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IJLEO 57250 1–6 ARTICLE IN PRESS

Optik xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

Optik
journal homepage: www.elsevier.de/ijleo

1 Structure, growth and characterization of picolinium perchlorate

2 single crystals
3 Q1 A. Arunkumar a,∗ , V. Mohankumar b , R. Jagan c , P. Ramasamy b
4 Q2 a
Department of Physics, Agni College of Technology, Thalambur, Chennai 603 110, India
b
5 SSN Research Center, SSN College of Engineering, Kalavakkam, Chennai 603 110, India
c
6 Sophisticated Analytical Instruments Facility, IIT Madras, Chennai, India
7

8
19 a r t i c l e i n f o a b s t r a c t
9
10 Article history: Picolinium perchlorate organic single crystals were grown using slow evaporation solution growth tech-
11 Received 9 December 2015 nique at room temperature using water as a solvent. The structure of the title compound was supported
12 Accepted 18 January 2016 by proton NMR analysis and the single crystal X-ray diffraction data. Crystallographic studies revealed
13 Available online xxx
that the compound crystallized in monoclinic system with space group C2/c. The HRXRD rocking curve
14 measurements revealed the crystalline perfection of grown crystal. First order hyperpolarizability, HOMO
15 Keywords:
and LUMO energies are calculated using Density Functional Theory (DFT) with a hybrid functional B3LYP
16 Crystal growth
and the 6-311++G(d,p) basis set. Global reactivity indices are calculated. Thermal studies were carried
17 Thermal properties
18 Single crystal X-ray diffraction
out on the title compound. The UV–vis–NIR spectrum was recorded to study the optical transparency
of the grown crystals. The mechanical stability of the crystal was analyzed by Vicker’s microhardness
studies.
© 2016 Elsevier GmbH. All rights reserved.

20 1. Introduction In order to satisfy the day-to-day technological requirements, 41

many scientists focused their attention on the growth of materi- 42

21 Organic crystals in terms of nonlinear optical property possess als which have a good nonlinear optical behavior and be optically 43

22 advantages, when compared to their inorganic counterparts. One of transparent in the visible and near IR regions. To study the 44

23 the intensely studied fields in chemistry and physics are the optical hydrogen-bonding pattern in pharmacologically important pic- 45

24 properties of molecular crystals. The importance of those materials olinic acid was treated with different inorganic acids and the 46

25 has been demonstrated in the recent years by the increased number structure of a complex with perchloric acid is reported in the 47

26 of applications in nonlinear optics and in electronics. Optical non- present investigation. Its hyperpolarizability was estimated by 48

27 linearities of conjugated organic systems have been widely studied using DFT theory. Its highest occupied molecular orbital (HOMO) 49

28 in view of their potential in photonic and electro-optic devices and the lowest unoccupied molecular orbital (LUMO) Energies were 50

29 [1,2]. Nonlinear optical materials are expected to be active elements calculated. 51

30 for optical communications and optoelectronics. Organic crystals

31 are highly recognized as the materials of the future because their
32 molecular nature combined with versatility of synthetic chem- 2. Experimental 52
33 istry can be used to alter their structure in order to maximize
34 the nonlinear properties [3–5]. The most important applications The starting material was synthesized by taking 2-picolinic 53
35 of NLO materials is their use for fast data transfer combined with a acid and perchloric acid in a 1:1 stoichiometric ratio. The reaction 54
36 very high Signal-to-Noise ratio, even over long distances. In recent scheme is depicted in Fig. 1. 55
37 years, different applications of NLO and photorefractive materials A calculated amount of the 2-picolinic acid is dissolved thor- 56
38 have been developed, for example, optical frequency conversion, oughly in the deionized water. Then perchloric acid was added to 57
39 electro-optical modulation, dynamic holography, optical writing the aqueous solution. The solution is stirred well using a magnetic 58
40 and optical guiding of laser beams [6]. stirrer to yield a saturated homogenous solution for six hours. The 59

solution was then filtered twice to remove the suspended impurity 60

and allowed to crystallize by slow evaporation. After growth period 61

∗ Corresponding author. Tel.: +91 9994457891; fax: +91 4427475166. of three weeks, best quality and highly transparent single crystal 62
Q3
E-mail address: arunkajini@gmail.com (A. Arunkumar). was harvested and is shown in Fig. 2. 63

http://dx.doi.org/10.1016/j.ijleo.2016.01.140
0030-4026/© 2016 Elsevier GmbH. All rights reserved.

