Crystal structure and Hirshfeld surface analysis of methyl 1-(2,4-dichlorobenzyl)-5-methyl-1H-pyrazole-3-carboxylate European Journal of Chemistry 9 (4) (2018) 347-352 European Journal of Chemistry View Journal Online View Article Online Crystal structure and Hirshfeld surface analysis of methyl 1-(2,4-dichlorobenzyl)-5-methyl-1H-pyrazole-3-carboxylate Abdullah Aydin 1,*, Mehmet Akkurt 2, Zehra Tugce Gur 3 and Erden Banoglu 3 1 Department of Mathematics and Science Education, Faculty of Education, Kastamonu University, 37200 Kastamonu, Turkey aaydin@kastamonu.edu.tr (A.A) 2 Department of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey akkurt@erciyes.edu.tr (M.A.) 3 Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Gazi University, 06330 Ankara, Turkey ztugcegur@gmail.com (Z.T.G.), ebanoglu@gmail.com (E.B.) * Corresponding author at: Department of Mathematics and Science Education, Faculty of Education, Kastamonu University, 37200 Kastamonu, Turkey. Tel: +90.366.2803310 Fax: +90.366.2123353 e-mail: aaydin@kastamonu.edu.tr (A. Aydin) 10.5155/eurjchem.9.4.347-352.1782 Received: 18 August 2018 Received in revised form: 16 September 2018 Accepted: 18 September 2018 Published online: 31 December 2018 Printed: 31 December 2018 The title compound, C13H12Cl2N2O2, crystallizes with six molecules in the asymmetric unit, such that, the 1H-pyrazole rings are essentially planar. The six molecules are stabilized by intramolecular C-H···N and C-H···Cl interactions and the crystal structure is stabilized by intermolecular C-H···O hydrogen bonds, forming molecular sheets into paralel to the (-1 1 0) plane. These sheets are connected to each other by C-H···O hydrogen bonds and C-H···π interactions. In the Hirshfeld surface analysis, the H···H, Cl···H/H···Cl, C···H/H···C, O···H/H···O, N···H/H···N, Cl···Cl, Cl···O/O···Cl interactions add to 95.8% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (2.9%) correspond to Cl···C/C···Cl, C···O/O···C, O···O and N···N interactions. Crystal Data for C13H12Cl2N2O2 (M = 299.15 g/mol): Triclinic, space group P-1 (no. 2), a = 12.0505(10) Å, b = 12.3189(11) Å, c = 29.184(3) Å, α = 88.565(4)°, β = 89.296(4)°, γ = 76.833(4)°, V = 4217.0(7) Å3, Z = 12, T = 296(2) K, μ(MoKα) = 0.460 mm-1, Dcalc = 1.414 g/cm3, 83073 reflections measured (2.8° ≤ 2Θ ≤ 47°), 12426 unique (Rint = 0.0411, Rsigma = 0.0235) which were used in all calculations. The final R1 was 0.0662 (I > 2σ(I)) and wR2 was 0.2481 (all data). Pyrazole ring Crystal structure Anticancer activity C—H···π interactions Hirshfeld surface analysis Antimycobacterial activity Cite this: Eur. J. Chem. 2018, 9(4), 347-352 Journal website: www.eurjchem.com 1. Introduction Pyrazole ring is a commonly found structural motif in bioactive compounds, and a large number of pyrazole deriva- tives with diverse pharmacological activities such as anti- inflammatory, antiplatelet, anticancer, antimycobacterial, anti- depressant and anticonvulsan activities have appeared in the literature [1-5]. In the last decade, we have reported a large series of pyrazole derivatives with promising antiinflammatory and anticancer activities, indicating the use of pyrazole core as a versatile tool for development of novel drug candidates with diverse biological activities [6-11]. In this work, we report the crystallographic characterization and Hirshfeld surface analysis of the methyl 1-[(2,4-dichlorophenyl)methyl]-5- methyl-1H-pyrazole-3-carboxylate (I), which is regiospeci- fically formed by benzylation of methyl 5-methyl-1H-pyrazole- 3-carboxylate (Scheme 1). N N O O Cl Cl Scheme 1 2. Experimental 2.1. Instrumentation Starting materials were purchased from commercial suppliers and used without further purification. 