The structures of the racemic and enantiopure forms of a primary sulfinamide reveal a key structure-defining N-H center dot center dot center dot O=S hydrogen bond motif that resembles the ubiquitous N-H center dot center dot center dot O=C hydrogen bond motif of central importance in protein structures. The presence of the inherently chiral sulfinamide functional group, in contrast to the planar amide, in the hydrogen bonded chains is notable. Halogen bonding with a chiral oxygen acceptor was demonstrated in the co-crystals of the sulfinamide with 1,4-diiodotetra-flurobenzene, which reveal a variety of moderate and weak hydrogen and halogen bonding acting cooperatively to form the overall architecture.