Crystallographic and Hirshfeld surface analysis of  10-(4-chlorophenyldiazenyl)-3-(3-chlorophenyl)-1-methyl-3,5a,6,11b-tetrahydro-5H-benzopyrano[4',3'-4,5]pyrano[2,3-c]pyrazole

Vivek Kumar Gupta; Naresh Sharma; Archna Sharma; Shashikant Bhikhubhai Teraiya; Narsidas Jeramdas Parmar; Deepak Sharma

doi:10.5155/eurjchem.16.3.311-318.2668

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Published: Sep 30, 2025

DOI: https://doi.org/10.5155/eurjchem.16.3.311-318.2668

Keywords:

Pyrazole, Triclinic crystal system, Half-chair conformation , Hirshfeld surface analysis, Tetrahydro-5H-benzopyrano, Direct methods using single-crystal XRD

Section

Research Article

Issue

Vol. 16 No. 3 (2025): September 2025

Dates

Received 2025-02-07
Accepted 2025-06-15
Published 2025-09-30

Vivek Kumar Gupta

Department of Physics, University of Jammu, Jammu Tawi-180006, India

https://orcid.org/0000-0003-2471-5943

Naresh Sharma

Department of Physics, Associate Professor of Physics, Government Degree College, Billawar-184204, India

https://orcid.org/0000-0002-1128-880X

Archna Sharma

Department of Physics, University of Jammu, Jammu Tawi-180006, India

https://orcid.org/0000-0002-4634-7486

Shashikant Bhikhubhai Teraiya

Department of Chemistry, Sheth Ranchhodlal Acharatlal College of Science, Ahmedabad-380001, Gujarat, India

https://orcid.org/0000-0003-2960-3967

Narsidas Jeramdas Parmar

Department of Chemistry, Sardar Patel University, Vallabh Vidyanagar-388120, Gujarat, India

https://orcid.org/0000-0003-4580-7249

Deepak Sharma

Principal Boys Higher Secondary School, Reasi-182311, India

https://orcid.org/0009-0004-3867-6468

Abstract

The title compound, 10-(4-chlorophenyldiazenyl)-3-(3-chlorophenyl)-1-methyl-3,5a,6,11b-tetrahydro-5H-benzopyrano [4',3'-4,5]pyrano[2,3-c]pyrazole, crystallizes in the triclinic crystal system having the space group P-1 with the following unit cell parameters: a = 7.599(2), b = 11.596(3), c = 12.796(3) Å, α = 90.092(5), β = 94.810(5), γ = 90.583(5)°, Z = 2. The crystal structure was solved by direct methods using single-crystal X-ray diffraction data collected at 100 K and refined by full-matrix least-squares procedures to a final R-value of 0.0636 for 2578 observed reflections. All three phenyl rings A, B, and F are planar. The pyrazole ring E is also planar. Rings C and D are in half-chair conformation with asymmetry parameters: ΔC₂(C7a-C11a) = 3.02 and ΔC₂(C3a-C11c) = 4.02, respectively. Hirshfeld surface is a 3D boundary around a molecule/crystal structure based on electron density. The Hirshfeld surface analysis revealed dominant H···H (31.0%), H···Cl (26%), and H···C (18%) interactions, contributing to crystal stability and packing efficiency. Molecular docking studies further indicated a strong and stable ligand-enzyme interaction, highlighting its potential for small-molecule inhibitor development.

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Gupta, V. K.; Sharma, N.; Sharma, A.; Teraiya, S. B.; Parmar, N. J.; Sharma, D. Crystallographic and Hirshfeld Surface Analysis of 10-(4-Chlorophenyldiazenyl)-3-(3-Chlorophenyl)-1-Methyl-3,5a,6,11b-Tetrahydro-5H-benzopyrano[4’,3’-4,5]pyrano[2,3-c]pyrazole. Eur. J. Chem. 2025, 16, 311-318.

