Third order nonlinear optical and electrical properties of new 2-aminopyridinium 2-chloro 4-nitrobenzoate single crystals

Accepted Manuscript Title: Third order nonlinear optical and electrical properties of new 2-aminopyridinium 2-chloro 4-nitrobenzoate single crystals Author: L. Chandra J. Chandrasekaran K. Perumal B. Babu PII: DOI: Reference:

S0030-4026(15)02001-X http://dx.doi.org/doi:10.1016/j.ijleo.2015.12.092 IJLEO 57030

To appear in: Received date: Accepted date:

5-7-2015 5-12-2015

Please cite this article as: L. Chandra, J. Chandrasekaran, K. Perumal, B. Babu, Third order nonlinear optical and electrical properties of new 2-aminopyridinium 2-chloro 4-nitrobenzoate single crystals, Optik - International Journal for Light and Electron Optics (2015), http://dx.doi.org/10.1016/j.ijleo.2015.12.092 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 proof before it is published in its final 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.

Third order nonlinear optical and electrical properties of new 2-aminopyridinium 2-chloro 4-nitrobenzoate single crystals L. Chandraa, J. Chandrasekaranb, *, K. Perumalb, B. Babub a

Department of Physics, Chikkaiah Naicker College, Erode – 638 004, Tamil Nadu, India. Department of Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore – 641 020, Tamil Nadu, India. *Corresponding author: Ph: +91-422-2692461, Fax: +91-422-2692676 E-mail address: [email protected] (J. Chandrasekaran)

cr

ip t

b

ABSTRACT New organic single crystals of 2-aminopyridinium 2-chloro 4-nitrobenzoate

us

(2AP2CL4N) were grown by the slow evaporation technique at room temperature. Single crystal XRD confirmed that the crystal belongs to the triclinic system with the space group P1. Various

an

functional groups present in the compound were confirmed by the FT-IR spectral analysis. UVVis studies showed that the crystal has a lower cutoff wave length at 399 nm. Dielectric studies were carried out at various temperatures. Nonlinear absorption coefficient (β), nonlinear were also evaluated for the grown crystal.

M

refraction (n2) and third order susceptibility

1.

ed

Keywords: Crystal growth, Nonlinear optics, X-ray diffraction, Z-scan.

Introduction

The recent research on organic non-linear optical materials has shown that they have

pt

more advantages over the inorganic non-linear optical materials with regard to scientific and technical applications. These materials offer applications in high density optical data storage,

Ac ce

color display, photonics, electro-optical amplitude modulation, ultra compact lasers, optical switching, optical logic, frequency shifting and optical parametric generation [1-5]. Compared to inorganic

materials, organic

materials possess

high

laser

damage

threshold, large

hyperpolarizability (β) and fast response to electro-optic devices, ease of device fabrication and flexibility of molecular design via proper synthetic method [6-10]. In particular, π-conjugated systems linking a donor (D) and acceptor (A) show a large NLO response and have been intensively investigated [11-13]. 2-aminopyridine is an organic heterocyclic molecule which is often used as a ligand in a metal complex and also as a model compound for understanding nucleic acid bases. Previously 2-aminopyridine–acid based crystals were grown by the slow evaporation technique and their properties were reported [14, 15]. Based on these facts in the 1

Page 1 of 21

present investigation for the first time 2-aminopyridinium was mixed with 2-chloro 4nitrobenzoic acid and their structural, spectral, optical, electrical and third order nonlinear optical properties are reported.

2.1.

Experiment

ip t

2.

Crystal growth

2AP2CL4N crystals were grown by the slow evaporation solution growth technique at

cr

room temperature. 2-aminopyridinium (GR grade, Himedia) and 2-chloro 4-nitrobenzoate (GR grade, Aldrich) were taken in 1:1 molar ratio dissolved separately in methanol and stirred well

us

for about 20 minutes. The solutions were mixed together and stirred for half an hour. To remove unsolvable impurities, the prepared solution was filtered using the Whatmann filter paper (No.

an

42 Grade) transferred to a crystallizing vessel and covered with a good quality perforated polythene sheet. This saturated solution was allowed to evaporate at room temperature. After two weeks good quality crystals were obtained from the mother solution. Fig. 1 depicts the quality of

3. Results and discussion 3.1. X-ray diffraction studies

ed

M

the crystals.

