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Synthesis, structural characterization and Hirshfeld surface analysis of 4-hydroxyanilinium picrate hydrate
Available online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 15 (2019) 645–653
www.materialstoday.com/proceedings
ICMAM-2018
Synthesis, structural characterization and Hirshfeld surface analysis of 4-hydroxyanilinium picrate hydrate M. Manonmani, C. Balakrishnan, SP. Meenakshisundaram and RM. Sockalingam* Department of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu, India
Abstract Structure characterization of single crystals of 4-hydroxyanilinium picrate hydrate (HAPH) by single-crystal X-ray diffraction (XRD) analysis shows that the compound C12H12N4O9 crystallizes in monoclinic space group P21/c. The band gap energy is estimated and photoluminescence studies exhibit fluorescent emission. High value of first-order molecular hyperpolarizability (β) estimated by theoretical calculation reveals good nonlinear optical (NLO) character of the material and the behaviour is rationalized. Intra- and intermolecular interactions are quantified by Hirshfeld surface analysis derived from single crystal XRD data.
© 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Band gap; Fluorescent emission; Hyperpolarizability; Fingerprint plot
*Corresponding author. Cell: +91 94436 65942 E-mail address: [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
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1. Introduction Picric acid forms picrates with organic molecules through π- bonding or ionic bonding interactions. The conjugated base picrate thus formed has enhanced molecular hyperpolarizability because of the proton transfer of phenolic hydroxyl group. The bonding of these picrate complexes depends on the nature of the hydrogen bonding and electron donor–acceptor system [1]. Crystal structures of anilinium picrate [2], 2-chloroanilinium picrate [3], 3-bromoanilinium picrate [4], 3-chloro-4-fluoroanilinium picrate[5], o-toluidinium picrate [6], m-toluidinium picrate [7],N-methyl anilinium picrate, o-phenylenediamine picrate, m-phenylenediamine picrate, p-phenylenediamine picrate [8], N,N-dimethyl anilinium picrate [9], N,N-diethyl anilinium picrate [10] have been reported. Recently we have investigated growth and characterization of 4-aminobenzophenonium picrate [11], 4-amino pyridinium picrate [12], 2-amino-5-nitrobenzophenonium picrate [13], ammonium picrate [14] and p-toludinium picrate [15] crystals. In the present work, we report the structural characterization and Hirshfeld surface analysis of 4-hydroxyanilinium picrate hydrate. Computational studies were used to investigate density of states, polarizability and first-order molecular hyperpolarizability. Molecular interactions are quantified by finger print plots derived from Hirshfeld surfaces. 2.0 Experimental 2.1 Synthesis HAPH was obtained using equimolar quantities of picric acid and acetaminophen in aqueous medium, stirred for 5 h and HAPH formed as a yellow precipitate. Crystallization took place in 14-16 d in ethanol medium and the crystals were collected. Optical image of the HAPH crystal is indicated in Fig. 1.
Fig. 1 Optical images of as-grown HAPH crystals
2.2 Characterization techniques Philips Xpert pro triple-axis X-ray diffractometer was used for recording powder XRD (wavelength of 1.540˚A). A Bruker AXS (Kappa Apex II) X-ray diffractometer was used for single crystal XRD studies. The UV–diffuse reflectance spectrum was analysed using Shimadzu UV2600 UV-Visible spectrophotometer. Photoluminescence spectrum was recorded by HJY:Fluorolg F3-111 spectrometer. Thermo gravimetric and differential thermal analysis (TG-DTA) were carried out using a NETZSCH STA 449 F3 instrument.
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3.0 Results and discussion 3.1 XRD analysis Simulated and experimental powder XRD patterns show the phase purity (Fig. 2). Simulated XRD patterns derived from Mercury 3.6 program. The 4-hydroxyanilinium picrate hydrate crystallizes in the monoclinic system with centrosymmetric space group P21/c. An ORTEP view and the unit cell are displayed in Fig. 3. As can be seen in Fig. 3(a), the proton of the –OH group of picric acid was transferred to the nitrogen atom in the 4-hydroxy aniline molecule, forming an N(4)-H(4A)….O(7) hydrogen bond with the distance 1.941(15) Å. The C(6)-O(7) and C(7)-O(8) bond distances are 1.266(19) and 1.372(2) Å respectively. Picrate C-O bond length is shorter than the 4hydroxyanilinium C-O bond length. The crystal data and structure refinement parameters are listed in Table 1. Crystal systems and space groups of some substituted anilinium and amine picrates are shown in Table 2 and it is observed that most of the picrates crystallize with centrosymmetric triclinic/ monoclinic space group. The -OH group hydrogen atom of the 4-hydroxyanilinium interacts with the oxygen atom of the solvent water molecule and bond distance O(8)-O(9) is 2.7058(17) Å (H(8A)….O(9) 1.90 A˚).