1H NMR and 13C NMR spectra were recorded on a Bruker Fourier 300 (Billerica, MA, USA) using tetramethylsilane as the internal standard. All chemical shifts were recorded as δ (ppm). ABSTRACT RESEARCH ARTICLE KEYWORDS European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2018 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. http://dx.doi.org/10.5155/eurjchem.9.4.347-352.1782 http://dx.doi.org/10.5155/eurjchem.9.4.347-352.1782 https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.9.4.347-352.1782&domain=pdf&date_stamp=2018-12-31 http://www.eurjchem.com/ http://dx.doi.org/10.5155/eurjchem.9.4.347-352.1782 mailto:aaydin@kastamonu.edu.tr mailto:akkurt@erciyes.edu.tr mailto:ztugcegur@gmail.com mailto:ebanoglu@gmail.com mailto:aaydin@kastamonu.edu.tr http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.9.4.347-352.1782&domain=pdf&date_stamp=2018-12-31� 348 Aydin et al. / European Journal of Chemistry 9 (4) (2018) 347-352 Table 1. Crystal data and structure refinement for the title compound. CCDC no 1843087 Empirical formula C13H12Cl2N2O2 Formula weight 299.15 Temperature (K) 296(2) Crystal system Triclinic Space group P-1 a (Å) 12.0505(10) b (Å) 12.3189(11) c (Å) 29.184(3) α (°) β (°) γ (°) Volume (Å3) 88.565(4) 89.296(4) 76.833( 4) 4217.0(7) Z 12 ρcalc (g/cm3) 1.414 μ (mm-1) 0.46 F(000) 1848 Crystal size (mm3) 0.83 × 0.74 × 0.48 Radiation MoKα (λ = 0.71073) 2Θ range for data collection (°) 2.80 to 47.00 Index ranges -13 ≤ h ≤ 13, -13 ≤ k ≤ 13, -32 ≤ l ≤ 32 Reflections collected 83073 Independent reflections 12426 [Rint = 0.0411, Rsigma = 0.0235] Data/restraints/parameters 12426/0/1039 Goodness-of-fit on F2 1.098 Final R indexes [I≥2σ (I)] R1 = 0.0662, wR2 = 0.2217 Final R indexes [all data] R1 = 0.1253, wR2 = 0.2481 Largest diff. peak/hole (e.Å-3) 0.76/-0.63 All coupling constants are reported as Hertz. High resolution mass spectra data (HRMS) were collected using Waters (Milford, MA, USA) LCT Premier XE Mass Spectrometer (high sensitivity orthogonal acceleration time-of-flight instrument) operating in ESI(+) or ESI(-) method, also coupled to an AQUITY Ultra Performance Liquid Chromatography system using a UV detector monitoring at 254 nm. Purity for the final compound was >95%, according to the UPLC-MS method using (A) water + 0.1% formic acid and (B) aceto- nitrile + 0.1% formic acid; flow rate = 0.3 mL/min, Column: Aquity BEH C18 column (2.1 × 100 mm, 1.7 mm). Flash column chromatography on silica gel was performed on Interchim prepacked disposable silica gel columns using Interchim Puriflash 4250 (Montlucon, France). Melting point (M.P.) was determined on Mettler Toledo-MP90 (Columbus, OH, USA) Melting Point System and was uncorrected. IR spectra was obtained using a Perkin Elmer (Waltham, MA, USA) Spectrum 400 FTIR/FTNIR spectrometer equipped with a Universal ATR Sampling accessory. 2.2. Synthesis of methyl 1-(2,4-dichlorobenzyl)-5-methyl- 1H-pyrazole-3-carboxylate (I) A solution of methyl 5-methyl-1H-pyrazole-3-carboxylate (350 mg, 2.49 mmol) in DMF, K2CO3 (1034 mg, 7.49 mmol) and 2,4-dichlorobenzylchloride (382 µL , 2.74 mmol) were added, and the resulting mixture was heated at 80 °C for 4 hours. The reaction mixture was cooled to room temperature, poured onto ice-water and extracted with ethyl acetate. The collected organic layer was dried, filtered and evaporated to give the crude, which was purified with automated-flash chroma- tography, eluting with a gradient of 0-50% ethyl acetate in hexane to separate two regioisomers. The product methyl 1- [(2, 4-dichlorophenyl)methyl]-5-methyl-1H-pyrazole-3-carboxy late was obtained as solid. The obtained product was recrys- tallized from hexane and ethyl acetate. Color: Translucent light white. Yield: 40.4%. M.p.: 90.1-90.6 °C. FTIR (ATR, ν, cm-1): 3094 (=C-H), 2946 (C-H), 1728 (C=O), 1587, 1229 (C-O). 1H NMR (300 MHz, CDCl3, δ, ppm): 7.42 (d, 1H, J = 2.1 Hz, Ar-H), 7.15 (dd, 1H, J = 8.4, 2.1 Hz, Ar-H), 6.67 (s, 1H, Ar-H), 6.56 (d, 1H, J = 8.4 Hz, Ar-H), 5.43 (s, 2H, -CH2-), 3.93 (s, 3H, -OCH3), 2.21 (s, 3H, -CH3). 