Synthesis, Crystal Structure and Hirshfeld Surface (HS) Analysis of Two New Phosphoric Triamides: A Comparison of HSs for Structures with Different Molecular Assemblies

Two new phosphoric triamides, N -(2-chloro-5-fluorobenzoyl)- N′,N" -bis(morpholin-4-yl)-phosphoric triamide, (2-Cl,5-F-C 6 H 3 C(O)NH)P(O)(NC 4 H 8 O) 2 , 1 , and N,N′ -dibenzyl- N"- (2-chloro-5-fluorobenzoyl)- N,N′ -diethylphosphoric triamide, (2-Cl,5-F-C 6 H 3 C(O)NH)P(O)(N(C 2 H 5 )(CH 2 C 6 H 5 )) 2 , 2 , were synthesized and characterized by 1 H-, 13 C-, 31 P-, 19 F-NMR and IR spectroscopies and single-crystal X-ray diffraction analysis. Different orientations of P(O) versus NH, anti in 1 and syn in 2 , lead to different hydrogen bond patterns, mediated by N–H⋯O, as a linear arrangement forming a C (4) motif and a dimeric aggregate with an R_2^2( 8 ) ring motif, respectively. The crystal packing of both compounds present a three-dimensional supramolecular assembly, made by the cooperation from weak intermolecular interactions, C–H⋯O and C–H⋯π, for 1 and 2 , and π⋯π for 2 . Hirshfeld surface analysis demonstrates that the H⋯H contacts are decisive for both structures with contribution portions of 39.1