The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O

Considering that Cu(tda) chelate (tda: dithioacetate) is a receptor for adenine and related 6-aminopurines, this study reports on the synthesis, molecular and crystal structures, thermal stability, spectral properties and DFT calculations related to [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H&l...

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Main Authors: Carmen Rosales-Martínez, Antonio Matilla-Hernádez, Duane Choquesillo-Lazarte, Antonio Frontera, Alfonso Castiñeiras, Juan Niclós-Gutiérrez
Format: Article
Language:English
Published: MDPI AG 2023-08-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/28/15/5830
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author Carmen Rosales-Martínez
Antonio Matilla-Hernádez
Duane Choquesillo-Lazarte
Antonio Frontera
Alfonso Castiñeiras
Juan Niclós-Gutiérrez
author_facet Carmen Rosales-Martínez
Antonio Matilla-Hernádez
Duane Choquesillo-Lazarte
Antonio Frontera
Alfonso Castiñeiras
Juan Niclós-Gutiérrez
author_sort Carmen Rosales-Martínez
collection DOAJ
description Considering that Cu(tda) chelate (tda: dithioacetate) is a receptor for adenine and related 6-aminopurines, this study reports on the synthesis, molecular and crystal structures, thermal stability, spectral properties and DFT calculations related to [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O (<b>1</b>) [9heade: N9-(2-hydroxyethyl)adenine]. Concerning the molecular recognition of (metal chelate)-(adenine synthetic nucleoside), <b>1</b> represents an unprecedented metal binding pattern (MBP) for 9heade. However, unprecedentedly, the Cu(tda)-9heade molecular recognition in <b>1</b> is essentially featured in the Cu-N1(9heade) bond, without any N6-H⋯O(carboxyl tda) interligand interaction. Nevertheless, N1 being the most basic donor for N9-substituted adenines, this Cu-N1 bond is now assisted by an O2–water-mediated interaction (N6-H⋯O2 and O2⋯Cu weak contact). Also, in the crystal packing, the O-H(ol) of 9heade interacts with its own adenine moiety as a result of an O3–water-mediated interaction (O(ol)-H⋯O3 plus O3-H36⋯π(adenine moiety)). Both water-mediated interactions seem to be responsible for serious alterations in the physical properties of crystalline or grounded samples. Density functional theory calculations were used to evaluate the interactions energetically. Moreover, the quantum theory of atoms-in-molecules (QTAIM), in combination with the noncovalent interaction plot (NCIPlot), was used to analyze the interactions and rationalize the existence and relative importance of hydrogen bonding, chalcogen bonding and π-stacking interactions. The novelty of this work resides in the discovery of a novel binding mode for N9-(2-hydroxyethyl)adenine. Moreover, the investigation of the important role of water in the solid state of <b>1</b> is also relevant, along with the chalcogen bonding interactions demonstrated by the density functional theory (DFT) study.
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spelling doaj.art-aa5214811fcb4031a006b46acf9fdb7d2023-11-18T23:19:25ZengMDPI AGMolecules1420-30492023-08-012815583010.3390/molecules28155830The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>OCarmen Rosales-Martínez0Antonio Matilla-Hernádez1Duane Choquesillo-Lazarte2Antonio Frontera3Alfonso Castiñeiras4Juan Niclós-Gutiérrez5Department of Inorganic Chemistry, Faculty of Pharmacy, University of Granada, 18071 Granada, SpainDepartment of Inorganic Chemistry, Faculty of Pharmacy, University of Granada, 18071 Granada, SpainLaboratorio de Estudios Cristalográficos, IACT, CSIC-Universidad de Granada, Avda. de las Palmeras 4, Armilla, 18100 Granada, SpainDepartament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca, SpainDepartment of Inorganic Chemistry, Faculty of Pharmacy, University of Santiago de Compostela, 15782 Santiago de Compostela, SpainDepartment of Inorganic Chemistry, Faculty of Pharmacy, University of Granada, 18071 Granada, SpainConsidering that Cu(tda) chelate (tda: dithioacetate) is a receptor for adenine and related 6-aminopurines, this study reports on the synthesis, molecular and crystal structures, thermal stability, spectral properties and DFT calculations related to [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O (<b>1</b>) [9heade: N9-(2-hydroxyethyl)adenine]. Concerning the molecular recognition of (metal chelate)-(adenine synthetic nucleoside), <b>1</b> represents an unprecedented metal binding pattern (MBP) for 9heade. However, unprecedentedly, the Cu(tda)-9heade molecular recognition in <b>1</b> is essentially featured in the Cu-N1(9heade) bond, without any N6-H⋯O(carboxyl tda) interligand interaction. Nevertheless, N1 being the most basic donor for N9-substituted adenines, this Cu-N1 bond is now assisted by an O2–water-mediated interaction (N6-H⋯O2 and O2⋯Cu weak contact). Also, in the crystal packing, the O-H(ol) of 9heade interacts with its own adenine moiety as a result of an O3–water-mediated interaction (O(ol)-H⋯O3 plus O3-H36⋯π(adenine moiety)). Both water-mediated interactions seem to be responsible for serious alterations in the physical properties of crystalline or grounded samples. Density functional theory calculations were used to evaluate the interactions energetically. Moreover, the quantum theory of atoms-in-molecules (QTAIM), in combination with the noncovalent interaction plot (NCIPlot), was used to analyze the interactions and rationalize the existence and relative importance of hydrogen bonding, chalcogen bonding and π-stacking interactions. The novelty of this work resides in the discovery of a novel binding mode for N9-(2-hydroxyethyl)adenine. Moreover, the investigation of the important role of water in the solid state of <b>1</b> is also relevant, along with the chalcogen bonding interactions demonstrated by the density functional theory (DFT) study.https://www.mdpi.com/1420-3049/28/15/5830copper(II)thiodiacetate chelatesynthetic adenine nucleosidemolecular and crystal structurechelate-nucleoside recognitionwater-mediated interligand interactions
spellingShingle Carmen Rosales-Martínez
Antonio Matilla-Hernádez
Duane Choquesillo-Lazarte
Antonio Frontera
Alfonso Castiñeiras
Juan Niclós-Gutiérrez
The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
Molecules
copper(II)
thiodiacetate chelate
synthetic adenine nucleoside
molecular and crystal structure
chelate-nucleoside recognition
water-mediated interligand interactions
title The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
title_full The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
title_fullStr The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
title_full_unstemmed The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
title_short The Copper(II)-Thiodiacetate (tda) Chelate as Efficient Receptor of N9-(2-Hydroxyethyl)Adenine (9heade): Synthesis, Molecular and Crystal Structures, Physical Properties and DFT Calculations of [Cu(tda)(9heade)(H<sub>2</sub>O)]·2H<sub>2</sub>O
title_sort copper ii thiodiacetate tda chelate as efficient receptor of n9 2 hydroxyethyl adenine 9heade synthesis molecular and crystal structures physical properties and dft calculations of cu tda 9heade h sub 2 sub o ·2h sub 2 sub o
topic copper(II)
thiodiacetate chelate
synthetic adenine nucleoside
molecular and crystal structure
chelate-nucleoside recognition
water-mediated interligand interactions
url https://www.mdpi.com/1420-3049/28/15/5830
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