N,N′-Bis(2-chloro­benz­yl)-N′′-(dichloro­acet­yl)phospho­ric triamide

Mehrdad Pourayoubi; Maryam Toghraee; Vladimir Divjakovic

doi:10.1107/S1600536811000845

. 2011 Jan 12;67(Pt 2):o333. doi: 10.1107/S1600536811000845

N,N′-Bis(2-chlorobenzyl)-N′′-(dichloroacetyl)phosphoric triamide

Mehrdad Pourayoubi ^a,^*, Maryam Toghraee ^a, Vladimir Divjakovic ^b

PMCID: PMC3051657 PMID: 21523017

Abstract

In the title compound, C₁₆H₁₆Cl₄N₃O₂P, the phosphoryl and carbonyl groups are anti to each other. The dihedral angle between the benzene rings is 33.59 (16)°. In the crystal, adjacent molecules are linked via N—H⋯O=P and N—H⋯O=C hydrogen bonds, into an extended chain running parallel to the a axis.

Related literature

For biologically active organophosphorus compounds, see: Ekstrom et al. (2006 ▶). For the anticancer activity of compounds with a C(O)NHP(O) skeleton, see: Gholivand et al. (2011 ▶). For related structures, see: Sabbaghi et al. (2010a ▶,b ▶).

Experimental

Crystal data

C₁₆H₁₆Cl₄N₃O₂P
M _r = 455.09
Triclinic,
a = 9.901 (1) Å
b = 10.179 (1) Å
c = 12.013 (2) Å
α = 90.403 (5)°
β = 112.851 (6)°
γ = 114.084 (6)°
V = 998.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 295 K
0.22 × 0.12 × 0.11 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.978, T _max = 1.000
6193 measured reflections
3510 independent reflections
2786 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.156
S = 1.02
3510 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000845/fi2102sup1.cif

e-67-0o333-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000845/fi2102Isup2.hkl

e-67-0o333-Isup2.hkl^{(168.6KB, 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
N2—H2⋯O1ⁱ	0.86	1.93	2.756 (4)	162
N3—H3⋯O2ⁱⁱ	0.86	2.24	3.024 (4)	151

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

Acknowledgments

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

supplementary crystallographic information

Comment

Organophosphorus compounds are well-known as the biologically active substances (Ekstrom et al., 2006). Among them the anticancer activity of compounds having a C(O)NHP(O) skeleton has been studied (Gholivand et al., 2011). In the previous works, some phosphoric triamides such as P(O)[NHC(O)C₆H₄(4-NO₂)][NHC₆H₁₁]₂ (Sabbaghi et al., 2010a) and P(O)[NHC(O)C₆H₄(4-NO₂)][N(CH₃)(C₆H₁₁)]₂ (Sabbaghi et al., 2010b) have been structurally investigated. We report here on the synthesis and crystal structure of P(O)[NHC(O)CHCl₂][NHCH₂(2-Cl—C₆H₄)]₂. Single crystals of title compound were obtained from a solution of CH₃OH and CH₃CN after a slow evaporation at room temperature. The phosphoryl and carbonyl groups are anti to each other and the phosphorus atom is in a slightly distorted tetrahedral environment (Fig. 1). The bond angles are in the range of 103.08 (16)°-117.84 (17)° around the P atom. The P—N1 and P—N3 (1.616 (3) Å and 1.619 (3) Å) bond lengths are shorter than the P—N2 bond (1.682 (3) Å). The environment of nitrogen atoms is essentially planar. The P═O bond length of 1.471 (3) Å is standard for phosphoramidate compounds.

In the crystal structure, adjacent molecules are linked via N–H···O═P and N–H···O═C hydrogen bonds, into an extended chain parallel to the a axis.

Experimental

The reaction of phosphorus pentachloride (16.91 mmol) and CHCl₂C(O)NH₂ (16.91 mmol) in dry CCl₄ at 358 K (3 h) and then the treatment of formic acid (16.91 mmol) at ice bath temperature leads to CHCl₂C(O)NHP(O)Cl₂.

To a solution of CHCl₂C(O)NHP(O)Cl₂ (1.04 mmol) in dry CHCl₃, a solution of 2-chlorobenzylamine (4.16 mmol) in dry CHCl₃ was added dropwise and stirred at 273 K. After 4 h, the solvent was evaporated at room temperature. The solid was washed with H₂O. The product was obtained after recrystallization from a methanol/acetonitrile mixture (4:1) after a slow evaporation at room temperature. IR (KBr, cm^-1): 3392 (NH), 3080 (NH), 2881, 1704 (C═O), 1465, 1203 (P═O), 1072, 887.