Please cite this article in press as: A. Arunkumar, et al., Structure, growth and characterization of picolinium perchlorate single crystals,
Optik - Int. J. Light Electron Opt. (2016), http://dx.doi.org/10.1016/j.ijleo.2016.01.140
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Table 1
Crystal data and structure refinement for PP.

Empirical formula C6 H6 ClNO6

Formula weight 223.57

Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system, space group Monoclinic, C2/c

Unit cell dimensions a = 13.98 (18) Å alpha = 90 deg.

Fig. 1. Reaction scheme of PP.
Volume
Z, Calculated density
Absorption coefficient
F(0 0 0)
Crystal size
Theta range for data collection
Limiting indices
Reflections collected/unique
Completeness to theta = 25.00
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma (I)]
R indices (all data)
Largest diff. peak and hole
b = 8.37(10) Å beta = 100.20(7) deg.
c = 15.26(18) Å gamma = 90 deg.
1758.1(4) A3
8, 1.689 Mg/m3
0.439 mm−1
912
0.30 × 0.25 × 0.25 mm
2.71 to 28.35 deg.
−18 ≤ h ≤ 18, −10 ≤ k ≤ 11, −20 ≤ l ≤ 18
8111/2552 [R(int) = 0.0229]
99.5%
Semi-empirical from equivalents
0.8981 and 0.8295
Full-matrix least-squares on F2
2152/0/131
1.074
R1 = 0.0496, wR2 = 0.1445
R1 = 0.0565, wR2 = 0.1527
0.440 and −0.397 e. A−3

Fig. 2. Photograph of as grown PP single crystals.

64 3. Single crystal X-ray diffraction studies

65 Intensity data for picolinium perchlorate was collected using

66 a Bruker AXS Kappa APEX II single crystal CCD diffractome-
67 ter equipped with graphite-monochromated MoK␣ radiation
68 ( = 0.71073 Å) at room temperature with a crystal dimension of
69 0.35 × 0.25 × 0.2 mm3 . Accurate unit cell parameters were deter-
70 mined from the reflections of 36 frames measured in three different
71 crystallographic zones. The data collection, data reduction and
72 absorption correction were performed by APEX2, SAINT-plus and
73 SADABS program [7]. The structures was solved by direct meth-
74 ods procedure and the non-hydrogen atoms were subjected to
75 anisotropic refinement by full-matrix least squares on F2 using Fig. 3. Molecular structure of PP.
76 SHELXL-97 program [8]. The positions of all the hydrogen atoms
77 were identified from difference electron density map, and they [−x + 1/2,y + 1/2,−z + 1/2] hydrogen bonds form a chain type 100
78 were constrained to ride on the corresponding non-hydrogen of architecture, C3 H3· · ·O4(2) [−x + 1/2,y + 1/2,−z + 1/2]. 101
79 atoms. The hydrogen atom bound to carbon atoms is constrained C4 H4· · ·O2(3) [x,−y,z = 1/2] hydrogen bond interlinks these 102
80 to a distance of C H = 0.93–0.97 Å and Uiso (H) = 1.2Ueq (C) and molecular chain to form an extended planar layer parallel to 103
81 1.5Ueq (C). The crystallographic data and the structure refinement the (1 0 0) plane and is shown in Fig. 5. The C6 H6· · ·O3 (6) 104
82 parameters of PP are presented in Table 1.
83 The title compound picolinium perchlorate crystallizes in
84 monoclinic space group C2/c with eight set of anions and cations
85 in the unit cell. Fig. 3 illustrates the molecular structure of PP.
86 Crystal packing diagram is shown in Fig. 4. The bond lengths
87Q4 of the perchlorate anion Cl1 O3 = 1.401 Å, Cl1 O4 = 1.410 Å,

