(E)-Methyl 3-[3-(2-chloro-3,3,3-trifluoro­prop-1-en­yl)-2,2-dimethyl­cyclo­propane­carboxamido]thio­phene-2-carboxyl­ate

Yan, F.-Y.; Liu, D.-Q.

doi:10.1107/S1600536807061120

(E)-Methyl 3-[3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxamido]thiophene-2-carboxylate

The title compound, C₁₅H₁₅ClF₃NO₃S, was synthesized from 3-[(E)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropanecarboxylic acid and methyl 3-aminothiophene-2-carboxylate. The propenyl and carboxamide substituents lie on the same side of the cyclopropane ring plane, with the two methyl substituents on either side of the plane. The molecular conformation is stabilized by an N—H

O hydrogen bond and the crystal packing shows C—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061120/bt2628sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061120/bt2628Isup2.hkl Contains datablock I

CCDC reference: 673066

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.005 Å
R factor = 0.055
wR factor = 0.164
Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C15

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        800 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     .....          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     .....          S

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound is known to possess insecticidal activity (Punja, 1981). The propenyl and carboxamide substituents lie on the same side of the cyclopropane ring plane, with two methyl substituents, on either side of this plane. The molecular conformation is stabilized by a N—H···O hydrogen bond and the crystal packing shows C—H···O hydrogen bonds.

Related literature top

For related literature, see: Liu & Yan (2007); Punja (1981).

Experimental top

The title compound was prepared according to the method of Liu et al. (2007). The product was recrystallized from methanol and ethyl acetate (5:1, v/v) over 4 days at ambient temperature, giving colourless prismatic crystals.

Computing details top

Data collection: SMART (Bruker, 1997'; cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

Fig. 1. The molecular structure of the title compound drawn with 30% probability ellipsoids. H atoms are drawn as spheres of arbitrary radius.

(E)-Methyl 3-[3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2- dimethylcyclopropanecarboxamido]thiophene-2-carboxylate top

Crystal data top

C₁₅H₁₅ClF₃NO₃S	Z = 2
M_r = 381.79	F(000) = 392
Triclinic, P1	D_x = 1.390 Mg m⁻³
a = 7.9342 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4940 (14) Å	Cell parameters from 1854 reflections
c = 13.8971 (16) Å	θ = 2.8–25.1°
α = 87.144 (8)°	µ = 0.37 mm⁻¹
β = 85.696 (8)°	T = 294 K
γ = 77.821 (8)°	Prism, colorless
V = 912.4 (2) Å³	0.32 × 0.28 × 0.24 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3188 independent reflections
Radiation source: fine-focus sealed tube	2206 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→8
T_min = 0.892, T_max = 0.918	k = −7→10
4678 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.074P)² + 0.6746P] where P = (F_o² + 2F_c²)/3
3188 reflections	(Δ/σ)_max = 0.001
224 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₁₅H₁₅ClF₃NO₃S	γ = 77.821 (8)°
M_r = 381.79	V = 912.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.9342 (12) Å	Mo Kα radiation
b = 8.4940 (14) Å	µ = 0.37 mm⁻¹
c = 13.8971 (16) Å	T = 294 K
α = 87.144 (8)°	0.32 × 0.28 × 0.24 mm
β = 85.696 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3188 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2206 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.918	R_int = 0.018
4678 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.88 e Å⁻³
3188 reflections	Δρ_min = −0.63 e Å⁻³
224 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C14	0.7383 (5)	−0.2156 (4)	0.6067 (2)	0.0576 (9)
C15	0.6041 (6)	−0.2568 (5)	0.5474 (3)	0.0746 (11)
Cl1	0.93950 (17)	−0.33682 (19)	0.58260 (10)	0.1170 (6)
F1	0.6345 (4)	−0.2276 (4)	0.45312 (18)	0.1239 (11)
F2	0.5909 (5)	−0.4098 (4)	0.5577 (2)	0.1330 (12)
F3	0.4476 (4)	−0.1713 (4)	0.5698 (2)	0.1175 (10)
S1	0.23568 (10)	0.41449 (12)	1.12716 (6)	0.0591 (3)
N1	0.5903 (3)	0.1716 (3)	0.94587 (19)	0.0509 (7)
H1A	0.681 (4)	0.180 (4)	0.972 (2)	0.045 (9)*
O1	0.4775 (3)	0.1059 (4)	0.81065 (19)	0.0813 (9)
O2	0.7451 (3)	0.2882 (3)	1.09510 (17)	0.0642 (7)
O3	0.5618 (3)	0.4482 (3)	1.19945 (17)	0.0664 (7)
C1	0.7882 (4)	0.0441 (4)	0.8196 (2)	0.0515 (8)
H1	0.8686	0.0144	0.8708	0.062*
C2	0.8663 (4)	0.1144 (4)	0.7273 (2)	0.0568 (9)
C3	0.8370 (4)	−0.0577 (4)	0.7302 (2)	0.0544 (8)
H3	0.9429	−0.1407	0.7348	0.065*
C4	0.6038 (4)	0.1073 (4)	0.8559 (2)	0.0523 (8)
C5	0.1460 (4)	0.3306 (5)	1.0390 (3)	0.0616 (9)
H5	0.0275	0.3411	1.0357	0.074*
C6	0.2653 (4)	0.2472 (4)	0.9744 (3)	0.0565 (9)
H6	0.2377	0.1958	0.9220	0.068*
C7	0.4381 (4)	0.2480 (4)	0.9970 (2)	0.0448 (7)
C8	0.4426 (4)	0.3336 (4)	1.0790 (2)	0.0464 (7)
C9	0.5988 (4)	0.3520 (4)	1.1234 (2)	0.0494 (8)
C10	0.7086 (5)	0.4736 (6)	1.2501 (3)	0.0818 (13)
H10A	0.7623	0.3743	1.2814	0.123*
H10B	0.6688	0.5537	1.2976	0.123*
H10C	0.7909	0.5093	1.2046	0.123*
C11	1.0542 (5)	0.1314 (6)	0.7309 (3)	0.0886 (14)
H11A	1.1142	0.0467	0.7717	0.133*
H11B	1.0566	0.2339	0.7564	0.133*
H11C	1.1094	0.1243	0.6670	0.133*
C12	0.7536 (6)	0.2431 (5)	0.6678 (3)	0.0771 (11)
H12A	0.7961	0.2367	0.6013	0.116*
H12B	0.7560	0.3474	0.6906	0.116*
H12C	0.6370	0.2269	0.6737	0.116*
C13	0.7063 (4)	−0.1026 (4)	0.6711 (2)	0.0584 (9)
H13	0.5928	−0.0461	0.6804	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C14	0.069 (2)	0.053 (2)	0.0512 (19)	−0.0107 (17)	−0.0092 (16)	−0.0099 (16)
C15	0.098 (3)	0.065 (3)	0.068 (3)	−0.025 (2)	−0.024 (2)	−0.014 (2)
Cl1	0.0915 (8)	0.1380 (12)	0.1102 (10)	0.0219 (8)	−0.0186 (7)	−0.0751 (9)
F1	0.140 (3)	0.190 (3)	0.0610 (16)	−0.068 (2)	−0.0300 (15)	−0.0095 (17)
F2	0.191 (3)	0.080 (2)	0.152 (3)	−0.061 (2)	−0.072 (2)	−0.0102 (18)
F3	0.0820 (18)	0.145 (3)	0.136 (2)	−0.0271 (18)	−0.0332 (17)	−0.054 (2)
S1	0.0384 (4)	0.0735 (6)	0.0617 (6)	−0.0048 (4)	0.0053 (4)	−0.0072 (4)
N1	0.0363 (14)	0.0666 (19)	0.0516 (16)	−0.0110 (12)	−0.0062 (12)	−0.0134 (13)
O1	0.0467 (14)	0.124 (2)	0.0735 (17)	−0.0060 (14)	−0.0139 (12)	−0.0396 (16)
O2	0.0357 (12)	0.0900 (18)	0.0681 (15)	−0.0116 (11)	0.0000 (10)	−0.0253 (13)
O3	0.0479 (13)	0.0865 (18)	0.0653 (15)	−0.0075 (12)	−0.0066 (11)	−0.0309 (13)
C1	0.0444 (17)	0.061 (2)	0.0494 (18)	−0.0067 (15)	−0.0102 (14)	−0.0120 (15)
C2	0.0545 (19)	0.065 (2)	0.056 (2)	−0.0200 (17)	−0.0035 (15)	−0.0178 (17)
C3	0.0475 (18)	0.058 (2)	0.056 (2)	−0.0029 (15)	−0.0073 (14)	−0.0193 (16)
C4	0.0440 (17)	0.062 (2)	0.0528 (19)	−0.0110 (15)	−0.0080 (14)	−0.0126 (16)
C5	0.0350 (16)	0.079 (3)	0.070 (2)	−0.0136 (16)	−0.0023 (15)	0.0043 (19)
C6	0.0402 (17)	0.068 (2)	0.065 (2)	−0.0162 (15)	−0.0086 (15)	−0.0029 (17)
C7	0.0362 (15)	0.0507 (18)	0.0481 (17)	−0.0107 (13)	−0.0043 (12)	0.0014 (14)
C8	0.0357 (15)	0.0545 (19)	0.0479 (18)	−0.0083 (13)	0.0019 (12)	−0.0019 (14)
C9	0.0410 (17)	0.060 (2)	0.0483 (18)	−0.0140 (14)	0.0003 (13)	−0.0051 (15)
C10	0.061 (2)	0.108 (3)	0.082 (3)	−0.017 (2)	−0.017 (2)	−0.034 (2)
C11	0.066 (3)	0.130 (4)	0.082 (3)	−0.046 (3)	0.005 (2)	−0.028 (3)
C12	0.095 (3)	0.068 (3)	0.072 (3)	−0.024 (2)	−0.011 (2)	−0.004 (2)
C13	0.056 (2)	0.057 (2)	0.063 (2)	−0.0095 (16)	−0.0102 (16)	−0.0148 (17)

