Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

Pourayoubi, Mehrdad; Abrishami, Mozhgan; Eigner, Václav; Nečas, Marek; Dušek, Michal; Delavar, Mahmoud

doi:10.1107/s2053229614022608

Cited by 8 publications

(6 citation statements)

References 21 publications

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“…The P S and P-N bond lengths are within the ranges observed in analogous structures (Pourayoubi, Abrishami et al, 2014). The P-N-C angles, with values greater than 120 show that the hybridization of the N atom is close to sp 2 .…”

Section: Resultssupporting

confidence: 74%

Hirshfeld surface analysis of two new phosphorothioic triamide structures

et al. 2015

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Hirshfeld surfaces and two-dimensional fingerprint plots are used to analyse the intermolecular interactions in two new phosphorothioic triamide structures, namely N,N',N''-tris(3,4-dimethylphenyl)phosphorothioic triamide acetonitrile hemisolvate, P(S)[NHC6H3-3,4-(CH3)2]3·0.5CH3CN or C24H30N3PS·0.5CH3CN, (I), and N,N',N''-tris(4-methylphenyl)phosphorothioic triamide-3-methylpiperidinium chloride (1/1), P(S)[NHC6H4(4-CH3)]3·[3-CH3-C5H9NH2](+)·Cl(-) or C21H24N3PS·C6H14N(+)·Cl(-), (II). The asymmetric unit of (I) consists of two independent phosphorothioic triamide molecules and one acetonitrile solvent molecule, whereas for (II), the asymmetric unit is composed of three components (molecule, cation and anion). In the structure of (I), the different components are organized into a six-molecule aggregate through N-H···S and N-H···N hydrogen bonds. The components of (II) are aggregated into a two-dimensional array through N-H···S and N-H···Cl hydrogen bonds. Moreover, interesting features of packing arise in this structure due to the presence of a double hydrogen-bond acceptor (the S atom of the phosphorothioic triamide molecule) and of a double hydrogen-bond donor (the N-H unit of the cation). For both (I) and (II), the full fingerprint plot of each component is asymmetric as a consequence of the presence of three fragments. These analyses reveal that H···H interactions [67.7 and 64.3% for the two symmetry-independent phosphorothioic triamide molecules of (I), 30.7% for the acetonitrile solvent of (I), 63.8% in the phosphorothioic triamide molecule of (II) and 62.9% in the 3-methylpiperidinium cation of (II)] outnumber the other contacts for all the components in both structures, except for the chloride anion of (II), which only receives the Cl···H contact. The phosphorothioic triamide molecules of both structures include unsaturated C atoms, thus presenting C···H/H···C interactions: 17.6 and 21% for the two symmetry-independent phosphorothioic triamide molecules in (I), and 22.7% for the phosphorothioic triamide molecule of (II). Furthermore, the N-H···S hydrogen bonds in both (I) and (II), and the N-H...Cl hydrogen bonds in (II), are the most prominent interactions, appearing as large red spots on the Hirshfeld surface maps. The N···H/H···N contacts in structure (I) are considerable, whereas for (II), they give a negligible contribution to the total interactions in the system.

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Section: Resultssupporting

confidence: 74%

Hirshfeld surface analysis of two new phosphorothioic triamide structures

et al. 2015

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“…The P S bond lengths [1.9156 (7) and 1.9109 (8) Å ] in compound (II) are within the expected range for compounds with an (O) 2 (N)P(S) skeleton. A recently published paper, based on a CSD analysis, shows that the maximum populations of P S bond lengths in this family of compounds are in the range 1.90-1.92 Å (Pourayoubi, Abrishami et al, 2014). The P-N bond lengths [1.6307 (17) and 1.6253 (18) Å for (II)] are within the expected range for (O) 2 (N)P(S)-based structures and are smaller than the maximum population of P-N bond lengths found for (N) 3 P(S)-based structures (Alamdar et al, 2015;Raissi Shabari et al, 2015).…”

Section: Resultsmentioning

confidence: 90%

“…The phosphorus signals of phosphoramide (I) and thiophosphoramide (II) appear at À0.30 and 69.56 ppm, respectively; in comparison with the signals of typical analogous compounds, e.g. P(O)(OC 6 H 5 ) 2 (NHNHC 6 H 5 ) at À1.49 ppm (Sabbaghi et al, 2016) and P(S)(OCH 2 CH 3 ) 2 (NH-NHC 6 H 5 ) at 71.08 ppm (Pourayoubi, Abrishami et al, 2014).…”

Section: Hirshfeld Surface Analysismentioning

confidence: 95%

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

et al. 2018

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The crystal structures of N,N′-(cyclohexane-1,4-diyl)bis(O,O′-diphenylphosphoramide), C30H32N2O6P2 or (C6H5O)2P(O)(1-NH)(C6H10)(4-NH)P(O)(OC6H5)2, (I), and N,N′-(1,4-phenylene)bis(O,O′-dimethylthiophosphoramide), C10H18N2O4P2S2 or (CH3O)2P(S)(1-NH)(C6H4)(4-NH)P(S)(OCH3)2, (II), have been investigated. In the structure of (I), with an (O)2(N)P(O) skeleton, two symmetry-independent phosphoramide molecules are linked through N—H...O=P hydrogen bonds. In the structure of (II), with an (O)2(N)P(S) skeleton, the ester O atoms take part in N—H...O—C hydrogen bonds as acceptors; the P=S groups do not participate in hydrogen-bonding interactions. The strengths of these hydrogen bonds were evaluated, using quantum chemical calculations with the GAUSSIAN09 software package at the B3LYP/6-311G(d,p) level of theory. For this, LP(O) to σ*(NH) charge transfers were studied, according to the second-order perturbation theory in natural bond orbital (NBO) methodology, for a three-component cluster of hydrogen-bonded molecules for both structures, including all of the independent N—H...O hydrogen bonds observed in the crystal packing. The details of the intermolecular interactions were studied by Hirshfeld surface maps and two-dimensional fingerprint plots.

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“…There is just one [RNH] 3 P(S) phosphorothioic triamide structure published to date (Pourayoubi, Abrishami et al, 2014) and only one example of a compound with a P(S) [NH] 3 skeleton different to the P…”

Section: Figurementioning

confidence: 99%

“…Recently, different structural features of phosphoramides (Pourayoubi et al, 2012;Pourayoubi, Toghraee et al, 2013, 2014) and thiophosphoramides (Pourayoubi, Abrishami et al, 2014) were studied through diffraction experiments on some derivatives and analysis of the structures deposited in the Cambridge Structural Database (CSD, Version 5.35, updated in February 2014;Groom & Allen, 2014). Here, we continue this investigation on compounds with a P(S) [N] 3 skeleton, especially phosphorothioic triamides, using a new phosphorothioic triamide structure, N,N 0 ,N 00 -tribenzylphosphorothioic triamide, P(S)[NHCH 2 C 6 H 5 ] 3 , (I), reported in this work, and database entries.…”

Section: Introductionmentioning

confidence: 99%

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃

et al. 2015

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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.

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Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

Cited by 8 publications

References 21 publications

Hirshfeld surface analysis of two new phosphorothioic triamide structures

Hirshfeld surface analysis of two new phosphorothioic triamide structures

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

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃

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Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

Cited by 8 publications

References 21 publications

Hirshfeld surface analysis of two new phosphorothioic triamide structures

Hirshfeld surface analysis of two new phosphorothioic triamide structures

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

A new phosphorothioic triamide structure: P(S)[NHCH2C6H5]3

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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

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