3-[(E)-2-Chloro-3,3,3-trifluoro­prop-1-en-1-yl]-N-(2-chloro­phen­yl)-2,2-dimethyl­cyclo­propane-1-carboxamide

Abstract

In the title compound, C₁₅H₁₄Cl₂F₃NO, synthesized by the reaction of 3-[(E)-2-chloro-3,3,3-trifluoro­prop-1-en­yl]-2,2-dimethyl­cyclo­propane­carb­oxy­lic acid and 2-chloro­aniline, the aromatic ring makes a dihedral angle of 76.7 (3)° with the plane of the cyclo­propane ring. In the crystal, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into chains running along the b axis.

Related literature

The title compound is an inter­mediate for tefluthrinn (2,3,5,6-tetrafluoro-4-methylbenzyl(1RS,3RS)-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropanecarboxylate), an insecticide controlling a wide range of soil insect pests, see: Punja (1981 ▶). For the preparation of the title compound, see Liu & Yan (2007 ▶). For a related structure, see: Yan et al. (2010 ▶).

Experimental

Crystal data

• C₁₅H₁₄Cl₂F₃NO

• M _r = 352.17

• Orthorhombic,

• a = 18.454 (4) Å

• b = 9.3350 (19) Å

• c = 18.981 (4) Å

• V = 3269.7 (11) ų

• Z = 8

• Mo Kα radiation

• μ = 0.43 mm⁻¹

• T = 113 K

• 0.40 × 0.06 × 0.06 mm

Data collection

• Rigaku Saturn CCD area-detector diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.848, T _max = 0.975

• 28276 measured reflections

• 3873 independent reflections

• 3325 reflections with I > 2σ(I)

• R _int = 0.045

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.115

• S = 1.08

• 3873 reflections

• 206 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.25 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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⋯O1i	0.81 (2)	2.26 (2)	3.0415 (19)	162 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

3-((E)-2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl cyclopropanecarboxylic acid is a very important intermediate for tefluthrin, an important insecticide controlling a wide range of soil insect pests in maize, sugar beet, and other crops (Punja, 1981). The title compound may 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. The dihedral angle between the aromatic ring and the cyclopropane groug is 76.7 (3)°. An N-H···O hydrogen bond links the molecules to chains running along the b-axis.

Experimental

The title compound was prepared according to the method of Liu & Yan (2007). The product was recrystallized from methanol and ethyl acetate (5:1) over 5 d at ambient temperature, gave colourless single crystals of (E)-3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-N-(2-chlorophenyl)-2,2- dimethylcyclopropanecarboxamide, suitable for X-ray analysis.

Refinement

H atoms were positioned geometrically with C—H = 0.93–0.98 Å and refined using riding model with U_iso(H) = 1.2Ueq(carrier). The amiino H atom was located from a difference map and freely refined.

Figures

Fig. 1.

The molecular structure of the title compound, drawn with 30% probability ellipsoids. H atoms are drawn as spheres of arbitrary radius.

