Context. Di-deuterated molecules are observed in the earliest stages of star formation at abundances of a few percent relative to their nondeuterated isotopologs, which is unexpected considering the scarcity of deuterium in the interstellar medium. With sensitive observations leading to the detection of a steadily increasing number of di-deuterated species, it is becoming possible to explore successive deuteration chains.

Aims. The accurate quantification of the column density of di-deuterated methanol is a key piece of the puzzle that is missing in the otherwise thoroughly constrained family of D-bearing methanol in the deeply embedded low-mass protostellar system and astrochemical template source IRAS 16293-2422. A spectroscopic dataset for astrophysical purposes was built for CHD2OH and made publicly available to facilitate the accurate characterization of this species in astrochemical surveys.

Methods. The newly computed line list and partition function were used to search for CHD2OH toward IRAS 16293-2422 A and B in data from the Atacama Large Millimeter/submillimeter Array (ALMA) Protostellar Interferometric Line Survey (PILS). Only nonblended, optically thin lines of CHD2OH were used for the synthetic spectral fitting.

Results. The constructed spectroscopic database contains line frequencies and strengths for 7417 transitions in the 0-500 GHz frequency range. ALMA-PILS observations in the 329-363 GHz range were used to identify 105 unique, nonblended, optically thin line frequencies of CHD2OH for synthetic spectral fitting. The derived excitation temperatures and column densities yield high D/H ratios of CHD2OH in IRAS 16293-2422 A and B of 7.5 +/- 1.1% and 7.7 +/- 1.2%, respectively.

Conclusions. Deuteration in IRAS 16293-2422 is not higher than in other low-mass star-forming regions (L483, SVS13-A, NGC 1333-IRAS2A, -IRAS4A, and -IRAS4B). Di-deuterated molecules consistently have higher D/H ratios than their mono-deuterated counterparts in all low-mass protostars, which may be a natural consequence of H-D substitution reactions as seen in laboratory experiments. The Solar System's natal cloud, as traced by comet 67P/Churyumov-Gerasimenko, may have had a lower initial abundance of D, been warmer than the cloud of IRAS 16293-2422, or been partially reprocessed. In combination with accurate spectroscopy, a careful spectral analysis, and the consideration of the underlying assumptions, successive deuteration is a robust window on the physicochemical provenance of star-forming systems.