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Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3,5-Dimethylpyrazolium-3-Nitrophthalate
Author’s Accepted Manuscript Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3, 5-Dimethylpyrazolium-3Nitrophthalate M. Rajkumar, A. Chandramohan www.elsevier.com
PII: DOI: Reference:
S0167-577X(16)30689-9 http://dx.doi.org/10.1016/j.matlet.2016.04.191 MLBLUE20788
To appear in: Materials Letters Received date: 16 April 2016 Revised date: 22 April 2016 Accepted date: 24 April 2016 Cite this article as: M. Rajkumar and A. Chandramohan, Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3, 5-Dimethylpyrazolium-3-Nitrophthalate, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2016.04.191 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3, 5-Dimethylpyrazolium-3-Nitrophthalate M. Rajkumar, A. Chandramohan* Post-Graduate and Research Department of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore - 641 020, Tamil Nadu, India. *Corresponding
author:
Tel.:
+919994283655,
E-mail
address:
[email protected](A.Chandramohan)
Abstract An organic salt, 3, 5-Dimethylpyrazolium- 3-Nitrophthalate (DMPNP) has been successfully synthesized and single crystals grown by slow solvent evaporation solution growth technique at room temperature using Millipore water of resistivity 18Ω. The formation of salt has been confirmed by single crystal X-ray diffraction and NMR spectroscopic techniques. The title crystal crystallizes in monoclinic crystal system with non-centrosymmetric space group, P21. FT-IR spectral analysis was used to confirm the presence of various functional groups in the grown crystal. The thermal stability of the compound was investigated by carrying out TG/DTA analyses simultaneously. The UV–vis–NIR transmission spectrum was recorded to find the optical transmittance window and lower cut off wavelength of the salt crystal. The Vicker’s microhardness test was carried out to find the mechanical strength of the crystal. The prevailing SHG property in the grown crystal was investigated by the modified Kurtz and Perry powder technique. Keywords: Crystal growth, Crystal structure, FTIR, Thermal analysis, Optical materials and properties 1. Introduction
Nonlinear optics has emerged as one of the most important fields of current research in view of its vital applications in areas of optical switching, optical data storage for the developing technologies in telecommunications and signal processing [1–3]. SHG materials are much warranted because of their potential applications in the field of optoelectronics
[4–7]. In recent
years, organic NLO materials have been intensively investigated due to their high nonlinearities, rapid response to electro-optic effect as compared to inorganic NLO materials [8]. Hydrogen bonding plays a crucial role in chemical, catalytic and biochemical processes, chemical and crystal engineering, as well as in supramolecular chemistry [9-11]. The hydrogen bonding between hydroxyl groups of carboxylic acids and heterocyclic nitrogen atoms has been proved to be an useful and powerful organizing force for the formation of supramolecules[12]. Stable nitrogen containing heterocycles play pivotal role in many diverse fields of chemistry [13]. Based on these aspects, in this paper, we report Synthesis, growth, spectral, thermal, optical and mechanical properties of an NLO active organic salt crystal: 3,5-Dimethylpyrazolium-3Nitrophthalate (DMPNP). 2. Experimental details The title salt was synthesized by reacting 1:1 molar ratios of 3,5-Dimethylpyrazole and 3Nitrophthalic acid (Fig.1 (a)). The slow solvent evaporation solution growth technique was employed to grow the single crystals of 3,5-Dimethylpyrazolium-3-Nitrophthalate. A saturated solution was prepared in methanol, stirred well to attain uniform concentration in the entire volume of the solution and filtered through a quantitative 41 grade filter paper. The clear filtrate so obtained was kept aside unperturbed in an atmosphere conductive for the growth of single crystals. Optical quality crystals were harvested in about 20 days time. The crystal structure was established from the single crystal X-ray diffraction data obtained with a
Bruker
Kappa
Apex-II diffractometer
