Crystal structure, electronic properties, and intermolecular interactions of the [Ag(imidazole)2]ClO4 complex: A combined DFT, Hirshfeld surface, QTAIM, and RDG study

Ceyhun Kucuk

doi:10.5155/eurjchem.17.3.218-228.2812

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Published: Sep 30, 2026

DOI: https://doi.org/10.5155/eurjchem.17.3.218-228.2812

Keywords:

DFT, RDG, QTAIM, Imidazole, Silver(I) complex, Hirshfeld surface analysis

Section

Research Article

Issue

Vol. 17 No. 3 (2026): September 2026

Dates

Received 2026-06-26
Accepted 2026-07-30
Published 2026-09-30

Ceyhun Kucuk

Ahmet Erdogan Vocational School of Health Services, Zonguldak Bulent Ecevit University, Zonguldak, 67600, Türkiye

https://orcid.org/0000-0003-4457-8798

Abstract

In this study, the [Ag(imidazole)₂]ClO₄ complex was successfully synthesized and its structural and electronic properties were comprehensively investigated using combined experimental and theoretical approaches. The crystal structure was determined by single-crystal X-ray diffraction analysis, while quantum chemical calculations were performed at the DFT/B3LYP/DGDZVP level of theory. A good agreement between the optimized geometry and the experimental structure confirmed the reliability of the theoretical model in describing the structural characteristics of the complex. Hirshfeld surface analysis together with two-dimensional fingerprint plots revealed that the crystal packing is predominantly stabilized by a cooperative network of H···O/O···H, H···H, C···H/H···C, and N···H/H···N intermolecular interactions. Molecular electrostatic potential (MEP) analysis demonstrated that the oxygen atoms of the perchlorate anion constitute the most electron-rich regions, in excellent agreement with the Hirshfeld surface results. Frontier molecular orbital analysis yielded a HOMO–LUMO energy gap of 6.41 eV, indicating high electronic stability and low chemical reactivity of the complex. The HOMO is mainly localized on the perchlorate counterion, whereas the LUMO is distributed over the Ag(I) coordination center and the coordinated imidazole ligands. Furthermore, the Quantum Theory of Atoms in Molecules (QTAIM) and reduced density gradient (RDG) analyses provided detailed insight into the nature of the coordination bonds and weak intermolecular interactions, confirming that van der Waals interactions together with weak hydrogen bonds play a key role in stabilizing the crystal lattice. The combined experimental and theoretical results demonstrate that the structural and electronic stability of the [Ag(imidazole)₂]ClO₄ complex originates from the synergistic contribution of its coordination geometry, favorable electron-density distribution, and cooperative supramolecular interactions.

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Kucuk, C. Crystal Structure, Electronic Properties, and Intermolecular Interactions of the [Ag(imidazole)2]ClO4 Complex: A Combined DFT, Hirshfeld Surface, QTAIM, and RDG Study. Eur. J. Chem. 2026, 17, 218-228.

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References

[1]. Ahmad, F.; Alam, M. J.; Alam, M.; Azaz, S.; Parveen, M.; Park, S.; Ahmad, S. Synthesis, spectroscopic, computational (DFT/B3LYP), AChE inhibition and antioxidant studies of imidazole derivative. J. Mol. Struc. 2018, 1151, 327-342.
https://doi.org/10.1016/j.molstruc.2017.09.056

[2]. Abu-Dief, A. M.; Abdel-Rahman, L. H.; Abdelhamid, A. A.; Marzouk, A. A.; Shehata, M. R.; Bakheet, M. A.; Almaghrabi, O. A.; Nafady, A. Synthesis and characterization of new Cr(III), Fe(III) and Cu(II) complexes incorporating multi-substituted aryl imidazole ligand: Structural, DFT, DNA binding, and biological implications. Spectrochim. Acta A 2020, 228, 117700.
https://doi.org/10.1016/j.saa.2019.117700

[3]. Zhang, H.; Zhang, X.; Chai, L.; Tang, L.; Zhang, H. Zinc(II) and Cadmium(II) complexes containing imidazole ring: Structural, spectroscopic, antibacterial, DFT calculations and Hirshfeld surface analysis. Inorg. Chim. Acta 2020, 507, 119610.
https://doi.org/10.1016/j.ica.2020.119610

