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In the title compound, C15H14BrClF3NO, the benzene and cyclopropane rings make a dihedral angle of 76.3 (3)°. The amide and methine H atoms are both linked to the amide O atom in an adjacent mol­ecule by a pair of inter­molecular hydrogen bonds, N—H...O...H—C, leading to the formation of chains along the b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045916/bv2066sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045916/bv2066Isup2.hkl
Contains datablock I

CCDC reference: 667268

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.011 Å
  • R factor = 0.054
  • wR factor = 0.205
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT213_ALERT_2_C Atom C8 has ADP max/min Ratio ............. 3.10 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.61 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.21 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 11
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C4 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C6 = ... R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

3-((E)-2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl cyclopropanecarboxylic 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). Bromine containing pesticides have the advantage of low toxicity, high activity and low residues (Zhang 2005). The present structure contains two active parts and thus might be expected to show some insecticide activity. The 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)—N-(2-bromophenyl)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2, 2-dimethylcyclopropanecarboxamide, (I), was synthesized and its structure is illustrated in Fig. 1. The dihedral angle between the benzene moiety and the cyclopropane group is 76.3 (3)°. The amide hydrogen and methine hydrogen link with the same amide oxygen in an adjacent molecule via an intermolecular N—H···O···H—C hydrogen bond. The packing can be described as a dimeric arrangement of molecules linked through N—H···O···H—C hydrogen bonds as shown in Fig. 2 and Table 1.

Related literature top

For related literature, see: Punja (1981); Zhang (2005).

Experimental top

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. The mixture was heated to reflux for 4 h. SOCl2 was removed by rotoevaporation. The crude product could be directly disolved in anhydrous toluene, already mixed with 2-bromoaniline (0.71 g, 4.1 mmol). Triethylamine was aded droppwise to the system to prevent white fumes coming out. After 12 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 (50:1) overnight at ambient temperature gave colorless single crystals of (E)—N-(2-bromophenyl)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2, 2-dimethylcyclopropanecarboxamide, suitable for X-ray analysis.

Refinement top

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

Structure description top

3-((E)-2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl cyclopropanecarboxylic 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). Bromine containing pesticides have the advantage of low toxicity, high activity and low residues (Zhang 2005). The present structure contains two active parts and thus might be expected to show some insecticide activity. The 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)—N-(2-bromophenyl)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2, 2-dimethylcyclopropanecarboxamide, (I), was synthesized and its structure is illustrated in Fig. 1. The dihedral angle between the benzene moiety and the cyclopropane group is 76.3 (3)°. The amide hydrogen and methine hydrogen link with the same amide oxygen in an adjacent molecule via an intermolecular N—H···O···H—C hydrogen bond. The packing can be described as a dimeric arrangement of molecules linked through N—H···O···H—C hydrogen bonds as shown in Fig. 2 and Table 1.

For related literature, see: Punja (1981); Zhang (2005).

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, 1990); 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
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids. H atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. The crystal structure of (I), viewed along a axis
(E)-N-(2-Bromophenyl)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)- 2,2-dimethylcyclopropanecarboxamide top
Crystal data top
C15H14BrClF3NODx = 1.546 Mg m3
Mr = 396.63Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 2447 reflections
a = 18.701 (3) Åθ = 2.4–19.3°
b = 9.4180 (16) ŵ = 2.60 mm1
c = 19.356 (3) ÅT = 294 K
V = 3409.2 (10) Å3Prism, colourless
Z = 80.24 × 0.22 × 0.18 mm
F(000) = 1584
Data collection top
Bruker SMART CCD area-detector
diffractometer
3004 independent reflections
Radiation source: fine-focus sealed tube1493 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1922
Tmin = 0.575, Tmax = 0.652k = 911
16318 measured reflectionsl = 1723
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.205H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0915P)2 + 5.7059P]
where P = (Fo2 + 2Fc2)/3
3004 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.46 e Å3
6 restraintsΔρmin = 0.71 e Å3
Crystal data top
C15H14BrClF3NOV = 3409.2 (10) Å3
Mr = 396.63Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 18.701 (3) ŵ = 2.60 mm1
b = 9.4180 (16) ÅT = 294 K
c = 19.356 (3) Å0.24 × 0.22 × 0.18 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3004 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1493 reflections with I > 2σ(I)
Tmin = 0.575, Tmax = 0.652Rint = 0.075
16318 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0556 restraints
wR(F2) = 0.205H-atom parameters constrained
S = 1.04Δρmax = 0.46 e Å3
3004 reflectionsΔρmin = 0.71 e Å3
201 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
xyzUiso*/Ueq
Br10.05485 (5)0.07635 (11)0.13989 (5)0.0912 (4)
Cl10.34565 (12)0.1240 (3)0.44233 (11)0.0843 (7)
F10.3114 (3)0.4319 (6)0.4070 (3)0.1145 (19)
F20.4226 (3)0.4018 (5)0.4192 (3)0.1077 (18)
F30.3800 (3)0.4432 (4)0.3209 (3)0.1038 (18)
O10.2896 (2)0.1847 (4)0.1711 (3)0.0588 (13)
N10.2144 (3)0.0086 (5)0.1403 (3)0.0464 (13)
H10.20440.07970.14610.056*
C10.3690 (4)0.3721 (9)0.3778 (5)0.070 (2)
C20.3568 (3)0.2181 (7)0.3663 (4)0.0515 (17)
C30.3552 (4)0.1605 (7)0.3053 (4)0.0552 (18)
H30.36310.21970.26760.066*
C40.3420 (4)0.0089 (7)0.2909 (4)0.061 (2)
H40.33430.04870.33240.073*
C50.3773 (4)0.0685 (7)0.2336 (4)0.070 (2)
C60.2990 (4)0.0395 (6)0.2287 (4)0.0567 (19)
H60.26870.12260.23740.068*
C70.4275 (4)0.0051 (12)0.1865 (5)0.099 (3)
H7A0.42700.04070.14220.148*
H7B0.47490.00130.20540.148*
H7C0.41320.10240.18130.148*