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References

[1]. Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. The Diels--Alder Reaction in Total Synthesis. Angew. Chem. Int. Ed Engl. 2002, 41 (10), 1668-1698.
https://doi.org/10.1002/1521-3773(20020517)41:10<1668::AID-ANIE1668>3.0.CO;2-Z

[2]. Matiychuk, V. S.; Lesyk, R. B.; Obushak, M. D.; Gzella, A.; Atamanyuk, D. V.; Ostapiuk, Y. V.; Kryshchyshyn, A. P. A new domino-Knoevenagel-hetero-Diels-Alder reaction. Tetrahedron Lett. 2008, 49 (31), 4648-4651.
https://doi.org/10.1016/j.tetlet.2008.05.062

[3]. Bryhas, A. O.; Horak, Y. I.; Ostapiuk, Y. V.; Obushak, M. D.; Matiychuk, V. S. A New Three-Step Domino Knoevenagel-Hetero-Diels-Alder Oxidation Reaction. Tetrahedron Lett. 2011, 52 (18), 2324-2326.
https://doi.org/10.1016/j.tetlet.2011.02.081

[4]. Tietze, L. F. Domino Reactions in Organic Synthesis. Chem. Rev. 1996, 96 (1), 115-136.
https://doi.org/10.1021/cr950027e

[5]. Tietze, L. F.; Beifuss, U. Sequential Transformations in Organic Chemistry: A Synthetic Strategy with a Future. Angew. Chem. Int. Ed. Engl. 1993, 32 (2), 131-163.
https://doi.org/10.1002/anie.199301313

[6]. Zhang, Z.; Zhang, Q.; Sun, S.; Xiong, T.; Liu, Q. Domino Ring‐Opening/Recyclization Reactions of Doubly Activated Cyclopropanes as a Strategy for the Synthesis of Furoquinoline Derivatives. Angew. Chem. Int. Ed. 2007, 46 (10), 1726-1729.
https://doi.org/10.1002/anie.200604276

[7]. Yadav, A. K.; Peruncheralathan, S.; Ila, H.; Junjappa, H. Domino Carbocationic Rearrangement of α-[Bis(methylthio)methylene]alkyl-2-(3/2-indolyl) Cyclopropyl Ketones. J. Org. Chem. 2007, 72 (4), 1388-1394.
https://doi.org/10.1021/jo062302a

[8]. Pellissier, H. Asymmetric domino reactions. Part B: Reactions based on the use of chiral catalysts and biocatalysts. Tetrahedron 2006, 62 (10), 2143-2173.
https://doi.org/10.1016/j.tet.2005.10.041

[9]. Ceulemans, E.; Voets, M.; Emmers, S.; Uytterhoeven, K.; Van Meervelt, L.; Dehaen, W. Diastereoselective Intramolecular Hetero Diels-Alder Approach towards Polycyclic Heterocycles. Tetrahedron 2002, 58 (3), 531-544.
https://doi.org/10.1016/S0040-4020(01)01153-X

[10]. Dat, N. T.; Lee, J.; Lee, K.; Hong, Y.; Kim, Y. H.; Lee, J. J. Phenolic Constituents of Amorpha fruticosa That Inhibit NF-κB Activation and Related Gene Expression. J. Nat. Prod. 2008, 71 (10), 1696-1700.
https://doi.org/10.1021/np800383q

[11]. Snider, B. B.; Lu, Q. Total Synthesis of (.+-.)-Pyridoxatin. J. Org. Chem. 1994, 59 (26), 8065-8070.
https://doi.org/10.1021/jo00105a024

[12]. Majumdar, K.; Taher, A.; Ray, K. Domino-Knoevenagel-hetero-Diels-Alder reactions: an efficient one-step synthesis of indole-annulated thiopyranobenzopyran derivatives. Tetrahedron Lett. 2009, 50 (27), 3889-3891.
https://doi.org/10.1016/j.tetlet.2009.04.054

[13]. Lee, Y. R.; Kim, Y. M.; Kim, S. H. Efficient one-pot synthesis of benzopyranobenzopyrans and naphthopyranobenzopyrans by domino aldol-type reaction/hetero Diels-Alder reaction of resorcinols and naphthols. Tetrahedron 2009, 65 (1), 101-108.
https://doi.org/10.1016/j.tet.2008.10.101

[14]. El-Tamany, E. S.; El-Shahed, F. A.; Mohamed, B. H. Synthesis and biological activity of some pyrazole derivatives. J. Serbian Chem. Soc. 1999, 64 (1), 9-19.

[15]. Ismail, Z. H.; Aly, G. M.; El-Degwi, M. S.; Heiba, H. I.; Ghorab, M. M. Synthesis and insecticidal activity of some new pyranopyrazoles, pyrazolopyranopyrimidines, and pyrazolopyranopyridines. Egypt. J. Biotechnol. 2003, 13, 73-82.