Crystal data

C15H14Cl2F3NO	Dx = 1.431 Mg m−3
Mr = 352.17	Melting point: 124 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 18.454 (4) Å	Cell parameters from 8396 reflections
b = 9.3350 (19) Å	θ = 2.2–27.2°
c = 18.981 (4) Å	µ = 0.43 mm−1
V = 3269.7 (11) Å3	T = 113 K
Z = 8	Block, colorless
F(000) = 1440	0.40 × 0.06 × 0.06 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer	3873 independent reflections
Radiation source: rotating anode	3325 reflections with I > 2σ(I)
confocal	Rint = 0.045
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 2.2°
ω and φ scans	h = −22→24
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −10→12
Tmin = 0.848, Tmax = 0.975	l = −24→24
28276 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0648P)2 + 0.6506P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
3873 reflections	Δρmax = 0.25 e Å−3
206 parameters	Δρmin = −0.37 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0143 (13)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.15849 (2)	0.37167 (5)	0.05290 (2)	0.03411 (15)
Cl2	0.44326 (2)	0.57979 (5)	0.35812 (2)	0.03963 (16)
F1	0.08112 (7)	0.08899 (12)	0.07614 (7)	0.0458 (3)
F2	0.19548 (7)	0.06413 (12)	0.09253 (7)	0.0490 (3)
F3	0.12256 (7)	0.05370 (11)	0.18026 (6)	0.0440 (3)
O1	0.20892 (6)	0.32062 (12)	0.32957 (6)	0.0293 (3)
N1	0.28640 (7)	0.50060 (15)	0.35929 (7)	0.0237 (3)
C1	0.13526 (10)	0.12238 (19)	0.12027 (10)	0.0320 (4)
C2	0.14360 (8)	0.27922 (17)	0.13093 (8)	0.0251 (3)
C3	0.14182 (9)	0.34166 (18)	0.19383 (9)	0.0275 (3)
H3	0.1325	0.2838	0.2327	0.033*
C4	0.15340 (10)	0.49437 (18)	0.20662 (9)	0.0313 (4)
H4	0.1598	0.5517	0.1638	0.038*
C5	0.19808 (9)	0.54696 (17)	0.27041 (9)	0.0281 (4)
H5	0.2278	0.6318	0.2611	0.034*
C6	0.11674 (10)	0.57294 (18)	0.26648 (10)	0.0346 (4)
C7	0.06647 (10)	0.4966 (2)	0.31580 (12)	0.0456 (5)
H7A	0.0198	0.4862	0.2940	0.068*
H7B	0.0616	0.5510	0.3585	0.068*
H7C	0.0858	0.4037	0.3266	0.068*
C8	0.09538 (13)	0.7269 (2)	0.24999 (14)	0.0590 (7)
H8A	0.0491	0.7279	0.2269	0.089*
H8B	0.1311	0.7692	0.2197	0.089*
H8C	0.0925	0.7807	0.2930	0.089*
C9	0.23019 (8)	0.44437 (16)	0.32159 (8)	0.0232 (3)