88 C1 O3 = 1.416 Å agrees with the Cl O value of the perchloric acid

89 whereas Cl1 O5 = 1.439 Å value lies between Cl O single and
90 double bond reveal that the dissociation of hydrogen atom to
91 the picolinic nitrogen atom. The picolinium N H atom is clearly
92 judged from the appearance of strong difference electron density
93 peak near the N atom. The presence of donor and acceptor sites
94 in the molecule form C3 H3· · ·O4(2) [−x + 1/2,y + 1/2,−z + 1/2].
95 C4 H4· · ·O2(3) [x,−y,z = 1/2]; C6 H6· · ·O3(6) [x − 1/2,y − 1,z = 1/2].
96 The supramolecular networks in the crystal structure are sta-
97 bilized by the presence of C H· · ·O and O H· · ·O hydrogen
98 bonds. The alternate anion and cation along the b-axis through
99 strong N1 H1A· · ·O6(2) [−x + 1/2,y + 1/2,−z + 1/2] O1 H1A· · ·O5(1) Fig. 4. Crystal packing diagram of PP.

Please cite this article in press as: A. Arunkumar, et al., Structure, growth and characterization of picolinium perchlorate single crystals,
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Fig. 5. Molecular chain to form an extended planar layer parallel to the (1 0 0) plane.
Fig. 6. Molecular structure with numbering scheme.

Table 2
Observed possible hydrogen bonds of PP. C15 O2, C15 O4 are found to be 1.1975 Å, 1.3487 Å, respectively. 142

D H· · ·A d(D H) d(H· · ·A) d(D· · ·A) <(DHA)

The shortening of C15 O2 bond shows considerable double bond 143

character typical in the carbonyl group. In this molecule, O7· · ·H20 144
O(1) H(1)· · ·O(5)#1 0.82 1.92 2.710 (3) 160.3
bond distance is calculated to be 1.4738 Å, which is significantly 145
N(1) H(1A)· · ·O(6)#2 0.83 (3) 2.08 (3) 2.903 (3) 174 (3)
shorter than the van der Waals radii (2.75 Å) [14] between O and 146
Symmetry transformations used to generate equivalent atoms: #1 − x + 1/2, −y +
H atoms indicates the existence of N H· · ·O hydrogen bonding. 147
1/2, −z #2 − x + 1/2, −y − 1/2, −z.
The calculated Cl O bond lengths are obtained Cl1 O5 (1.5016 Å), 148

Cl1 O7 (1.5534 Å), Cl1 O8 (1.4825 Å) and Cl1 O14 (1.4666 Å), the 149

105 [x − 1/2,y − 1,z = 1/2] act as a bridging hydrogen bond between corresponding XRD values are 1.4392 Å and 1.4164 Å, 1.4098 Å and 150

106 the inversion relation (1 0 0) layer to form a two dimensional 1.4010 Å, respectively. The lengthening of Cl1 O7 bond length is 151

107 parallel to the bc-plane. Three such sheet cuts the unit cell at due to the presence of N H· · ·O hydrogen bonding. The bond angle 152

Q5 (0 0 0), (1/2,0,0) and (1,0,0) which constitutes the molecular

108 of N6 H20· · ·O7 (167.68◦ ) is nearly to be 180◦ , this reveals the 153

109 packing in the crystal. The torsion angle of picolinium residue strong intermolecular charge transfer (ICT) in the molecule. 154

110 (O2 C1 C2 N1) relative orientation of the carboxyl group and In the presence of an applied electric field, the energy of a system 155

111 the amino-N-atom is 14.37(3). The H atom of the Perchloric acid is a function of the electric field and the first hyperpolarizability is 156

112 links the Picolinium residues by a normal O H· · ·O hydrogen a third rank tensor that can be described by a 3 × 3 × 3 matrix. The 157

