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1-Butyl-3-methylimidazolium fluoride hydrate has been identified crystallographically as a decomposition product created during purification of the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. This highlights the need to treat ionic liquids much as one would any other research chemical with potentially hazardous properties, unknown toxicity and/or stability, particularly when searching for 'green solvents'.