Geometric parameters (Å, º) top

C14—C13	1.317 (5)	C2—C3	1.526 (5)
C14—C15	1.501 (5)	C2—C11	1.532 (5)
C14—Cl1	1.726 (4)	C3—C13	1.491 (4)
C15—F3	1.323 (5)	C3—H3	0.9800
C15—F2	1.326 (5)	C5—C6	1.363 (5)
C15—F1	1.335 (5)	C5—H5	0.9300
S1—C5	1.716 (4)	C6—C7	1.430 (4)
S1—C8	1.738 (3)	C6—H6	0.9300
N1—C4	1.377 (4)	C7—C8	1.389 (4)
N1—C7	1.404 (4)	C8—C9	1.465 (4)
N1—H1A	0.85 (3)	C10—H10A	0.9600
O1—C4	1.225 (4)	C10—H10B	0.9600
O2—C9	1.218 (4)	C10—H10C	0.9600
O3—C9	1.345 (4)	C11—H11A	0.9600
O3—C10	1.464 (4)	C11—H11B	0.9600
C1—C4	1.506 (4)	C11—H11C	0.9600
C1—C3	1.528 (4)	C12—H12A	0.9600
C1—C2	1.532 (5)	C12—H12B	0.9600
C1—H1	0.9800	C12—H12C	0.9600
C2—C12	1.512 (5)	C13—H13	0.9300

C13—C14—C15	124.1 (4)	C6—C5—H5	123.3
C13—C14—Cl1	123.7 (3)	S1—C5—H5	123.3
C15—C14—Cl1	112.1 (3)	C5—C6—C7	111.9 (3)
F3—C15—F2	105.7 (4)	C5—C6—H6	124.0
F3—C15—F1	105.5 (4)	C7—C6—H6	124.0
F2—C15—F1	106.7 (3)	C8—C7—N1	121.5 (3)
F3—C15—C14	112.4 (3)	C8—C7—C6	112.2 (3)
F2—C15—C14	113.5 (4)	N1—C7—C6	126.3 (3)
F1—C15—C14	112.4 (4)	C7—C8—C9	125.8 (3)
C5—S1—C8	91.01 (16)	C7—C8—S1	111.4 (2)
C4—N1—C7	126.8 (3)	C9—C8—S1	122.7 (2)
C4—N1—H1A	120 (2)	O2—C9—O3	123.7 (3)
C7—N1—H1A	113 (2)	O2—C9—C8	124.3 (3)
C9—O3—C10	116.6 (3)	O3—C9—C8	112.0 (3)
C4—C1—C3	123.0 (3)	O3—C10—H10A	109.5
C4—C1—C2	121.4 (3)	O3—C10—H10B	109.5
C3—C1—C2	59.8 (2)	H10A—C10—H10B	109.5
C4—C1—H1	114.0	O3—C10—H10C	109.5
C3—C1—H1	114.0	H10A—C10—H10C	109.5
C2—C1—H1	114.0	H10B—C10—H10C	109.5
C12—C2—C3	119.2 (3)	C2—C11—H11A	109.5
C12—C2—C1	119.5 (3)	C2—C11—H11B	109.5
C3—C2—C1	59.9 (2)	H11A—C11—H11B	109.5
C12—C2—C11	115.6 (3)	C2—C11—H11C	109.5
C3—C2—C11	115.9 (3)	H11A—C11—H11C	109.5
C1—C2—C11	115.3 (3)	H11B—C11—H11C	109.5
C13—C3—C2	121.1 (3)	C2—C12—H12A	109.5
C13—C3—C1	122.9 (3)	C2—C12—H12B	109.5
C2—C3—C1	60.2 (2)	H12A—C12—H12B	109.5
C13—C3—H3	114.1	C2—C12—H12C	109.5
C2—C3—H3	114.1	H12A—C12—H12C	109.5
C1—C3—H3	114.1	H12B—C12—H12C	109.5
O1—C4—N1	122.5 (3)	C14—C13—C3	125.4 (3)
O1—C4—C1	124.6 (3)	C14—C13—H13	117.3
N1—C4—C1	112.9 (3)	C3—C13—H13	117.3
C6—C5—S1	113.4 (2)