(Graphitemono-chromated,
MoKα
radiation
(λ=0.71073 Aº). Other characterisations, UV-Vis-NIR (200-1500 nm), FTIR (4000–400 cm-1),
1
H and
13
C NMR (Bruker AV III 500 MHz), TG/DTA (NETZSCH STA 409 C/CD TG/DTA),
Hardness measurements (Vickers microhardness hardness tester) and NLO properties (modified Kurtz and Perry powder technique) were also carried out for the title crystal. 3. Results and discussion The crystallographic data and structure refinements of DMAPB crystal are given in Table 1. The asymmetric unit of the title crystal comprises of a 3,5-Dimethylpyrazolium ion and a 3Nitrophthalate ion. The title crystal belongs to monoclinic crystallographic system with noncentrosymmetry space group, P21. The cell parameters are a =7.5026(4) Å, b =7.7207(4) Å, c=12.7575(6) and volume V = 715.91(6) Å3. The intermolecular N—H---O, O—H---O and C—H---O type hydrogen bonds between the cationic and anionic species help to create a delicate balance between the molecular and supramolecular charge transfer processes by creating a non-centrosymmetric structure. Fig.1 (b) shows the ORTEP of the molecule drawn at 40% probability thermal displacement ellipsoids with the atom numbering scheme. From the UV-vis-NIR transmission spectrum (Fig.2 (a)), it is observed that there is no significant absorption in the entire visible and infrared regions enabling the title crystal to be a most suitable candidate for various optical applications. The attained percentage of transmittance is 85 % in the visible region. The lower wavelength cut-off is around 300 nm. The good transmittance coupled with very low wavelength cut off ensures its suitability for second harmonic generation applications. In the FT-IR spectrum (Fig.2 (b)), the medium intensity band observed at 3155 cm-1 is due to the N+-H/aromatic C-H stretching vibration. The absorption bands at 2924 and 2854 cm-1 correspond to the asymmetric and symmetric C-H stretching vibrations of methyl group respectively. The asymmetric and symmetric stretching vibrations of COO- group of 3-Nitrophthalate are observed at 1604 and 1458 cm-1 respectively. The aromatic C=C stretching vibration is exhibited at 1666 cm-1. The NO2 asymmetric stretching vibration and the corresponding symmetric stretching vibration of 3-Nitrophthalate moiety appear at 1527 and
1357 cm-1 respectively. The vibrational bands observed below 500 cm-1 are due to the skeletal vibrations. In the 1H NMR Spectrum (Fig.2 (b)), two doublets at 8.30 and 8.24 ppm are due to the C4 and C6 aromatic protons of the 3-Nitrophthalate moiety respectively. The triplet centered at 7.79 ppm is attributed to C5 aromatic proton of the 3-Nitrophthalate moiety. The C4 aromatic proton of 3,5-Dimethylpyrazolium moiety appears as a singlet at 5.7 ppm. The singlet at 2.1 ppm owes to the six methyl protons of the 3,5-Dimethylpyrazolium moiety. The appearance of eleven distinct carbon signals in the
13
C spectrum (Fig.2 (c)) explicitly confirms the molecular
structure. In the downfield two carbon signals at 165.9 and 165.7 ppm owe to the highly deshielded C1 and C2 carboxyl carbons of the 3-Nitrophthalate moiety. The signal at 146.5 ppm is assigned to the C3 carbon in the same moiety. The carbon signal at 142.7 ppm is due to the C1 and C3 carbons of the same kind in 3, 5-Dimethylpyrazolium moiety. The signal at 134.9 ppm is attributed to the C6 carbon of the 3-Nitrophthalate moiety. The signal appearing at 131.3 ppm is attributed to the C5 carbon of 3-Nitrophthalate moiety. The signals at 130.7, 130.4 and 127.4 ppm owe to the C1, C4, C2 carbons of 3-Nitrophthalate moiety respectively. The C4 carbon of 3,5-Dimethylpyrazolium moiety appears at 103.2 ppm. The sharp and intense signal appearing at 11.8 ppm owes to two methyl carbon atoms of 3,5-Dimethylpyrazolium moiety. The hardness of the crystals was calculated using the relation, Hv=1.8544P/d2 MPa Where Hv is Vicker’s microhardness number, P is the indentor load and d is the diagonal length of the impression. From the Fig.3 (a), it is observed that the grown crystal exhibits reverse indentation size effect (ISE). By plotting log p verses log d, the value of the work hardening coefficient n was found to be 2.231 (Fig.3(b)). Hence, it is concluded that crystal belongs to the soft material category.