The single crystal X-ray data for the title compound were collected at room temperature

pt

using the Enraf–Nonius CAD4 diffractometer with MoKα radiation, λ = 0.71073 Å, graphite monochromator. A suitable prismatic crystal was selected for X-ray diffraction and mounted on

Ac ce

the goniometer. Cell refinement and data reduction were carried out using CAD-4 EXPRESS [16] and XCAD4 [17]. The intensities were corrected for Lorentz and polarization effects. The structure was solved by direct methods as implemented in the SHELXS-97 [18] program. The position of all the non-hydrogen atoms was included in the full-matrix least squares refinement using the SHELXL-97 [18] program. The molecular graphics were depicted by the program ORTEP-3 for windows [19] and MERCURY (version 1.4.1) [20]. All the hydrogen atoms were placed in geometrically calculated positions and included in the refinement in the riding model approximation with Uiso (H) equal to 1.2 Ueq of the carrier atom. The crystal data and details pertaining to data collection and the structure refinement are given in Table 1. Selected bond lengths and bond angles are presented in Table 2. The hydrogen bond data is presented in Table 2

Page 2 of 21

3. Fig. 2 shows the ORTEP view of the molecule drawn at 50% probability thermal displacement ellipsoids with the atom numbering scheme. The crystal was formed by the proton transfer reaction between 2-aminopyridine and 2-chloro-4-nitrobenzoic acid molecules. The asymmetric unit of the title compound (C5 H7 N2+. C7 H3 N Cl O4-) consists of a 2-aminopyridinium cation

ip t

and a 2-chloro-4-nitrobenzoate anion. Protonation occurred at the N1 atom of the pyridine ring in the 2-aminopyridine molecule, which leads to the formation of cation and the anion. It is due to the loss of one H atom at the carboxyl group in the 2-chloro-4-nitrobenzoic acid. This was

cr

confirmed by the variations of the carboxyl C__O bond’s distance (d(C12 O1) = 1.245(2) Å,

us

d(C12 O2) = 1.240(2) Å). Variation of these bond length values denotes that the negative charges located on the carboxylate O atoms are delocalized. The molecular configuration of the cation is quite similar to that of the 2-aminopyridine molecule in the complex of 2-

an

aminopyridinium norcantharidate [21]. The 2-aminopyridinium cation and 2-chloro-4nitrobenzoate anion were essentially planar, with maximum deviations of 0.010 (1) Å and 0.29

M

(2) Å, respectively. The cation and anion were deviated with a dihedral angle of 55.90 (6)º. The angle between the plane of the ring and the plane determined by the NO2 group in the anion was 9.70 (3)°. The carboxylate group was twisted at an angle of 40.73 (2)º from the plane of the

ed

anion. In crystal packing the protonated N1 atom and the amino group N2 atom at the cation is hydrogen bonded to the carboxylate oxygen atoms (O1 and O2) at the anion via a pair of N— (8) ring motif [22]. The same type of ring

pt

H···O intermolecular hydrogen bonds forming a

motif was observed in the 2-aminopyridinium 3-aminobenzoate crystal structure [23]. The

Ac ce

crystal structure of the title compound was stabilized by the N__H…O and weak C__H…O intermolecular hydrogen bonds. The powder XRD spectrum of 2AP2CL4N were carried out by using the RICH SIEFERT X-ray powder diffractometer using CuKα (λ = 1.5405 Å) radiation. The grown crystals were finely crushed into powder and then subjected to analysis. The sample was scanned over the 2θ range of 5-90◦ with the rate of 3◦/min. Fig. 3 shows the recorded powder XRD spectrum of the 2AP2CL4N. A well defined sharp peak at the specific 2θ angle verified the crystalline nature of the compound. For the title crystal the maximum intensity was observed at 3566 counts per second. The hkl values were indexed by using the TREOR 90 programme. 3.2.

FT-IR studies

3

Page 3 of 21

The FT-IR spectrum of the 2AP2CL4N sample was scanned in the frequency region of 400-4000 cm-1 using a JASCO-FT/IR 5300 infrared spectrometer by employing the KBr pellet technique with a resolution of 4.0 cm-1. The IR spectrum of 2AP2CL4N is presented in Fig. 4. Vibrations at 3698 and 3103 cm-1 were assigned to OH and N+-H stretching vibrations. The

ip t

absorption bands at 1593 and 1382 cm-1 correspond to the asymmetric and symmetric stretching vibrations of the COO- group. Aromatic CH stretching vibration appears at 2571 and 2777 cm-1 respectively. Vibrations at 625 and 543 cm-1 were assigned to NH2 and C-N-C out of the plane

cr

bending vibration. C-C and CH out of the plane bending vibrations were observed at 813 and 737 cm-1. The bands at 737 and 664 cm-1 were due to the C-Cl vibrations. The band at 737 cm-1 is

us

due to the CH out of the plane bending vibration. The peaks at 1382, 1526 and 1593 cm-1 were attributed to the aromatic C=C stretching vibration. C-N stretching mode appeared at 1247 cm-1.

an

OH out of plane deformation and NH out of plane bending vibrations were exhibited at 625 and

3.3.

Optical transmittance studies

M

675 cm-1.

The optical transmittance spectra of the grown crystals were taken using the Perkin-Elmer

ed

lambda 35 spectrophotometer in the wavelength range of 200-1100 nm. Fig. 5a shows the recorded spectrum of the title crystal. The lower cut-off wavelength of the crystal occurred at 399 nm. From the figure it is observed that the crystal is highly transparent in the entire visible

pt

region. The absence of absorption in the region between 400 to 1100 nm is one of the most desirable properties of the crystal for the fabrication of optoelectronic devices [24, 25]. The

Ac ce

optical absorption coefficient (α) is evaluated by the following relation,

where T is the measured transmittance of the sample and t the thickness of the sample. The optical band gap (Eg) is estimated from the transmittance spectra and the optical absorption coefficient near the absorption edge is given by

where A is a proportional constant, h the plank’s constant, υ the frequency of the incident photons and Eg the optical band gap of the crystal. Eg is obtained by the extrapolation of the linear part (Fig. 5b). The estimated band gap is about 2.93eV. 4

Page 4 of 21

3.4.

Dielectric studies The dielectric characteristics of the material are important to study the lattice dynamics

ip t

in the crystal. Hence the grown crystals were subjected to dielectric studies using an LCR meter (HIOKI 3532-50). Studies were carried out in the frequency range 50Hz to 5MHz at various

cr

temperatures. The dielectric constant of the crystals was calculated using the given formula,

crystal and

us

where C is the capacitance and d the thickness of the sample, A the cross sectional area of the the free space permitivity (8.854 x 10-12 F/m). Fig. 6a illustrates the dielectric

an

constant versus log frequency for the grown crystal. The dielectric constant had higher value in the lower frequency region and then it decreased with the applied frequency. The very high at low frequency enumerated the presence of space charge, orientation, electronic

and ionic polarizations. The low value of

M

values of

at higher frequencies might be due to the loss of

significance of these polarizations gradually [16]. The variation of dielectric loss with frequency

ed

is shown in Fig. 6b. The lower value of dielectric loss at high frequency suggests that the sample possesses better optical quality with low defect density. Hence the grown 2AP2CL4N can be

TG-DTA studies

Ac ce

3.5.

pt

useful for microelectronics industries.

In order to study the thermal stability of the grown crystal, thermo gravimetric (TG) and differential thermal analyses were carried out using an STA 1500 thermal analyzer in the temperature range of 30oC to 500oC in a nitrogen atmosphere at a heating rate of 10 °C min-1. Fig. 7 shows the TG-DTA curves of the 2AP2CL4N crystal. From the plot it is observed that the thermal decomposition of the 2AP2CL4N has taken place in two stages. The TG curve shows the first weight loss at 168oC and beyond 100°C no obvious weight loss is observed. This confirms the absence of water molecules during the crystallization. In DTA the sharp endothermic peak at 170°C corresponds to the melting point of the crystal and weight loss in this stage is 8%. The sharp endothermic peak exhibits a good degree of crystallinity of the sample. In TG the second weight loss observed at 265oC is attributed to the liberation of pyridine fragments. The second 5

