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Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide
A new supramolecular Pb(II) complex [PbL(NO(2))](n) was synthesized from Pb(NO(3))(2), N’-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL) and NaNO(2). [PbL(NO(2))](n) is constructed from discrete [PbL(NO(2))] units with an almost ideal N(2)O(3) square pyramidal coordination environment around...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7571010/ https://www.ncbi.nlm.nih.gov/pubmed/32899863 http://dx.doi.org/10.3390/molecules25184056 |
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author | Mahmoudi, Ghodrat Abedi, Marjan Lawrence, Simon E. Zangrando, Ennio Babashkina, Maria G. Klein, Axel Frontera, Antonio Safin, Damir A. |
author_facet | Mahmoudi, Ghodrat Abedi, Marjan Lawrence, Simon E. Zangrando, Ennio Babashkina, Maria G. Klein, Axel Frontera, Antonio Safin, Damir A. |
author_sort | Mahmoudi, Ghodrat |
collection | PubMed |
description | A new supramolecular Pb(II) complex [PbL(NO(2))](n) was synthesized from Pb(NO(3))(2), N’-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL) and NaNO(2). [PbL(NO(2))](n) is constructed from discrete [PbL(NO(2))] units with an almost ideal N(2)O(3) square pyramidal coordination environment around Pb(II). The ligand L(−) is coordinated through the 2-pyridyl N-atom, one aza N-atom, and the carbonyl O-atom. The nitrite ligand binds in a κ(2)-O,O coordination mode through both O-atoms. The Pb(II) center exhibits a hemidirected coordination geometry with a pronounced coordination gap, which allows a close approach of two additional N-atoms arising from the N=C(O) N-atom of an adjacent molecule and from the 4-pyridyl N-atom from the another adjacent molecule, yielding a N(4)O(3) coordination, constructed from two Pb–N and three Pb–O covalent bonds, and two Pb⋯N tetrel bonds. Dimeric units in the structure of [PbL(NO(2))](n) are formed by the Pb⋯N=C(O) tetrel bonds and intermolecular electrostatically enforced π(+)⋯π(−) stacking interactions between the 2- and 4-pyridyl rings and further stabilized by C–H⋯π intermolecular interactions, formed by one of the methyl H-atoms and the 4-pyridyl ring. These dimers are embedded in a 2D network representing a simplified uninodal 3-connected fes (Shubnikov plane net) topology defined by the point symbol (4∙8(2)). The Hirshfeld surface analysis of [PbL(NO(2))] revealed that the intermolecular H⋯X (X = H, C, N, O) contacts occupy an overwhelming majority of the molecular surface of the [PbL(NO(2))] coordination unit. Furthermore, the structure is characterized by intermolecular C⋯C and C⋯N interactions, corresponding to the intermolecular π⋯π stacking interactions. Notably, intermolecular Pb⋯N and, most interestingly, Pb⋯H interactions are remarkable contributors to the molecular surface of [PbL(NO(2))]. While the former contacts are due to the Pb⋯N tetrel bonds, the latter contacts are mainly due to the interaction with the methyl H-atoms in the π⋯π stacked [PbL(NO(2))] molecules. Molecular electrostatic potential (MEP) surface calculations showed marked electrostatic contributions to both the Pb⋯N tetrel bonds and the dimer forming π(+)⋯π(−) stacking interactions. Quantum theory of atoms in molecules (QTAIM) analyses underlined the tetrel bonding character of the Pb⋯N interactions. The manifold non-covalent interactions found in this supramolecular assembly are the result of the proper combination of the polyfunctional multidentate pyridine-hydrazide ligand and the small nitrito auxiliary ligand. |
format | Online Article Text |
id | pubmed-7571010 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-75710102020-10-28 Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide Mahmoudi, Ghodrat Abedi, Marjan Lawrence, Simon E. Zangrando, Ennio Babashkina, Maria G. Klein, Axel Frontera, Antonio Safin, Damir A. Molecules Article A new supramolecular Pb(II) complex [PbL(NO(2))](n) was synthesized from Pb(NO(3))(2), N’-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL) and NaNO(2). [PbL(NO(2))](n) is constructed from discrete [PbL(NO(2))] units with an almost ideal N(2)O(3) square pyramidal coordination environment around Pb(II). The ligand L(−) is coordinated through the 2-pyridyl N-atom, one aza N-atom, and the carbonyl O-atom. The nitrite ligand binds in a κ(2)-O,O coordination mode through both O-atoms. The Pb(II) center exhibits a hemidirected coordination geometry with a pronounced coordination gap, which allows a close approach of two additional N-atoms arising from the N=C(O) N-atom of an adjacent molecule and from the 4-pyridyl N-atom from the another adjacent molecule, yielding a N(4)O(3) coordination, constructed from two Pb–N and three Pb–O covalent bonds, and two Pb⋯N tetrel bonds. Dimeric units in the structure of [PbL(NO(2))](n) are formed by the Pb⋯N=C(O) tetrel bonds and intermolecular electrostatically enforced π(+)⋯π(−) stacking interactions between the 2- and 4-pyridyl rings and further stabilized by C–H⋯π intermolecular interactions, formed by one of the methyl H-atoms and the 4-pyridyl ring. These dimers are embedded in a 2D network representing a simplified uninodal 3-connected fes (Shubnikov plane net) topology defined by the point symbol (4∙8(2)). The Hirshfeld surface analysis of [PbL(NO(2))] revealed that the intermolecular H⋯X (X = H, C, N, O) contacts occupy an overwhelming majority of the molecular surface of the [PbL(NO(2))] coordination unit. Furthermore, the structure is characterized by intermolecular C⋯C and C⋯N interactions, corresponding to the intermolecular π⋯π stacking interactions. Notably, intermolecular Pb⋯N and, most interestingly, Pb⋯H interactions are remarkable contributors to the molecular surface of [PbL(NO(2))]. While the former contacts are due to the Pb⋯N tetrel bonds, the latter contacts are mainly due to the interaction with the methyl H-atoms in the π⋯π stacked [PbL(NO(2))] molecules. Molecular electrostatic potential (MEP) surface calculations showed marked electrostatic contributions to both the Pb⋯N tetrel bonds and the dimer forming π(+)⋯π(−) stacking interactions. Quantum theory of atoms in molecules (QTAIM) analyses underlined the tetrel bonding character of the Pb⋯N interactions. The manifold non-covalent interactions found in this supramolecular assembly are the result of the proper combination of the polyfunctional multidentate pyridine-hydrazide ligand and the small nitrito auxiliary ligand. MDPI 2020-09-04 /pmc/articles/PMC7571010/ /pubmed/32899863 http://dx.doi.org/10.3390/molecules25184056 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Mahmoudi, Ghodrat Abedi, Marjan Lawrence, Simon E. Zangrando, Ennio Babashkina, Maria G. Klein, Axel Frontera, Antonio Safin, Damir A. Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title | Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title_full | Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title_fullStr | Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title_full_unstemmed | Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title_short | Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide |
title_sort | tetrel bonding and other non-covalent interactions assisted supramolecular aggregation in a new pb(ii) complex of an isonicotinohydrazide |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7571010/ https://www.ncbi.nlm.nih.gov/pubmed/32899863 http://dx.doi.org/10.3390/molecules25184056 |
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