[4]. Abdou, A.; Khalaf, M.; Abd El‐Lateef, H. Synthesis and Characterization of Octahedral Ni(II) and Cu(II) Complexes With Imidazole‐Based Ligands: Structural, DFT, and Molecular Docking, Enhanced Antimicrobial, and Anti‐Inflammatory Activity. Appl. Organom. Chem. 2025, 39 (5), e70158 https://doi.org/10.1002/aoc.70158.
https://doi.org/10.1002/aoc.70158

[5]. Yue, S.; Li, N.; Bian, J.; Hou, T.; Ma, J. Synthesis, crystal structure and luminescent properties of transition metals complexes based on imidazole derivatives. Synthetic Metals 2012, 162 (3-4), 247-256.
https://doi.org/10.1016/j.synthmet.2011.11.030

[6]. Njogu, E. M.; Omondi, B.; Nyamori, V. O. Review: Multimetallic silver(I)-pyridinyl complexes: coordination of silver(I) and luminescence. J. Coord. Chem. 2015, 68 (19), 3389-3431.
https://doi.org/10.1080/00958972.2015.1070147

[7]. Demirci, Ö.; Demir, Y.; Gök, Y.; Yakalı, G.; Taskin‐Tok, T.; Muhammed, M.; Aktaş, A.; Aygün, M.; Gülçin, İ. Imidazol‐2‐Ylidene‐Silver(I) Complexes Bearing 4‐Acetylphenyl Side Arm: Design, Synthesis, Characterization, Crystal Structure, and Inhibitory Properties Against Some Metabolic Enzymes. Applied. Organom. Chem. 2025, 39 (7), e70258 https://doi.org/10.1002/aoc.70258.
https://doi.org/10.1002/aoc.70258

[8]. Kucuk, C.; Erdem-Kucuk, M.; Coteli, E.; Celik, S.; Özdemir, N. Crystal structure, spectroscopic investigation (FT-IR, NMR, and UV-Vis), DFT calculations, and in vitro antioxidant, α-glucosidase, and α-amylase inhibitor activity determination of the ethyl 1H-imidazole-1-carboxylate molecule and its new synthesized silver perchlorate complex. Inorg. Chem. Commun. 2025, 179, 114876.
https://doi.org/10.1016/j.inoche.2025.114876

[9]. Orujova, N. S.; Abbasov, V. M.; Jafarova, R. A.; Mammadov, A. M.; Bayil, I.; Muradova, S. A.; Djadi, N.; Alqahtani, T.; Al-Dies, A. M.; Zerihun, Y. A.; Guendouzi, A.; Zaki, M. E. In vitro, in silico, and DFT evaluation of antimicrobial imidazole derivatives with insights into mechanism of action. Sci. Rep. 2025, 15 (1), 37723 https://doi.org/10.1038/s41598-025-24847-2.
https://doi.org/10.1038/s41598-025-24847-2

[10]. Murthy, P. K.; Suneetha, V.; Armaković, S.; Armaković, S. J.; Suchetan, P.; Giri, L.; Rao, R. S. Synthesis, characterization and computational study of the newly synthetized sulfonamide molecule. J. Mol. Struct. 2018, 1153, 212-229.
https://doi.org/10.1016/j.molstruc.2017.10.028

[11]. Sampathkumar, J.; Rajamanickam, R. Synthesis, crystal structure, Hirshfeld surface, QTAIM, NCI-RDG, DFT and molecular docking studies of 4-(aryl)-1,4-dihydro-N,1-dimethyl-6-(methylthio)-3,5-dinitropyridin-2-amines. J. Mol. Struct. 2024, 1299, 137063.
https://doi.org/10.1016/j.molstruc.2023.137063

[12]. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 16, Revision C.01, Gaussian, Inc., Wallingford CT, 2016.

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

[14]. Bilkan, M. T.; Yurdakul, Ş. Experimental and theoretical studies on molecular structures and vibrational modes of novel compounds containing silver. Russ. J. Inorg. Chem. 2017, 62 (7), 910-924.
https://doi.org/10.1134/S0036023617070038

[15]. 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 (3), 1006-1011.
https://doi.org/10.1107/S1600576721002910

[16]. Silvi, B.; Savin, A. Classification of chemical bonds based on topological analysis of electron localization functions. Nature 1994, 371 (6499), 683-686.
https://doi.org/10.1038/371683a0

[17]. Bruker. APEX2 and SAINT; Bruker AXS Inc.: Madison, WI, USA, 2013.

