Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

Abstract

Different molecular assemblies were compared in two new structures [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NH] 2 (-CH 2 ) 3 , 1, and [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NHC 6 H 3 (3, ) 2 ] 2 , 2, belonging to the families of "cyclic phosphoric triamide" and "phosphoric triamide", respectively. The differences in the hydrogen bond motifs were discussed (by single crystal X-ray diffraction) as a result of three factors: (1) action of two N atoms with a non-planar environment in 1 as an H-bond acceptor, (2) different orientations of three N-H bond vectors in two molecules and (3) different conformations of C=O and P=O groups. These differences lead to more complicated hydrogen bond pattern of 1, with respect to that of 2, as structure 1 may be considered as a model of four-acceptor-three-donor versus a two-acceptorthree-donor system in 2. The main discrepancies of 1 and 2, monitored by the Hirshfeld surface analysis, are related to the contribution portions of O···H/H···O contacts, in which compound 1 not only involves the greater existence of classical hydrogen bonds but also contains the further C-H···O weak interactions in its crystal packing with respect to compound 2. Instead, in 2, the shortage of O···H/H···O contacts has been partially compensated by the C···H/H···C interactions, due to the presence of more unsaturated carbon acceptors. The differences in assemblies are also reflected in the solid-state IR spectra, especially for the N-H vibration frequencies. The new compounds were further studied by 1D NMR experiments ( 1 H, 13 C, 31 P), 2D NMR techniques [HMQC and HMBC (H-C correlation), HSQC (N-H correlation)], high-resolution ESI-MS, EI-MS spectrometry and IR spectroscopy.

Crystal structure and Hirshfeld surface analysis of 1,2-ethylene-bis(para-methylpyridinium) dichromate as a new selective and mild agent in oxidation of alcohols

“…23,24 This method extends the study of intermolecular interactions to all of the contacts in the structure, including the weak ones. 25 In a HS map, the red regions imply contacts shorter than van der Waals (vdW) radii, while the blue and white areas indicate contacts longer than and equal to the sum of vdW radii, respectively. 26 In our study, the HS analysis was performed for the major disordered component.…”

An insight into the synthesis, crystal structure, geometrical modelling of crystal morphology, Hirshfeld surface analysis and characterization ofN-(4-methylbenzyl)benzamide single crystals

“…Relative contributions of various intermolecular contacts for several aryl amide crystals. (1) N-(4-Methylbenzyl)benzamide (present work), (2) (E)-4-amino-N 0 -[1-(4-methylphenyl)ethylidene]benzohydrazide (Sivajeyanthi et al, 2017), (3) N-(2-aminophenyl)-2-methylbenzamide(Nagaraju et al, 2016), (4) 4-methyl-N-(2-oxido-1,3,2-diazaphosphinan-2-yl)benzamide(Saneei et al, 2017) and(5)N-{bis[(3,4-dimethylphenyl)amino]-phosphoryl}-4-methylbenzamide(Saneei et al, 2017).…”

The synergistic co-operation of N—H...O=P hydrogen bonds and C—H...OX weak intermolecular interactions (X is =P or —C) in the (CH3O)2P(O)(NH–NHC6F5) amidophosphoester: a combined X-ray crystallographic and theoretical study

“…Phosphoramides, with a highly polarized phosphoryl O atom (P O), are interesting in the area of crystal engineering from the point of view of the formation of nearly strong N-HÁ Á ÁO P hydrogen bonds to weak C-HÁ Á ÁO P contacts (Pourayoubi et al, 2014;Saneei et al, 2018Saneei et al, , 2017, and the synergistic co-operation of hydrogen bonds noted was studied in the phosphoric triamide family (Saneei et al, 2018). In various published articles, statistical analyses of hydrogenbond strengths were carried out (Pourayoubi, Toghraee et al, 2013;Hamzehee, Pourayoubi, Nečas et al, 2017) in different classes of phosphoryl-based structures retrieved from the Cambridge Structural Database (CSD; Groom et al, 2016).…”