C80.3977 (5)0.2211 (8)0.2502 (6)0.120 (4)
H8A0.41530.26660.20920.180*
H8B0.35650.27120.26690.180*
H8C0.43430.22170.28500.180*
C90.2686 (3)0.0626 (6)0.1782 (3)0.0464 (15)
C100.1729 (3)0.0846 (7)0.0919 (3)0.0479 (16)
C110.2031 (4)0.1875 (8)0.0496 (4)0.069 (2)
H110.25200.20490.05190.083*
C120.1613 (5)0.2639 (9)0.0045 (5)0.088 (3)
H120.18260.33070.02430.106*
C130.0887 (5)0.2433 (10)0.0011 (5)0.091 (3)
H130.06070.29900.02790.109*
C140.0579 (4)0.1393 (9)0.0411 (4)0.071 (2)
H140.00920.12120.03790.086*
C150.0995 (3)0.0624 (7)0.0859 (3)0.0514 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0698 (6)0.1091 (8)0.0947 (8)0.0272 (5)0.0041 (5)0.0263 (5)
Cl10.0942 (16)0.0951 (16)0.0636 (13)0.0040 (13)0.0020 (11)0.0041 (11)
F10.110 (3)0.095 (3)0.139 (4)0.022 (3)0.014 (3)0.040 (3)
F20.103 (4)0.089 (4)0.130 (5)0.012 (3)0.040 (4)0.035 (3)
F30.161 (5)0.042 (2)0.109 (4)0.022 (3)0.000 (4)0.007 (3)
O10.064 (3)0.034 (3)0.078 (3)0.004 (2)0.016 (3)0.003 (2)
N10.048 (3)0.035 (3)0.056 (3)0.001 (2)0.005 (3)0.003 (3)
C10.064 (5)0.060 (5)0.086 (6)0.005 (4)0.000 (5)0.021 (5)
C20.046 (4)0.049 (4)0.060 (5)0.000 (3)0.000 (3)0.002 (3)
C30.073 (5)0.041 (4)0.052 (4)0.004 (3)0.004 (4)0.002 (3)
C40.086 (5)0.032 (4)0.065 (5)0.002 (4)0.027 (4)0.002 (3)
C50.080 (6)0.043 (4)0.086 (6)0.018 (4)0.031 (5)0.022 (4)
C60.066 (5)0.031 (3)0.073 (5)0.002 (3)0.021 (4)0.002 (3)
C70.068 (6)0.118 (8)0.109 (8)0.032 (6)0.015 (6)0.049 (7)
C80.148 (9)0.046 (5)0.166 (10)0.046 (5)0.098 (8)0.044 (6)
C90.044 (4)0.036 (4)0.059 (4)0.003 (3)0.002 (3)0.005 (3)
C100.053 (4)0.045 (4)0.046 (4)0.002 (3)0.003 (3)0.001 (3)
C110.062 (5)0.076 (5)0.069 (5)0.009 (4)0.004 (4)0.025 (4)
C120.103 (7)0.077 (6)0.085 (6)0.012 (5)0.020 (5)0.038 (5)
C130.089 (6)0.081 (6)0.102 (7)0.006 (6)0.033 (6)0.026 (5)
C140.062 (5)0.080 (5)0.073 (5)0.007 (4)0.013 (4)0.001 (5)
C150.048 (4)0.054 (4)0.053 (4)0.002 (3)0.001 (3)0.004 (3)
Geometric parameters (Å, º) top
Br1—C151.870 (7)C6—C91.484 (9)
Cl1—C21.730 (7)C6—H60.9800
F1—C11.341 (9)C7—H7A0.9600
F2—C11.313 (9)C7—H7B0.9600
F3—C11.306 (10)C7—H7C0.9600
O1—C91.223 (7)C8—H8A0.9600
N1—C91.351 (8)C8—H8B0.9600
N1—C101.412 (8)C8—H8C0.9600
N1—H10.8600C10—C111.389 (9)
C1—C21.485 (10)C10—C151.393 (9)
C2—C31.300 (9)C11—C121.375 (10)
C3—C41.475 (9)C11—H110.9300
C3—H30.9300C12—C131.373 (11)
C4—C51.482 (11)C12—H120.9300
C4—C61.518 (9)C13—C141.375 (11)
C4—H40.9800C13—H130.9300
C5—C71.482 (13)C14—C151.370 (10)
C5—C61.492 (10)C14—H140.9300
C5—C81.521 (10)
C9—N1—C10125.7 (5)C5—C7—H7A109.5
C9—N1—H1117.2C5—C7—H7B109.5
C10—N1—H1117.2H7A—C7—H7B109.5
F3—C1—F2106.6 (7)C5—C7—H7C109.5
F3—C1—F1105.5 (7)H7A—C7—H7C109.5
F2—C1—F1105.5 (7)H7B—C7—H7C109.5
F3—C1—C2113.4 (7)C5—C8—H8A109.5
