Interplay Between Conformation and Hydrogen Bond Pattern: Crystal Structure of N-(2,2-dichloroacetyl)-N',N"-dipropylphosphoric Triamide and a Database Survey

Abstract

The interplay between conformation and hydrogen bond pattern was studied in 211 (C(O)NH)(N)₂P(O)-based phosphoric triamides retrieved from the Cambridge Structural Database (CSD) and one new molecular structure, (CHCl₂C(O)NH)(CH₃CH₂CH₂NH)₂P(O). The O═C–N–P and C–N–P═O torsion angles were extracted for the conformational study of the C(O)NP(O) segment, and the conformations of ±sp±ap, ±sp±sc and ±ap±sp were found (sp = synperiplanar, ap = antiperiplanar, sc = synclinal). The conformations of hydrogen bond donor group(s) with respect to the acceptor group(s) were also considered. The investigated structures belong to three classes of (RC(O)NH)(R¹R²N)₂P(O) (R¹ and R² ≠ H), (RC(O)NH)(R¹NH)₂P(O) (R¹ ≠ H) and heterocyclic (RC(O)NH)P(O)[NR¹]₂R² phosphoric triamides (R¹ = H or ≠ H, R² = a hydrocarbon fragment), and the hydrogen bond patterns include dimer, tetramer, chain, tape, ladder, two-dimensional assembly and three-dimensional architecture. In the new structure, the conformation of the C(O)NP(O) fragment is –sp+ap, and molecules are assembled in a tape arrangement (parallel to the [110] axis) through N_CP–H···O═P and N_P–H···O═C hydrogen bonds (N_CP is the nitrogen atom of the C(O)NHP(O) fragment and N_P is the other N atom bonded to phosphorus).

Graphical Abstract

The interplay between conformation and hydrogen bond pattern was studied in 211 (C(O)NH)(N)₂P(O)-based phosphoric triamides retrieved from the Cambridge Structural Database (CSD) and one new structure, (CHCl₂C(O)NH)(CH₃CH₂CH₂NH)₂P(O).