N,N′-Dibenzyl-N′′-(2-chloro­acet­yl)-N,N′-dimethyl­phospho­ric triamide

Mehrdad Pourayoubi; Mojtaba Keikha; Marek Nečas

doi:10.1107/S1600536811033204

. 2011 Aug 27;67(Pt 9):o2439. doi: 10.1107/S1600536811033204

N,N′-Dibenzyl-N′′-(2-chloroacetyl)-N,N′-dimethylphosphoric triamide

Mehrdad Pourayoubi ^a,^*, Mojtaba Keikha ^a, Marek Nečas ^b

PMCID: PMC3200640 PMID: 22059012

Abstract

In the title molecule, C₁₈H₂₃ClN₃O₂P, the P atom is bonded in a distorted tetrahedral environment. The P=O and N—H groups are syn with respect to each other. The angles at the tertiary N atoms confirm their sp ² character. In the crystal, pairs of intermolecular P=O⋯H—N hydrogen bonds form centrosymmetric dimers.

Related literature

For background to compounds having a C(=O)NHP(=O) skeleton, see: Toghraee et al. (2011 ▶); Pourayoubi et al. (2011 ▶).

Experimental

Crystal data

C₁₈H₂₃ClN₃O₂P
M _r = 379.81
Triclinic,
a = 9.5891 (8) Å
b = 9.9259 (7) Å
c = 10.2543 (8) Å
α = 89.509 (6)°
β = 74.945 (7)°
γ = 79.921 (6)°
V = 927.27 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 120 K
0.40 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.983, T _max = 1.000
5838 measured reflections
3253 independent reflections
2594 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.083
S = 1.06
3253 reflections
232 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811033204/lh5303sup1.cif

e-67-o2439-sup1.cif^{(27KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033204/lh5303Isup2.hkl

e-67-o2439-Isup2.hkl^{(159.5KB, 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	0.773 (18)	2.037 (19)	2.795 (2)	167.1 (19)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.

supplementary crystallographic information

Comment

The structure determination of the title compound was performed as part of a project in our laboratory on the synthesis of new phosphoramidates with formula RC(O)NHP(O)[NR'R"]₂ (Toghraee et al., 2011). The molecular structure of the title compound is shown in Fig. 1. The P1—N2 and P1—N3 bonds are shorter than the P1—N1 bond. The sp² character of the tertiary N atoms is indicated by the angles around N2 and N3. The C1—N1—P1 angle is the most distorted from the expected 120° (in terms of sp² hybridization). The P═O bond length is standard for this type of phosphoramidate compounds (Pourayoubi et al., 2011). The hydrogen atom of the C(═O)NHP(═O) group is involved in an intermolecular –P═O···H—N– hydrogen bond (Table 1). Pair of this type of hydrogen bond forms centrosymmetric dimer which is the usual H-bond pattern for compounds with the general formula RC(O)NHP(O)[NR'R"]₂, where R' and R" ≠ H, in the case of syn orientation of P═O versus N—H (Toghraee et al., 2011).

Experimental

Synthesis of CH₂ClC(O)NHP(O)Cl₂: The reaction of phosphorus pentachloride (20 mmol) and 2-chloroacetamide (20 mmol) in dry benzene (40 ml) at 353 K (3 h) and then the treatment of formic acid 85% (20 mmol) at room temperature leads to the formation of CH₂ClC(O)NHP(O)Cl₂ as solid product.

Synthesis of title compound: To a solution of (3.47 mmol) CH₂ClC(O)NHP(O)Cl₂ in CHCl₃ (25 ml), a solution of N-methylbenzylamine (13.88 mmol) in CHCl₃ (5 ml) was added dropwise at 273 K. After 6 h of stirring, the solvent was evaporated in vacuum. The solid was washed with distilled water. Single crystals were obtained from a solution of the title compound in chloroform and n-heptane after slow evaporation at room temperature. IR (KBr, cm^-1): 3116, 2920, 1728, 1494, 1341, 1193, 1011, 949, 867, 800, 743, 695.