[18]. Sheldrick, G. M. SHELXT- Integrated space-group and crystal-structure determination. Acta. Crystallogr. A. Found. Adv. 2015, 71 (1), 3-8.
https://doi.org/10.1107/S2053273314026370

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

[20]. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A.; Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42 (2), 339-341.
https://doi.org/10.1107/S0021889808042726

[21]. Gatfaoui, S.; Issaoui, N.; Brandán, S. A.; Roisnel, T.; Marouani, H. Synthesis and characterization of p -xylylenediaminium bis(nitrate). Effects of the coordination modes of nitrate groups on their structural and vibrational properties. J. Mol. Struct. 2018, 1151, 152-168.
https://doi.org/10.1016/j.molstruc.2017.09.027

[22]. Ben Rached, A.; Maalej, W.; Guionneau, P.; Daro, N.; Mhiri, T.; Feki, H.; Elaoud, Z. Synthesis, crystal structure, and vibrational and DFT simulation studies of benzylammonium dihydrogen phosphite. J. Phys. Chem. Solids 2018, 123, 150-156.
https://doi.org/10.1016/j.jpcs.2018.07.017

[23]. Kucuk, C.; Celik, S.; Yurdakul, S.; Özdemir, N.; Bülbül, H. Characterization of the synthesized diaqua-bis(indazole-κN2)bis(nitrato-κO)zinc(II) complex and DFT calculations. J. Mol. Struct. 2024, 1304, 137666.
https://doi.org/10.1016/j.molstruc.2024.137666

[24]. Kanmazalp, S. D. Investigation of theoretical calculations of 2-(1-Phenylethylideneamino)guanidine compound: NBO, NLO, HOMO-LUMO and MEP analysis by DFT method. Karaelmas Fen Müh. Derg. 2017, 7(2), 491-496.

[25]. Bakri, Y. E.; Kurbanova, M.; Ahsin, A.; Gurbanova, F.; Ashfaq, M.; Şahin, O.; Tahir, M. N.; Qamar, A.; Abuelizz, H. A.; Al-Salahi, R. Single crystal XRD, Hirshfeld surface analysis and computational approach for exploration of novel xanthene derivative. J. Mol. Struct. 2025, 1321, 139896.
https://doi.org/10.1016/j.molstruc.2024.139896

[26]. Seth, S. K. Structural elucidation and contribution of intermolecular interactions in O-hydroxy acyl aromatics: Insights from X-ray and Hirshfeld surface analysis. J. Mol. Struct. 2014, 1064, 70-75.
https://doi.org/10.1016/j.molstruc.2014.01.068

[27]. Hachani, A.; Dridi, I.; Elleuch, S.; Roisnel, T.; Kefi, R. Crystal structure, spectroscopic and biological study of a new inorganic-organic hybrid compound [Cd4Cl12(H2O)2]n (C10N4H28)n. Inorg. Chem. Commun. 2019, 100, 134-143.
https://doi.org/10.1016/j.inoche.2018.12.006

[28]. Mustaphi, N. E.; Chlouchi, A.; El Hafi, M.; Mague, J. T.; Hökelek, T.; El Monfalouti, H.; Haoudi, A.; Mazzah, A. Crystal structure determination and analyses of Hirshfeld surface, crystal voids, intermolecular interaction energies and energy frameworks of 1-benzyl-4-(methylsulfanyl)-3a,7a-dihydro-1H-pyrazolo[3,4-d]pyrimidine. Acta. Crystallogr. E. Cryst. Commun. 2024, 80 (7), 783-788.
https://doi.org/10.1107/S2056989024005954

[29]. Soliman, S. M.; Badr, A. M. Synthesis, structure and Hirshfeld analysis of the potent antimicrobial [Ag(4-bromopyrazole)2ClO4] complex. Polyhedron 2019, 171, 323-329.
https://doi.org/10.1016/j.poly.2019.07.026

[30]. Polo-Cuadrado, E.; Ferrer, K.; Osorio, E.; Brito, I.; Cisterna, J.; Gutiérrez, M. Crystal structure, Hirshfeld surface analysis and DFT studies of N-(4-acetylphenyl)quinoline-3-carboxamide. J. Mol. Struct. 2021, 1246, 131162.
https://doi.org/10.1016/j.molstruc.2021.131162