From the thermogram (Fig.3(c)), it is understood that the compound undergoes decomposition in two stages when the sample is heated from room temperature to 500 °C. The first stage weight loss amounts to about 33.3 % due to the elimination of volatile gases, probably CO2, NO2 and a mixture of hydrocarbon gases. In the second stage weight loss about 67.2 % of the substance has been eliminated around 234 °C into various gaseous products. In the DTA curve, the thermogram indicates that endothermic dip at 145°C corresponds to the melting point of the crystal. An exothermic peak at 227°C is the major decomposition temperature which coincides with the major weight loss indicated in the TG trace. The SHG property of DMPNP crystal was investigated by the modified Kurtz and Perry powder technique. A Q-switched 8 ns Nd:YAG laser beam of wavelength 1064 nm and 8 mm diameter with 10 Hz repetition rate and the beam energy of 6.3 mJ/pulse is used in this experiment. The emission of green radiation from the DMPNP confirms the second harmonic generation in the crystal. The relative SHG conversion efficiency of the grown crystal was found to be 1.34 times that of the KDP crystal. The presence of π conjugated bands in the 3,5-Dimethylpyrazolium moiety is the responsible for NLO properties of title crystal[14]. 4. Conclusion The new organic salt crystal of DMPNP was grown by the slow solvent evaporation solution growth technique. The molecular structure was established by single crystal XRD analysis and further confirmed by NMR spectroscopic study. The presence of various functional groups in the title salt has been confirmed by FT-IR spectroscopic study. The UV–vis–NIR spectrum suggests the suitability of crystal for various optical applications. The thermal stability of the title crystal was determined by TG/DTA studies. The Vicker’s microhardness study reveals the soft nature of the crystal. The relative SHG efficiency of DMPNP was found to be 1.34 times that of standard KDP crystal.
References [1] P.N. Prasad, D.J. Williams, Introduction to Nonlinear Optical effects in Organic Molecules and Polymers, John Wiley & Sons Inc., New York, USA, 1991. [2] H.O. Marcy, L.F. Warren, M.S. Webb, C.A. Ebbers, S.P. Velsko, G.C. Kennedy, G.C. Catella, Appl. Opt. 31 (1992) 5051-5060. [3] X.Q. Wang, D. Xu, D.R. Yuan, Y.P. Tian, W.T. Yu, S.Y. Sun, Z.H. Yang, Q. Fang, M.K. Lu, Y.X. Yan, F.Q. Meng, S.Y. Guo, G.H. Zhang, M.G. Jiang, Mater. Res. Bull. 34 (1999) 2003-2011. [4] X.Q. Wang, D. Xu, M. Lu, D. Yuan, J. Huang, X. Cheng, T. Xie, G.H. Zhang, S.L. Wang, S.Y. Guo, J.R. Liu, Z.H. Yang, P. Wang, J. Cryst. Growth. 234 (2002) 469-479. [5] X.L. Duan, D.R. Yuan, X.Q. Wang, S.Y. Guo, J.G. Zhang, D. Xu, M.K. Lu, Cryst. Res. Technol. 37 (2002) 1066-1074. [6] M.H. Jiang, Q. Fang, Organic and semiorganic nonlinear optical materials, Adv. Mater. 11 (1999) 1147-1151. [7] J.B. Gaudry, L. Caps, P. Langot, S. Marcen, M. Kollmannsberger, O. Lavastre, E. Freysh, J.F. Letard, O. Kahn, Chem. Phys. Lett. 324 (2000) 321-329. [8] J. Yabu Zaki, Y. Takahashi, H. Adiuchi, Y. Mori, T. Sasaki, Bull.Mater.Sci.22(1999)11-13. [9] G.A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures, Springer- Verlag, Berlin, 1991. [10] G.A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997. [11] L.M. Epstein, E.S. Shubina, Coord. Chem. Rev. 231 (2002) 165-181. [12] S. Jin, X.H. Lu, D.Wang, W.Chen, J. Mol. Struct. 1010 (2012) 17-25. [13] S.Pellizzeri, S. P. Delaney, T.M. Korter , J. Zubieta, J Mol Struct. 1050 (2013) 27-34.