113 bond. All the O atoms of the perchlorate anion are involved 27 components of the 3D matrix can be reduced to 10 components 158

114 in hydrogen bonding. The observed hydrogen bonds of PP are because of the Kleinman symmetry [15]. The hyperpolarizability 159

115 summarized in Table 2. CCDC 899229 contains the supplementary components are listed in Table 5. The first hyperpolarizability was 160

116 crystallographic data for this paper. These data can be obtained calculated using the following equation: 161

117 free of charge via http://www.ccdc.cam.ac.uk/data request/cif 162

118 or by emailing data request@ccdc.cam.ac.uk or by contacting  2  2  2 1/2

ˇ= ˇXXX + ˇXYY + ˇXZZ + ˇYYY + ˇYZZ + ˇYXX + ˇZZZ + ˇZXX + ˇZYY 163
119 The Cambridge Crystallographic Data Centre, 12 Union Road,
120 CAMBRIDGE CB21EZ, UK; fax: Facsimile: 44 01223 336033 (1) 164

121 4. Computational studies Table 3

Calculated geometrical parameters of bond lengths.

122 The Cartesian coordinates of the title compound were derived Structural parameters B3LYP/6-311++G(d,p) XRD
123 from single crystal X-ray CIF file using AVOGADRO package. From
Cl1 O5 1.50157 1.43920
124 derived Cartesian coordinates the quantum mechanical calcula- Cl1 O7 1.55335 1.41633
125 tions were done. The computations were carried out using Density Cl1 O8 1.48242 1.40980
126 Functional Theory (DFT) calculations with a hybrid functional Cl1 O14 1.46655 1.40094
127 B3LYP/6-311++G(d,p). The executions were performed with the O2 H3 0.96974 0.81961
O2 C15 1.34869 1.30688
128 Gaussian 09 package. The ground state DFT geometry optimiza- O4 C15 1.19750 1.19574
129 tion of isolated picolinium perchlorate was performed at the level N6 O8 3.77605 4.89289
130 of Becke’s three Lee–Yang–Parr (B3LYP) hybrid method exchange N6 C9 1.34832 1.33315
131 correlation functional parameters with 6-311++G(d,p) [9–12] basis N6 C18 1.33923 1.33046
N6 H20 1.11106 0.82915
132 set using Gaussian’09 program package [13]. Fig. 6 shows Molecular
O7· · ·H20 1.47375 2.07776
133 structure with numbering scheme. Calculated geometrical param- O8 C9 4.83145 5.91073
134 eters of bond lengths and bond angles are listed in Tables 3 and 4, C9 C10 1.38635 1.37055
135 respectively, with the experimental values of PP obtained from the C9 C15 1.50252 1.49499
136 X-ray diffraction study. Deviations in the XRD data from the com- C10 H11 1.08050 0.93013
C10 C12 1.39623 1.37759
137 puted geometry are probably due to the intermolecular interactions C12 H13 1.08353 0.92996
138 in the crystalline state. The calculated C C bond lengths of C9 C10 C12 C16 1.38855 1.36480
139 (1.3864 Å), C10 C12 (1.3963 Å), C12 C16 (1.3886 Å), C16 C18 C16 H17 1.08183 0.92952
140 (1.3907 Å), these deviations in bond length is due to the substitution C16 C18 1.39070 1.37090
C18 H19 1.08707 0.92964
141 of carboxylic acid in the ring. The calculated C O bond lengths of

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Table 4
Calculated geometrical parameters of bond angles.