Page 5 of 21

stage shows a weight loss of about 78.4%. The same is confirmed from the DTA curve. In addition, it is important to note that the title compound has no phase transition till the substance reaches its melting point. From the results it is concluded that 2AP2CL4N may be useful for

ip t

fabricating NLO devices below its melting point. 3.6. Z-scan studies

The single beam Z-scan technique is a simple, highly sensitive and accurate method for

cr

the determination of both the nonlinear refractive index (n2) and nonlinear absorption coefficient (β). The greatest advantage of this method is that it was possible to measure both the magnitude

us

and sign of the nonlinear refractive index and the nonlinear absorption coefficient of the samples simultaneously [26]. The nonlinear refractive index is proportional to the real part of the third-

an

order susceptibility whereas the nonlinear absorption coefficient is proportional to the imaginary part. The experiments were performed using the single beam Z-scan technique with He-Ne laser (632.8 nm) at a repetition rate of 1 KHz as the excitation source. In this study, the sample

M

translated in the Z-direction along the axis of a focused Gaussian beam and the far field intensity was measured as a function of the sample position. Fig. 8a and 8b show the normalized

ed

transmittance T with the open and closed aperture as a function of distance Z along the lens axis in the far field. The transmittance difference between the peak and valley transmittances (ΔT p-

pt

v), as a function of │Δф│ is given by

Ac ce

where Δф is the on axis phase shift at the focus and S the linear aperture transmittance. It is calculated by the given relation

where ra is the radius of aperture and ⍵a the beam radius at the aperture. The third order

nonlinear refractive index (n2) is evaluated by the following relation

6

Page 6 of 21

where k=2π/λ, λ is the wavelength of the laser, Io the on-axis irradiance at the focus (Z=0) and

ip t

Leff the effective thickness of the sample.

where α is the linear absorption coefficient and L the thickness of the sample. Nonlinear optical

us

cr

absorption coefficient (β) is evaluated by using the open aperture curve

The real and imaginary parts of the third order nonlinear optical susceptibility are determined

M

an

from the experimental determination of n2 and β according to the following relations

ed

where ɛ˳ is the vacuum permittivity and C the velocity of light in vacuum. The absolute value of

pt

is obtained from the following relation

The estimated nonlinear refractive index, nonlinear absorption coefficient and third order

Ac ce

susceptibility values of 2AP2CL4N are 2.94x10-08 cm/W, 0.000112 cm2/W and 8.52x10-08 esu. As the material reveals the positive refractive index, it results in self-focusing nature and exhibits the two-photo absorption process. This is one of the essential parameters for optical limiting applications [26].

4. Conclusion

New organic single crystals of 2-aminopyridinium 2-chloro 4-nitrobenzoate were grown by the slow evaporation solution growth technique at room temperature. The single crystal XRD analysis confirmed that the crystal belongs to the triclinic system with the space group P1. The crystallinity nature of the compound was confirmed by the powder XRD analysis. The functional groups present in the system were confirmed through the FT-IR analysis. The optical 7

Page 7 of 21

transmittance study revealed the wide transparency in the entire visible region. Dielectric constant and loss values were found to show normal dielectric behavior with lower values at higher frequencies. TG-DTA studies confirmed that title compound is stable up to 170°C. Z-scan

cr

ip t

studies revealed the two photon absorption with the self-focusing nature of the crystal.

Acknowledgments

us

The authors gratefully acknowledge the financial support from the DST, Government of India, for the major research project (SB/EMEQ-293/2013). They also thank Prof. D.

an

Sastikumar, NIT, Trichy, for extending Z-scan facilities.

References

A. Senthil, P. Ramasamy, Investigation on the SR method growth, etching, birefringence,

M

[1]

laser damage threshold and thermal characterization of strontium bis (hydrogen L-malate) [2]

ed

hexahydrate single crystal, J. Cryst. Growth 401 (2014) 200-204. B. Babu, J. Chandrasekaran, S. Balaprabhakaran, Growth, structural, spectral, optical and electrical properties of 2-aminophenol single crystals, Optik 125 (2014) 3005-3008. S. Senthil, S. Pari, P. Sagayaraj, J. Madhavan, Studies on the electrical, linear and

pt

[3]

nonlinear optical properties of Meta nitroaniline, an efficient NLO crystal, Physica B 404 [4]

Ac ce

(2009) 1655-1660.

P. Geetha, S. Krishnan, R.K. Natarajan, V. Chithambaram, Growth and characterization of semi organic nonlinear optical l-Valine Ferric Chloride single crystal by solution growth technique, Current Applied Physics 15 (2015) 201-207.

