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A chalcogen-bonded complex H3N⋅⋅⋅S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy

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A chalcogen-bonded complex H3N⋅⋅⋅S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy. / Legon, Anthony; Walker, Nicholas; Gougoula, Eva; Medcraft, Chris; Alkorta, Ibon.

In: Journal of Chemical Physics, Vol. 150, No. 8, 084307, 28.02.2019.

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Legon, Anthony ; Walker, Nicholas ; Gougoula, Eva ; Medcraft, Chris ; Alkorta, Ibon. / A chalcogen-bonded complex H3N⋅⋅⋅S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy. In: Journal of Chemical Physics. 2019 ; Vol. 150, No. 8.

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@article{7ad38f1f27c64fe792fe6815127f3aaa,
title = "A chalcogen-bonded complex H3N⋅⋅⋅S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy",
abstract = "Ground-state rotational spectra were observed for ten symmetric-top isotopologues H3N⋯S=C=S, H3N⋯34S=C=S, H3N⋯S=C=34S, H3N⋯S=13C=S, H315N⋯S=C=S, H315N⋯34S=C=S, H315N⋯S=C=34S, H315N⋯S=13C=S, H315N⋯33S=C=S and H315N⋯S=C=33S, the first five in their natural abundance in a mixture of ammonia and carbon disulphide in argon and the second group with enriched 15NH3. The four asymmetric-rotor isotopomers H2DN⋯S=C=S, H2DN⋯34S=C=S, H2DN⋯S=C=34S, and HD2N⋯S=C=S were investigated by using a sample composed of ND3 mixed with CS2. Rotational constants, centrifugal distortion constants and 33S nuclear quadrupole coupling constants were determined from spectral analyses and were interpreted with the aid of models of the complex to determine its symmetry, geometry, one measure of the strength of the intermolecular binding, and information about the subunit dynamics. The complex has C3v symmetry, with nuclei in the order H3N⋯S=C=S, thereby establishing that the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of ammonia as the nucleophile and the axial region near one of the S atoms as the electrophile. The small intermolecular stretching force constant k = 3.97(5) N m-1 indicates a weak interaction and suggests the assumption of unperturbed component geometries on complex formation. A simple model used to account for the contribution of the subunit angular oscillations to the zero-point motion leads to the intermolecular bond length r(N⋯S) = 3.388(10) {\AA}.",
author = "Anthony Legon and Nicholas Walker and Eva Gougoula and Chris Medcraft and Ibon Alkorta",
year = "2019",
month = "2",
day = "28",
doi = "10.1063/1.5085281",
language = "English",
volume = "150",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics (AIP)",
number = "8",

}

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TY - JOUR

T1 - A chalcogen-bonded complex H3N⋅⋅⋅S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy

AU - Legon, Anthony

AU - Walker, Nicholas

AU - Gougoula, Eva

AU - Medcraft, Chris

AU - Alkorta, Ibon

PY - 2019/2/28

Y1 - 2019/2/28

N2 - Ground-state rotational spectra were observed for ten symmetric-top isotopologues H3N⋯S=C=S, H3N⋯34S=C=S, H3N⋯S=C=34S, H3N⋯S=13C=S, H315N⋯S=C=S, H315N⋯34S=C=S, H315N⋯S=C=34S, H315N⋯S=13C=S, H315N⋯33S=C=S and H315N⋯S=C=33S, the first five in their natural abundance in a mixture of ammonia and carbon disulphide in argon and the second group with enriched 15NH3. The four asymmetric-rotor isotopomers H2DN⋯S=C=S, H2DN⋯34S=C=S, H2DN⋯S=C=34S, and HD2N⋯S=C=S were investigated by using a sample composed of ND3 mixed with CS2. Rotational constants, centrifugal distortion constants and 33S nuclear quadrupole coupling constants were determined from spectral analyses and were interpreted with the aid of models of the complex to determine its symmetry, geometry, one measure of the strength of the intermolecular binding, and information about the subunit dynamics. The complex has C3v symmetry, with nuclei in the order H3N⋯S=C=S, thereby establishing that the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of ammonia as the nucleophile and the axial region near one of the S atoms as the electrophile. The small intermolecular stretching force constant k = 3.97(5) N m-1 indicates a weak interaction and suggests the assumption of unperturbed component geometries on complex formation. A simple model used to account for the contribution of the subunit angular oscillations to the zero-point motion leads to the intermolecular bond length r(N⋯S) = 3.388(10) Å.

AB - Ground-state rotational spectra were observed for ten symmetric-top isotopologues H3N⋯S=C=S, H3N⋯34S=C=S, H3N⋯S=C=34S, H3N⋯S=13C=S, H315N⋯S=C=S, H315N⋯34S=C=S, H315N⋯S=C=34S, H315N⋯S=13C=S, H315N⋯33S=C=S and H315N⋯S=C=33S, the first five in their natural abundance in a mixture of ammonia and carbon disulphide in argon and the second group with enriched 15NH3. The four asymmetric-rotor isotopomers H2DN⋯S=C=S, H2DN⋯34S=C=S, H2DN⋯S=C=34S, and HD2N⋯S=C=S were investigated by using a sample composed of ND3 mixed with CS2. Rotational constants, centrifugal distortion constants and 33S nuclear quadrupole coupling constants were determined from spectral analyses and were interpreted with the aid of models of the complex to determine its symmetry, geometry, one measure of the strength of the intermolecular binding, and information about the subunit dynamics. The complex has C3v symmetry, with nuclei in the order H3N⋯S=C=S, thereby establishing that the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of ammonia as the nucleophile and the axial region near one of the S atoms as the electrophile. The small intermolecular stretching force constant k = 3.97(5) N m-1 indicates a weak interaction and suggests the assumption of unperturbed component geometries on complex formation. A simple model used to account for the contribution of the subunit angular oscillations to the zero-point motion leads to the intermolecular bond length r(N⋯S) = 3.388(10) Å.

U2 - 10.1063/1.5085281

DO - 10.1063/1.5085281

M3 - Article

VL - 150

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

M1 - 084307

ER -