13C NMR (75 MHz, CDCl3, δ, ppm): 162.8, 143.0, 140.6, 134.4, 132.5, 132.4, 129.3, 128.7, 127.8, 109.0, 52.0, 50.5, 11.0. HRMS (m/z) calcd. for C13H13Cl2N2O2 [M+H]+ 299.0354; found: 299.0351. 2.3. X-ray crystallography Data collection and cell refinement for compound I were carried out using a diffractometer Bruker APEX-II CCD [12] with graphite monochromated MoKα radiation at 296 K and Bruker SAINT [12], respectively. The absorption correction was applied using Multi-scan SADABS [12]. The structure was solved by using SHELXT-2014 [13] and refined by using SHELXL-2014 [14]. The structure was drawn with ORTEP-3 for Windows [15] and Software used to prepare material for publication with PLATON [16] and WinGX [15]. The crystal data, conditions of data collection and refinement are reported in Table 1. 2.4. Refinement Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were position- ned geometrically and treated as riding with C-H = 0.93-0.97 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). The measured crystal was of poor quality. It has been unable to grow a suitable crystal. The (-2 9 3), (5 -6 9), (0 -1 11), (1 1 17), (4 -6 9), (3 10 0), (-3 -15 15), (6 1 9), (5 -4 10), (5 10 1), (5 -1 11), (11 1 14), (5 -2 10), (10 10 2), (-2 -1 9), (8 -6 5), (3 -3 14), (8 3 12), (0 1 24), (7 -2 31), (-2 2 1), (-2 -3 1), (2 5 1), (-5 -4 1), (-4 -5 1), (-6 6 4), (2 -8 7), (1 -2 5), (3 1 0), (4 -2 10), (7 3 10), (-7 -9 2), (0 -2 1), (5 -3 5), (-4 -12 5), (-8 9 3), (-7 1 20), (-8 -8 9), (-10 -8 1), (-9 -10 11), (5 5 1), (2 9 1) and (-4 5 1) reflections were omitted owing to bad disagreement. 3. Result and discussion 3.1. Description of crystal structure of compound I Figure 1 shows the asymmetric unit with the six molecules of the title compound. The 1H-pyrazole ring of each of these molecules are essentially planar. In all six molecules, the dicholoro benzene ring and the 1H-pyrazole ring plane, which is essentialy coplanar with the methyl-carboxalate group are nearly orthogonal, the dihedral angle between the C1-C6 and 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.4.347-352.1782 Aydin et al. / European Journal of Chemistry 9 (4) (2018) 347-352 349 Table 2. Selected geometric parameters (Å, °) for compound I. Cl1—C3 1.736 (5) Cl2—C5 1.752 (5) O1—C12 1.225 (7) N1—N2 1.325 (5) N2—C11 1.328 (6) Cl1—C3—C4 118.8 (4) Cl2—C5—C4 118.2 (4) N1—C7—C6 112.7 (4) O1—C12—O2 124.9 (5) C9—C8—C10 130.0 (5) C13—O2—C12—C11 -178.9 (5) N2—N1—C8—C9 -177.2 (5) Cl1—C3—C4—C5 -177.8 (4) Cl1—C5—C6—C1 178.3 (4) N2—C11—C12—O2 -1.4 (7) Figure 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. Figure 2. Packing diagram of the title compound viewed down the a axis. Hydrogen bonds are indicated by broken lines. C8-C10-C11-N1-N2 planes of the rings is 87.5 (3)° for the molecule with the atom Cl1, 81.8 (3)° for the one with the atom Cl1A, 87.8 (2)° for the one with the atom Cl1B, 87.8 (2)° for the one with the atom Cl1C, 81.8 (2)° for the one with the atom Cl1D and 82.1 (2)° for the one with the atom Cl1E. All bond length and bond angle values for each molecule of the six molecules in the asymmetric unit (Table 2) are normal and comparable to those observed in the crystal structures of the related compounds, via.: Ethyl 1-(2,4-dichlorophenyl)-5- phenyl-1H-pyrazole-3-carboxylate [17] and dimethyl 1-{4- [4,5-bis(methoxycarbonyl)-1,2,3-triazol-1-ylmethylcarbonyl]- phenyl}-1H-pyrazole-3,4-dicarboxylate [18]. The six molecules in the asymmetric unit are stabilized by intramolecular C-H···N and C-H···Cl interactions (Table 3). In the crystal, molecules are linked by intermolecular C-H···O hydrogen bonds, forming molecular sheets into paralel to the (-1 1 0) plane (Table 3; Figures 2 and 3). These sheets are connected to each other by C-H···O hydrogen bonds and C- H···π interactions. 