Context. Complex organic molecules are detected in many sources in the warm inner regions of envelopes surrounding deeply embedded protostars. Exactly how these species form remains an open question. Aims. This study aims to constrain the formation of complex organic molecules through comparisons of their abundances towards the Class 0 protostellar binary IRAS 16293-2422. Methods. We utilised observations from the ALMA Protostellar Interferometric Line Survey of IRAS 16293-2422. The species identification and the rotational temperature and column density estimation were derived by fitting the extracted spectra towards IRAS 16293-2422 A and IRAS 16293-2422 B with synthetic spectra. The majority of the work in this paper pertains to the analysis of IRAS 16293-2422 A for a comparison with the results from the other binary component, which have already been published. Results. We detect 15 different complex species, as well as 16 isotopologues towards the most luminous companion protostar IRAS 16293-2422 A. Tentative detections of an additional 11 isotopologues are reported. We also searched for and report on the first detections of methoxymethanol (CH3OCH2OH) and trans-ethyl methyl ether (t-C2H5OCH3) towards IRAS 16293-2422 B and the follow-up detection of deuterated isotopologues of acetaldehyde (CH2DCHO and CH3CDO). Twenty-four lines of doubly-deuterated methanol (CHD2OH) are also identified. Conclusions. The comparison between the two protostars of the binary system shows significant differences in abundance for some of the species, which are partially correlated to their spatial distribution. The spatial distribution is consistent with the sublimation temperature of the species; those with higher expected sublimation temperatures are located in the most compact region of the hot corino towards IRAS 16293-2422 A. This spatial differentiation is not resolved in IRAS 16293-2422 B and will require observations at a higher angular resolution. In parallel, the list of identified CHD2OH lines shows the need of accurate spectroscopic data including their line strength.

Nitrogen oxides are thought to play a significant role as a nitrogen reservoir and to potentially participate in the formation of more complex species. Until now, only NO, NO, and HNO have been detected in the interstellar medium. We report the first interstellar detection of nitrous acid (HONO). Twelve lines were identified towards component B of the low-mass protostellar binary IRAS 16293-2422 with the Atacama Large Millimeter/submillimeter Array, at the position where NO and NO have previously been seen. A local thermodynamic equilibrium model was used to derive the column density (∼9 × 1014 cm in a 0 .″5 beam) and excitation temperature (∼100 K) of this molecule. HNO, NO, NO+, and HNO3 were also searched for in the data, but not detected. We simulated the HONO formation using an updated version of the chemical code Nautilus and compared the results with the observations. The chemical model is able to reproduce satisfactorily the HONO, NO, and NO abundances, but not the NO, HNO, and NHOH abundances. This could be due to some thermal desorption mechanisms being destructive and therefore limiting the amount of HNO and NHOH present in the gas phase. Other options are UV photodestruction of these species in ices or missing reactions potentially relevant at protostellar temperatures.