The collision-induced fundamental vibration-rotation band at 6.4 μm is the strongest absorption feature from O2 in the infrared1-3, yet it has not been previously incorporated into exoplanet spectral analyses for several reasons. Either collision-induced absorptions (CIAs) were not included or incomplete/obsolete CIA databases were used. Also, the current version of HITRAN does not include CIAs at 6.4 μm with other collision partners (O2-X). We include O2-X CIA features in our transmission spectroscopy simulations by parameterizing the 6.4-μm O2-N2 CIA based on ref. 3 and the O2-CO2 CIA based on ref. 4. Here we report that the O2-X CIA may be the most detectable O2 feature for transit observations. For a potential TRAPPIST-1 e analogue system within 5 pc of the Sun, it could be the only O2 signature detectable with the James Webb Space Telescope (JWST) (using MIRI LRS (Mid-Infrared Instrument low-resolution spectrometer)) for a modern Earth-like cloudy atmosphere with biological quantities of O2. Also, we show that the 6.4-μm O2-X CIA would be prominent for O2-rich desiccated atmospheres5 and could be detectable with JWST in just a few transits. For systems beyond 5 pc, this feature could therefore be a powerful discriminator of uninhabited planets with non-biological `false-positive' O2 in their atmospheres, as they would only be detectable at these higher O2 pressures.