[14] M. Makowska-Janusika, E. Gondek, I.V. Kityk , J. Wisła, J. Sanetra, A. Danel, Chem. Phys. 306 (2004) 265–271.
Figure caption Fig.1 (a) and (b) The reaction scheme and ORTEP of DMAPB crystal Fig.2(a)-(d) UV-Vis-NIR Transmission, FT-IR, 1H and 13C spectrum of DMAPB crystal Fig.3(a)-(c) Vicker’s hardness profile as a function of applied load, Plot of log d Vs log p and TG/DTA Thermogram of DMPNP Crystal
Table 1. Crystal data and structure refinement for DMPNP crystal Empirical formula
C13H13N3O6
Formula weight
307.26
Temperature
296K
Wavelength
0.71073Å
Crystal system
Monoclinic
Space group
P21
Unit cell dimensions
a=7.5026(4)
α =90
b=7.7207(4) β =104.356(1) c=12.7575(6) γ =90 Volume
715.91(6)Å3
Z
2
Density (calculated)
1.425 Mg m-3
Absorption coefficient
0.115mm-1
F(000)
320
Theta range for data collection
2.8° to 27.1
Index ranges
-9<=h<=9, -9<=k<=9, -16<=l<=16
Reflections collected
3136
Independent reflections
2973 [R(int) = 0.032]
Completeness to theta = 27.1
99%
Absorption correction
Semi-empirical from equivalents
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
3136 / 1 / 203
Goodness-of-fit on F2
1.84
Final R indices [I>2sigma(I)]
R1 = 0.0344, wR2 = 0.1161
Absolute structure parameter
0.2 (9)
Largest diff. peak and hole
0.21 and -0.12e.Å-3
Highlights
Single crystals were grown by slow evaporation solution growth technique.
The crystal structure was confirmed by single crystal X-ray diffraction analysis.
The thermal stability of the compound was investigated by TG/DTA analyses.
The SHG efficiency was found to be 1.34 times that of the KDP crystal.
PII: DOI: Reference:
S0167-577X(16)30689-9 http://dx.doi.org/10.1016/j.matlet.2016.04.191 MLBLUE20788
To appear in: Materials Letters Received date: 16 April 2016 Revised date: 22 April 2016 Accepted date: 24 April 2016 Cite this article as: M. Rajkumar and A. Chandramohan, Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3, 5-Dimethylpyrazolium-3-Nitrophthalate, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2016.04.191 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Synthesis, spectral, thermal, mechanical and structural characterization of NLO active organic salt crystal: 3, 5-Dimethylpyrazolium-3-Nitrophthalate M. Rajkumar, A. Chandramohan* Post-Graduate and Research Department of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore - 641 020, Tamil Nadu, India. *Corresponding
author:
Tel.:
+919994283655,
address:
[email protected](A.Chandramohan)
Abstract An organic salt, 3, 5-Dimethylpyrazolium- 3-Nitrophthalate (DMPNP) has been successfully synthesized and single crystals grown by slow solvent evaporation solution growth technique at room temperature using Millipore water of resistivity 18Ω. The formation of salt has been confirmed by single crystal X-ray diffraction and NMR spectroscopic techniques. The title crystal crystallizes in monoclinic crystal system with non-centrosymmetric space group, P21. FT-IR spectral analysis was used to confirm the presence of various functional groups in the grown crystal. The thermal stability of the compound was investigated by carrying out TG/DTA analyses simultaneously. The UV–vis–NIR transmission spectrum was recorded to find the optical transmittance window and lower cut off wavelength of the salt crystal. The Vicker’s microhardness test was carried out to find the mechanical strength of the crystal. The prevailing SHG property in the grown crystal was investigated by the modified Kurtz and Perry powder technique. Keywords: Crystal growth, Crystal structure, FTIR, Thermal analysis, Optical materials and properties 1. Introduction
Nonlinear optics has emerged as one of the most important fields of current research in view of its vital applications in areas of optical switching, optical data storage for the developing technologies in telecommunications and signal processing [1–3]. SHG materials are much warranted because of their potential applications in the field of optoelectronics