[5]

Tianliang Chen, Zhihua Sun, Lina Li, Shuyun Wang, Yan Wang, JunhuaLuon, Maochun Hong,

Growth

and

characterization

of

a

nonlinear

optical

crystal—2,6-

diaminopyridinium 4-nitrophenolate 4-nitrophenol (DAPNP), J. Cryst. Growth 338, (2012) 157-161.

8

Page 8 of 21

[6]

G. Shanmugam, S. Brahadeeswaran, Spectroscopic, thermal and mechanical studies on 4methylanilinium

p-toluenesulfonate

–

a

new

organic

NLO

single

crystal,

Spectrochim. Acta A: Mol. Biomol. Spectrosc, 95 (2012) 177-183. [7]

L. Guruprasad, V. Krishnakumar, R. Nagalakshmi, S. Manohar, Physicochemical

ip t

properties of highly efficient organic NLO crystal: 4-Aminobenzamide, Mater. Chem. Phys. 128 (2011) 90-95. [8]

P. Krishnan, K. Gayathri, N. Sivakumar, S. Gunasekaran, G. Anbalagan, Nucleation

cr

kinetics, growth, crystalline perfection, mechanical, thermal, optical and electrical characterization of brucinium 2-carboxy-6-nitrophthalate dihydrate single crystal, J. [9]

us

Cryst. Growth 396 (2014) 85-94.

AmirdhaSher Gill, S. Kalainathan, Thermal, optical, mechanical and dielectric properties Phys. Chem. Solids 72 (2011) 1002-1007.

[10]

an

of nonlinear optical crystal 4-methoxy benzaldehyde-N-methyl 4-stilbazolium tosylate, J. D. Joseph Daniel, P. Ramasamy, Studies on the nonlinear optical single crystal:

[11]

M

Ammonium D,L-tartrate (C4H9NO6) Mater. Res. Bull. 47 (2012) 708-713. G. Anandha Babu, P. Ramasamy, Studies on the growth and physical properties of 46 (2011) 631-634. [12]

ed

nonlinear optical crystal: 2-Amino-5-nitropyridinium-toluenesulfonate, Mater. Res. Bull. S. Janarthanan, R. Sugaraj Samuel, S. Selvakumar, Y.C. Rajan, D. Jayaraman and S.

pt

Pandi, Growth and Characterization of Organic NLO Crystal: β-Naphthol, J. Mater. Sci. Technol. 27 (2011) 271-274.

S. Balaprabhakaran, J. Chandrasekaran, B. Babu, R. Thirumurugan, K. Anitha, Synthesis,

Ac ce

[13]

crystal growth and physiochemical characterization of organic NLO crystal: Lornithiniumdipicrate (LODP), Spectrochim. Acta A: Mol. Biomol. Spectrosc, 136 (2015) 700-706. [14]

P.V. Dhanaraj, N.P. Rajesh, G. Vinitha, G. Bhagavannarayana, Crystal structure and characterization of a novel organic optical crystal: 2-Aminopyridinium trichloroacetate, Mater. Res. Bull. 46 (2011) 726-731.

[15]

P.V. Dhanaraj, N.P. Rajesh, G. Bhagavannarayana, Synthesis, crystal growth and characterization of an organic NLO material: Bis(2-aminopyridinium) maleate, Physica B, 405 (2010) 3441-3445. 9

Page 9 of 21

[16]

Enraf-Nonius, CAD-4 EXPRESS Version 5.1/1.2., 1994, Enraf-Nonius, Delft, The Netherlands.

[17]

A.C.T. North, D.C. Phillips & F.S. Mathews, A semi-empirical method of absorption correction, Acta Cryst. Sect. A 24 (1968) 351-359. G.M. Sheldrick, SHELXL97 and SHELXS97, 1997, University of Gottingen, Germany.

[19]

L.J. Farrugia, WinGX Suite for Single Crystal Small Molecule Crystallography, J. Appl.

ip t

[18]

Cryst. B 32 (1999) 837-838.

C.F. Macrae, P.R. Edington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.

cr

[20]

Towler& J. Van de Streek, Mercury: visualization and analysis of crystal structures, J. [21]

us

Appl. Cryst. 39 (2006) 453-457.