C10	0.33010 (8)	0.42237 (17)	0.40673 (8)	0.0236 (3)
C11	0.30110 (10)	0.31756 (19)	0.45095 (9)	0.0316 (4)
H11	0.2515	0.3001	0.4505	0.038*
C12	0.34543 (11)	0.2394 (2)	0.49541 (11)	0.0416 (5)
H12	0.3253	0.1699	0.5246	0.050*
C13	0.41935 (11)	0.2637 (2)	0.49691 (11)	0.0418 (5)
H13	0.4489	0.2092	0.5262	0.050*
C14	0.44927 (10)	0.3692 (2)	0.45467 (10)	0.0342 (4)
H14	0.4988	0.3872	0.4560	0.041*
C15	0.40456 (9)	0.44771 (17)	0.41045 (8)	0.0269 (3)
H1	0.2974 (11)	0.583 (2)	0.3510 (11)	0.032 (5)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0350 (2)	0.0409 (3)	0.0265 (2)	−0.00101 (17)	0.00151 (16)	0.00143 (16)
Cl2	0.0316 (2)	0.0479 (3)	0.0394 (3)	−0.01434 (18)	0.00113 (18)	0.0092 (2)
F1	0.0431 (7)	0.0421 (6)	0.0521 (7)	−0.0071 (5)	−0.0118 (5)	−0.0169 (5)
F2	0.0400 (6)	0.0392 (7)	0.0680 (8)	0.0103 (5)	0.0079 (6)	−0.0207 (6)
F3	0.0638 (8)	0.0226 (5)	0.0454 (6)	−0.0048 (5)	0.0009 (6)	−0.0010 (5)
O1	0.0333 (6)	0.0187 (6)	0.0361 (6)	−0.0026 (4)	−0.0067 (5)	0.0029 (5)
N1	0.0257 (7)	0.0187 (7)	0.0266 (7)	−0.0020 (5)	−0.0024 (5)	0.0029 (5)
C1	0.0296 (9)	0.0295 (9)	0.0369 (9)	0.0017 (7)	−0.0015 (7)	−0.0092 (7)
C2	0.0225 (7)	0.0246 (8)	0.0281 (7)	0.0002 (6)	−0.0006 (6)	0.0002 (6)
C3	0.0323 (8)	0.0223 (8)	0.0279 (8)	0.0016 (6)	−0.0043 (6)	0.0002 (6)
C4	0.0443 (10)	0.0204 (8)	0.0292 (8)	−0.0010 (7)	−0.0113 (7)	−0.0002 (6)
C5	0.0339 (9)	0.0186 (7)	0.0318 (8)	−0.0012 (6)	−0.0089 (7)	0.0004 (6)
C6	0.0380 (10)	0.0258 (9)	0.0401 (10)	0.0094 (7)	−0.0186 (8)	−0.0117 (7)
C7	0.0307 (9)	0.0539 (13)	0.0521 (12)	0.0106 (9)	−0.0046 (8)	−0.0234 (10)
C8	0.0721 (15)	0.0283 (10)	0.0766 (16)	0.0212 (10)	−0.0477 (13)	−0.0202 (10)
C9	0.0243 (7)	0.0195 (7)	0.0257 (7)	0.0034 (6)	−0.0004 (6)	−0.0026 (6)
C10	0.0232 (8)	0.0250 (8)	0.0225 (7)	0.0012 (6)	−0.0010 (6)	−0.0002 (6)
C11	0.0300 (8)	0.0332 (9)	0.0316 (8)	−0.0042 (7)	−0.0022 (7)	0.0078 (7)
C12	0.0437 (11)	0.0382 (11)	0.0429 (10)	−0.0058 (8)	−0.0092 (8)	0.0168 (8)
C13	0.0429 (10)	0.0370 (10)	0.0454 (10)	0.0061 (8)	−0.0147 (9)	0.0081 (8)
C14	0.0251 (8)	0.0380 (10)	0.0394 (9)	0.0038 (7)	−0.0053 (7)	−0.0040 (8)
C15	0.0273 (8)	0.0263 (8)	0.0270 (8)	−0.0014 (6)	0.0014 (6)	−0.0015 (6)

