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

Akbar Raissi Shabari; Mehrdad Pourayoubi; Anahid Saneei

doi:10.1107/S1600536811005423

. 2011 Feb 19;67(Pt 3):o663–o664. doi: 10.1107/S1600536811005423

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

Akbar Raissi Shabari ^a,^*, Mehrdad Pourayoubi ^b, Anahid Saneei ^b

PMCID: PMC3052170 PMID: 21522414

Abstract

In the title molecule, C₁₈H₂₁ClF₂N₃O₂P, the P=O and N—H groups are syn to each other. The P atom adopts a slightly distorted tetrahedral environment and the N atoms of the tertiary amine groups are bonded in an essentially planar geometry. In the crystal, pairs of intermolecular N—H⋯O(P) hydrogen bonds form centrosymmetric dimers.

Related literature

For metal complexes with phosphoryl donor ligands, see: Gholivand et al. (2010 ▶). For a polyoxometalate-based inorganic–organic compound containing a phosphoryl ligand, see: Niu et al. (1996 ▶). For phosphoric triamide compounds having a C(=O)NHP(=O) skeleton, see: Pourayoubi & Sabbaghi (2009 ▶) and references cited therein. For bond lengths in related structures, see: Sabbaghi et al. (2010 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For the synthesis of the starting material, CClF₂C(O)NHP(O)Cl₂, see: Iriarte et al. (2008 ▶).

Experimental

Crystal data

C₁₈H₂₁ClF₂N₃O₂P
M _r = 415.80
Triclinic,
a = 10.3059 (9) Å
b = 10.5030 (9) Å
c = 10.9473 (9) Å
α = 71.743 (2)°
β = 67.294 (2)°
γ = 63.265 (2)°
V = 962.15 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 120 K
0.28 × 0.22 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.916, T _max = 0.954
9258 measured reflections
4148 independent reflections
3359 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.111
S = 1.00
4148 reflections
247 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005423/lh5205sup1.cif

e-67-0o663-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005423/lh5205Isup2.hkl

e-67-0o663-Isup2.hkl^{(203.2KB, hkl)}

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

Table 1. Selected bond angles (°).

O1—P1—N2	112.34 (9)
O1—P1—N1	117.13 (9)
N2—P1—N1	107.02 (9)
O1—P1—N3	105.06 (9)
N2—P1—N3	110.57 (9)
N1—P1—N3	104.38 (9)
C1—N1—C2	114.36 (17)
C1—N1—P1	126.21 (15)
C2—N1—P1	119.42 (14)
C9—N2—C10	115.45 (17)
C9—N2—P1	121.56 (14)
C10—N2—P1	122.42 (15)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1ⁱ	0.87	1.91	2.772 (3)	174

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

Phosphoryl donor ligands have been used to prepare coordination complexes (Gholivand et al., 2010) and polyoxometalate-based inorganic-organic hybrid compounds (Niu et al., 1996). The structure determination of title compound was performed as a part of a project on the synthesis of new potential phosphoric triamide ligands having a C(═O)NHP(═O) skeleton (Pourayoubi & Sabbaghi, 2009).

In the title compound, C₁₈H₂₁ClF₂N₃O₂P, the phosphoryl group and NH unit are syn to each other and the phosphorus atom has a slightly distorted tetrahedral configuration (Fig. 1). The P atom adopts a slightly distorted tetrahedral environment and the N atoms of the tertiary amine groups are bonded in an essentially planar geometry (see Table 1). The P═O bond length is comparable to those in similar compounds e.g. in P(O)[NHC(O)C₆H₄(4-NO₂)][NHC₆H₁₁]₂ (Sabbaghi et al., 2010). In the (CClF₂)C(O) unit, the O—C—C—F dihedral angles showing the orientation of flourine atoms relative to carbonyl group are 17.7 (3) and 137.1 (2)° and the O—C—C—Cl dihedral angle is -101.9 (2)°.

The phosphoryl is a better H-acceptor relative to the carbonyl counterpart (Pourayoubi & Sabbaghi, 2009); so, the hydrogen atom of the C(═ O)NHP(═ O) group is involved in an intermolecular –P═O···H—N– hydrogen bond (see Table 2) to form a centrosymmetric dimeric aggregate [graph set: R₂²(8) (Etter et al., 1990; Bernstein et al., 1995)], Fig. 2.

Experimental

Synthesis of CClF₂C(O)NHP(O)Cl₂: CClF₂C(O)NHP(O)Cl₂ was prepared according to procedure reported by Iriarte et al. (2008) from a reaction between phosphorus pentachloride (16.91 mmol) and CClF₂C(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; then removing of solvent in vacuum to yield CClF₂C(O)NHP(O)Cl₂.

Synthesis of title compound: To a solution of CClF₂C(O)NHP(O)Cl₂ (1.04 mmol) in dry CHCl₃, a solution of N-methylbenzylamine (4.16 mmol) in dry CHCl₃ was added dropwise and stirred at 273 K. After 4 h, the solvent was removed at room temperature. The solid was washed with H₂O. The product was obtained after recrystallization from a methanol/n-heptane mixture (4:1) after a slow evaporation at room temperature. IR (KBr, cm^-1): 3066, 2886, 1729 (C═O), 1592, 1481, 1359, 1286, 1218, 1150, 1009, 965, 863, 809, 698. ¹⁹F NMR (470.59 MHz, DMSO-d6, 300 K, CFCl₃): -63.69 p.p.m. (s). ³¹P{¹H} NMR (202.46 MHz, DMSO-d6, 300 K, 85% H₃PO₄): 12.80 p.p.m. (s). ¹H NMR (500.13 MHz, DMSO-d6, 300 K, TMS): 2.48 (s, 3H, CH₃), 2.50 (s, 3H, CH₃), 4.16 (m, 4H, CH₂), 7.25–7.38 (m, 10H, Ar–H), 10.60 p.p.m. (s, 1H, NH). ¹³C NMR (125.76 MHz, DMSO-d6, 300 K, TMS): 33.16 (d, ²J(P,C) = 4.6 Hz, 2 C, CH₃), 51.78 (d, ²J(P,C) = 5.1 Hz, 2 C, CH₂), 118.08 (dt, 1C, CClF₂), 127.17 (s), 127.96 (s), 128.32 (s), 137.68 (d, ³J(P,C) = 3.9 Hz, 2 C, C_ipso), 159.81 p.p.m. (t, ²J(F,C) = 35.0 Hz, 1 C, C═O).