C13—C14—C15—F3	−2.7 (6)	C2—C1—C4—N1	−118.3 (3)
Cl1—C14—C15—F3	176.0 (3)	C8—S1—C5—C6	−1.0 (3)
C13—C14—C15—F2	−122.6 (4)	S1—C5—C6—C7	0.8 (4)
Cl1—C14—C15—F2	56.1 (5)	C4—N1—C7—C8	−168.2 (3)
C13—C14—C15—F1	116.2 (5)	C4—N1—C7—C6	12.8 (5)
Cl1—C14—C15—F1	−65.1 (4)	C5—C6—C7—C8	−0.1 (4)
C4—C1—C2—C12	−3.8 (4)	C5—C6—C7—N1	179.0 (3)
C3—C1—C2—C12	108.7 (3)	N1—C7—C8—C9	−1.7 (5)
C4—C1—C2—C3	−112.5 (3)	C6—C7—C8—C9	177.4 (3)
C4—C1—C2—C11	141.0 (3)	N1—C7—C8—S1	−179.8 (2)
C3—C1—C2—C11	−106.5 (4)	C6—C7—C8—S1	−0.7 (3)
C12—C2—C3—C13	3.5 (5)	C5—S1—C8—C7	1.0 (3)
C1—C2—C3—C13	112.7 (3)	C5—S1—C8—C9	−177.2 (3)
C11—C2—C3—C13	−141.7 (3)	C10—O3—C9—O2	−0.7 (5)
C12—C2—C3—C1	−109.2 (3)	C10—O3—C9—C8	179.3 (3)
C11—C2—C3—C1	105.6 (3)	C7—C8—C9—O2	−3.0 (5)
C4—C1—C3—C13	0.3 (5)	S1—C8—C9—O2	175.0 (3)
C2—C1—C3—C13	−109.8 (4)	C7—C8—C9—O3	177.0 (3)
C4—C1—C3—C2	110.0 (4)	S1—C8—C9—O3	−5.0 (4)
C7—N1—C4—O1	−2.5 (6)	C15—C14—C13—C3	−179.3 (3)
C7—N1—C4—C1	176.1 (3)	Cl1—C14—C13—C3	2.2 (6)
C3—C1—C4—O1	−12.0 (6)	C2—C3—C13—C14	122.6 (4)
C2—C1—C4—O1	60.2 (5)	C1—C3—C13—C14	−164.9 (4)
C3—C1—C4—N1	169.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.85 (3)	2.12 (3)	2.809 (3)	138 (3)
C5—H5···O2ⁱ	0.93	2.45	3.307 (4)	153

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅ClF₃NO₃S
M_r	381.79
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.9342 (12), 8.4940 (14), 13.8971 (16)
α, β, γ (°)	87.144 (8), 85.696 (8), 77.821 (8)
V (Å³)	912.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.32 × 0.28 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.892, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	4678, 3188, 2206
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.164, 1.03
No. of reflections	3188
No. of parameters	224
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.63

Computer programs: SMART (Bruker, 1997', SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).