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

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Abstract

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.

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Notes

  1. A price comparison can be found in Table S3.

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Acknowledgements

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.

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Authors and Affiliations

  1. Department of Chemistry, The Pennsylvania State University, Hazleton, PA, 18202, USA

    Dinesh G. Patel & Nicholas R. LeValley

  2. Department of Chemistry, University at Buffalo, Buffalo, NY, 14228, USA

    Eric D. Sylvester, Travis B. Mitchell & Jason B. Benedict

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Patel, D.G., Sylvester, E.D., LeValley, N.R. et al. The Structure and Characterization of 3,4,5-Triiodo-2-Methylthiophene: An Unexpected Iodination Product of 2-Methylthiophene. J Chem Crystallogr 49, 206–212 (2019). https://doi.org/10.1007/s10870-019-00770-z

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