Bleaching the Record: After 200 Years, Single Crystal X-Ray Crystallography Reveals the Structure and Hydrogen-Bonding Properties of Hypochlorite and Hypobromite Ions in the Solid State

01 June 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We report the first single crystal structures of hypochlorite and hypobromite salts, including hydrated sodium hypochlorite - a ubiquitous bleaching and disinfection agent in use for almost 200 years. The structures represent the first characterization of fundamentally important hypochlorite and hypobromite anions in the solid state, by X-ray crystallography and are supported by Raman spectroscopy on individual crystals. The structural analysis provides insight into supramolecular chemistry of the hypohalite ions in the hydrated environment of the NaOCl.5H2O and NaOBr.5H2O solid salts, and reveals measured Cl-O and Br-O bond lengths of 1.69 A and 1.82 A, respectively, which are significantly longer than those for corresponding higher-valence oxoanions, and in agreement with the values spectroscopically determined for hypohalous acids and corresponding oxides in the gas phase.


hypochlorite anion
Hypobromite Ion
Crystal structure
X-ray crystallography

Supplementary materials

SI Chemrxiv


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