Qiu-Yue Lin, Wen-Zhong Zhu, Jian-Ping Cheng and Hong Su, Crystal structure of 2-

an

aminopyridinium norcantharidate,(C5H7N2)(C8H9O5), Z. Kristallogr. NCS 222 (2007) 445-446. [22]

J. Bernstein, R.E. Davis, L. Shimoni, & N.L. Chang, Patterns in Hydrogen Bonding:

M

Functionality and Graph Set Analysis in Crystals, Angew. Chem. Int. Ed. Engl. 34 (1995) 1555-1573.

S. Banerjee, R. Murugavel, Formation of One-Dimensional Water Inside an Organic

ed

[23]

Solid:  Supramolecular Architectures Derived by the Interaction of Aminobenzoic Acids with Nitrogen Bases and H2SO4, Cryst. Growth Des. 4 (2004) 545-552. B. Babu, J. Chandrasekaran, S. Balaprabhakaran, Growth and characterization of

pt

[24]

hexamethylenetetramine crystals grown from solution, Mater. Sci-Pol. 32 (2014) 164[25]

Ac ce

170.

S. Gowri, T. Uma Devi, D. Sajan, S.R. Bheeter, N. Lawrence, Spectral, thermal and optical properties of adenosinium picrate: A nonlinear optical single crystal, Spectrochim. Acta AMol. Biomol. Spectrosc, 89 (2012) 119-122.

[26]

Mansoor Sheik-Bahae, Ali A. Said, Tai-Huei Wei, David J. Hagan, and E.W. Van Stryland, Sensitive Measurement of Optical Nonlinearities Using a Single Beam, IEEE J Quantum Electron. 26 (1990) 760-769.

10

Page 10 of 21

ip t cr us an

Figure captions Fig. 1. Grown 2AP2CL4N crystals.

M

Fig. 2. ORTEP view of the 2AP2CL4N crystal structure. Fig. 3. Powder XRD spectrum of 2AP2CL4N. Fig. 4. FT-IR spectrum of 2AP2CL4N.

ed

Fig. 5(a). Optical transmittance spectrum of 2AP2CL4N and (b). (αhv)2 Vs hv. Fig. 6(a). Dielectric constant Vs Log f at 303, 333, and 363 K and (b). Dielectric loss Vs log f at

pt

303, 333, and 363 K.

Fig. 7. TG-DTA spectrum of 2AP2CL4N.

Ac ce

Fig. 8(a). Normalized transmittance with open aperture as a function of Z position and (b). Normalized transmittance with closed aperture as a function of Z position. Table Captions

Table 1 Crystal data and structure refinement results for 2AP2CL4N. Table 2 Selected bond lengths (Å) and angles (°) in the 2AP2CL4N crystal structure. Table 3 Selected hydrogen bond geometries (Å and °) in the 2AP2CL4N crystal structure.

11

Page 11 of 21

M

an

us

cr

ip t

Fig. 1 and 3

te

d

Fig. 1

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

12 Page 12 of 21

te

d

M

an

us

cr

ip t

Fig. 2.

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

13 Page 13 of 21

te

d

M

an

us

cr

ip t

Fig. 4.

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

14 Page 14 of 21

te

d

M

an

us

cr

ip t

Fig. 5a and 5b

Fig. 5b

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

15 Page 15 of 21

Fig. 6b

te

d

M

an

us

cr

ip t

Fig. 6a and 6b

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

16 Page 16 of 21

an

us

cr

ip t

Fig. 7.

