Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies

Two new Co(II) coordination compounds <i>viz.</i> [Co(H<sub>2</sub>O)(bz)<sub>2</sub>(μ-3-Ampy)<sub>2</sub>]<sub>n</sub> (<b>1</b>) and [Co(4-Mebz)<sub>2</sub>(2-Ampy)<sub>2</sub>] (<b>2</b>)...

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Main Authors: Kamal K. Dutta, Trishnajyoti Baishya, Rosa M. Gomila, Antonio Frontera, Miquel Barcelo-Oliver, Akalesh Kumar Verma, Jumi Das, Manjit K. Bhattacharyya
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Language:English
Published: MDPI AG 2025-02-01
Series:Inorganics
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Online Access:https://www.mdpi.com/2304-6740/13/2/51
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author Kamal K. Dutta
Trishnajyoti Baishya
Rosa M. Gomila
Antonio Frontera
Miquel Barcelo-Oliver
Akalesh Kumar Verma
Jumi Das
Manjit K. Bhattacharyya
author_facet Kamal K. Dutta
Trishnajyoti Baishya
Rosa M. Gomila
Antonio Frontera
Miquel Barcelo-Oliver
Akalesh Kumar Verma
Jumi Das
Manjit K. Bhattacharyya
author_sort Kamal K. Dutta
collection DOAJ
description Two new Co(II) coordination compounds <i>viz.</i> [Co(H<sub>2</sub>O)(bz)<sub>2</sub>(μ-3-Ampy)<sub>2</sub>]<sub>n</sub> (<b>1</b>) and [Co(4-Mebz)<sub>2</sub>(2-Ampy)<sub>2</sub>] (<b>2</b>) (wherebz = benzoate, 4-Mebz = 4-Methylbenzoate and Ampy = Aminopyridine) were synthesized and characterized via elemental (CHN), electronic spectroscopy, FT-IR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures were determined by single-crystal X-ray diffraction analysis, inferring that compound <b>1</b> crystallizes as a <i>3-Ampy</i> bridged Co(II) coordination polymer, whereas compound <b>2</b> crystallizes as a mononuclear Co(II) compound. Compound <b>1</b> unfolds the presence of N–H⋯O, C–H⋯O, O–H⋯O, C–H⋯N and aromatic π⋯π interactions, while for compound <b>2</b>, N–H⋯O, C–H⋯O, C–H⋯C and C–H⋯π interactions are observed. Both the compounds showcase scarcely reported chelate ring interactions involving the benzoate moiety (chelate ring⋯π in <b>1</b> and N–H⋯chelate ring in <b>2</b>). We also conducted theoretical evaluations comprising of combined QTAIM/NCI plot analysis, DFT energy calculation and MEP surface analysis to analyze the supramolecular interactions present in the crystal structures. As per QTAIM parameters, the predominance of π-stacking interactions over hydrogen bonds in stabilizing the assembly in compound <b>1</b> is affirmed. Likewise, in compound <b>2</b>, both hydrogen bonding (HBs) and C–H⋯π interactions are deemed pivotal in stabilizing the dimeric assemblies. The in vitro antiproliferative activities of compounds <b>1</b> and <b>2</b> were performed against Dalton’s lymphoma (DL) cancer cell lines through cytotoxicity and apoptosis assays, showcasing higher cytotoxicity of compound <b>1</b> (IC<sub>50</sub> = 28 μM) over compound <b>2</b> (IC<sub>50</sub> = 34 μM). Additionally, a molecular docking study investigated the structure–activity relationship of these compounds and allowed an understanding of the molecular behaviour after treatment.
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spelling doaj-art-e9deb1f4f6ac4f9da126ba00f557523f2025-08-20T03:12:14ZengMDPI AGInorganics2304-67402025-02-011325110.3390/inorganics13020051Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical StudiesKamal K. Dutta0Trishnajyoti Baishya1Rosa M. Gomila2Antonio Frontera3Miquel Barcelo-Oliver4Akalesh Kumar Verma5Jumi Das6Manjit K. Bhattacharyya7Department of Chemistry, Cotton University, Guwahati 781001, Assam, IndiaDepartment of Chemistry, Cotton University, Guwahati 781001, Assam, IndiaDepartament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.7, 07122 Palma de Mallorca, Baleares, SpainDepartament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.7, 07122 Palma de Mallorca, Baleares, SpainDepartament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.7, 07122 Palma de Mallorca, Baleares, SpainCell and Biochemical Technology Laboratory, Department of Zoology, Cotton University, Guwahati 781001, Assam, IndiaCell and Biochemical Technology Laboratory, Department of Zoology, Cotton University, Guwahati 781001, Assam, IndiaDepartment of Chemistry, Cotton University, Guwahati 781001, Assam, IndiaTwo new Co(II) coordination compounds <i>viz.</i> [Co(H<sub>2</sub>O)(bz)<sub>2</sub>(μ-3-Ampy)<sub>2</sub>]<sub>n</sub> (<b>1</b>) and [Co(4-Mebz)<sub>2</sub>(2-Ampy)<sub>2</sub>] (<b>2</b>) (wherebz = benzoate, 4-Mebz = 4-Methylbenzoate and Ampy = Aminopyridine) were synthesized and characterized via elemental (CHN), electronic spectroscopy, FT-IR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures were determined by single-crystal X-ray diffraction analysis, inferring that compound <b>1</b> crystallizes as a <i>3-Ampy</i> bridged Co(II) coordination polymer, whereas compound <b>2</b> crystallizes as a mononuclear Co(II) compound. Compound <b>1</b> unfolds the presence of N–H⋯O, C–H⋯O, O–H⋯O, C–H⋯N and aromatic π⋯π interactions, while for compound <b>2</b>, N–H⋯O, C–H⋯O, C–H⋯C and C–H⋯π interactions are observed. Both the compounds showcase scarcely reported chelate ring interactions involving the benzoate moiety (chelate ring⋯π in <b>1</b> and N–H⋯chelate ring in <b>2</b>). We also conducted theoretical evaluations comprising of combined QTAIM/NCI plot analysis, DFT energy calculation and MEP surface analysis to analyze the supramolecular interactions present in the crystal structures. As per QTAIM parameters, the predominance of π-stacking interactions over hydrogen bonds in stabilizing the assembly in compound <b>1</b> is affirmed. Likewise, in compound <b>2</b>, both hydrogen bonding (HBs) and C–H⋯π interactions are deemed pivotal in stabilizing the dimeric assemblies. The in vitro antiproliferative activities of compounds <b>1</b> and <b>2</b> were performed against Dalton’s lymphoma (DL) cancer cell lines through cytotoxicity and apoptosis assays, showcasing higher cytotoxicity of compound <b>1</b> (IC<sub>50</sub> = 28 μM) over compound <b>2</b> (IC<sub>50</sub> = 34 μM). Additionally, a molecular docking study investigated the structure–activity relationship of these compounds and allowed an understanding of the molecular behaviour after treatment.https://www.mdpi.com/2304-6740/13/2/51coordination polymerDFTQTAIM/NCI plotapoptosiscytotoxicity
spellingShingle Kamal K. Dutta
Trishnajyoti Baishya
Rosa M. Gomila
Antonio Frontera
Miquel Barcelo-Oliver
Akalesh Kumar Verma
Jumi Das
Manjit K. Bhattacharyya
Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
Inorganics
coordination polymer
DFT
QTAIM/NCI plot
apoptosis
cytotoxicity
title Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
title_full Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
title_fullStr Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
title_full_unstemmed Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
title_short Supramolecular Assemblies and Anticancer Activities of Aminopyidine-Based Polynuclear and Mononuclear Co(II) Benzoates: Experimental and Theoretical Studies
title_sort supramolecular assemblies and anticancer activities of aminopyidine based polynuclear and mononuclear co ii benzoates experimental and theoretical studies
topic coordination polymer
DFT
QTAIM/NCI plot
apoptosis
cytotoxicity
url https://www.mdpi.com/2304-6740/13/2/51
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