N,N,N′,N′-Tetra­benzyl-N′′-(2,6-difluoro­benzo­yl)phospho­ric triamide

Akbar Raissi Shabari; Mehrdad Pourayoubi; Atekeh Tarahhomi; Arnold L Rheingold; James A Golen

doi:10.1107/S1600536812042481

. 2012 Oct 20;68(Pt 11):o3186. doi: 10.1107/S1600536812042481

N,N,N′,N′-Tetrabenzyl-N′′-(2,6-difluorobenzoyl)phosphoric triamide

Akbar Raissi Shabari ^a,^*, Mehrdad Pourayoubi ^b, Atekeh Tarahhomi ^b, Arnold L Rheingold ^c, James A Golen ^c

PMCID: PMC3515277 PMID: 23284497

Abstract

In the C(O)NHP(O) fragment of the title compound, C₃₅H₃₂F₂N₃O₂P, the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and O—P—N angles. The P atom adopts a distorted tetrahedral environment and the phosphoryl and carbonyl groups are anti with respect to each other. The two tertiary N atoms of the dibenzylamido groups show sp ² character with a slight deviation from planarity. In the crystal, pairs of N—H⋯O(P) hydrogen bonds form inversion dimers.

Related literature

For related structures with a [C(O)NH]P(O)[N]₂ configuration, see: Sabbaghi et al. (2010 ▶); Pourayoubi et al. (2010 ▶). For the geometries of the tertiary N atoms in phosphoric triamides with a C(O)NHP(O)[N]₂ core, see: Pourayoubi et al. (2012 ▶).

Experimental

Crystal data

C₃₅H₃₂F₂N₃O₂P
M _r = 595.61
Monoclinic,
a = 12.3079 (7) Å
b = 19.5089 (12) Å
c = 13.0131 (6) Å
β = 105.430 (3)°
V = 3012.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 K
0.18 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.975, T _max = 0.986
23928 measured reflections
6199 independent reflections
4332 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.111
S = 1.01
6199 reflections
391 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Click here for additional data file.^{(35.2KB, cif)}

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536812042481/sj5269sup1.cif

e-68-o3186-sup1.cif^{(35.2KB, cif)}

Click here for additional data file.^{(303.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042481/sj5269Isup2.hkl

e-68-o3186-Isup2.hkl^{(303.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.86 (2)	1.90 (2)	2.761 (2)	176 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Support of this investigation by the North Tehran Branch, Islamic Azad University, is gratefully acknowledged.

supplementary crystallographic information

Comment

The structure determination of the title compound, [2,6-F₂—C₆H₃C(O)NH]P(O)[N(CH₂C₆H₅)₂]₂ (Fig. 1), was performed as part of a project on the synthesis of new phosphoric triamides with a [C(O)NH]P(O)[N]₂ skeleton, where '[N]₂' denotes two tertiary N atoms belonging to an amide group.

The phosphoryl and carbonyl groups, which are separated by an N atom, have a relative anti disposition. In the C(O)NHP(O) fragment, the P1—N1 bond is longer and the O2—P1—N1 angle is contracted compared with the other two P—N bonds and O—P—N angles, similar to what is found for related phosphoramide derivatives (Sabbaghi et al., 2010; Pourayoubi et al., 2010).

The two tertiary N atoms show sp² character with a slight deviation from planarity, wherein one of the two dibenzylamido N atoms shows a slightly greater deviation than the other [viz N3 with the sum of the surrounding bond angles = 353.48 (2)°]. The tertiary N3 atom is more pyramidal than N2 and is oriented so that the lone pair of electrons is anti with respect to the P═O group (Pourayoubi et al., 2012).

In the crystal, the hydrogen atom of the C(O)NHP(O) moiety is involved in an intermolecular N—H···O(P) hydrogen bond (see Table 1) to form an inversion dimer.

Experimental

2,6-F₂—C₆H₃C(O)NHP(O)Cl₂ was prepared according to a procedure reported by Pourayoubi et al. (2010).

To a solution of 2,6-F₂—C₆H₃C(O)NHP(O)Cl₂ (1.5 mmol) in chloroform (25 ml), a solution of dibenzylamine (6 mmol) in chloroform (5 ml) was added at 273 K. After 4 h stirring, the solvent was removed and the product was washed with distilled water and recrystallized from a mixture of CH₃OH/CHCl₃ (4:1 v/v) at room temperature.