Bis(2-chloroethyl)sulfane revisited: (ClH4C2)2S···S(C2H4Cl) dimers by S···S interaction in the solid state

Florian Kraus; Tim Graubner; Magnus R. Buchner; Manfred Metzulat; Antti J. Karttunen

doi:10.1515/znb-2024-0039

Bis(2-chloroethyl)sulfane revisited: (ClH₄C₂)₂S···S(C₂H₄Cl) dimers by S···S interaction in the solid state

Florian Kraus^*
, Tim Graubner
, Magnus R. Buchner
, Manfred Metzulat
, Antti J. Karttunen

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

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Abstract

We synthesized bis(2-chloroethyl)sulfane, S(C₂H₄Cl)₂, and showed its purity by various analytic methods. Its previously unknown crystal structure shows a peculiar intermolecular S···S interaction leading to (ClH₄C₂)₂S···S(C₂H₄Cl)₂ dimers. The S···S interaction could also be reproduced and investigated by quantum chemical calculations. As the C-C bonds have been observed unexpectedly short in the range from 1.505(2) to 1.509(2) Å, the chemical bonds within S(C₂H₄Cl)₂ have also been investigated quantum chemically. Intrinsic bonding orbitals (IBOs) showed that while the C-Cl bond is slightly polarized, the C-C and C-S bonds appear purely covalent, as expected. The electron density between the respective two C atoms is decreased by the attached Cl atom so that the two C atoms move closer to each other. High-resolution low-temperature Raman spectra of solid S(C₂H₄Cl)₂ are presented, and the bands are assigned with the aid of quantum chemical solid-state calculations.

Original language	English
Pages (from-to)	605-617
Number of pages	13
Journal	Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume	79
Issue number	12
DOIs	https://doi.org/10.1515/znb-2024-0039
Publication status	Published - 17 Dec 2024
MoE publication type	A1 Journal article-refereed

Funding

A. J. K. thanks CSC, the Finnish IT Center for Science, for computational resources. We thank the analytics department, Dr. Uwe Linne and Jan Bamberger, for recording the gas chromatogram and the mass spectra.

Keywords

bis(2-chloroethyl)sulfane
crystal structure
IR spectroscopy
quantum chemical calculations
Raman spectroscopy
sulfur-sulfur interaction

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Cite this

@article{72c6e8b65cc841edb4fe1a90b378e2e5,

title = "Bis(2-chloroethyl)sulfane revisited: (ClH4C2)2S···S(C2H4Cl) dimers by S···S interaction in the solid state",

abstract = "We synthesized bis(2-chloroethyl)sulfane, S(C2H4Cl)2, and showed its purity by various analytic methods. Its previously unknown crystal structure shows a peculiar intermolecular S···S interaction leading to (ClH4C2)2S···S(C2H4Cl)2 dimers. The S···S interaction could also be reproduced and investigated by quantum chemical calculations. As the C-C bonds have been observed unexpectedly short in the range from 1.505(2) to 1.509(2) {\AA}, the chemical bonds within S(C2H4Cl)2 have also been investigated quantum chemically. Intrinsic bonding orbitals (IBOs) showed that while the C-Cl bond is slightly polarized, the C-C and C-S bonds appear purely covalent, as expected. The electron density between the respective two C atoms is decreased by the attached Cl atom so that the two C atoms move closer to each other. High-resolution low-temperature Raman spectra of solid S(C2H4Cl)2 are presented, and the bands are assigned with the aid of quantum chemical solid-state calculations.",

keywords = "bis(2-chloroethyl)sulfane, crystal structure, IR spectroscopy, quantum chemical calculations, Raman spectroscopy, sulfur-sulfur interaction",

author = "Florian Kraus and Tim Graubner and Buchner, \{Magnus R.\} and Manfred Metzulat and Karttunen, \{Antti J.\}",

note = "Publisher Copyright: {\textcopyright} 2024 Walter de Gruyter GmbH, Berlin/Boston.",

year = "2024",

month = dec,

day = "17",

doi = "10.1515/znb-2024-0039",

language = "English",

volume = "79",

pages = "605--617",

journal = "Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences",

issn = "0932-0776",

publisher = "De Gruyter",

number = "12",

}

Bis(2-chloroethyl)sulfane revisited: (ClH₄C₂)₂S···S(C₂H₄Cl) dimers by S···S interaction in the solid state. / Kraus, Florian; Graubner, Tim; Buchner, Magnus R. et al.
In: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, Vol. 79, No. 12, 17.12.2024, p. 605-617.

Research output: Contribution to journal › Article › Scientific › peer-review

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T1 - Bis(2-chloroethyl)sulfane revisited: (ClH4C2)2S···S(C2H4Cl) dimers by S···S interaction in the solid state

AU - Kraus, Florian

AU - Graubner, Tim

AU - Buchner, Magnus R.

AU - Metzulat, Manfred

AU - Karttunen, Antti J.

PY - 2024/12/17

Y1 - 2024/12/17

N2 - We synthesized bis(2-chloroethyl)sulfane, S(C2H4Cl)2, and showed its purity by various analytic methods. Its previously unknown crystal structure shows a peculiar intermolecular S···S interaction leading to (ClH4C2)2S···S(C2H4Cl)2 dimers. The S···S interaction could also be reproduced and investigated by quantum chemical calculations. As the C-C bonds have been observed unexpectedly short in the range from 1.505(2) to 1.509(2) Å, the chemical bonds within S(C2H4Cl)2 have also been investigated quantum chemically. Intrinsic bonding orbitals (IBOs) showed that while the C-Cl bond is slightly polarized, the C-C and C-S bonds appear purely covalent, as expected. The electron density between the respective two C atoms is decreased by the attached Cl atom so that the two C atoms move closer to each other. High-resolution low-temperature Raman spectra of solid S(C2H4Cl)2 are presented, and the bands are assigned with the aid of quantum chemical solid-state calculations.

AB - We synthesized bis(2-chloroethyl)sulfane, S(C2H4Cl)2, and showed its purity by various analytic methods. Its previously unknown crystal structure shows a peculiar intermolecular S···S interaction leading to (ClH4C2)2S···S(C2H4Cl)2 dimers. The S···S interaction could also be reproduced and investigated by quantum chemical calculations. As the C-C bonds have been observed unexpectedly short in the range from 1.505(2) to 1.509(2) Å, the chemical bonds within S(C2H4Cl)2 have also been investigated quantum chemically. Intrinsic bonding orbitals (IBOs) showed that while the C-Cl bond is slightly polarized, the C-C and C-S bonds appear purely covalent, as expected. The electron density between the respective two C atoms is decreased by the attached Cl atom so that the two C atoms move closer to each other. High-resolution low-temperature Raman spectra of solid S(C2H4Cl)2 are presented, and the bands are assigned with the aid of quantum chemical solid-state calculations.

KW - bis(2-chloroethyl)sulfane

KW - crystal structure

KW - IR spectroscopy

KW - quantum chemical calculations

KW - Raman spectroscopy

KW - sulfur-sulfur interaction

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