N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoro­acet­yl)phospho­ric triamide

Mehrdad Pourayoubi; Mojtaba Keikha; Jerry P Jasinski; Amanda C Keeley

doi:10.1107/S1600536812039712

. 2012 Sep 26;68(Pt 10):o3009. doi: 10.1107/S1600536812039712

N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoroacetyl)phosphoric triamide

Mehrdad Pourayoubi ^a,^*, Mojtaba Keikha ^a, Jerry P Jasinski ^b, Amanda C Keeley ^b

PMCID: PMC3470367 PMID: 23125780

Abstract

In the title molecule, C₁₆H₁₇ClF₂N₃O₂P, the N—H unit of the C(=O)NHP(=O) fragment adopts a syn orientation with respect to the P=O group. The two F atoms and the Cl atom of the ClF₂C group are disordered over two sets of sites with refined occupancies of 0.605 (6) and 0.395 (6). In the crystal, molecules are linked via N—H⋯O=C hydrogen bonds the and the (N—H⋯)(N—H⋯)O=P group into chains along [010].

Related literature

For related structures with a P(=O)[NHC(=O)CClF₂] fragment, and for reference values of P=O, C=O and P—N bond lengths and P—N—C bond angles, see: Pourayoubi et al. (2011 ▶); Raissi Shabari et al. (2011 ▶); Pourayoubi & Saneei (2011 ▶). For the double hydrogen-bond acceptor capability of the phosphoryl O atom in phosphoramidates, see: Pourayoubi et al. (2012 ▶). For the synthesis of the starting material, CClF₂C(=O)NHP(=O)Cl₂, see: Iriarte et al. (2008 ▶).

Experimental

Crystal data

C₁₆H₁₇ClF₂N₃O₂P
M _r = 387.75
Monoclinic,
a = 12.9734 (5) Å
b = 4.9900 (2) Å
c = 13.7750 (4) Å
β = 96.482 (3)°
V = 886.06 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 173 K
0.35 × 0.22 × 0.12 mm

Data collection

Oxford Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.890, T _max = 0.960
9633 measured reflections
5460 independent reflections
4909 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.122
S = 1.09
5460 reflections
263 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.71 e Å⁻³
Absolute structure: Flack (1983 ▶), with 2216 Friedel pairs
Flack parameter: 0.06 (11)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812039712/lh5506sup1.cif

e-68-o3009-sup1.cif^{(27.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039712/lh5506Isup2.hkl

e-68-o3009-Isup2.hkl^{(267.3KB, 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⋯O1ⁱ	0.88 (2)	2.30 (3)	3.092 (3)	151 (3)
N2—H2N⋯O1ⁱ	0.86 (2)	2.05 (2)	2.867 (3)	158 (3)
N3—H3N⋯O2ⁱⁱ	0.86 (2)	2.01 (2)	2.854 (3)	166 (3)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

MP thanks Ferdowsi University of Mashhad for a Research University Grant (No. 15144/2). JPJ acknowledges the NSF-MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

In the previous studies, the structures of some compounds with a P(O)[NHC(O)CClF₂] fragment have been investigated; for example, [4-CH₃-C₆H₄NH]₂P(O)[NHC(O)CClF₂] (Pourayoubi, Tarahhomi et al., 2011), [(C₆H₅CH₂)(CH₃)N]₂P(O)[NHC(O)CClF₂] (Raissi Shabari et al., 2011) and [(CH₃)₂CHNH]₂P(O)[NHC(O)CClF₂] (Pourayoubi & Saneei, 2011). Here, the structure determination of the title compound (Fig. 1) is reported.

Atoms F1, F2 and Cl1 were refined as disordered over two sets of sites with occupancies of 0.605 (6) and 0.395 (6). The N—H unit of the C(O)NHP(O) fragment adopts a syn orientation with respect to the phosphoryl group. The P atom is bonded in a distorted tetrahedral environment as has been noted for other phosphoric triamides. The P═O, C═O and P—N bond lengths and P—N—C bond angles are within the expected values (Pourayoubi, Tarahhomi et al., 2011; Raissi Shabari et al., 2011; Pourayoubi & Saneei, 2011).

In the crystal, the O atom of P═O group acts as a double-hydrogen bond acceptor (Pourayoubi et al., 2012) and molecules are linked by N—H···O═C hydrogen bonds and (N—H···)₂O═P group, into a linear arrangement along the b axis (Fig. 2).

Experimental

ClF₂CC(O)NHP(O)Cl₂ was prepared according to the literature method reported by Iriarte et al. (2008).

To a solution of ClF₂CC(O)NHP(O)Cl₂ (0.473 g, 1.92 mmol) in dry chloroform (25 ml), a solution of benzylamine (0.823 g, 7.68 mmol) in the same solvent (5 ml) was added at 273 K. After 6 h stirring, the solvent was removed and the product was washed with distilled water and recrystallized from CH₃CN at room temperature.