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

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2017-07, Vol.73 (7), p.508-516
• Main Authors: Sabbaghi, Fahimeh, Pourayoubi, Mehrdad, Farhadipour, Abolghasem, Ghorbanian, Nazila, Andreev, Pavel V.
• Format: Article
• Language: English
• Subjects: Atomic properties; computational chemistry; Coupling (molecular); crystal structure; Crystallography; DFT; diazaphosphole oxide; Hydrogen bonding; Hydrogen bonds; Molecular structure; natural bond orbital; Nitrogen; NMR; Nuclear magnetic resonance; tubular hydrogen‐bond pattern; X-rays
• ISSN: 2053-2296; 0108-2701; 2053-2296; 1600-5759
• DOI: 10.1107/S205322961700794X

In the structure of 2‐(4‐chloroanilino)‐1,3,2λ4‐diazaphosphol‐2‐one, C12H11ClN3OP, each molecule is connected with four neighbouring molecules through (N—H)2…O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R33(12) and R43(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 1H NMR experiment, the nitrogen‐bound proton of the diazaphosphole ring has a high value of 17.2 Hz for the 2JH–P coupling constant. The first X‐ray diffraction study of an (R1NH)P(O)(NH)2X diazaphosphole oxide (R1 and X are hydrocarbon groups) reveals that each molecule is connected with four neighbouring molecules through (N—H)2…O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction.