title: A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃.
abstract: The structure of N,N',N''-tribenzylphosphorothioic triamide, C21H24N3PS, (I), and analysis of the bond-angle sums at the N atoms for this compound, and for 74 structures with a P(S)[N]3 skeleton and the N atom in a three-coordinate geometry found in the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671], are reported. For (I), the bond-angle sum at one of the N atoms [359 (1)°] shows a nearly planar configuration, while the other two show a nonplanar geometry with bond-angle sums of 342 (1) and 347 (1)°. The location of the atoms attached to the nonplanar N atoms suggests an anti orientation of the corresponding lone electron pairs (LEPs) on these N atoms with respect to the P=S group. For 74 structures with a P(S)[N]3 skeleton and with the N atom in a three-coordinate geometry, the bond-angle sums at the N atoms were found to be in the range 293-360°. Among 307 such three-coordinate N atoms, 39% (120 N atoms) have bond-angle sums in the range 359-360°, in accordance with sp(2) hybridization, and 45% (138 N atoms) have bond-angle sums in the range 352-359°, with hybridization close to sp(2). For the orientation of the LEP with respect to the P=S group, the anti orientation was found to be a general rule for N atoms, with the corresponding bond-angle sums deviating by more than 8° from the planar value of 360°. In the title structure, the S atom takes part in intermolecular (N-H···)(N-H···)S hydrogen bonds, connecting the molecules into extended chains parallel to the b axis. The co-operation of one N atom in an N-H···S hydrogen bond as an H-atom donor, and in an N-H···N hydrogen bond as an acceptor, is a novel feature of the crystal structure.
authors.affiliation: Faculty of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.
authors.forename: Akbar
authors.initials: A
authors.lastname: Raissi Shabari
authors.affiliation: Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran.
authors.forename: Mehrdad
authors.initials: M
authors.lastname: Pourayoubi
authors.affiliation: Faculty of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.
authors.forename: Pari
authors.initials: P
authors.lastname: Marandi
authors.affiliation: Institute of Physics, Czech Academy of Sciences v.v.i., Na Slovance 2, 182 21 Prague 8, Czech Republic.
authors.forename: Michal
authors.initials: M
authors.lastname: Dušek
authors.affiliation: Institute of Physics, Czech Academy of Sciences v.v.i., Na Slovance 2, 182 21 Prague 8, Czech Republic.
authors.forename: Václav
authors.initials: V
authors.lastname: Eigner
keywords: bond-angle sum; crystal structure; database survey; phosphorothioic triamide