[16]. Zaki, M. E.; Soliman, H. A.; Hiekal, O. A.; Rashad, A. E. Pyrazolopyranopyrimidines as a Class of Anti-Inflammatory Agents. Zeitschrift Naturforschung. C 2006, 61 (1-2), 1-5.
https://doi.org/10.1515/znc-2006-1-201

[17]. Abdelrazek, F. M.; Metz, P.; Kataeva, O.; Jäger, A.; El-Mahrouky, S. F. Synthesis and Molluscicidal Activity of New Chromene and Pyrano[2,3-c]Pyrazole Derivatives. Arch. Pharm. (Weinheim) 2007, 340 (10), 543-548.
https://doi.org/10.1002/ardp.200700157

[18]. Photochromism: Molecules and Systems, 2nd ed.; Durr, H., Bouas-Laurent, H., Eds.; Elsevier Science: London, England, 2003.

[19]. Organic Photochromic and Thermochromic Compounds: Main Photochromic Families, 1999th ed.; Crano, J. C., Guglielmetti, R. J., Eds.; Kluwer Academic/Plenum: New York, NY, 1999.

[20]. Mannhold, R.; Cruciani, G.; Weber, H.; Lemoine, H.; Derix, A.; Weichel, C.; Clementi, M. 6-Substituted Benzopyrans as Potassium Channel Activators: Synthesis, Vasodilator Properties, and Multivariate Analysis. J. Med. Chem. 1999, 42 (6), 981-991.
https://doi.org/10.1021/jm981047m

[21]. Brown, C. W.; Liu, S.; Klucik, J.; Berlin, K. D.; Brennan, P. J.; Kaur, D.; Benbrook, D. M. Novel Heteroarotinoids as Potential Antagonists of Mycobacteriumbovis BCG. J. Med. Chem. 2004, 47 (4), 1008-1017.
https://doi.org/10.1021/jm0303453

[22]. Parmar, N. J.; Teraiya, S. B.; Patel, R. A.; Talpada, N. P. Tetrabutylammonium Hydrogen Sulfate Mediated Domino Reaction: Synthesis of Novel Benzopyran-Annulated Pyrano[2,3-c]Pyrazoles. Tetrahedron Lett. 2011, 52 (22), 2853-2856.
https://doi.org/10.1016/j.tetlet.2011.03.108

[23]. Conti, C.; Desideri, N. New 4H-Chromen-4-One and 2H-Chromene Derivatives as Anti-Picornavirus Capsid-Binders. Bioorg. Med. Chem. 2010, 18 (17), 6480-6488.
https://doi.org/10.1016/j.bmc.2010.06.103

[24]. Parmar, N. J.; Teraiya, S. B.; Patel, R. A.; Talpada, N. P. Tetrabutylammonium Hydrogen Sulfate Mediated Domino Reaction: Synthesis of Novel Benzopyran-Annulated Pyrano[2,3-c]Pyrazoles. Tetrahedron Lett. 2011, 52 (22), 2853-2856.
https://doi.org/10.1016/j.tetlet.2011.03.108

[25]. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta. Crystallogr. C. Struct. Chem. 2015, 71 (1), 3-8.
https://doi.org/10.1107/S2053229614024218

[26]. Spackman, P. R.; Turner, M. J.; McKinnon, J. J.; Wolff, S. K.; Grimwood, D. J.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer: a program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. J. Appl. Crystallogr. 2021, 54, 1006-1011.
https://doi.org/10.1107/S1600576721002910

[27]. Ritchie, D. W.; Kemp, G. J. Protein Docking Using Spherical Polar Fourier Correlations. Proteins 2000, 39 (2), 178-194.
https://doi.org/10.1002/(SICI)1097-0134(20000501)39:2<178::AID-PROT8>3.0.CO;2-6

[28]. Dennington, R.; Keith, T. A.; Millam, J. M. GaussView, Version 6, Semichem Inc.; Shawnee Mission, KS, 2016.

[29]. Morris, G. M.; Huey, R.; Lindstrom, W.; Sanner, M. F.; Belew, R. K.; Goodsell, D. S.; Olson, A. J. AutoDock4 and AutoDockTools4: Automated docking with selective receptor flexibility. J. Comput. Chem. 2009, 30 (16), 2785-2791.
https://doi.org/10.1002/jcc.21256

[30]. Pettersen, E. F.; Goddard, T. D.; Huang, C. C.; Couch, G. S.; Greenblatt, D. M.; Meng, E. C.; Ferrin, T. E. UCSF Chimera-A visualization system for exploratory research and analysis. J. Comput. Chem. 2004, 25 (13), 1605-1612.
https://doi.org/10.1002/jcc.20084

[31]. BIOVIA, Dassault Systemes. Discovery Studio Visualizer, v20.1.0.19295; Dassault Systemes: San Diego, 2020.

