Structural Chemistry

, Volume 30, Issue 6, pp 2205–2215 | Cite as

Halogen bonds in N-bromosuccinimide and other N-halosuccinimides

  • Pakorn BovonsombatEmail author
  • Samantha Stone
  • Miriam Rossi
  • Francesco CarusoEmail author
Original Research


Our crystal data shows marked intermolecular Br interaction with a neighboring O (carbonyl) in the crystal, Br---O(carbonyl) = 2.767(1) Å, well below the sum of the corresponding van der Waals radii, 3.37 Å. This C=O---Br interaction is among the shortest in the CSD (only 8/2185 examples have a similar distance 2.725–2.800 Å). Only one carbonyl group interacts with the halogen atom, thus inducing a helical intermolecular arrangement. The halogen bond was also studied with density functional theory (DFT) methods, based on coordinates of two molecules in the crystal packing, widely modifying the N-Br---O(carbonyl) angle. In each calculation, this angle was fixed, and the corresponding arrangements were analyzed for potential structural correlation. Indeed, the widening of the N-Br---O(carbonyl) angle correlates with a gradual increase of halogen bond interaction Br---O(carbonyl), that is, shorter separation. It is also seen that decreasing the N-Br---O(carbonyl) angle is associated with decreasing Br---Br separation. Isosurface electron density shows the presence of Br sigma-holes in the two-molecule arrangements.


Halogen bond N-Bromosuccinimide Crystal structure DFT 



We thank the US National Science Foundation through grant 0521237 for the X-ray diffractometer. PB is grateful to the support of Mahidol University International College, Mahidol University, Thailand.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2019_1321_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1775 kb)


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Authors and Affiliations

  1. 1.Mahidol University International CollegeMahidol UniversitySalayaThailand
  2. 2.Department of ChemistryVassar CollegePoughkeepsieUSA

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