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Acta Cryst. (2008). E64, o2253    [ doi:10.1107/S1600536808034855 ]

(1SR,3SR)-[(SR)-Cyano(3-phenoxyphenyl)methyl] 3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate

J. Cheng, G. Ju and J. Dong

Abstract top

In the crystal of the title compound, C23H19ClF3NO3, molecules are linked by one C-H...O hydrogen bond and two C-H...[pi] interactions into a three-dimensional network.

Comment top

The title compound, also known as λ-cyhalothrin, exhibits wide-spectrum insecticidal activitiy and represents a good compromise between efficacy and toxicity [Anadón et al., 2006; Whittle, 1991]. In order to research into the relationship between structure and activity, we re-synthesized the title compound and report its crystal structure.

The two benzene rings (defined by atoms C1—C6 and C7—C12, respectively) connected via the O1 atom form a dihedral angle of 89.4 (1)° (Fig.1). The –CF3 group in this appears as a relative rare ordered one which may be due to a close approach of H21···F3 0.93/2.37 Å (idealized: 1.08/2.34 Å) (Table 1). No other unusual features are worth of mention.

In the crystal packing, the molecules at (x, y, z) and (-x + 2, -y + 1, z - 1) are linked together by C13—H13···O3i interactions (Table 1), forming a dimer. Further analysis (Spek, 2003) indicates that these dimers are joined by C—H···π interactions, forming a three-dimensional network (Fig.2). In more detail, one C—H···π interaction is C5—H5···Cg1ii [C5···Cg1=3.721 (1) Å, C5—H5···Cg1=142.8 (1)°, symmetry code: (ii) 3/2 - x, 1/2 + y, 1/2 - z, Cg1 is the centroid defined by phenyl C atoms C1 to C6] and the other one is C9—H9···Cg1iii(C9···Cg1=3.768 (1) Å, C9—H9···Cg1=134.0 (1)°, symmetry code: (iii) x, y - 1,z].

Related literature top

For the insecticidal activity of the title compound, see: Anadón et al. (2006). For the synthesis, see: Whittle (1991). Cg1 is the centroid of the C1–C6 ring.

Experimental top

The title compound was synthesized according to a standard procedure (Whittle, 1991). Light blue crystals appropriate for data collection were obtained by slow evaporation of a 2-propanol solution at room temperature.

Refinement top

All the H atoms were placed at idealized geometry positions with C—H=0.93Å (aromatic), 0.98 Å (methyne) and 0.96Å (methyl), respectively. Uiso values were 1.2 times (aromatic and methyne group) or 1.5 times (methyl) of their carrier atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the crystal structure showing the short C—H···O distances as dashed lines.
(1S,3S)-[(S)-Cyano(3-phenoxyphenyl)methyl] 3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-\ dimethylcyclopropane-1-carboxylate top
Crystal data top
C23H19ClF3NO3F(000) = 1856
Mr = 449.84Dx = 1.347 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4557 reflections
a = 34.7685 (13) Åθ = 2.2–23.4°
b = 7.0159 (3) ŵ = 0.22 mm−1
c = 18.6075 (7) ÅT = 298 K
β = 102.113 (1)°Block, light blue
V = 4437.9 (3) Å30.30 × 0.20 × 0.20 mm
Z = 8
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4361 independent reflections
Radiation source: fine focus sealed Siemens Mo tube2721 reflections with I > 2σ(I)
graphiteRint = 0.040
0.3° wide ω exposures scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −42→35
Tmin = 0.927, Tmax = 0.957k = −8→8
18537 measured reflectionsl = −22→22
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) = 0.174H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.1013P)2]
where P = (Fo2 + 2Fc2)/3
4361 reflections(Δ/σ)max = 0.001
282 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C23H19ClF3NO3V = 4437.9 (3) Å3
Mr = 449.84Z = 8
Monoclinic, C2/cMo Kα radiation
a = 34.7685 (13) ŵ = 0.22 mm−1
b = 7.0159 (3) ÅT = 298 K
c = 18.6075 (7) Å0.30 × 0.20 × 0.20 mm
β = 102.113 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4361 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2721 reflections with I > 2σ(I)
Tmin = 0.927, Tmax = 0.957Rint = 0.040
18537 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.174Δρmax = 0.31 e Å−3
S = 1.03Δρmin = −0.31 e Å−3
4361 reflectionsAbsolute structure: ?
282 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.82508 (6)0.7813 (3)0.26163 (12)0.0597 (5)
C20.82592 (6)0.7796 (3)0.33556 (12)0.0629 (6)
H20.84300.69890.36670.076*
C30.80102 (8)0.8999 (4)0.36309 (14)0.0784 (7)
H30.80100.89890.41310.094*
C40.77628 (9)1.0207 (4)0.31715 (18)0.0913 (8)
H40.75991.10270.33610.110*
C50.77568 (8)1.0206 (4)0.24306 (17)0.0874 (8)
H50.75861.10160.21200.105*
C60.80008 (7)0.9018 (3)0.21453 (13)0.0737 (7)
H60.79980.90220.16450.088*
C70.87410 (7)0.5401 (3)0.27252 (10)0.0620 (6)
C80.86173 (8)0.3602 (4)0.28285 (13)0.0772 (7)
H80.83590.32380.26320.093*
C90.88769 (10)0.2333 (4)0.32258 (16)0.0874 (8)
H90.87970.10890.32860.105*
C100.92547 (9)0.2877 (3)0.35373 (13)0.0758 (7)
H100.94270.20070.38110.091*
C110.93796 (6)0.4725 (3)0.34439 (11)0.0573 (5)
C120.91198 (6)0.5985 (3)0.30277 (10)0.0559 (5)
H120.91990.72210.29510.067*
C130.97833 (6)0.5304 (3)0.38318 (12)0.0702 (6)
H130.98140.49490.43500.084*
C140.98580 (8)0.7324 (5)0.3802 (2)0.1129 (12)
C151.04198 (6)0.3962 (3)0.40121 (11)0.0623 (6)
C161.06771 (6)0.2730 (3)0.36835 (11)0.0636 (6)
H161.05830.24730.31580.076*
C171.09040 (6)0.1102 (3)0.41174 (12)0.0649 (6)
C181.11249 (7)0.2809 (3)0.39356 (12)0.0645 (6)
H181.12650.25790.35390.077*
C191.08716 (8)0.0740 (4)0.48990 (14)0.0892 (8)
H19A1.10950.00160.51450.134*
H19B1.06350.00400.49040.134*
H19C1.08640.19350.51470.134*
C201.09345 (9)−0.0686 (4)0.36638 (17)0.0966 (9)
H20A1.0969−0.03240.31840.145*
H20B1.0698−0.14240.36190.145*
H20C1.1156−0.14340.39040.145*
C211.13247 (7)0.4171 (3)0.44884 (12)0.0647 (6)
H211.11730.47990.47700.078*
C221.16996 (7)0.4567 (3)0.46149 (12)0.0679 (6)
C231.18909 (8)0.6047 (4)0.51402 (15)0.0848 (8)
Cl11.20240 (2)0.34527 (17)0.41744 (5)0.1270 (4)
F11.21955 (6)0.5406 (3)0.56238 (9)0.1209 (6)
F21.20212 (7)0.7498 (3)0.48102 (12)0.1395 (8)
F31.16466 (6)0.6767 (3)0.55237 (11)0.1256 (7)
N10.99126 (9)0.8901 (5)0.3787 (3)0.183 (2)
