A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate

Ravi Shankar; Rohit Singh; Gabriele Kociok-Köhn; Antonio Frontera

doi:10.1016/j.molstruc.2019.127206

A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate

Ravi Shankar, Rohit Singh, Gabriele Kociok-Köhn, Antonio Frontera

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Abstract

Studies based on the role of non-covalent interactions in physical, chemical, and biological phenomena in supramolecular assemblies have gained considerable interest. Herein, we report a supramolecular assembly, [Zn(phen)₂(H₂O)₂](EtSO₃)₂·2H₂O (1) afforded by the reaction of a preformed zincate salt, [Et₄N]₂[Zn(OSO₂Et)₄] and 1,10-phenanthroline (phen). Compound 1 has been characterized by FTIR, ¹H/¹³C NMR, elemental analysis, and single-crystal X-ray crystallography. Crystal structure of 1 reveals two different stacking modes (π … π) between the aromatic rings of phen ligands of dicationic moieties, [Zn(phen)₂(H₂O)₂]²⁺ leading to the formation of one-dimensional (1D) supramolecular motifs. Furthermore, the ability of the ethanesulfonate group to act as prolific H-bond acceptor (O–H⋯O/C–H⋯O type hydrogen bonds) between the water dimer/tetramer, and aromatic phen rings perpetuates 1D cationic units into a 3D supramolecular motif. Density functional theory (DFT) calculations were carried out to understand the relative importance of such interactions by evaluating their individual bonding energies. Additionally, the 3D Hirshfeld surfaces analysis and 2D fingerplots suggested that the assembly is dominated by H⋯H and O⋯H supramolecular contacts. Remarkably, the interplay of secondary interactions between cationic moieties, weakly-coordinating ethanesulfonate anions, and water dimer/tetramers forming a 3D supramolecular assembly has not been reported in the literature earlier.

Original language	English
Article number	127206
Journal	Journal of Molecular Structure
Volume	1202
Early online date	18 Oct 2019
DOIs	https://doi.org/10.1016/j.molstruc.2019.127206
Publication status	Published - 15 Feb 2020

Keywords

Alkanesulfonate
Crystal structure
DFT
Hirshfeld surfaces
Supramolecular

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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10.1016/j.molstruc.2019.127206

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title = "A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate",

abstract = "Studies based on the role of non-covalent interactions in physical, chemical, and biological phenomena in supramolecular assemblies have gained considerable interest. Herein, we report a supramolecular assembly, [Zn(phen)2(H2O)2](EtSO3)2·2H2O (1) afforded by the reaction of a preformed zincate salt, [Et4N]2[Zn(OSO2Et)4] and 1,10-phenanthroline (phen). Compound 1 has been characterized by FTIR, 1H/13C NMR, elemental analysis, and single-crystal X-ray crystallography. Crystal structure of 1 reveals two different stacking modes (π … π) between the aromatic rings of phen ligands of dicationic moieties, [Zn(phen)2(H2O)2]2+ leading to the formation of one-dimensional (1D) supramolecular motifs. Furthermore, the ability of the ethanesulfonate group to act as prolific H-bond acceptor (O–H⋯O/C–H⋯O type hydrogen bonds) between the water dimer/tetramer, and aromatic phen rings perpetuates 1D cationic units into a 3D supramolecular motif. Density functional theory (DFT) calculations were carried out to understand the relative importance of such interactions by evaluating their individual bonding energies. Additionally, the 3D Hirshfeld surfaces analysis and 2D fingerplots suggested that the assembly is dominated by H⋯H and O⋯H supramolecular contacts. Remarkably, the interplay of secondary interactions between cationic moieties, weakly-coordinating ethanesulfonate anions, and water dimer/tetramers forming a 3D supramolecular assembly has not been reported in the literature earlier.",

keywords = "Alkanesulfonate, Crystal structure, DFT, Hirshfeld surfaces, Supramolecular",

author = "Ravi Shankar and Rohit Singh and Gabriele Kociok-K{\"o}hn and Antonio Frontera",

year = "2020",

month = feb,

day = "15",

doi = "10.1016/j.molstruc.2019.127206",

language = "English",

volume = "1202",

journal = "Journal of Molecular Structure",

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T1 - A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate

AU - Shankar, Ravi

AU - Singh, Rohit

AU - Kociok-Köhn, Gabriele

AU - Frontera, Antonio

PY - 2020/2/15

Y1 - 2020/2/15

N2 - Studies based on the role of non-covalent interactions in physical, chemical, and biological phenomena in supramolecular assemblies have gained considerable interest. Herein, we report a supramolecular assembly, [Zn(phen)2(H2O)2](EtSO3)2·2H2O (1) afforded by the reaction of a preformed zincate salt, [Et4N]2[Zn(OSO2Et)4] and 1,10-phenanthroline (phen). Compound 1 has been characterized by FTIR, 1H/13C NMR, elemental analysis, and single-crystal X-ray crystallography. Crystal structure of 1 reveals two different stacking modes (π … π) between the aromatic rings of phen ligands of dicationic moieties, [Zn(phen)2(H2O)2]2+ leading to the formation of one-dimensional (1D) supramolecular motifs. Furthermore, the ability of the ethanesulfonate group to act as prolific H-bond acceptor (O–H⋯O/C–H⋯O type hydrogen bonds) between the water dimer/tetramer, and aromatic phen rings perpetuates 1D cationic units into a 3D supramolecular motif. Density functional theory (DFT) calculations were carried out to understand the relative importance of such interactions by evaluating their individual bonding energies. Additionally, the 3D Hirshfeld surfaces analysis and 2D fingerplots suggested that the assembly is dominated by H⋯H and O⋯H supramolecular contacts. Remarkably, the interplay of secondary interactions between cationic moieties, weakly-coordinating ethanesulfonate anions, and water dimer/tetramers forming a 3D supramolecular assembly has not been reported in the literature earlier.

AB - Studies based on the role of non-covalent interactions in physical, chemical, and biological phenomena in supramolecular assemblies have gained considerable interest. Herein, we report a supramolecular assembly, [Zn(phen)2(H2O)2](EtSO3)2·2H2O (1) afforded by the reaction of a preformed zincate salt, [Et4N]2[Zn(OSO2Et)4] and 1,10-phenanthroline (phen). Compound 1 has been characterized by FTIR, 1H/13C NMR, elemental analysis, and single-crystal X-ray crystallography. Crystal structure of 1 reveals two different stacking modes (π … π) between the aromatic rings of phen ligands of dicationic moieties, [Zn(phen)2(H2O)2]2+ leading to the formation of one-dimensional (1D) supramolecular motifs. Furthermore, the ability of the ethanesulfonate group to act as prolific H-bond acceptor (O–H⋯O/C–H⋯O type hydrogen bonds) between the water dimer/tetramer, and aromatic phen rings perpetuates 1D cationic units into a 3D supramolecular motif. Density functional theory (DFT) calculations were carried out to understand the relative importance of such interactions by evaluating their individual bonding energies. Additionally, the 3D Hirshfeld surfaces analysis and 2D fingerplots suggested that the assembly is dominated by H⋯H and O⋯H supramolecular contacts. Remarkably, the interplay of secondary interactions between cationic moieties, weakly-coordinating ethanesulfonate anions, and water dimer/tetramers forming a 3D supramolecular assembly has not been reported in the literature earlier.

KW - Alkanesulfonate

KW - Crystal structure

KW - DFT

KW - Hirshfeld surfaces

KW - Supramolecular

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DO - 10.1016/j.molstruc.2019.127206

M3 - Article

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SN - 0022-2860

VL - 1202

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

M1 - 127206

ER -

A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate

Abstract

Keywords

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