[4–7]. In recent
years, organic NLO materials have been intensively investigated due to their high nonlinearities, rapid response to electro-optic effect as compared to inorganic NLO materials [8]. Hydrogen bonding plays a crucial role in chemical, catalytic and biochemical processes, chemical and crystal engineering, as well as in supramolecular chemistry [9-11]. The hydrogen bonding between hydroxyl groups of carboxylic acids and heterocyclic nitrogen atoms has been proved to be an useful and powerful organizing force for the formation of supramolecules[12]. Stable nitrogen containing heterocycles play pivotal role in many diverse fields of chemistry [13]. Based on these aspects, in this paper, we report Synthesis, growth, spectral, thermal, optical and mechanical properties of an NLO active organic salt crystal: 3,5-Dimethylpyrazolium-3Nitrophthalate (DMPNP). 2. Experimental details The title salt was synthesized by reacting 1:1 molar ratios of 3,5-Dimethylpyrazole and 3Nitrophthalic acid (Fig.1 (a)). The slow solvent evaporation solution growth technique was employed to grow the single crystals of 3,5-Dimethylpyrazolium-3-Nitrophthalate. A saturated solution was prepared in methanol, stirred well to attain uniform concentration in the entire volume of the solution and filtered through a quantitative 41 grade filter paper. The clear filtrate so obtained was kept aside unperturbed in an atmosphere conductive for the growth of single crystals. Optical quality crystals were harvested in about 20 days time. The crystal structure was established from the single crystal X-ray diffraction data obtained with a
Bruker
Kappa
Apex-II diffractometer
(Graphitemono-chromated,
MoKα
radiation
(λ=0.71073 Aº). Other characterisations, UV-Vis-NIR (200-1500 nm), FTIR (4000–400 cm-1),
1
H and
13
C NMR (Bruker AV III 500 MHz), TG/DTA (NETZSCH STA 409 C/CD TG/DTA),
Hardness measurements (Vickers microhardness hardness tester) and NLO properties (modified Kurtz and Perry powder technique) were also carried out for the title crystal. 3. Results and discussion The crystallographic data and structure refinements of DMAPB crystal are given in Table 1. The asymmetric unit of the title crystal comprises of a 3,5-Dimethylpyrazolium ion and a 3Nitrophthalate ion. The title crystal belongs to monoclinic crystallographic system with noncentrosymmetry space group, P21. The cell parameters are a =7.5026(4) Å, b =7.7207(4) Å, c=12.7575(6) and volume V = 715.91(6) Å3. The intermolecular N—H---O, O—H---O and C—H---O type hydrogen bonds between the cationic and anionic species help to create a delicate balance between the molecular and supramolecular charge transfer processes by creating a non-centrosymmetric structure. Fig.1 (b) shows the ORTEP of the molecule drawn at 40% probability thermal displacement ellipsoids with the atom numbering scheme. From the UV-vis-NIR transmission spectrum (Fig.2 (a)), it is observed that there is no significant absorption in the entire visible and infrared regions enabling the title crystal to be a most suitable candidate for various optical applications. The attained percentage of transmittance is 85 % in the visible region. The lower wavelength cut-off is around 300 nm. The good transmittance coupled with very low wavelength cut off ensures its suitability for second harmonic generation applications. In the FT-IR spectrum (Fig.2 (b)), the medium intensity band observed at 3155 cm-1 is due to the N+-H/aromatic C-H stretching vibration. The absorption bands at 2924 and 2854 cm-1 correspond to the asymmetric and symmetric C-H stretching vibrations of methyl group respectively. The asymmetric and symmetric stretching vibrations of COO- group of 3-Nitrophthalate are observed at 1604 and 1458 cm-1 respectively. The aromatic C=C stretching vibration is exhibited at 1666 cm-1. The NO2 asymmetric stretching vibration and the corresponding symmetric stretching vibration of 3-Nitrophthalate moiety appear at 1527 and