3.2. Hirshfeld surface analysis Visulization and exploration of intermolecular close contacts in the crystal structure of the title complex is invaluable. Thus, a Hirshfeld surface analysis [19,20]; was carried out by using CrystalExplorer 17.5 [21] to investigate the locations of atom–atom short contacts with potential to form hydrogen bonds and the quantitative ratios of these interactions, using the coordinates of the atoms of the first one (with non-suffix) of the six molecules in the asymmetric unit. The Hirshfeld surface of a molecule in a crystal is constructed by calculating the spherical atom electron densities. In the Hirshfeld surface plotted over dnorm (Figure 4), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively [22]. The contact distances to the closest atom inside (di) and outside (de) of the Hirshfeld surface analyze the intermolecular interaction via 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.4.347-352.1782 350 Aydin et al. / European Journal of Chemistry 9 (4) (2018) 347-352 Table 3. Hydrogen-bond parameters (Å, °) for compound I *. D—H···A D—H H···A D···A D—H···A C1—H1···N1 0.93 2.53 2.856(6) 101 C7A—H7A1···Cl2A 0.97 2.68 3.051(5) 104 C1A—H1A···N1A 0.93 2.51 2.847(6) 102 C1B—H1B···N1B 0.93 2.54 2.859(6) 100 C1C—H1C···N1C 0.93 2.54 2.858(5) 100 C1D—H1D···N1D 0.93 2.51 2.858(6) 102 C1E—H1E···N1E 0.93 2.51 2.855(6) 102 C4—H4···O1C i 0.93 2.32 3.189(6) 156 C4B—H4B···O1 0.93 2.30 3.186(6) 160 C4C—H4C···O1B 0.93 2.31 3.181(6) 156 C7B—H7B2···Cl2B 0.97 2.62 3.058(5) 108 C7—H7B···Cl2 0.97 2.61 3.052(5) 108 C10—H10···O1A 0.93 2.58 3.454(7) 157 C10B—H10B···O1E 0.93 2.58 3.457(6) 157 C7C—H7C2···Cl2C 0.97 2.60 3.055(5) 109 C7D—H7D2···Cl2D 0.97 2.67 3.037(5) 103 C7E—H7E1···Cl2E 0.97 2.69 3.049(5) 102 C4A—H4A···Cg2 ii 0.93 2.78 3.655(5) 158 C4D—H4D···Cg8 iii 0.93 2.74 3.630(5) 159 C4E—H4E···Cg6 ii 0.93 2.76 3.646(5) 159 * Symmetry codes: (i) x−1, y−1, z−1; (ii) x+1, y+1, z; (iii) −x+1, −y+1, −z+1. Cg2, Cg6 and Cg8 are the centroids of the benzene rings (C1A–C6A), (C1D–C6D) and (C1E–C6E). Figure 3. Packing diagram of the title compound viewed down the b axis. Hydrogen bonds are indicated by broken lines. Figure 4. View of the three-dimensional Hirshfeld surface of the title complex plotted over dnorm in the range -0.3431 to 1.9396 a.u., highlighting C—H···O hydrogen bonds by dashed lines.. the mapping of dnorm. In a dnorm surface, any intermolecular interactions will appear as a red spot. The shape-index of the Hirshfeld surfaces is a tool to visualize the π-π stacking interactions by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π-π interactions. Figure 5 clearly suggests that there are no π-π interactions in the title compound. The Hirshfeld surfaces of the one with the atom Cl1 of six independent molecules in the asymmetric unit were obtained using a standard (high) surface resolution with the three- dimentional dnorm surfaces mapped over a fixed colour scale of -0.3431 (red) to 1.9396 (blue). In the Hirshfeld surfaces plotted over dnorm and the fingerprint plots [23], shown in Figures 6 and 7, respectively, the points indicated by b, c, d, e, f, g and h correspond to H···H, Cl···H/H···Cl, C···H/H···C, O···H/H···O, N···H/H···N, Cl···Cl, Cl···O/O···Cl interactions with relative contributions of 32.0, 20.9, 15.6, 13.9, 6.3, 5.0 and 2.1%, respectively. These types of interactions add to 95.8% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (2.9%) correspond to Cl···C/C···Cl (1.3%), C···O/O···C (0.7%), O···O (0.5%) and N···N (0.4%), and other less-important interactions (< 1%). 4. Conclusions In this study, we have determined the crystal structure of methyl 1-[(2,4-dichlorophenyl)methyl]-5-methyl-1H-pyrazole- 3-carboxylate using single crystal X-ray diffraction analysis. Also, we report Hirshfeld surface analysis of it. All bond length and bond angle values for each molecule in the asymmetric unit are normal and comparable to those observed in the crystal structures of the related compounds. 