The Structure and Characterization of 3,4,5-Triiodo-2-Methylthiophene: An Unexpected Iodination Product of 2-Methylthiophene

  • Dinesh G. PatelEmail author
  • Eric D. Sylvester
  • Nicholas R. LeValley
  • Travis B. Mitchell
  • Jason B. Benedict
Brief Communication


We report the structure and characterization of 3,4,5-triiodo-2-methylthiophene, obtained as an unexpected, unreported, and significant side product from the iodination of 2-methylthiophene using iodine and iodic acid. Identity of this unexpected product was confirmed by X-ray crystallography and 1H and 13C NMR. The compound crystallizes in the P21/c space group with unit cell parameters a = 16.4183(10) Å, b = 4.1971(3) Å, c = 14.3888(9) Å, β = 111.4442(14), Z = 4, and Dcalc = 3.425 g cm−3. Analysis of residual electron density maps indicated the presence of crystallographic disorder between the 2-methyl and 5-iodo positions leading to a model of two distinct molecules of 3,4,5-triiodo-2-methylthiophene where the atoms of these two groups were exchanged. Non-covalent iodine–iodine and sulfur–iodine interactions are observed.

Graphical Abstract

Three products, two of which are constitutional isomers, are possible when installing multiple iodine atoms on 2-methylthiophene; X-ray structural analysis and spectral characterization show that the 4,5-diiodo isomer is not formed and that the 3,4,5-triiodo isomer is unexpectedly obtained. Halogen and chalcogen bonding are clearly observed.


Iodination reaction Thiophene Iodothiophene Halogen bonding Sigma-hole Chalcogen bonding 



DGP thanks Penn State Hazleton for funding in the form of a Research Development Grant. JBB acknowledges support from the National Science Foundation under Grant No. DMR-1455039.

Supplementary material

10870_2019_770_MOESM1_ESM.docx (1.5 mb)
Supplementary material 1 (DOCX 1575 KB)


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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryThe Pennsylvania State UniversityHazletonUSA
  2. 2.Department of ChemistryUniversity at BuffaloBuffaloUSA

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