Structural parameters B3LYP/6-311++G(d,p) XRD

O5 Cl1 O7 106.62431 109.28911

O5 Cl1 O8 109.94691 108.33897
O5 Cl1 O14 111.49819 108.58755
O7 Cl1 O8 107.88850 110.36071
O7 Cl1 O14 108.03586 111.01504
O8 Cl1 O14 112.58350 109.18888
H3 O2 Cl15 107.70898 109.46718 Fig. 7. The HOMO and LUMO orbitals of PP.
O8 N6 C18 86.43074 100.70823
O8 N6 H20 43.79707 17.79908
C9 N6 C18 121.92456 122.39504
Table 6
C9 N6 H20 123.16096 125.65473
HOMO, LUMO and global indices values.
C18 N6 H20 114.87468 111.94543
Cl1 O7 H20 116.89861 118.95983 HOMO −7.37880 eV
Cl1 O8 N6 66.81477 32.77526 LUMO −3.9269 eV
Cl1 O8 C9 75.34907 41.36931 Chemical potential (V) −5.6528 eV
N6 C9 C10 120.10369 119.88915 Chemical hardness () 1.92818 eV
N6 C9 C15 116.16174 115.13507 Electrophilicity index (ω) 8.2860 eV
O8 C9 C10 132.07985 152.55124
O8 C9 C15 96.71092 80.87200
C10 C9 C15 123.72542 124.97182 a constant external potential. The chemical potential (V), hardness 184
C9 C10 H11 119.27835 120.58340
(ŋ), and the electrophilicity index (ω) have been calculated using 185
C9 C10 C12 119.03695 118.80363
H11 C10 C12 121.68449 120.61293 Eqs. (2)–(4); and the results are reported in Table 6. The energy gap 186

C10 C12 H13 119.92178 120.07297 of PP is 3.4151 eV. 187

C10 C12 C16 119.60012 119.84891
EHOMO − ELUMO
H13 C12 C16 120.47803 120.07806 = (2) 188
O2 C15 O4 125.01934 127.26766 2
O2 C15 C9 111.20950 111.17852 EHOMO + ELUMO
O4 C15 C9 123.76949 121.55355 V= (3) 189
2
C12 C16 H17 121.64323 120.19564
C12 C16 C18 119.00592 119.70509 V2
H17 C16 C18 119.35012 120.09924 ω= (4) 190
2
N6 C18 C16 120.32698 119.33855
N6 C18 H19 115.12001 120.35184
C16 C18 H19 124.55012 120.30957 5. HRXRD studies 191
N6 H20 O7 167.68370 173.82179
The crystalline perfection of the grown single crystals was 192

characterized by HRXRD by employing a multi crystal X-ray diffrac- 193

165
tometer developed at NPL [19]. The well-collimated and mono Q6 194
166 The calculated first hyperpolarizability of PP is 2.6439 × chromated MoK␣1 beam obtained from the three monochroma- 195
167 10−30 e.s.u. The theoretical calculation noticed that the PP have NLO tor Si crystals set in dispersive (+,−,−) configuration has been used 196
168 property and the ˇ value is 3.4 times greater than that of urea. as the exploring X-ray beam. The specimen crystal is aligned in the 197
169 The electron donor highest occupied molecular orbital (HOMO) (+,−,−,+) configuration. Due to dispersive configuration, though the 198
170 and the electron acceptor important lowest unoccupied molecular lattice constant of the monochromator crystal(s) and the specimen 199
171 orbital (LUMO) are very important parameters for quantum chem- are different, the unwanted dispersion broadening in the diffraction 200
172 istry [16]. The energies of the HOMO and LUMO are computed at curve (DC) of the specimen crystal is insignificant. The specimen 201
173 the B3LYP/6-311++G(d,p) basis set. The HOMO and LUMO orbitals can be rotated about the vertical axis, which is perpendicular to the 202
174 are shown in Fig. 7. The positive and negative phases are repre- plane of diffraction, with minimum angular interval of 0.4 arcs. The 203
175 sented in red and green color, respectively. The HOMO and LUMO rocking or diffraction curves were recorded by changing the glanc- 204
176 delocalized over the whole molecule and the calculated energy gap ing angle (angle between the incident X-ray beam and the surface of 205
177 of HOMO–LUMO explains the ultimate charge transfer within the the specimen) around the Bragg diffraction peak position ␪B (taken 206
178 molecule. The eigen values of HOMO–LUMO and their energy gap as zero for the sake of convenience) starting from a suitable arbi- 207
179 reflect the chemical activity of the molecule. The chemical potential trary glancing angle and ending at a glancing angle after the peak 208
180 (V), hardness (), and the electrophilicity index (ω) are quite suc- so that all the meaningful scattered intensities on both sides of the 209
181 cessful in providing qualitative chemical concepts of the molecules. peak include in the diffraction curve. The DC was recorded by the 210
182 The chemical hardness [17,18] is defined as the second derivative so-called ␻ scan wherein the detector was kept at the same angu- 211
183 of the electronic energy with respect to the number of electrons for lar position 2␪B with wide opening for its slit. This arrangement is 212