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.4.347-352.1782 Aydin et al. / European Journal of Chemistry 9 (4) (2018) 347-352 351 Figure 5. Hirshfeld surface of the title complex plotted over shape-index. Figure 6. The full two-dimensional fingerprint plots for the title complex, showing (a) all interactions, and delineated into (b) H···H, (c) Cl···H/H···Cl, (d) C···H/H···C, (e) O···H/H···O, (f) N···H/H···N, (g) Cl···Cl, (h) Cl···O/O···Cl interactions. The di and de values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts. The asymmetric unit of the title compound contains six molecules which the 1H-pyrazole rings are essentially planar. The crystal structure is stabilized by intermolecular C-H···O hydrogen bonds, forming molecular sheets into paralel to the (-1 1 0) plane. According to the Hirshfeld surface analysis, the H···H, Cl···H/H···Cl, C···H/H···C, O···H/H···O, N···H/H···N, Cl···Cl, Cl···O/O···Cl interactions add to 95.8% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions correspond to other less-important interactions. Figure 7. The Hirshfeld surface representations with the function dnorm plotted onto the surface for (a) all interactions, and (b) H···C/C···H, (c) H···H, (d) H···Cl, (e) O···H/H···O, (f) Cl···H, (g) Cl···Cl and (h) H···O interactions. Acknowledgements This research was financially supported by Gazi University Scientific Research Projects Coordination Unit (Project No: Gazi University BAP-02/2017-23). The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (Grant No. 2010K120480 of The State of Planning Organization). Supplementary information CCDC-1843087 contains the supplementary crystallo- graphic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e- mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interests: The authors declare that they have no conflict of interest. 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.4.347-352.1782 https://www.ccdc.cam.ac.uk/structures/ mailto:data_request@ccdc.cam.ac.uk 352 Aydin et al. / European Journal of Chemistry 9 (4) (2018) 347-352 Author contributions: All authors contributed equally to this work. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. ORCID Abdullah Aydin http://orcid.org/0000-0003-2805-9314 Mehmet Akkurt http://orcid.org/0000-0003-2421-0929 Zehra Tugce Gur http://orcid.org/0000-0001-8916-2492 Erden Banoglu http://orcid.org/0000-0003-4737-1733 References [1]. Kucukguzel, S. G.; Senkardes, S. Eur. J. Med. Chem. 2015, 97, 786-815. [2]. Caliskan, B.; Yilmaz, A.; Evren, I.; Menevse, S.; Uludag, O.; Banoglu, E. Med. Chem. Res. 2013, 22, 782-793. [3]. Ding, X. L.; Zhang H. 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CrystalExplorer17. The University of Western Australia, 2017. [22]. Venkatesan, P.; Thamotharan, S.; Ilangovan, A.; Liang, H.; Sundius, T. Spectrochim. Acta A 2016, 153, 625-636. [23]. Rohl, A. L.; Moret, M.; Kaminsky, W.; Claborn, K.; McKinnon, J. J.; Kahr, B. Cryst. Growth Des. 2008, 8, 4517-4525. Copyright © 2018 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. 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Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.4.347-352.1782 http://orcid.org/0000-0003-2805-9314 http://orcid.org/0000-0003-2421-0929 http://orcid.org/0000-0001-8916-2492 http://orcid.org/0000-0003-4737-1733 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Instrumentation 2.2. Synthesis of methyl 1-(2,4-dichlorobenzyl)-5-methyl-1H-pyrazole-3-carboxylate (I) 2.3. X-ray crystallography 2.4. Refinement 3. Result and discussion 3.1. Description of crystal structure of compound I 3.2. Hirshfeld surface analysis 4. Conclusions Supplementary information Disclosure statement ORCID References PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField15: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: PrintField25: