The crystal structures of two single-enantiomer amidophosphoesters with an (O) 2 P(O)(N) skeleton, i.e. diphenyl [(R)-(+)--methylbenzylamido]phosphate, (I), and diphenyl [(S)-(À)--methylbenzylamido]phosphate, (II), both C 20 H 20 -NO 3 P, are reported. In both structures, chiral one-dimensional hydrogenbonded architectures, along [010], are mediated by N-HÁ Á ÁOP interactions. The statistically identical assemblies include the noncentrosymmetric graph-set motif C(4) and the compounds crystallize in the chiral space group P2 1 . As a result of synergistic co-operation from C-HÁ Á ÁO interactions, a two-dimensional superstructure is built including a noncentrosymmetric R 4 4 (22) hydrogenbonded motif. A Cambridge Structural Database survey was performed on (O) 2 P(O)(N)-based structures in order to review the frequency of space groups observed in this family of compounds; the hydrogen-bond motifs in structures with chiral space groups and the types of groups inducing chirality are discussed. The 2,3 J X-P (X = H or C) coupling constants from the NMR spectra of (I) and (II) have been studied. In each compound, the two diastereotopic C 6 H 5 O groups are different, which is reflected in the different chemical shifts and some coupling constants.