Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide

N. Bricklebank, P.J. Skabara, D.E. Hibbs, M.B. Hursthouse, K.M.A. Malik

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH2Cl2 resulted in the formation of molecular charge-transfer complexes 1 . I-2 and 1 . IBr respectively. Both complexes have been characterised crystallographically and contain a linear S-I-X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S-I [2.716(3)] and I-I [2.808(3) Angstrom] bond lengths in 1 . I-2 are similar to those reported for diiodine complexes of related thione donors. The adduct 1 . IBr is the first crystallographically characterised thione-iodine monobromide charge-transfer complex. The S-I distance [2.589(2) Angstrom] is shorter than that in 1 . I-2, consistent with IBr being a stronger acceptor than I-2. The I-Br distance [2.7138(11) Angstrom] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Angstrom). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1 . Br-2 and the dithiolylium salt [C5H6S4Br][Br-3]. 1/2Br(2) 2. Treatment of 1 with Br-2 in toluene led to the isolation of 1 . Br-2 only. The crystal structure of 1 . Br-2 shows the compound to contain a linear Br-S-Br moiety with the sulfur in a T-shaped or Psi-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C5H6S4Br](+) cation, the [Br-3](-) anion and a molecule of Br-2 in a 2:2:1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.
LanguageEnglish
Pages3007-3014
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Volume1999
Issue number17
DOIs
Publication statusPublished - 7 Sep 1999

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Thiones
Sulfur
Charge transfer
Bromine
Molecules
Toluene
Bond length
Iodine
Anions
Cations
Salts
Crystal structure
Ions
Geometry
iodobromine

Keywords

  • charge-transfer complexes
  • crystal-structures
  • x-ray
  • molecular-structure
  • n-methylthiazolidine-2(3h)-selone 1
  • triphenylphosphine sulfide
  • diiodine
  • i-2
  • bromine
  • solvent

Cite this

@article{9753fe672bda40d98d2a16c7dbbd3835,
title = "Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide",
abstract = "Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH2Cl2 resulted in the formation of molecular charge-transfer complexes 1 . I-2 and 1 . IBr respectively. Both complexes have been characterised crystallographically and contain a linear S-I-X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S-I [2.716(3)] and I-I [2.808(3) Angstrom] bond lengths in 1 . I-2 are similar to those reported for diiodine complexes of related thione donors. The adduct 1 . IBr is the first crystallographically characterised thione-iodine monobromide charge-transfer complex. The S-I distance [2.589(2) Angstrom] is shorter than that in 1 . I-2, consistent with IBr being a stronger acceptor than I-2. The I-Br distance [2.7138(11) Angstrom] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Angstrom). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1 . Br-2 and the dithiolylium salt [C5H6S4Br][Br-3]. 1/2Br(2) 2. Treatment of 1 with Br-2 in toluene led to the isolation of 1 . Br-2 only. The crystal structure of 1 . Br-2 shows the compound to contain a linear Br-S-Br moiety with the sulfur in a T-shaped or Psi-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C5H6S4Br](+) cation, the [Br-3](-) anion and a molecule of Br-2 in a 2:2:1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.",
keywords = "charge-transfer complexes, crystal-structures, x-ray, molecular-structure, n-methylthiazolidine-2(3h)-selone 1, triphenylphosphine sulfide, diiodine, i-2, bromine, solvent",
author = "N. Bricklebank and P.J. Skabara and D.E. Hibbs and M.B. Hursthouse and K.M.A. Malik",
year = "1999",
month = "9",
day = "7",
doi = "10.1039/a903068i",
language = "English",
volume = "1999",
pages = "3007--3014",
journal = "Journal of the Chemical Society, Dalton Transactions",
issn = "0300-9246",
number = "17",

}

Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide. / Bricklebank, N.; Skabara, P.J.; Hibbs, D.E.; Hursthouse, M.B.; Malik, K.M.A.

In: Journal of the Chemical Society, Dalton Transactions, Vol. 1999, No. 17, 07.09.1999, p. 3007-3014.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide

AU - Bricklebank, N.

AU - Skabara, P.J.

AU - Hibbs, D.E.

AU - Hursthouse, M.B.

AU - Malik, K.M.A.

PY - 1999/9/7

Y1 - 1999/9/7

N2 - Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH2Cl2 resulted in the formation of molecular charge-transfer complexes 1 . I-2 and 1 . IBr respectively. Both complexes have been characterised crystallographically and contain a linear S-I-X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S-I [2.716(3)] and I-I [2.808(3) Angstrom] bond lengths in 1 . I-2 are similar to those reported for diiodine complexes of related thione donors. The adduct 1 . IBr is the first crystallographically characterised thione-iodine monobromide charge-transfer complex. The S-I distance [2.589(2) Angstrom] is shorter than that in 1 . I-2, consistent with IBr being a stronger acceptor than I-2. The I-Br distance [2.7138(11) Angstrom] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Angstrom). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1 . Br-2 and the dithiolylium salt [C5H6S4Br][Br-3]. 1/2Br(2) 2. Treatment of 1 with Br-2 in toluene led to the isolation of 1 . Br-2 only. The crystal structure of 1 . Br-2 shows the compound to contain a linear Br-S-Br moiety with the sulfur in a T-shaped or Psi-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C5H6S4Br](+) cation, the [Br-3](-) anion and a molecule of Br-2 in a 2:2:1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.

AB - Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH2Cl2 resulted in the formation of molecular charge-transfer complexes 1 . I-2 and 1 . IBr respectively. Both complexes have been characterised crystallographically and contain a linear S-I-X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S-I [2.716(3)] and I-I [2.808(3) Angstrom] bond lengths in 1 . I-2 are similar to those reported for diiodine complexes of related thione donors. The adduct 1 . IBr is the first crystallographically characterised thione-iodine monobromide charge-transfer complex. The S-I distance [2.589(2) Angstrom] is shorter than that in 1 . I-2, consistent with IBr being a stronger acceptor than I-2. The I-Br distance [2.7138(11) Angstrom] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Angstrom). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1 . Br-2 and the dithiolylium salt [C5H6S4Br][Br-3]. 1/2Br(2) 2. Treatment of 1 with Br-2 in toluene led to the isolation of 1 . Br-2 only. The crystal structure of 1 . Br-2 shows the compound to contain a linear Br-S-Br moiety with the sulfur in a T-shaped or Psi-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C5H6S4Br](+) cation, the [Br-3](-) anion and a molecule of Br-2 in a 2:2:1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.

KW - charge-transfer complexes

KW - crystal-structures

KW - x-ray

KW - molecular-structure

KW - n-methylthiazolidine-2(3h)-selone 1

KW - triphenylphosphine sulfide

KW - diiodine

KW - i-2

KW - bromine

KW - solvent

UR - http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=a903068i&JournalCode=DT

UR - http://dx.doi.org/10.1039/a903068i

U2 - 10.1039/a903068i

DO - 10.1039/a903068i

M3 - Article

VL - 1999

SP - 3007

EP - 3014

JO - Journal of the Chemical Society, Dalton Transactions

T2 - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

SN - 0300-9246

IS - 17

ER -