(E)-3-(2-Chloro-3,3,3-trifluoro­prop-1-en­yl)-2,2-dimethyl-N-p-tolyl­cyclo­propane­carboxamide

Fan-Yong Yan; Dong-Qing Liu

doi:10.1107/S160053680706816X

. 2008 Jan 16;64(Pt 2):o451. doi: 10.1107/S160053680706816X

(E)-3-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl-N-p-tolylcyclopropanecarboxamide

Fan-Yong Yan ^a,^*, Dong-Qing Liu ^a

PMCID: PMC2960375 PMID: 21201478

Abstract

There are two molecules in the asymmetric unit of the title compound, C₁₆H₁₇ClF₃NO. The benzene ring in each molecule makes a dihedral angle of 66.6 (3)° [116.3 (4)° in the second molecule] with the plane of the cyclopropane ring. The F atoms of the CF₃ groups are disordered equally over two positions. The amide hydrogen is linked with the amide oxygen in another molecule by an intermolecular N—H⋯O hydrogen bond. The packing can be described as a dimeric arrangement of molecules linked through N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Liu et al. (2006 ▶); Punja (1981 ▶); Zhang (2005 ▶).

Experimental

Crystal data

C₁₆H₁₇ClF₃NO
M _r = 331.76
Triclinic,
a = 9.400 (2) Å
b = 12.482 (3) Å
c = 16.201 (4) Å
α = 70.910 (4)°
β = 88.921 (5)°
γ = 72.517 (4)°
V = 1706.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 294 (2) K
0.22 × 0.18 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,1996 ▶) T _min = 0.945, T _max = 0.967
8849 measured reflections
5945 independent reflections
3077 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.207
S = 1.09
5945 reflections
457 parameters
137 restraints
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SMART; data reduction: SAINT (Bruker, 1997 ▶); program(s) used to solve structure: SHELXTL (Bruker, 2001 ▶); 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/S160053680706816X/bv2081sup1.cif

e-64-0o451-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706816X/bv2081Isup2.hkl

e-64-0o451-Isup2.hkl^{(291KB, 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	0.86	2.15	2.978 (4)	161
N2—H2⋯O1	0.86	2.14	2.959 (4)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation (No. 20376059)

supplementary crystallographic information

Comment

3-[(E)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropanecarboxylic acid is a very important intermediate for tefluthrin, a important insecticide controlling a wide range of soil insect pests in maize, sugar beet, and other crops (Punja 1981). p-Toluidine containing pesticides have the advantage of low toxicity, high activity and low residues (Zhang 2005). The structure in this article containing both of two active parts is expected to show some insecticide activity. The present X-ray crystal structure analysis was undertaken in order to study the stereochemistry and crystal packing of the title compound, (I). In this paper, the title compound, (E)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl-N-p-tolylcyclopropane-carboxamide, (I), was synthesized and the structure of (I) is illustrated in Fig. 1. The dihedral angles between the benzene moiety and the cyclopropane group is 66.6 (3)°. The amide hydrogen is linked with the amide oxygen in an adjoining molecule by an intermolecular N—H···O hydrogen bond. The packing can be described as a dimeric arrangement of molecules linked through N—H···O hydrogen bonds (Table 1).

Experimental

The title compound was prepared according to the method of Liu et al. (2006). 3-((E)-2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2- dimethylcyclopropanecarboxylic acid (0.97 g, 4.0 mmol) was dispersed in SOCl₂ (15 ml), and a drop of anhydrous DMF was added in. The mixture was heated to reflux for 1 h. SOCl₂ was removed by a rotoevaporator. The crude the product could be directly disolved in anhydrous toluene, already mixed with p-toluidine(0.44 g, 4.1 mmol). Triethylamine was dropped into the system, preventing the release of white fumes. After 5 h stirring at room temperature, the reaction mixture was treated with hexane. Recrystallization of the off-white product from methanol and a small amount of water (80:1) overnight at ambient temperature gave colorless single crystals of (E)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl -N-p-tolylcyclopropanecarboxamide, suitable for X-ray analysis.