 -1
Laser Raman spectrum was taken for the powdered sample in the wavelength range 4000-400 cm 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
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
Experimental value
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Assignments
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Theoretical value
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Laser Ramam
Functional groups
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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.
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 © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org
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Photoluminescence studies
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Figure 6 UV-Visible absorption & transmittance spectrum of PCP
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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.
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