Staff View: Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations

Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations

The Cambridge Structural Database was surveyed for crystals featuring Hg⋯S secondary-bonding interactions for mercury(II) compounds (excluding organomercury compounds). In all, 43 examples of crystals including intermolecular Hg⋯S interactions operating largely in isolation from other directional in...

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Main Authors:	Gomila, Rosa M., Frontera, Antonio, Tiekink, Edward R. T. *
Format:	Article
Published:	Royal Society of Chemistry 2023
Subjects:	QC Physics QD Chemistry
Online Access:	http://eprints.sunway.edu.my/2828/
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spelling	my.sunway.eprints.28282024-07-16T03:13:43Z http://eprints.sunway.edu.my/2828/ Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations Gomila, Rosa M. Frontera, Antonio Tiekink, Edward R. T. * QC Physics QD Chemistry The Cambridge Structural Database was surveyed for crystals featuring Hg⋯S secondary-bonding interactions for mercury(II) compounds (excluding organomercury compounds). In all, 43 examples of crystals including intermolecular Hg⋯S interactions operating largely in isolation from other directional interactions were detected with the Hg⋯S interactions within zero-, one- and two-dimensional aggregation patterns. Over 50% of the aggregates are one-dimensional with topologies ranging from linear, zigzag and helical chains, and ribbons to tapes; 30% of the crystals exhibit zero-dimensional aggregates. Crucially, selected examples were subjected to DFT calculations with mapping of the molecular electrostatic potentials (MEPs) of the molecules as well as quantum theory of atoms in molecules (QTAIM), non-covalent interaction plot (NCIPLOT) and natural bond order (NBO) investigations. This study confirms the presence of σ-/π-holes or positive belts at the mercury atom depending on the coordination geometry, defined by covalently and non-covalently bound donor atoms. In molecules coordinated by sulphur donors, the σ-hole at the sulphur atom merges with the positive belt around the mercury atoms, assisting in the formation of spodium bonds and providing higher directionality. The QTAIM/NCIPLOT analysis supports both the existence and non-covalent nature of the spodium bonds. Finally, the NBO analysis reveals charge transfer effects indicating the existence of LP → σ* orbital interactions in the studied molecules; LP is a lone-pair. The energy of stabilisation provided by spodium bonds ranges from a low 3 kcal mol−1 to a high 19 kcal mol−1, i.e. values often greater than those by conventional hydrogen-bonding interactions. Royal Society of Chemistry 2023 Article PeerReviewed Gomila, Rosa M. and Frontera, Antonio and Tiekink, Edward R. T. * (2023) Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations. CrystEngComm, 37. ISSN 1466-8033 DOI https://doi.org/10.1039/D3CE00590A 10.1039/D3CE00590A
institution	Sunway University
building	Sunway Campus Library
collection	Institutional Repository
continent	Asia
country	Malaysia
content_provider	Sunway University
content_source	Sunway Institutional Repository
url_provider	http://eprints.sunway.edu.my/
topic	QC Physics QD Chemistry
spellingShingle	QC Physics QD Chemistry Gomila, Rosa M. Frontera, Antonio Tiekink, Edward R. T. * Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
description	The Cambridge Structural Database was surveyed for crystals featuring Hg⋯S secondary-bonding interactions for mercury(II) compounds (excluding organomercury compounds). In all, 43 examples of crystals including intermolecular Hg⋯S interactions operating largely in isolation from other directional interactions were detected with the Hg⋯S interactions within zero-, one- and two-dimensional aggregation patterns. Over 50% of the aggregates are one-dimensional with topologies ranging from linear, zigzag and helical chains, and ribbons to tapes; 30% of the crystals exhibit zero-dimensional aggregates. Crucially, selected examples were subjected to DFT calculations with mapping of the molecular electrostatic potentials (MEPs) of the molecules as well as quantum theory of atoms in molecules (QTAIM), non-covalent interaction plot (NCIPLOT) and natural bond order (NBO) investigations. This study confirms the presence of σ-/π-holes or positive belts at the mercury atom depending on the coordination geometry, defined by covalently and non-covalently bound donor atoms. In molecules coordinated by sulphur donors, the σ-hole at the sulphur atom merges with the positive belt around the mercury atoms, assisting in the formation of spodium bonds and providing higher directionality. The QTAIM/NCIPLOT analysis supports both the existence and non-covalent nature of the spodium bonds. Finally, the NBO analysis reveals charge transfer effects indicating the existence of LP → σ* orbital interactions in the studied molecules; LP is a lone-pair. The energy of stabilisation provided by spodium bonds ranges from a low 3 kcal mol−1 to a high 19 kcal mol−1, i.e. values often greater than those by conventional hydrogen-bonding interactions.
format	Article
author	Gomila, Rosa M. Frontera, Antonio Tiekink, Edward R. T. *
author_facet	Gomila, Rosa M. Frontera, Antonio Tiekink, Edward R. T. *
author_sort	Gomila, Rosa M.
title	Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
title_short	Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
title_full	Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
title_fullStr	Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
title_full_unstemmed	Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
title_sort	supramolecular aggregation featuring hg⋯s secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations
publisher	Royal Society of Chemistry
publishDate	2023
url	http://eprints.sunway.edu.my/2828/
_version_	1805893818909720576
score	13.211869

Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations

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