Two single-enantiomer amidophosphoesters: a database study on the chirality of (O)₂P(O)(N)-based structures

The crystal structures of two single-enantiomer amidophosphoesters with an (O)₂P(O)(N) skeleton, i.e. diphenyl [(R)-(+)-α-methylbenzylamido]phosphate, (I), and diphenyl [(S)-(-)-α-methylbenzylamido]phosphate, (II), both C₂₀H₂₀NO₃P, are reported. In both structures, chiral one-dimensional hydrogen-bonded architectures, along [010], are mediated by N-H...OP interactions. The statistically identical assemblies include the noncentrosymmetric graph-set motif C(4) and the compounds crystallize in the chiral space group P2₁. As a result of synergistic co-operation from C-H...O interactions, a two-dimensional superstructure is built including a noncentrosymmetric R₄⁴(22) hydrogen-bonded motif. A Cambridge Structural Database survey was performed on (O)₂P(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 ^2,3J_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 C₆H₅O groups are different, which is reflected in the different chemical shifts and some coupling constants.