very appropriate to record the short range order scattering caused 213

Table 5 by the defects or by the scattering from local Bragg diffractions from 214
The hyperpolarizability components of PP. agglomerated point defects or due to low angle and very low angle 215

ˇxxx 4.14486 × 10−30 structural grain boundaries [20]. Before recording the diffraction 216

ˇxyy 8.60264 × 10−31 curve to remove the non-crystallized solute atoms remained on 217
ˇxzz 2.86739 × 10−31 the surface of the crystal and the possible layers which may some- 218
ˇyyy −8.32111 × 10−31 times form on the surfaces on crystals grown by solution methods 219
ˇyzz 2.89465 × 10−31
ˇxxy 1.28559 × 10−30
[21] and also to ensure the surface planarity, the specimen was 220

ˇzzz −1.68886 × 10−31 first lapped and chemically etched in a non-preferential etchant of 221

ˇxxz −5.28532 × 10−32 water and acetone mixture in 1:2 volume ratio. 222
ˇyyz 5.53971 × 10−32 Fig. 8 shows the high resolution X-ray diffraction curve recorded 223
ˇyyz −3.97106 × 10−33
for (3 1 2) diffraction planes using MoK␣1 radiation for a typical PP 224

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Fig. 8. High resolution X-ray diffraction curve of PP. Fig. 9. 1

H proton NMR spectrum of PP.

225 single crystal specimen. On careful observation, the curve does not
226 seem to be a single peak. The solid line (convoluted curve) is well 7. Optical properties 270

227 fitted with the experimental points represented by the filled cir-
228 cles. On deconvolution of the diffraction curve, it is clear that the Linear optical properties of the crystals were studied using a 271

229 curve contains an additional peak, which is 18 arcs away from the PerkinElmer Lambda 35 UV–vis–NIR spectrometer in the region 272

230 higher intensity peak. The additional peak corresponds to an inter- 200–1100 nm. The crystal with thickness of about 1.5 mm was used 273

231 nal structural very low angle boundary. For a better understanding, for this study. The transparent behavior of the grown crystal was 274

232 the schematic of a structural grain boundary is given in the inset illustrated in Fig. 10. From the recorded spectrum, it is observed 275

233 of Fig. 8. As seen in the inset two regions of the crystal are misori- that PM crystal has transmission of above 70% up to 1100 nm. The 276

234 ented by a finite angle ˛ also known as tilt angle. Tilt angle may PP crystal is active in the UV–vis–NIR region and the compound 277

235 be defined as the misorientation angle between the two crystalline material could be a viable alternative for optical materials in that 278

236 regions on both sides of the structural grain boundary. The two entire region. 279

237 regions may be perfect. If the value of ˛ is ≤1 arcmin, we may call

238 it as very low angle boundary. If ˛ > 1 arcmin but less than a deg,
239 we call it as low angle boundary. For more details of such structural 8. Microhardness 280

240 grain boundaries including their effect on physical properties, ref-

241 erence is made available elsewhere [22,23]. The angular separation Microhardness The structure and molecular composition of 281

242 between the two peaks gives the tilt angle ˛ which is 18 arcs for crystals greatly influence on mechanical properties. Microhardness 282

243 the specimen crystal as seen in the figure. The FWHM (full width at measurement was carried out on as-grown flat face of PP crystal 283