[31]. Spackman, M. A.; Jayatilaka, D. Hirshfeld surface analysis. CrystEngComm. 2009, 11 (1), 19-32.
https://doi.org/10.1039/B818330A

[32]. Mumit, M. A.; Pal, T. K.; Alam, M. A.; Islam, M. A.; Paul, S.; Sheikh, M. C. DFT studies on vibrational and electronic spectra, HOMO-LUMO, MEP, HOMA, NBO and molecular docking analysis of benzyl-3-N-(2,4,5-trimethoxyphenylmethylene)hydrazinecarbodithioate. J. Mol. Struct. 2020, 1220, 128715.
https://doi.org/10.1016/j.molstruc.2020.128715

[33]. Akbari, Z.; Stagno, C.; Iraci, N.; Efferth, T.; Omer, E. A.; Piperno, A.; Montazerozohori, M.; Feizi-Dehnayebi, M.; Micale, N. Biological evaluation, DFT, MEP, HOMO-LUMO analysis and ensemble docking studies of Zn(II) complexes of bidentate and tetradentate Schiff base ligands as antileukemia agents. J. Mol. Struct. 2024, 1301, 137400.
https://doi.org/10.1016/j.molstruc.2023.137400

[34]. Abdou, A. Synthesis, Structural, Molecular Docking, DFT, Vibrational Spectroscopy, HOMO-LUMO, MEP Exploration, antibacterial and antifungal activity of new Fe(III), Co(II) and Ni(II) hetero-ligand complexes. J. Mol. Struct. 2022, 1262, 132911.
https://doi.org/10.1016/j.molstruc.2022.132911

[35]. Costa, R. A.; Pitt, P. O.; Pinheiro, M. L.; Oliveira, K. M.; Salomé, K. S.; Barison, A.; Costa, E. V. Spectroscopic investigation, vibrational assignments, HOMO-LUMO, NBO, MEP analysis and molecular docking studies of oxoaporphine alkaloid liriodenine. Spectrochim. Acta A 2017, 174, 94-104.
https://doi.org/10.1016/j.saa.2016.11.018

[36]. Kucuk, C.; Coteli, E. Spectroscopic Characterization (FT-IR, NMR, and UV-Vis), DFT Calculation, Solvent Effect, and Biological Activity (In Vitro Antioxidant and Antidiabetic) Studies of the N-methoxy-N-methyl-1H-imidazole-1-carboxamide Molecule. J. Solution. Chem. 2026, https://doi.org/10.1007/s10953-026-01617-w.
https://doi.org/10.1007/s10953-026-01617-w

[37]. Belhachemi, S.; Argoub, K.; Rahmani, R.; Boulakoud, M.; Djafri, A.; Kheddam, N.; Tabti, C.; Toubal, K.; Chouaih, A. Synthesis, Crystal Structure, Intermolecular Interactions, HOMO-LUMO, MEP, NLO Properties, and DFT/TD-DFT Investigation of (Z)-5-(4-Nitrobenzylidene)-3-N(3-Chlorophenyl)-2-Thioxothiazolidin-4-One. Polycyclic. Arom. Comp. 2024, 45 (5), 810-842.
https://doi.org/10.1080/10406638.2024.2417717

[38]. Zeng, W.; Yue, D.; Wang, X.; Kong, X. Vibrational spectroscopy, DFT calculations, MEP, NBO, NLO and Hirshfeld surface studies of a new Meldrum's acid derivative containing 2-hydroxyphenylamino moiety. J. Mol. Struct. 2025, 1341, 142675.
https://doi.org/10.1016/j.molstruc.2025.142675

[39]. Dey, P.; Islam, S.; Seth, S. K. Quantitative analysis of the interplay of hydrogen bonds in M(II)-hexaaqua complexes with HMTA [M(II) = Co(II), Mg(II); HMTA = hexamethylenetetramine]. J. Mol. Struct. 2023, 1284, 135448.
https://doi.org/10.1016/j.molstruc.2023.135448

[40]. Khalili, B.; Haddad, B.; Ghauri, K.; Rizehbandi, M.; Fetouhi, B.; Touil, A. K.; Paolone, A.; Villemin, D.; Rahmouni, M.; Bresson, S. Synthesis, vibrational, thermal, topological, electronic, electrochemical stability and DFT studies of new DABCO based ionic liquids. J. Mol. Struct. 2025, 1321, 140193.
https://doi.org/10.1016/j.molstruc.2024.140193

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