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Structural and DFT studies of dibromine and diiodine adducts of a sulfur-rich thiocarbonyl donor

Structural and DFT studies of dibromine and diiodine adducts of a sulfur-rich thiocarbonyl donor
Structural and DFT studies of dibromine and diiodine adducts of a sulfur-rich thiocarbonyl donor
4,5-Bis(benzoylthio)-1,3-dithiole-2-thione (1) forms molecular adducts with dibromine (2) and diiodine (3), which display a range of complementary primary X-X and S-X and secondary S center dot X and X center dot X bonding interactions. Compounds 2 and 3 were characterised by X-ray diffraction analysis and FT-Raman spectroscopy. Compound 2, which is derived from the additive dibromine oxidation of 1, features a near linear BrSBr moiety that is coplanar with the dithiole-2-thione heterocycle. The SBr bonds in 2 are asymmetric; the asymmetry arises mainly through a combination of intramolecular S center dot Br bonds between the Br atoms and the thioether S atoms of the donor, and an intermolecular S center dot Br contact between one of the bromine atoms and the hypervalent S atom of an adjacent molecule. DFT calculations carried out on 2 with different functionals agree and show that the geometry featuring the SBr2 moiety coplanar with the heterocycle is more stable by about 9 kcal mol1 than that with the SBr2 unit perpendicular to the plane of the heterocycle. DFT calculations indicate that the formation of 2 can be explained based on the charge distribution on the hypothetical cationic intermediate [1-Br]+. Diiodine complex 3 is a molecular charge-transfer species, with an almost linear S-I-I moiety. The unit cell contains two molecules of donor 1, related by a centre of inversion, which form a dimer pair held together by two intermolecular S center dot S and two S center dot O contacts. The packing of the dimers generates various cavities that are able to accommodate I2 molecules as guests, in one case the guest diiodine molecule bonds with the sulfur atoms of the benzoylthio-groups and acts as a bridge between adjacent dimers, in another the diiodine is disordered along the channel-like cavity. The terminal iodine atom of each SII fragment interacts with two additional I2 molecules leading to infinite chains in the [011] direction.
1434-1948
2373-2380
Mancini, Annalisa
da134433-ee68-449c-9d2f-cad90b37a553
Pala, Luca
b8113155-21e3-417d-a511-789578bccb8c
Aragoni, M. Carla
3e73ed7a-2cf7-4f5e-9359-61d6e34a6cd5
Arca, Massimiliano
f90b59f6-4dfb-471d-912e-3515e6507165
Devillanova, Francesco A.
a1015716-6d8a-4517-aac8-593b78e91561
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Bricklebank, Neil
6e082c98-a747-4690-bb37-f05f24d621f5
Mancini, Annalisa
da134433-ee68-449c-9d2f-cad90b37a553
Pala, Luca
b8113155-21e3-417d-a511-789578bccb8c
Aragoni, M. Carla
3e73ed7a-2cf7-4f5e-9359-61d6e34a6cd5
Arca, Massimiliano
f90b59f6-4dfb-471d-912e-3515e6507165
Devillanova, Francesco A.
a1015716-6d8a-4517-aac8-593b78e91561
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Bricklebank, Neil
6e082c98-a747-4690-bb37-f05f24d621f5

Mancini, Annalisa, Pala, Luca, Aragoni, M. Carla, Arca, Massimiliano, Devillanova, Francesco A., Hursthouse, Michael B., Light, Mark E., Skabara, Peter J. and Bricklebank, Neil (2012) Structural and DFT studies of dibromine and diiodine adducts of a sulfur-rich thiocarbonyl donor. European Journal of Inorganic Chemistry, 2012 (14), 2373-2380. (doi:10.1002/ejic.201101028).

Record type: Article

Abstract

4,5-Bis(benzoylthio)-1,3-dithiole-2-thione (1) forms molecular adducts with dibromine (2) and diiodine (3), which display a range of complementary primary X-X and S-X and secondary S center dot X and X center dot X bonding interactions. Compounds 2 and 3 were characterised by X-ray diffraction analysis and FT-Raman spectroscopy. Compound 2, which is derived from the additive dibromine oxidation of 1, features a near linear BrSBr moiety that is coplanar with the dithiole-2-thione heterocycle. The SBr bonds in 2 are asymmetric; the asymmetry arises mainly through a combination of intramolecular S center dot Br bonds between the Br atoms and the thioether S atoms of the donor, and an intermolecular S center dot Br contact between one of the bromine atoms and the hypervalent S atom of an adjacent molecule. DFT calculations carried out on 2 with different functionals agree and show that the geometry featuring the SBr2 moiety coplanar with the heterocycle is more stable by about 9 kcal mol1 than that with the SBr2 unit perpendicular to the plane of the heterocycle. DFT calculations indicate that the formation of 2 can be explained based on the charge distribution on the hypothetical cationic intermediate [1-Br]+. Diiodine complex 3 is a molecular charge-transfer species, with an almost linear S-I-I moiety. The unit cell contains two molecules of donor 1, related by a centre of inversion, which form a dimer pair held together by two intermolecular S center dot S and two S center dot O contacts. The packing of the dimers generates various cavities that are able to accommodate I2 molecules as guests, in one case the guest diiodine molecule bonds with the sulfur atoms of the benzoylthio-groups and acts as a bridge between adjacent dimers, in another the diiodine is disordered along the channel-like cavity. The terminal iodine atom of each SII fragment interacts with two additional I2 molecules leading to infinite chains in the [011] direction.

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More information

Published date: May 2012
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 347407
URI: http://eprints.soton.ac.uk/id/eprint/347407
ISSN: 1434-1948
PURE UUID: 63711ae0-3b18-490d-bb38-04f69b0cb0c0
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 23 Jan 2013 10:03
Last modified: 18 Feb 2021 16:52

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