8 .0 %

0 .0 0

1 2 0 .0

1 0 0 .0

M

7 8 .4 %

- 1 0 .0 0

8 0 .0

6 0 .0

d

- 2 0 .0 0

te

1 7 0 .6 C e l - 2 1 .5 8 u V

- 3 0 .0 0

4 0 .0

1 8 .3 %

2 0 0 .0

2 0 .0

0 .0

- 4 0 .0 0

1 0 0 .0

TG %

2 6 5 .3 C e l -9 .2 9 u V

Ac ce p

DTA uV

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

- 2 0 .0 3 0 0 .0 Te m p C el

4 0 0 .0

17 Page 17 of 21

te

d

M

an

us

cr

ip t

Fig. 8a and 8b

Fig. 8b

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

18 Page 18 of 21

Table 1 C12 H10 Cl N3 O4

Formula weight

295.68

Temperature

293(2) K

Wavelength

0.71069 Å

Crystal system, space group

Triclinic, P1Y a = 5.725(1) Å b = 10.590(2) Å c = 11.290(4) Å

Volume

657.1(7) Å3

Z, Calculated density

2, 1.494 Mgm-3

Absorption coefficient

0.308 mm-1

an

M 304

d

F000

1.87 to 26.47 θ

te

θ range for data collection Limiting indices

α = 95.952(5) º β = 103.739(3) º γ = 94.802(6) º

us

Unit cell dimensions

cr

ip t

Empirical formula

-7ZhZ7, -13ZkZ12, -14ZlZ14

Reflections collected / unique

9863 / 2702 [Rint= 0.0279]

Completeness to θ = 26.47 º

99.2 %

Refinement method

Full-matrix least-squares on F2

Data / restraints / parameters

2702 / 0 / 222

Goodness-of-fit on F2

1.041

Final R indices [I>2σ(I)]

R1 = 0.0332, wR2 = 0.0892

R indices (all data)

R1 = 0.0386, wR2 = 0.0942

Extinction coefficient

0.060(5)

Largest diff. peak and hole CCDC No

0.183 and -0.260 e.Å-3 1017899

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

19 Page 19 of 21

cr us an M d

1.7350(16) 1.245(2) 1.240(2) 1.3454(19) 1.353(2) 1.218(2) 1.218(2) 1.321(2) 1.4744(19) 1.383(2) 1.391(2) 1.391(2) 1.5201(19) 1.372(2) 1.413(2) 1.381(2) 1.373(2) 1.351(2) 1.396(3) 1.353(3) 122.89(13) 124.13(15) 118.00(15) 117.86(15) 121.78(13) 116.21(11) 121.95(11) 117.43(12) 125.04(12) 117.54(12) 118.13(13) 118.36(14) 124.09(14) 117.55(13) 122.07(14) 122.69(13) 118.14(14) 119.16(14) 121.10(16) 117.87(14) 125.73(13) 118.74(11) 115.49(12) 120.50(15) 118.32(15) 119.61(15)

te

Cl(1)-C(7) O(1)-C(12) O(2)-C(12) N(1)-C(1) N(1)-C(5) O(3)-N(3) O(4)-N(3) N(2)-C(1) N(3)-C(9) C(7)-C(8) C(7)-C(6) C(6)-C(11) C(6)-C(12) C(8)-C(9) C(1)-C(2) C(11)-C(10) C(9)-C(10) C(3)-C(2) C(3)-C(4) C(5)-C(4) C(1)-N(1)-C(5) O(4)-N(3)-O(3) O(4)-N(3)-C(9) O(3)-N(3)-C(9) C(8)-C(7)-C(6) C(8)-C(7)-Cl(1) C(6)-C(7)-Cl(1) C(7)-C(6)-C(11) C(7)-C(6)-C(12) C(11)-C(6)-C(12) C(9)-C(8)-C(7) N(2)-C(1)-N(1) N(2)-C(1)-C(2) N(1)-C(1)-C(2) C(10)-C(11)-C(6) C(8)-C(9)-C(10) C(8)-C(9)-N(3) C(10)-C(9)-N(3) C(2)-C(3)-C(4) C(9)-C(10)-C(11) O(2)-C(12)-O(1) O(2)-C(12)-C(6) O(1)-C(12)-C(6) N(1)-C(5)-C(4) C(5)-C(4)-C(3) C(3)-C(2)-C(1)

ip t

Table 2 _____________________________________

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

_________________________________________________ 20 Page 20 of 21

d (D_H) (Å)

d (H…A) (Å) d (D…A) (Å) < (DHA) (°)

N1_H1…O2i 0.869(2) N2_H2…O1 i 0.896(2) N2_H3…O1 ii 0.888(4)

1.885(2) 1.908(5) 2.076(2)

2.743(4) 2.803(3) 2.821(2)

169.23(2) 176.36(2) 140.81(2)

us

cr

D_H…A

ip t

Table 3

te

d

M

an

Symmetry codes: (i) x,y,z (ii) -x+2,-y+1,-z+1

Ac ce p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

21 Page 21 of 21