1357 cm-1 respectively. The vibrational bands observed below 500 cm-1 are due to the skeletal vibrations. In the 1H NMR Spectrum (Fig.2 (b)), two doublets at 8.30 and 8.24 ppm are due to the C4 and C6 aromatic protons of the 3-Nitrophthalate moiety respectively. The triplet centered at 7.79 ppm is attributed to C5 aromatic proton of the 3-Nitrophthalate moiety. The C4 aromatic proton of 3,5-Dimethylpyrazolium moiety appears as a singlet at 5.7 ppm. The singlet at 2.1 ppm owes to the six methyl protons of the 3,5-Dimethylpyrazolium moiety. The appearance of eleven distinct carbon signals in the
13
C spectrum (Fig.2 (c)) explicitly confirms the molecular
structure. In the downfield two carbon signals at 165.9 and 165.7 ppm owe to the highly deshielded C1 and C2 carboxyl carbons of the 3-Nitrophthalate moiety. The signal at 146.5 ppm is assigned to the C3 carbon in the same moiety. The carbon signal at 142.7 ppm is due to the C1 and C3 carbons of the same kind in 3, 5-Dimethylpyrazolium moiety. The signal at 134.9 ppm is attributed to the C6 carbon of the 3-Nitrophthalate moiety. The signal appearing at 131.3 ppm is attributed to the C5 carbon of 3-Nitrophthalate moiety. The signals at 130.7, 130.4 and 127.4 ppm owe to the C1, C4, C2 carbons of 3-Nitrophthalate moiety respectively. The C4 carbon of 3,5-Dimethylpyrazolium moiety appears at 103.2 ppm. The sharp and intense signal appearing at 11.8 ppm owes to two methyl carbon atoms of 3,5-Dimethylpyrazolium moiety. The hardness of the crystals was calculated using the relation, Hv=1.8544P/d2 MPa Where Hv is Vicker’s microhardness number, P is the indentor load and d is the diagonal length of the impression. From the Fig.3 (a), it is observed that the grown crystal exhibits reverse indentation size effect (ISE). By plotting log p verses log d, the value of the work hardening coefficient n was found to be 2.231 (Fig.3(b)). Hence, it is concluded that crystal belongs to the soft material category.
From the thermogram (Fig.3(c)), it is understood that the compound undergoes decomposition in two stages when the sample is heated from room temperature to 500 °C. The first stage weight loss amounts to about 33.3 % due to the elimination of volatile gases, probably CO2, NO2 and a mixture of hydrocarbon gases. In the second stage weight loss about 67.2 % of the substance has been eliminated around 234 °C into various gaseous products. In the DTA curve, the thermogram indicates that endothermic dip at 145°C corresponds to the melting point of the crystal. An exothermic peak at 227°C is the major decomposition temperature which coincides with the major weight loss indicated in the TG trace. The SHG property of DMPNP crystal was investigated by the modified Kurtz and Perry powder technique. A Q-switched 8 ns Nd:YAG laser beam of wavelength 1064 nm and 8 mm diameter with 10 Hz repetition rate and the beam energy of 6.3 mJ/pulse is used in this experiment. The emission of green radiation from the DMPNP confirms the second harmonic generation in the crystal. The relative SHG conversion efficiency of the grown crystal was found to be 1.34 times that of the KDP crystal. The presence of π conjugated bands in the 3,5-Dimethylpyrazolium moiety is the responsible for NLO properties of title crystal[14]. 4. Conclusion The new organic salt crystal of DMPNP was grown by the slow solvent evaporation solution growth technique. The molecular structure was established by single crystal XRD analysis and further confirmed by NMR spectroscopic study. The presence of various functional groups in the title salt has been confirmed by FT-IR spectroscopic study. The UV–vis–NIR spectrum suggests the suitability of crystal for various optical applications. The thermal stability of the title crystal was determined by TG/DTA studies. The Vicker’s microhardness study reveals the soft nature of the crystal. The relative SHG efficiency of DMPNP was found to be 1.34 times that of standard KDP crystal.
