N-(2-Chloro-2,2-difluoro­acet­yl)-N′,N′′-diisopropyl­phospho­ric triamide

Mehrdad Pourayoubi; Anahid Saneei

doi:10.1107/S1600536811005435

. 2011 Feb 19;67(Pt 3):o665. doi: 10.1107/S1600536811005435

N-(2-Chloro-2,2-difluoroacetyl)-N′,N′′-diisopropylphosphoric triamide

Mehrdad Pourayoubi ^a,^*, Anahid Saneei ^a

PMCID: PMC3052045 PMID: 21522415

Abstract

In the title compound, C₈H₁₇ClF₂N₃O₂P, the phosphoryl group and the NH unit of the C(O)NHP(O) moiety adopt a syn conformation with respect to each other. The P atom is in a tetrahedral coordination environment and the environment of the N atom of the C(O)NHP(O) moiety is essentially planar. In the crystal, adjacent molecules are linked via N—H⋯O =P and N—H⋯O =C hydrogen bonds, building R ₂ ²(8) and R ₂ ²(12) rings in a linear arrangement parallel to [110].

Related literature

For metal complexes of phosphoryl donor ligands, see: Gholivand et al. (2010 ▶). For a phosphoric triamide compound having a C(=O)NHP(=O) skeleton, see: Pourayoubi 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

C₈H₁₇ClF₂N₃O₂P
M _r = 291.67
Triclinic,
a = 8.1993 (7) Å
b = 9.6735 (9) Å
c = 9.8331 (9) Å
α = 99.784 (2)°
β = 105.999 (2)°
γ = 110.770 (2)°
V = 669.18 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 100 K
0.26 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.602, T _max = 0.750
9089 measured reflections
4218 independent reflections
3337 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.095
S = 1.04
4218 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005435/dn2655sup1.cif

e-67-0o665-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005435/dn2655Isup2.hkl

e-67-0o665-Isup2.hkl^{(206.7KB, 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	1.87	2.7295 (13)	164
N3—H3⋯O1ⁱⁱ	0.85	2.14	2.9645 (14)	163

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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

Carbacylamidophosphates with a –C(O)NHP(O)- skeleton have attracted attention because of their roles as the O,O'-donor ligands for metal complexation (Gholivand et al., 2010). Following our previous works about phosphorus compounds containing C(O)NHP(O) moiety such as P(O)[NHC(O)C₆H₃(2,6-F₂)][NHC(CH₃)₃]₂ (Pourayoubi et al., 2010), we report here on the synthesis and crystal structure of P(O)[NHC(O)CClF₂][NH(C₃H₇)]₂. Single crystals of title compound were obtained from a solution of CH₃OH and CH₃CN after a slow evaporation at room temperature.

The phosphoryl group and NH unit are syn to each other and the phosphorus atom has a slightly distorted tetrahedral configuration (Fig. 1). The bond angles around the P atom are in the range of 103.30 (6)° to 119.69 (6)°. The P—N2 and P—N3 bonds (with bond lengths of 1.6262 (12) Å and 1.6190 (11) Å) are shorter than the P—N1 bond (1.7039 (11) Å). The environment of nitrogen N1 atom is essentially planar. The P═O bond length of 1.4768 (9) 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, building R₂²(8) and R₂²(12) rings (Etter et al., 1990; Bernstein et al., 1995) in a linear arrangement parallel to the ab plane in the direction of [110] axis (Table 1, 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 (2.09 mmol) in dry CHCl₃, a solution of N-iso-propylamine (8.36 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): 3400, 3057, 2910, 2890, 2730, 1740 (C═O), 1500, 1260, 1218, 1165, 1118, 1095, 978, 920, 840, 738, 720.