F2—C1—C2114.6 (7)C5—C8—H8B109.5
F1—C1—C2110.5 (7)H8A—C8—H8B109.5
C3—C2—C1123.2 (7)C5—C8—H8C109.5
C3—C2—Cl1123.8 (5)H8A—C8—H8C109.5
C1—C2—Cl1113.0 (6)H8B—C8—H8C109.5
C2—C3—C4125.4 (7)O1—C9—N1122.3 (6)
C2—C3—H3117.3O1—C9—C6124.1 (6)
C4—C3—H3117.3N1—C9—C6113.6 (5)
C3—C4—C5122.9 (7)C11—C10—C15117.2 (6)
C3—C4—C6122.0 (6)C11—C10—N1121.3 (6)
C5—C4—C659.6 (5)C15—C10—N1121.4 (6)
C3—C4—H4113.9C12—C11—C10120.5 (7)
C5—C4—H4113.9C12—C11—H11119.8
C6—C4—H4113.9C10—C11—H11119.8
C7—C5—C4120.8 (6)C13—C12—C11121.3 (8)
C7—C5—C6119.8 (7)C13—C12—H12119.4
C4—C5—C661.4 (5)C11—C12—H12119.4
C7—C5—C8114.4 (8)C12—C13—C14119.2 (8)
C4—C5—C8114.8 (8)C12—C13—H13120.4
C6—C5—C8115.7 (7)C14—C13—H13120.4
C9—C6—C5122.4 (6)C15—C14—C13119.7 (7)
C9—C6—C4122.0 (5)C15—C14—H14120.2
C5—C6—C459.0 (5)C13—C14—H14120.2
C9—C6—H6114.2C14—C15—C10122.1 (7)
C5—C6—H6114.2C14—C15—Br1118.0 (5)
C4—C6—H6114.2C10—C15—Br1119.9 (5)
F3—C1—C2—C31.8 (11)C5—C4—C6—C9111.2 (8)
F2—C1—C2—C3124.6 (8)C3—C4—C6—C5112.1 (8)
F1—C1—C2—C3116.4 (9)C10—N1—C9—O14.1 (10)
F3—C1—C2—Cl1177.7 (5)C10—N1—C9—C6175.6 (6)
F2—C1—C2—Cl154.9 (9)C5—C6—C9—O151.3 (10)
F1—C1—C2—Cl164.1 (8)C4—C6—C9—O119.8 (11)
C1—C2—C3—C4178.8 (7)C5—C6—C9—N1129.0 (6)
Cl1—C2—C3—C41.7 (11)C4—C6—C9—N1159.9 (6)
C2—C3—C4—C5144.9 (7)C9—N1—C10—C1137.4 (10)
C2—C3—C4—C6142.9 (8)C9—N1—C10—C15140.7 (7)
C3—C4—C5—C71.1 (11)C15—C10—C11—C120.5 (11)
C6—C4—C5—C7109.5 (8)N1—C10—C11—C12177.7 (7)
C3—C4—C5—C6110.7 (7)C10—C11—C12—C131.6 (14)
C3—C4—C5—C8142.4 (7)C11—C12—C13—C143.4 (15)
C6—C4—C5—C8107.0 (7)C12—C13—C14—C152.9 (14)
C7—C5—C6—C90.6 (10)C13—C14—C15—C100.8 (12)
C4—C5—C6—C9110.5 (7)C13—C14—C15—Br1179.3 (7)
C8—C5—C6—C9144.0 (8)C11—C10—C15—C140.9 (10)
C7—C5—C6—C4111.1 (8)N1—C10—C15—C14177.3 (6)
C8—C5—C6—C4105.5 (8)C11—C10—C15—Br1179.0 (5)
C3—C4—C6—C90.9 (11)N1—C10—C15—Br12.8 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.273.110 (7)164
C6—H6···01i0.982.482.39137
Symmetry code: (i) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC15H14BrClF3NO
Mr396.63
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)294
a, b, c (Å)18.701 (3), 9.4180 (16), 19.356 (3)
V3)3409.2 (10)
Z8
Radiation typeMo Kα
µ (mm1)2.60
Crystal size (mm)0.24 × 0.22 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.575, 0.652
No. of measured, independent and
observed [I > 2σ(I)] reflections
16318, 3004, 1493
Rint0.075
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.205, 1.04
No. of reflections3004
No. of parameters201
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.71

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.273.110 (7)163.9
C6—H6···01i0.982.482.39137
Symmetry code: (i) x+1/2, y1/2, z.
 

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