244 half maximum) of the main peak and the low angle boundary are, using Leitz–Weitzlar hardness tester fitted with a Vickers’ diamond 284

245 respectively, 7 and 13 arcs. These relatively lower values reveal the indenter. Hardness of the material is a measure of the resistance 285

246 fact that both the regions of the crystal are quite perfect. These types and it offers to local deformation [25]. The Vickers’ hardness num- 286

247 of structural defects are probably generated in the crystals due to ber (Hv ) was calculated from the relation [26], Hv = 1.8544 (P/d2 ) 287

248 strains developed in the crystals may be by impurities or dopants kg/mm2 , where P is the applied indenter load in kg and d is the 288

249 which might have segregated along the boundaries. It may be men- average diagonal length of the impression in mm. The variation of 289

250 tioned here that such minute defects could be detected with well hardness (Hv ) with load (P) ranging from 5 to 30 g on the flat sur- 290

251 resolved peaks in the diffraction curve only because of the high- face of crystal is shown in Fig. 11. This type of behavior wherein 291

252 resolution of the diffractometer, characterized by very low values the hardness number increases with increase in applied load and 292

253 of wavelength spread i.e. / and horizontal divergence for the is called reverse indentation size effect. 293

254 exploring or incident beam, which are, respectively, around 10–5

255 and much less than 3 arcs of the multicrystal X-ray diffractome-
256 ter used in the present studies. The influence of such defects may
80
257 not influence much on the NLO properties. However, a quantitative
258 analysis of such defects is of great importance, particularly in case 70

259 of phase matching applications as explained in our recent article

60
[24].
Transmittance (%)

260
50

261 6. NMR 40

30
262 The 1 H NMR spectrum of PP is shown in Fig. 9. The spectrum con-
263 tains five prominent signals indicating the presence of five different 20
264 proton environments. The intense signal appears around 4.7 ppm is
10
265 due to the fast deuterium ion exchange of D2 O. The protons ortho to
266 carboxylic group and ortho to nitrogen of picolinium moiety yielded 0
200 400 600 800 1000 1200
267 the signals at 8.6 and 8.7 ppm, respectively. The protons meta and
wavelength(nm)
268 para to nitrogen atom of picolinium moiety yielded the signals at
269 8.0 and 8.3 ppm, respectively. Fig. 10. UV–vis transmittance spectrum of PP crystal.

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100 70
solvent. Single crystal structure X-ray diffraction study of the 308

TGA
crystal reveals that the crystal belongs to monoclinic system with 309
DTA 60
80
space group P21 /c. In the crystal, the cations and the anions are 310

linked into chains along the (0 1 0) direction by N H· · ·O hydrogen

weight percentage(%)

50 311

Heat flow (mV)

bonds and these chains are cross linked by C H· · ·O hydrogen 312
60 40
bonds forming a two dimensional network lying parallel to (1 0 1) 313

30 resulting the formation supramolecular structure. The result 314

40 obtained from computational studies is compared with single 315
20
crystal X-ray diffraction analysis. The calculated first hyperpo- 316

20 10 larizability of PP is 2.6439 × 10−30 e.s.u. The proton NMR spectral 317

analyzes verify the identity and expected chemical structure of 318

0
0
the PP grown crystals. Thermal studies revealed that PP crystals 319
100 200 300 400 500 were stable up to 245 ◦ C. Mechanical strength was analyzed using 320
o
Temperature ( C)
Vickers micro hardness measurements. 321

Fig. 11. TGA and DTA curve of PP.

Appendix A. Supplementary data 322

50
Supplementary data associated with this article can be found, in 323

the online version, at http://dx.doi.org/10.1016/j.ijleo.2016.01.140. 324

40
Hardness number (Hv)(Kg/mm )
2

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30
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307 The picolinium perchlorate single crystals were synthesized

and grown using slow evaporation technique with water as a

Please cite this article in press as: A. Arunkumar, et al., Structure, growth and characterization of picolinium perchlorate single crystals,
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