References [1] P.N. Prasad, D.J. Williams, Introduction to Nonlinear Optical effects in Organic Molecules and Polymers, John Wiley & Sons Inc., New York, USA, 1991. [2] H.O. Marcy, L.F. Warren, M.S. Webb, C.A. Ebbers, S.P. Velsko, G.C. Kennedy, G.C. Catella, Appl. Opt. 31 (1992) 5051-5060. [3] X.Q. Wang, D. Xu, D.R. Yuan, Y.P. Tian, W.T. Yu, S.Y. Sun, Z.H. Yang, Q. Fang, M.K. Lu, Y.X. Yan, F.Q. Meng, S.Y. Guo, G.H. Zhang, M.G. Jiang, Mater. Res. Bull. 34 (1999) 2003-2011. [4] X.Q. Wang, D. Xu, M. Lu, D. Yuan, J. Huang, X. Cheng, T. Xie, G.H. Zhang, S.L. Wang, S.Y. Guo, J.R. Liu, Z.H. Yang, P. Wang, J. Cryst. Growth. 234 (2002) 469-479. [5] X.L. Duan, D.R. Yuan, X.Q. Wang, S.Y. Guo, J.G. Zhang, D. Xu, M.K. Lu, Cryst. Res. Technol. 37 (2002) 1066-1074. [6] M.H. Jiang, Q. Fang, Organic and semiorganic nonlinear optical materials, Adv. Mater. 11 (1999) 1147-1151. [7] J.B. Gaudry, L. Caps, P. Langot, S. Marcen, M. Kollmannsberger, O. Lavastre, E. Freysh, J.F. Letard, O. Kahn, Chem. Phys. Lett. 324 (2000) 321-329. [8] J. Yabu Zaki, Y. Takahashi, H. Adiuchi, Y. Mori, T. Sasaki, Bull.Mater.Sci.22(1999)11-13. [9] G.A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures, Springer- Verlag, Berlin, 1991. [10] G.A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997. [11] L.M. Epstein, E.S. Shubina, Coord. Chem. Rev. 231 (2002) 165-181. [12] S. Jin, X.H. Lu, D.Wang, W.Chen, J. Mol. Struct. 1010 (2012) 17-25. [13] S.Pellizzeri, S. P. Delaney, T.M. Korter , J. Zubieta, J Mol Struct. 1050 (2013) 27-34.
[14] M. Makowska-Janusika, E. Gondek, I.V. Kityk , J. Wisła, J. Sanetra, A. Danel, Chem. Phys. 306 (2004) 265–271.
Figure caption Fig.1 (a) and (b) The reaction scheme and ORTEP of DMAPB crystal Fig.2(a)-(d) UV-Vis-NIR Transmission, FT-IR, 1H and 13C spectrum of DMAPB crystal Fig.3(a)-(c) Vicker’s hardness profile as a function of applied load, Plot of log d Vs log p and TG/DTA Thermogram of DMPNP Crystal
Table 1. Crystal data and structure refinement for DMPNP crystal Empirical formula
C13H13N3O6
Formula weight
307.26
Temperature
296K
Wavelength
0.71073Å
Crystal system
Monoclinic
Space group
P21
Unit cell dimensions
a=7.5026(4)
α =90
b=7.7207(4) β =104.356(1) c=12.7575(6) γ =90 Volume
715.91(6)Å3
Z
2
Density (calculated)
1.425 Mg m-3
Absorption coefficient
0.115mm-1
F(000)
320
Theta range for data collection
2.8° to 27.1
Index ranges
-9<=h<=9, -9<=k<=9, -16<=l<=16
Reflections collected
3136
Independent reflections
2973 [R(int) = 0.032]
Completeness to theta = 27.1
99%
Absorption correction
Semi-empirical from equivalents
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
3136 / 1 / 203
Goodness-of-fit on F2
1.84
Final R indices [I>2sigma(I)]
R1 = 0.0344, wR2 = 0.1161
Absolute structure parameter
0.2 (9)
Largest diff. peak and hole
0.21 and -0.12e.Å-3
Highlights
Single crystals were grown by slow evaporation solution growth technique.
The crystal structure was confirmed by single crystal X-ray diffraction analysis.
The thermal stability of the compound was investigated by TG/DTA analyses.
The SHG efficiency was found to be 1.34 times that of the KDP crystal.