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

Mehrdad Pourayoubi; Hassan Fadaei; Masood Parvez

doi:10.1107/S1600536811027681

. 2011 Jul 16;67(Pt 8):o2046. doi: 10.1107/S1600536811027681

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

Mehrdad Pourayoubi ^a,^*, Hassan Fadaei ^a, Masood Parvez ^b

PMCID: PMC3213494 PMID: 22091073

Abstract

The P atom in the title compound, C₁₆H₁₅Cl₅N₃O₂P, exhibits a tetrahedral coordination geometry and the phosphoryl and carbonyl groups are anti with respect to one another. The dihedral angle between the benzene rings is 44.90 (15)°. One of the 2-chlorobenzylamido fragments is disordered over two sets of sites with occupancies of 0.8823 (17) and 0.1177 (17). 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 details of compounds having a C(O)NHP(O) skeleton, see: Toghraee et al. (2011 ▶). For bond lengths in related structures, see: Pourayoubi et al. (2011 ▶); Rudd et al. (1996 ▶).

Experimental

Crystal data

C₁₆H₁₅Cl₅N₃O₂P
M _r = 489.53
Triclinic,
a = 9.9789 (2) Å
b = 10.6058 (3) Å
c = 10.8386 (3) Å
α = 75.8920 (13)°
β = 72.2250 (15)°
γ = 69.6050 (15)°
V = 1011.66 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 173 K
0.18 × 0.14 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer with APEXII CCD detector
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.867, T _max = 0.909
8947 measured reflections
4638 independent reflections
4083 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.129
S = 1.05
4638 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 1.42 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); 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: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027681/sj5176sup1.cif

e-67-o2046-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027681/sj5176Isup2.hkl

e-67-o2046-Isup2.hkl^{(222.6KB, 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
N1—H1⋯O2ⁱ	0.88	1.94	2.804 (3)	168
N2—H2⋯O1ⁱⁱ	0.88	2.38	3.106 (3)	141
N2′—H2′⋯O1	0.88	2.42	3.025 (3)	126
N3—H3⋯O1ⁱⁱ	0.88	2.34	3.129 (3)	149

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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

The structure determination of the title compound, P(O)[NHC(O)CCl₃][NHCH₂C₆H₄(2-Cl)]₂ (Fig. 1), was performed as a part of a project in our laboratory on the synthesis of new phosphoramidate compounds having a C(O)NHP(O) skeleton (Toghraee et al., 2011). Single crystals of the title compound were obtained from a solution of CH₃OH after slow evaporation at room temperature.

The P═O (1.472 (2) Å) and C═O (1.212 (3) Å) bond lengths are standard for this category of compounds (Pourayoubi et al., 2011). The P atom has a distorted tetrahedral configuration (Fig. 1) as has been noted for other phosphoric triamides and their chalco-derivatives (Rudd et al., 1996). The bond angles at the P atom vary in the range 103.26 (13)- 116.10 (12)°. The P—N2 and P—N3 bonds (with lengths of 1.621 (2) Å and 1.622 (2) Å) are shorter than the P—N1 bond (1.715 (2) Å). As can be expected the C1—N1 bond distance (1.339 (3) Å) is shorter than the other C—N bond distances. The N—H unit of C(O)NHP(O) moiety and the phosphoryl group have a syn orientation with respect to each other. One of the 2-chlorobenzylamido fragments is disordered over two sites with occupancies of 0.8823 (17) and 0.1177 (17).

In the crystal, each molecule is hydrogen-bonded to two adjacent molecules through N_C(O)NHP(O)—H···O(P) and N—H···O(C) hydrogen bonds forming linear chains parallel to [100] (Table 1).

Experimental

The reaction of phosphorus pentachloride (35.6 mmol) and 2,2,2-trichloroacetamide (35.6 mmol) in dry CCl₄ (25 ml) at 353 K (3 h) and then treatment with formic acid 85% (35.6 mmol) at 271 K leads to the formation of CCl₃C(O)NHP(O)Cl₂ as a white solid.

To a solution of CCl₃C(O)NHP(O)Cl₂ (2.5 mmol) in dry CHCl₃ (30 ml), a solution of 2-chlorobenzylamine (10 mmol) in dry CHCl₃ (10 ml) was added dropwise at 271 K. After 4 h stirring, the solvent was evaporated at room temperature. The solid was washed with distilled water and recrystallized from CH₃OH.