Geometric parameters (Å, °)

Cl1—C2	1.7360 (17)	C6—C7	1.498 (3)
Cl2—C15	1.7368 (17)	C6—C8	1.523 (3)
F1—C1	1.340 (2)	C7—H7A	0.9600
F2—C1	1.345 (2)	C7—H7B	0.9600
F3—C1	1.328 (2)	C7—H7C	0.9600
O1—C9	1.2294 (19)	C8—H8A	0.9600
N1—C9	1.365 (2)	C8—H8B	0.9600
N1—C10	1.412 (2)	C8—H8C	0.9600
N1—H1	0.81 (2)	C10—C11	1.396 (2)
C1—C2	1.486 (2)	C10—C15	1.396 (2)
C2—C3	1.329 (2)	C11—C12	1.383 (3)
C3—C4	1.462 (2)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.383 (3)
C4—C6	1.512 (3)	C12—H12	0.9300
C4—C5	1.545 (2)	C13—C14	1.385 (3)
C4—H4	0.9800	C13—H13	0.9300
C5—C9	1.487 (2)	C14—C15	1.387 (2)
C5—C6	1.522 (2)	C14—H14	0.9300
C5—H5	0.9800
C9—N1—C10	124.70 (14)	C6—C7—H7A	109.5
C9—N1—H1	117.0 (15)	C6—C7—H7B	109.5
C10—N1—H1	118.1 (15)	H7A—C7—H7B	109.5
F3—C1—F1	106.98 (15)	C6—C7—H7C	109.5
F3—C1—F2	106.64 (15)	H7A—C7—H7C	109.5
F1—C1—F2	106.10 (14)	H7B—C7—H7C	109.5
F3—C1—C2	112.16 (14)	C6—C8—H8A	109.5
F1—C1—C2	113.04 (15)	C6—C8—H8B	109.5
F2—C1—C2	111.48 (15)	H8A—C8—H8B	109.5
C3—C2—C1	123.50 (16)	C6—C8—H8C	109.5
C3—C2—Cl1	123.52 (13)	H8A—C8—H8C	109.5
C1—C2—Cl1	112.95 (12)	H8B—C8—H8C	109.5
C2—C3—C4	124.99 (16)	O1—C9—N1	122.64 (14)
C2—C3—H3	117.5	O1—C9—C5	123.94 (14)
C4—C3—H3	117.5	N1—C9—C5	113.42 (13)
C3—C4—C6	122.17 (16)	C11—C10—C15	117.76 (15)
C3—C4—C5	121.21 (14)	C11—C10—N1	121.81 (15)
C6—C4—C5	59.72 (11)	C15—C10—N1	120.43 (14)
C3—C4—H4	114.3	C12—C11—C10	120.65 (16)
C6—C4—H4	114.3	C12—C11—H11	119.7
C5—C4—H4	114.3	C10—C11—H11	119.7
C9—C5—C6	121.83 (15)	C13—C12—C11	120.64 (18)
C9—C5—C4	121.32 (14)	C13—C12—H12	119.7
C6—C5—C4	59.07 (11)	C11—C12—H12	119.7
C9—C5—H5	114.5	C12—C13—C14	119.84 (17)
C6—C5—H5	114.5	C12—C13—H13	120.1
C4—C5—H5	114.5	C14—C13—H13	120.1
C7—C6—C4	121.05 (15)	C13—C14—C15	119.29 (17)
C7—C6—C5	120.27 (15)	C13—C14—H14	120.4
C4—C6—C5	61.21 (11)	C15—C14—H14	120.4
C7—C6—C8	114.65 (18)	C14—C15—C10	121.78 (16)
C4—C6—C8	114.78 (18)	C14—C15—Cl2	118.48 (13)
C5—C6—C8	114.56 (17)	C10—C15—Cl2	119.74 (13)
F3—C1—C2—C3	2.9 (2)	C9—C5—C6—C8	144.09 (17)
F1—C1—C2—C3	123.98 (18)	C4—C5—C6—C8	−105.95 (19)
F2—C1—C2—C3	−116.59 (19)	C10—N1—C9—O1	5.5 (2)
F3—C1—C2—Cl1	−178.82 (11)	C10—N1—C9—C5	−174.29 (14)
F1—C1—C2—Cl1	−57.75 (18)	C6—C5—C9—O1	50.0 (2)
F2—C1—C2—Cl1	61.67 (17)	C4—C5—C9—O1	−20.8 (2)
C1—C2—C3—C4	176.79 (16)	C6—C5—C9—N1	−130.28 (15)
Cl1—C2—C3—C4	−1.3 (2)	C4—C5—C9—N1	159.01 (15)
C2—C3—C4—C6	148.84 (17)	C9—N1—C10—C11	−38.7 (2)
C2—C3—C4—C5	−139.55 (18)	C9—N1—C10—C15	141.04 (16)
C3—C4—C5—C9	−0.7 (3)	C15—C10—C11—C12	−1.7 (3)
C6—C4—C5—C9	110.81 (18)	N1—C10—C11—C12	178.02 (17)
C3—C4—C5—C6	−111.54 (19)	C10—C11—C12—C13	0.0 (3)
C3—C4—C6—C7	0.1 (2)	C11—C12—C13—C14	1.4 (3)
C5—C4—C6—C7	−109.91 (18)	C12—C13—C14—C15	−1.1 (3)
C3—C4—C6—C5	109.97 (17)	C13—C14—C15—C10	−0.7 (3)
C3—C4—C6—C8	−144.45 (17)	C13—C14—C15—Cl2	179.85 (14)
C5—C4—C6—C8	105.58 (17)	C11—C10—C15—C14	2.0 (2)
C9—C5—C6—C7	1.2 (2)	N1—C10—C15—C14	−177.69 (15)
C4—C5—C6—C7	111.14 (18)	C11—C10—C15—Cl2	−178.50 (13)
C9—C5—C6—C4	−109.96 (17)	N1—C10—C15—Cl2	1.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.81 (2)	2.26 (2)	3.0415 (19)	162 (2)

Symmetry codes: (i) −x+1/2, y+1/2, z.