A novel tubular hydrogen-bond pattern in a new diazaphosphole oxide: a combination of X-ray crystallography and theoretical study of hydrogen bonds

Abstract

In the structure of 2-(4-chloroanilino)-1,3,2λ-diazaphosphol-2-one, CHClNOP, each molecule is connected with four neighbouring molecules through (N-H)...O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R(12) and R(14) hydrogen-bond ring motifs, combined with a C(4) chain motif. The hole constructed in the tubular architecture includes a 12-atom arrangement (three P, three N, three O and three H atoms) belonging to three adjacent molecules hydrogen bonded to each other. One of the N-H groups of the diazaphosphole ring, not co-operating in classical hydrogen bonding, takes part in an N-H...π interaction. This interaction occurs within the tubular array and does not change the dimension of the hydrogen-bond pattern. The energies of the N-H...O and N-H...π hydrogen bonds were studied by NBO (natural bond orbital) analysis, using the experimental hydrogen-bonded cluster of molecules as the input file for the chemical calculations. In the H NMR experiment, the nitrogen-bound proton of the diazaphosphole ring has a high value of 17.2 Hz for theJ coupling constant.

Hydrogen-bond directionality and symmetry in [C(O)NH](N)2P(O)-based structures: a comparison between X-ray crystallography data and neutron-normalized values, and evaluation of reliability

“…This is in agreement with the P + -O À model for representation of the phosphoryl group (Gilheany, 1994), i.e. including three lone electron pairs at the O atom, as was supported by quantum chemical calculations for a phosphoric triamide (Sabbaghi et al, 2017 Histogram of the HÁ Á ÁOX (X = C and P) angles extracted from the CSD for [RC(O)NH]P(O)[NHR 1 ] 2 structures. The hollow columns relate to HÁ Á ÁO C angles, as black frame (before) and orange frame (after) normalization.…”

A combined X-ray crystallography and theoretical study of N—H...OX (X is =P and —C) hydrogen bonds in two new structures with a (C—O)2(N)P(=Y) (Y is O and S) skeleton

“…It should be noted that the N atom is not usually a potential hydrogen-bond-acceptor group in phosphoramide compounds, as it is usually involved in a resonance interaction with the P atom and shows sp 2 character. This is supported by the recently published CSD analysis of bond-angle sums at the N atoms bonded to P O and P S examined for (N) 3 P(Y)based structures (Y = O and S) (Pourayoubi, Jasinski et al, 2012;Raissi Shabari et al, 2015), where a value near 360 was obtained, and also such an N atom shows a very weak Lewis base characteristic and is not capable as a hydrogen-bond acceptor (Sabbaghi et al, 2017).…”

The (CF3C(O)NH)(C6H5CH2NH)2P(O) phosphoric triamide as a novel carrier with excellent efficiency for Cu(ii) in a liquid membrane transport system

“…Phosphoramides are studied due to their interesting structural and spectroscopic features, [16][17][18] and owing to their extensive applications in coordination chemistry, catalysis and medicine. [19][20][21][22] According to data from Cambridge Structural Database (CSD), 23 thirty copper-phosphoric triamide complexes have been studied by X-ray diffraction analysis.…”