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[Display omitted] • Infrared spectrum of the adduct of H 2 S and NH 3 measured in solid argon matrices. • Anharmonic frequency calculations agreed well with the experimental values. • Binding energy of 8.6 kJ mol−1 (720 cm−1) calculated for the complex. Hydrogen bonding in S H⋯N systems has received little attention compared to other hydrogen bond motifs. To characterise S H⋯N bonding, infrared spectra of the most fundamental S H⋯N system—the H 2 S·NH 3 complex—were recorded in solid argon. These experiments were complemented by high level ab initio and density functional theory calculations. The H 2 S symmetric stretch was observed to shift by −155.3 cm−1 when mixed with NH 3 , while the NH 3 umbrella mode was found to shift by +31.8 cm−1. These, as well as deuterium and 15 N isotopologue studies indicated the formation of a complex. The structure of the H 2 S·NH 3 complex was determined to be almost identical to that of the H 2 O·NH 3 complex, with a nearly linear S H⋯N bond. A binding energy of 8.6 kJ mol−1 (720 cm−1) was calculated at the CCSD(T) level of theory extrapolated to the complete basis set limit. Anharmonic frequency calculations at the DSD-PBEP86-D3BJ/aug-cc-pV(D+d)Z level of theory produced frequencies with a RMSD of 13 cm−1 for the complex, relative to the experimental values. Comparison with previous work showed that the S H⋯N bond is weaker in H 2 S·NH 3 than the O H⋯N bond in the H 2 O·NH 3 system. [ABSTRACT FROM AUTHOR]