Fig. 2 Simulated and experimental powder XRD patterns
The packing projections are indicated in Fig. 4. The molecular crystal packing along the a- axis with the C-H….O interaction produces the sandwich type of architecture (Fig. 4(a)). Crystal packing along the b and c- axes with the N-H….O and O-H….O interactions are shown as Fig. 4(b, c). The strong and weak H- bonding interactions are listed in Table 3. Weak intermolecular hydrogen bond with a bond, C(12)—H(12)….O(6) distance of 3.504(2) Å, and strong intermolecular interaction, O(9)-H(9B)….O(7) with a bond distance of 2.6955(18) Å are observed. The interactions between chains are van der Waals interaction. a
b
Fig. 3 (a) ORTEP and (b) Packing diagram of HAPH
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Table 1. Crystal data and structure refinement for HAPH Crystal Data Empirical formula Formula weight Temperature Crystal system Space group Unit cell dimensions Volume Z Density (calculated) Absorption coefficient Goodness-of-fit on F2 Final R indices [I>2sigma(I)] R indices (all data) CCDC
HAPH C12H12N4O9 356.26 296(2) K Monoclinic P 21/c a = 15.0655(3) Å α=90° b = 7.81240(10) Å β=109.52(2)° c = 13.2616(2) Å γ =90° 1471.08(4) Å3 4 1.609 Mg/m3 0.140 mm-1 1.072 R1 = 0.0382, wR2 = 0.0922 R1 = 0.0435, wR2 = 0.0996 1827584
a
b
c
Fig. 4 (a) Crystal packing projection along a-axis with the C-H….O (b) b-axis with the N-H….O and (c) c-axis with the O-H….O interactions
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Table 2. Crystal systems and space groups of some substituted anilinium and amine picrates Picrates Anilinium picrate 2 - Chloroanilinium picrate 3-Bromoanilinium picrate 3-Chloro-4-fluoroanilinium picrate o-Toluidinium Picrate m-Toluidinium picrate o-Phenylenediamine picrate m-Phenylenediamine picrate p-Phenylenediamine picrate N-Methylaniline picrate N,N-Dimethylanilinium picrate N,N-Diethylanilinium picrate p-Toludinium picrate 4-hydroxyanilinium picrate hydrate
Crystal System Monoclinic Monoclinic Triclinic Triclinic Monoclinic Monoclinic Monoclinic Monoclinic Orthorhombic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21/c P21/c Pī Pī P21/c P21/c C2/c P21/a Pbca P21/n P21/n P21/c P21/c P21/c
Ref 2,8 3 4 5 6 7 8 8 8 8 8,9 10 15 Present work
Table 3. Hydrogen bonds for HAPH [Å and °] D-H...A C(4)-H(4)....O(2)#1 C(11)-H(11)....O(1)#2 C(12)-H(12)….O(6)#3 O(8)-H(8A)….O(9) O(9)-H(9A)....O(4)#4 O(9)-H(9B)….O(7) N(4)-H(4A)....O(7)#2 N(4)-H(4B)….O(6)#5 N(4)-H(4B)....O(9)#6 N(4)-H(4C)….O(8)#1
d(D-H) 0.93 0.93 0.93 0.82 0.852(16) 0.860(17) 0.858(14) 0.845(15) 0.845(15) 0.888(15)
Symmetry transformations used to generate equivalent atoms: #1 x,y-1,z #2 -x,y-1/2,-z+3/2 #3 x-1,-y+3/2,z-1/2 #4 x,y+1,z
d(H….A) 2.28 2.61 2.62 1.90 2.186(19) 1.840(17) 1.941(15) 2.52(2) 2.224(17) 2.144(19)
d(D....A) 3.078(2) 3.077(2) 3.504(2) 2.7058(17) 2.998(2) 2.6955(18) 2.781(2) 2.9910(19) 2.977(2) 2.978(2)
<(DHA) 143.8 111.5 159.7 165.8 159(2) 173(3) 166(2) 116.1(18) 148(2) 156(2)
#5 x-1,-y+1/2,z-1/2 #6 -x,-y+1,-z+1
3.2 Hirshfeld surface analysis
CrystalExplorer (Version 3.1) program was used for analysing the Hirshfeld surface [16-18] using single crystal XRD data Fig. 5. A clear separation of the electropositive and electronegative regions was observed. 2D-Finger print plots [19] are used for quantification of molecular interactions as illustrated in Fig. 6. The O….H and H….O short interactions with 45.7% of the area of Hirshfeld surface marked as red and blue in 2D fingerprint plots. The H….O interactions are represented as spikes in upper left area and right side represents O…H interactions. Strong interactions (H….H, O….H, and H…O) and weak interactions (C….C, C….H, C….N, N….C, H….C, N….H, H….N, N….N, N….O, O….C,C….O, O….N and O….O) are quantified in the pie chart in (Fig. 7). It appears that the major interactions particularly H….O, O….H are mainly accountable for charge transfer leading to nonlinearity at microlevel.