[32]. Schrödinger, LLC. The PyMOL Molecular Graphics System, Version 2.0; Schrödinger, LLC: New York, 2015.

[33]. Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. J. Chem. Soc., Perkin. Trans. 2 1987, S1.
https://doi.org/10.1039/p298700000s1

[34]. Spek, A. L. Structure validation in chemical crystallography. Acta. Crystallogr. D. Biol. Crystallogr. 2009, 65 (2), 148-155.
https://doi.org/10.1107/S090744490804362X

[35]. McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. Towards quantitative analysis of intermolecular interactions with Hirshfeld surfaces. Chem. Commun. 2007, 3814.
https://doi.org/10.1039/b704980c

[36]. Matsuno, T.; Sato, S.; Isobe, H. Curved π-Receptors. Comprehensive Supramolecular Chemistry II 2017, 311-328.
https://doi.org/10.1016/B978-0-12-409547-2.12518-1

[37]. Harchani, A.; Haddad, A. Application of Hirshfeld surfaces, semiempirical calculations and molecular dynamics analysis to study the intermolecular interactions, reactivity and dynamics of two polyoxometalate compounds. Theor. Chem. Acc. 2018, 137 (7), https://doi.org/10.1007/s00214-018-2279-z.
https://doi.org/10.1007/s00214-018-2279-z

[38]. Ortiz de Montellano, P. R.; Wilks, A. Heme Oxygenase Structure and Mechanism. In Advances in Inorganic Chemistry; Elsevier, 2000; pp 359-407.
https://doi.org/10.1016/S0898-8838(00)51007-1

[39]. Skaar, E. P. The Battle for Iron between Bacterial Pathogens and Their Vertebrate Hosts. PLoS. Pathog. 2010, 6 (8), e1000949.
https://doi.org/10.1371/journal.ppat.1000949

[40]. Létoffé, S.; Heuck, G.; Delepelaire, P.; Lange, N.; Wandersman, C. Bacteria Capture Iron from Heme by Keeping Tetrapyrrol Skeleton Intact. Proc. Natl. Acad. Sci. U. S. A. 2009, 106 (28), 11719-11724.
https://doi.org/10.1073/pnas.0903842106

[41]. Lansky, I. B.; Lukat-Rodgers, G. S.; Block, D.; Rodgers, K. R.; Ratliff, M.; Wilks, A. The Cytoplasmic Heme-Binding Protein (PhuS) from the Heme Uptake System of Pseudomonas Aeruginosa Is an Intracellular Heme-Trafficking Protein to the Delta-Regioselective Heme Oxygenase. J. Biol. Chem. 2006, 281 (19), 13652-13662.
https://doi.org/10.1074/jbc.M600824200

[42]. Ritchie, D. W.; Venkatraman, V. Ultra-fast FFT protein docking on graphics processors. Bioinformatics 2010, 26 (19), 2398-2405.
https://doi.org/10.1093/bioinformatics/btq444

[43]. Wilcken, R.; Zimmermann, M. O.; Lange, A.; Joerger, A. C.; Boeckler, F. M. Principles and Applications of Halogen Bonding in Medicinal Chemistry and Chemical Biology. J. Med. Chem. 2013, 56 (4), 1363-1388.
https://doi.org/10.1021/jm3012068

[44]. McGaughey, G. B.; Gagné, M.; Rappé, A. K. π-Stacking Interactions. Journal of Biological Chemistry 1998, 273 (25), 15458-15463.
https://doi.org/10.1074/jbc.273.25.15458

[45]. Hollingsworth, S. A.; Dror, R. O. Molecular Dynamics Simulation for All. Neuron 2018, 99 (6), 1129-1143.
https://doi.org/10.1016/j.neuron.2018.08.011

[46]. Durrant, J. D.; McCammon, J. A. Molecular dynamics simulations and drug discovery. BMC. Biol. 2011, 9 (1), https://doi.org/10.1186/1741-7007-9-71.
https://doi.org/10.1186/1741-7007-9-71

Supporting Agencies

University of Jammu, Jammu, India, The Department of Science and Technology, New Delhi, (SR/WOS-A/PM-3/2018).

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