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a
b
c
d
Fig. 5 Hirshfeld surfaces of HAPH (a) dnorm (b) di (c) de (d) electrostatic potential (ESP) (Bright red area – dominant interactions Light color - weaker and longer contacts)
H….O, O….H (45.7 %)
H….H (15.9 %)
H….C, C….H (11.3 %)
Fig. 6 Hirshfeld surface of the HAPH molecule mapped with ESP and the 2D fingerprint plots
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Fig. 7 Quantities of molecular interactions represented in a pie chart
3.3 Optical studies
The cut-off wave length is observed at ~ 434 nm. Kubelka-Munk equation [20] correlating reflectance and concentration, F(R) = (1-R)2 / 2R =Ac / s the estimation of the direct band-gap energy of the specimen as 2.70 eV, from the Tauc plot (Fig. 8). The HAPH and picric acid exhibit fluorescent emission at λmax 468 nm (~2.65 eV) in the solid state at 30 ᵒC (Fig. 9).
Fig. 8 UV-Vis spectrum of HAPH
Fig. 9 Photoluminescence emission spectra
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3.4 TG/DTA studies
TG and DTA studies have been carried out simultaneously under nitrogen atmosphere at heating at rate of 20 K min1 in the temperature range 30 – 500°C. The first step in TG curve (Fig. 10) occurs in the range 87–110 °C, attributed to the removal of water molecule. The observed weight loss is 4.43% and the calculated value is 5.06 %. The second stage weight loss starts at 202 °C, corresponding to the decomposition of product. The DTA curve shows two endothermic peaks appearing at 108 and 204°C.
Fig. 10 TG/DTA curves of HAPH
3.5 First-order molecular hyperpolarizability
First-order molecular hyperpolarizability (β) was calculated by the GAUSSIAN 09W [21] program using density functional theory (DFT) B3LYP method with 6-311G (d,p) as the basis set. Calculated β of the specimen is 12.3431 x 10-30 esu ( ̴ 63.4 times of urea) (Table 4). Microlevel nonlinearity is associated with charge transfer. Weak and strong hydrogen bonding interactions play a major role for the good NLO response and also responsible for crystal cohesion. Nonlinearity is not sustained at macrolevel because charge transfer gets cancelled because of centrosymmetric crystallization. Table 4. The calculated β components (a.u.), (βtot value (in esu)) First-order molecular hyperpolarizability (β)
βxxx βxxy βxyy βyyy βxxz βxyz βyyz βxzz βyzz βzzz βtotal (x 10-30) esu
-1123.5715 -292.2920 -246.9578 -92.4584 68.9834 10.8882 16.4056 -0.2936 -7.8730 3.5825 12.3431
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4. Conclusion The charge transfer complex 4-hydroxyanilinium picrate hydrate was synthesized and the single crystals were successfully grown. It belongs to the monoclinic system with centrosymmetric space group P21/c. The band gap energy of picrate estimated from the optical transmittance spectrum is 2.70 eV. The decomposition temperature and percentage weight loss of the material at different stages were found out from thermal analysis. High NLO response at the molecular level is attributed to strong intra- and intermolecular hydrogen bonding interactions quantified by finger print plots. Acknowledgements The authors thank the IIT SAIF, Madras for providing the SXRD facility. Sincere thanks to Department of Nanoscience & Technology, Bharathiyar University and CSIL, Annamalai University for providing the necessary facilities. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.
Valerio Bertolasi, Paola Gilli, Gastone Gilli, Cryst. Growth Des., 11(2011) 2724–2735. G. Smith, U.D. Wermuth, P.C. Healy, Acta Cryst., E 60(2004) o1800-o1803. C. Muthamizhchelvan, K. Saminathan, J. Fraanje, R. Peschar, K. Sivakumar, Anal. Sci., 21(2005) x61-x62. Y. Li, B. Zhao, Acta Cryst., E 65(2009) o3218. B. K. Sarojini, B. Narayana, H.S. Yathirajan, Thomas Gerber, Benjamin van Brecht, Richard Betz, Acta Cryst., E 69(2013) 240. K. Mohana Priyadarshini, A. Chandramohan, T. Uma Devi, Journal of Crystallization Process and Technology, 3(2013) 123-129. K. Mohana Priyadarshini, A. Chandramohan, T. Uma Devi, S. Selvanayagam, B. Sridhar, Int. J. ChemTech Res., 5(2013) 2678-2689. H. Takayanagi, T. Kai, S. Yamaguchi, K. Takeda, M. Goto, Chem. Pharm. Bull., 44(1996) 2199-2204. A. Chandramohan, R. Bharathikannan, M.A. Kandhaswamy, J. Chandrasekaran, R. Renganathan, V. Kandavelu, J. Cryst. Res. Technol., 43(2008) 173 – 178. R. Subramaniyan@Raja, G. Anandha Babu, P. Ramasamy, J. Cryst. Growth., 334(2011) 159–164. A. Aditya Prasad, K. Muthu, M. Rajasekar, V. Meenatchi, S.P. Meenakshisundaram, Spectrochim. Acta, Part A., 135(2015) 46–54. A. Aditya Prasad, K. Muthu, M. Rajasekar, V. Meenatchi, S.P. Meenakshisundaram, Spectrochim. Acta, Part A., 135(2015) 805–813. A. Aditya Prasad, K. Muthu, V. Meenatchi, M. Rajasekar, S.P. Meenakshisundaram, S.C. Mojumdar, J. Therm Anal Calorim., 119(2015) 885–890. A. Aditya Prasad, S. Kalainathan, S.P. Meenakshisundaram, Optik., 127(2016) 6134–6149. K. Muthu, Subbiah Meenakshisundaram, J. Cryst. Growth., 352(2012) 163–166. M.A. Spackman, D. Jayatilaka, CrystEngComm., 11(2009) 19-32. F.L. Hirshfeld, Theoret. Chim. Acta (Berl.)., 44(1977) 129-138. S.K. Wolff, D.J. Grimwood, J.J. McKinnon, M.J. Turner, D. Jayatilaka, M.A. Spackman, (2012). CrystalExplorer (Version 3.1), Crawley, WA: University of Western Australia. M.A. Spackman, J.J. McKinnon, CrystEngComm., 4(2002) 378-392. P. Kubelka, F. Munk, Z. Tech Phys., 12(1931) 593-601. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, et al. (2009). Gaussian09 Revision C.01, Wallingford, CT: Gaussian, Inc.,
ScienceDirect Materials Today: Proceedings 15 (2019) 645–653
www.materialstoday.com/proceedings
ICMAM-2018
Synthesis, structural characterization and Hirshfeld surface analysis of 4-hydroxyanilinium picrate hydrate M. Manonmani, C. Balakrishnan, SP. Meenakshisundaram and RM. Sockalingam* Department of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu, India
Abstract Structure characterization of single crystals of 4-hydroxyanilinium picrate hydrate (HAPH) by single-crystal X-ray diffraction (XRD) analysis shows that the compound C12H12N4O9 crystallizes in monoclinic space group P21/c. The band gap energy is estimated and photoluminescence studies exhibit fluorescent emission. High value of first-order molecular hyperpolarizability (β) estimated by theoretical calculation reveals good nonlinear optical (NLO) character of the material and the behaviour is rationalized. Intra- and intermolecular interactions are quantified by Hirshfeld surface analysis derived from single crystal XRD data.
© 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Band gap; Fluorescent emission; Hyperpolarizability; Fingerprint plot
*Corresponding author. Cell: +91 94436 65942 E-mail address: [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
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1. Introduction Picric acid forms picrates with organic molecules through π- bonding or ionic bonding interactions. The conjugated base picrate thus formed has enhanced molecular hyperpolarizability because of the proton transfer of phenolic hydroxyl group. The bonding of these picrate complexes depends on the nature of the hydrogen bonding and electron donor–acceptor system [1]. Crystal structures of anilinium picrate [2], 2-chloroanilinium picrate [3], 3-bromoanilinium picrate [4], 3-chloro-4-fluoroanilinium picrate[5], o-toluidinium picrate [6], m-toluidinium picrate [7],N-methyl anilinium picrate, o-phenylenediamine picrate, m-phenylenediamine picrate, p-phenylenediamine picrate [8], N,N-dimethyl anilinium picrate [9], N,N-diethyl anilinium picrate [10] have been reported. Recently we have investigated growth and characterization of 4-aminobenzophenonium picrate [11], 4-amino pyridinium picrate [12], 2-amino-5-nitrobenzophenonium picrate [13], ammonium picrate [14] and p-toludinium picrate [15] crystals. In the present work, we report the structural characterization and Hirshfeld surface analysis of 4-hydroxyanilinium picrate hydrate. Computational studies were used to investigate density of states, polarizability and first-order molecular hyperpolarizability. Molecular interactions are quantified by finger print plots derived from Hirshfeld surfaces. 2.0 Experimental 2.1 Synthesis HAPH was obtained using equimolar quantities of picric acid and acetaminophen in aqueous medium, stirred for 5 h and HAPH formed as a yellow precipitate. Crystallization took place in 14-16 d in ethanol medium and the crystals were collected. Optical image of the HAPH crystal is indicated in Fig. 1.
Fig. 1 Optical images of as-grown HAPH crystals
2.2 Characterization techniques Philips Xpert pro triple-axis X-ray diffractometer was used for recording powder XRD (wavelength of 1.540˚A). A Bruker AXS (Kappa Apex II) X-ray diffractometer was used for single crystal XRD studies. The UV–diffuse reflectance spectrum was analysed using Shimadzu UV2600 UV-Visible spectrophotometer. Photoluminescence spectrum was recorded by HJY:Fluorolg F3-111 spectrometer. Thermo gravimetric and differential thermal analysis (TG-DTA) were carried out using a NETZSCH STA 449 F3 instrument.
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3.0 Results and discussion 3.1 XRD analysis Simulated and experimental powder XRD patterns show the phase purity (Fig. 2). Simulated XRD patterns derived from Mercury 3.6 program. The 4-hydroxyanilinium picrate hydrate crystallizes in the monoclinic system with centrosymmetric space group P21/c. An ORTEP view and the unit cell are displayed in Fig. 3. As can be seen in Fig. 3(a), the proton of the –OH group of picric acid was transferred to the nitrogen atom in the 4-hydroxy aniline molecule, forming an N(4)-H(4A)….O(7) hydrogen bond with the distance 1.941(15) Å. The C(6)-O(7) and C(7)-O(8) bond distances are 1.266(19) and 1.372(2) Å respectively. Picrate C-O bond length is shorter than the 4hydroxyanilinium C-O bond length. The crystal data and structure refinement parameters are listed in Table 1. Crystal systems and space groups of some substituted anilinium and amine picrates are shown in Table 2 and it is observed that most of the picrates crystallize with centrosymmetric triclinic/ monoclinic space group. The -OH group hydrogen atom of the 4-hydroxyanilinium interacts with the oxygen atom of the solvent water molecule and bond distance O(8)-O(9) is 2.7058(17) Å (H(8A)….O(9) 1.90 A˚).
Fig. 2 Simulated and experimental powder XRD patterns
The packing projections are indicated in Fig. 4. The molecular crystal packing along the a- axis with the C-H….O interaction produces the sandwich type of architecture (Fig. 4(a)). Crystal packing along the b and c- axes with the N-H….O and O-H….O interactions are shown as Fig. 4(b, c). The strong and weak H- bonding interactions are listed in Table 3. Weak intermolecular hydrogen bond with a bond, C(12)—H(12)….O(6) distance of 3.504(2) Å, and strong intermolecular interaction, O(9)-H(9B)….O(7) with a bond distance of 2.6955(18) Å are observed. The interactions between chains are van der Waals interaction. a
b
Fig. 3 (a) ORTEP and (b) Packing diagram of HAPH
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Table 1. Crystal data and structure refinement for HAPH Crystal Data Empirical formula Formula weight Temperature Crystal system Space group Unit cell dimensions Volume Z Density (calculated) Absorption coefficient Goodness-of-fit on F2 Final R indices [I>2sigma(I)] R indices (all data) CCDC
HAPH C12H12N4O9 356.26 296(2) K Monoclinic P 21/c a = 15.0655(3) Å α=90° b = 7.81240(10) Å β=109.52(2)° c = 13.2616(2) Å γ =90° 1471.08(4) Å3 4 1.609 Mg/m3 0.140 mm-1 1.072 R1 = 0.0382, wR2 = 0.0922 R1 = 0.0435, wR2 = 0.0996 1827584
a
b
c
Fig. 4 (a) Crystal packing projection along a-axis with the C-H….O (b) b-axis with the N-H….O and (c) c-axis with the O-H….O interactions
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Table 2. Crystal systems and space groups of some substituted anilinium and amine picrates Picrates Anilinium picrate 2 - Chloroanilinium picrate 3-Bromoanilinium picrate 3-Chloro-4-fluoroanilinium picrate o-Toluidinium Picrate m-Toluidinium picrate o-Phenylenediamine picrate m-Phenylenediamine picrate p-Phenylenediamine picrate N-Methylaniline picrate N,N-Dimethylanilinium picrate N,N-Diethylanilinium picrate p-Toludinium picrate 4-hydroxyanilinium picrate hydrate
Crystal System Monoclinic Monoclinic Triclinic Triclinic Monoclinic Monoclinic Monoclinic Monoclinic Orthorhombic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21/c P21/c Pī Pī P21/c P21/c C2/c P21/a Pbca P21/n P21/n P21/c P21/c P21/c
Ref 2,8 3 4 5 6 7 8 8 8 8 8,9 10 15 Present work
Table 3. Hydrogen bonds for HAPH [Å and °] D-H...A C(4)-H(4)....O(2)#1 C(11)-H(11)....O(1)#2 C(12)-H(12)….O(6)#3 O(8)-H(8A)….O(9) O(9)-H(9A)....O(4)#4 O(9)-H(9B)….O(7) N(4)-H(4A)....O(7)#2 N(4)-H(4B)….O(6)#5 N(4)-H(4B)....O(9)#6 N(4)-H(4C)….O(8)#1
d(D-H) 0.93 0.93 0.93 0.82 0.852(16) 0.860(17) 0.858(14) 0.845(15) 0.845(15) 0.888(15)
Symmetry transformations used to generate equivalent atoms: #1 x,y-1,z #2 -x,y-1/2,-z+3/2 #3 x-1,-y+3/2,z-1/2 #4 x,y+1,z
d(H….A) 2.28 2.61 2.62 1.90 2.186(19) 1.840(17) 1.941(15) 2.52(2) 2.224(17) 2.144(19)
d(D....A) 3.078(2) 3.077(2) 3.504(2) 2.7058(17) 2.998(2) 2.6955(18) 2.781(2) 2.9910(19) 2.977(2) 2.978(2)
<(DHA) 143.8 111.5 159.7 165.8 159(2) 173(3) 166(2) 116.1(18) 148(2) 156(2)
#5 x-1,-y+1/2,z-1/2 #6 -x,-y+1,-z+1
3.2 Hirshfeld surface analysis
CrystalExplorer (Version 3.1) program was used for analysing the Hirshfeld surface [16-18] using single crystal XRD data Fig. 5. A clear separation of the electropositive and electronegative regions was observed. 2D-Finger print plots [19] are used for quantification of molecular interactions as illustrated in Fig. 6. The O….H and H….O short interactions with 45.7% of the area of Hirshfeld surface marked as red and blue in 2D fingerprint plots. The H….O interactions are represented as spikes in upper left area and right side represents O…H interactions. Strong interactions (H….H, O….H, and H…O) and weak interactions (C….C, C….H, C….N, N….C, H….C, N….H, H….N, N….N, N….O, O….C,C….O, O….N and O….O) are quantified in the pie chart in (Fig. 7). It appears that the major interactions particularly H….O, O….H are mainly accountable for charge transfer leading to nonlinearity at microlevel.
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a
b
c
d
Fig. 5 Hirshfeld surfaces of HAPH (a) dnorm (b) di (c) de (d) electrostatic potential (ESP) (Bright red area – dominant interactions Light color - weaker and longer contacts)
H….O, O….H (45.7 %)
H….H (15.9 %)
H….C, C….H (11.3 %)
Fig. 6 Hirshfeld surface of the HAPH molecule mapped with ESP and the 2D fingerprint plots
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Fig. 7 Quantities of molecular interactions represented in a pie chart
3.3 Optical studies
The cut-off wave length is observed at ~ 434 nm. Kubelka-Munk equation [20] correlating reflectance and concentration, F(R) = (1-R)2 / 2R =Ac / s the estimation of the direct band-gap energy of the specimen as 2.70 eV, from the Tauc plot (Fig. 8). The HAPH and picric acid exhibit fluorescent emission at λmax 468 nm (~2.65 eV) in the solid state at 30 ᵒC (Fig. 9).
Fig. 8 UV-Vis spectrum of HAPH
Fig. 9 Photoluminescence emission spectra
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3.4 TG/DTA studies
TG and DTA studies have been carried out simultaneously under nitrogen atmosphere at heating at rate of 20 K min1 in the temperature range 30 – 500°C. The first step in TG curve (Fig. 10) occurs in the range 87–110 °C, attributed to the removal of water molecule. The observed weight loss is 4.43% and the calculated value is 5.06 %. The second stage weight loss starts at 202 °C, corresponding to the decomposition of product. The DTA curve shows two endothermic peaks appearing at 108 and 204°C.
Fig. 10 TG/DTA curves of HAPH
3.5 First-order molecular hyperpolarizability
First-order molecular hyperpolarizability (β) was calculated by the GAUSSIAN 09W [21] program using density functional theory (DFT) B3LYP method with 6-311G (d,p) as the basis set. Calculated β of the specimen is 12.3431 x 10-30 esu ( ̴ 63.4 times of urea) (Table 4). Microlevel nonlinearity is associated with charge transfer. Weak and strong hydrogen bonding interactions play a major role for the good NLO response and also responsible for crystal cohesion. Nonlinearity is not sustained at macrolevel because charge transfer gets cancelled because of centrosymmetric crystallization. Table 4. The calculated β components (a.u.), (βtot value (in esu)) First-order molecular hyperpolarizability (β)
βxxx βxxy βxyy βyyy βxxz βxyz βyyz βxzz βyzz βzzz βtotal (x 10-30) esu
-1123.5715 -292.2920 -246.9578 -92.4584 68.9834 10.8882 16.4056 -0.2936 -7.8730 3.5825 12.3431
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4. Conclusion The charge transfer complex 4-hydroxyanilinium picrate hydrate was synthesized and the single crystals were successfully grown. It belongs to the monoclinic system with centrosymmetric space group P21/c. The band gap energy of picrate estimated from the optical transmittance spectrum is 2.70 eV. The decomposition temperature and percentage weight loss of the material at different stages were found out from thermal analysis. High NLO response at the molecular level is attributed to strong intra- and intermolecular hydrogen bonding interactions quantified by finger print plots. Acknowledgements The authors thank the IIT SAIF, Madras for providing the SXRD facility. Sincere thanks to Department of Nanoscience & Technology, Bharathiyar University and CSIL, Annamalai University for providing the necessary facilities. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.
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