O10.84875 (5)0.6664 (3)0.22854 (8)0.0822 (5)
O21.00732 (4)0.4254 (2)0.35359 (7)0.0663 (4)
O31.04889 (5)0.4637 (3)0.46189 (8)0.0848 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0391 (11)0.0637 (13)0.0713 (13)−0.0075 (10)0.0002 (10)0.0006 (10)
C20.0509 (13)0.0650 (13)0.0686 (13)−0.0005 (11)0.0028 (10)0.0014 (10)
C30.0761 (18)0.0697 (15)0.0884 (16)0.0005 (13)0.0146 (14)−0.0031 (13)
C40.0773 (19)0.0685 (16)0.128 (2)0.0105 (14)0.0213 (17)−0.0024 (17)
C50.0674 (17)0.0660 (16)0.119 (2)0.0060 (13)−0.0019 (15)0.0178 (15)
C60.0554 (14)0.0761 (15)0.0808 (14)−0.0074 (13)−0.0056 (12)0.0131 (13)
C70.0586 (14)0.0718 (15)0.0553 (11)0.0046 (11)0.0112 (10)−0.0011 (10)
C80.0673 (16)0.0902 (19)0.0738 (14)−0.0221 (15)0.0141 (12)−0.0038 (13)
C90.108 (2)0.0645 (16)0.0941 (18)−0.0241 (16)0.0301 (17)−0.0003 (14)
C100.0889 (19)0.0599 (15)0.0778 (14)0.0141 (14)0.0157 (14)0.0110 (12)
C110.0534 (13)0.0582 (13)0.0603 (11)0.0078 (10)0.0123 (9)−0.0030 (10)
C120.0518 (13)0.0520 (11)0.0639 (11)0.0010 (10)0.0120 (10)0.0011 (9)
C130.0504 (14)0.0838 (17)0.0741 (13)0.0169 (12)0.0080 (11)−0.0148 (12)
C140.0446 (15)0.089 (2)0.198 (4)0.0039 (15)0.0085 (18)−0.043 (2)
C150.0502 (13)0.0796 (15)0.0567 (12)0.0140 (11)0.0105 (10)0.0005 (11)
C160.0570 (14)0.0797 (15)0.0551 (11)0.0162 (11)0.0140 (10)−0.0037 (10)
C170.0475 (12)0.0663 (14)0.0805 (14)0.0074 (11)0.0129 (10)0.0040 (11)
C180.0540 (13)0.0745 (15)0.0702 (13)0.0096 (11)0.0245 (10)−0.0003 (11)
C190.0715 (17)0.100 (2)0.0950 (17)−0.0010 (14)0.0155 (13)0.0306 (15)
C200.0759 (19)0.0710 (16)0.141 (2)0.0087 (14)0.0185 (17)−0.0167 (16)
C210.0573 (15)0.0660 (14)0.0759 (13)0.0057 (11)0.0256 (11)0.0025 (11)
C220.0564 (15)0.0767 (15)0.0733 (13)0.0060 (12)0.0194 (11)0.0116 (12)
C230.0679 (18)0.0958 (19)0.0901 (17)−0.0137 (15)0.0157 (15)0.0084 (16)
Cl10.0578 (5)0.2056 (10)0.1202 (6)0.0220 (5)0.0247 (4)−0.0386 (6)
F10.0990 (13)0.1413 (15)0.1050 (12)−0.0063 (11)−0.0183 (10)0.0062 (11)
F20.1411 (17)0.1298 (15)0.1407 (15)−0.0612 (13)0.0139 (13)0.0315 (12)
F30.1030 (14)0.1286 (15)0.1494 (15)−0.0232 (11)0.0360 (12)−0.0558 (12)
N10.075 (2)0.086 (2)0.377 (6)−0.0026 (17)0.022 (3)−0.054 (3)
O10.0645 (10)0.1168 (14)0.0603 (9)0.0232 (10)0.0019 (8)0.0091 (9)
O20.0542 (9)0.0836 (11)0.0590 (8)0.0222 (8)0.0071 (7)−0.0039 (7)
O30.0577 (10)0.1282 (14)0.0655 (9)0.0242 (9)0.0065 (7)−0.0257 (9)
Geometric parameters (Å, °) top
C1—C21.370 (3)C13—H130.9800
C1—C61.385 (3)C14—N11.124 (4)
C1—O11.386 (3)C15—O31.201 (2)
C2—C31.382 (3)C15—O21.353 (2)
C2—H20.9300C15—C161.467 (3)
C3—C41.371 (4)C16—C171.521 (3)
C3—H30.9300C16—C181.530 (3)
C4—C51.374 (4)C16—H160.9800
C4—H40.9300C17—C181.499 (3)
C5—C61.373 (4)C17—C191.504 (3)
C5—H50.9300C17—C201.528 (3)
C6—H60.9300C18—C211.468 (3)
C7—C81.360 (3)C18—H180.9800
C7—C121.381 (3)C19—H19A0.9600
C7—O11.389 (3)C19—H19B0.9600
C8—C91.369 (4)C19—H19C0.9600
C8—H80.9300C20—H20A0.9600
C9—C101.374 (4)C20—H20B0.9600
C9—H90.9300C20—H20C0.9600
C10—C111.390 (3)C21—C221.305 (3)
C10—H100.9300C21—H210.9300
C11—C121.379 (3)C22—C231.485 (4)
C11—C131.494 (3)C22—Cl11.716 (2)
C12—H120.9300C23—F11.317 (3)
C13—C141.444 (4)C23—F21.317 (3)
C13—O21.448 (2)C23—F31.319 (3)
C2—C1—C6121.3 (2)O2—C15—C16110.69 (17)
C2—C1—O1123.49 (19)C15—C16—C17121.01 (18)
C6—C1—O1115.2 (2)C15—C16—C18121.43 (18)
C1—C2—C3118.9 (2)C17—C16—C1858.87 (14)
C1—C2—H2120.5C15—C16—H16114.7
C3—C2—H2120.5C17—C16—H16114.7
C4—C3—C2120.4 (2)C18—C16—H16114.7
C4—C3—H3119.8C18—C17—C19119.9 (2)
C2—C3—H3119.8C18—C17—C1660.88 (14)
C3—C4—C5120.0 (3)C19—C17—C16120.3 (2)
C3—C4—H4120.0C18—C17—C20115.7 (2)
C5—C4—H4120.0C19—C17—C20115.1 (2)
C6—C5—C4120.5 (2)C16—C17—C20114.3 (2)
C6—C5—H5119.7C21—C18—C17123.46 (18)
C4—C5—H5119.7C21—C18—C16122.67 (18)
C5—C6—C1118.8 (2)C17—C18—C1660.26 (15)
C5—C6—H6120.6C21—C18—H18113.5
C1—C6—H6120.6C17—C18—H18113.5
C8—C7—C12121.4 (2)C16—C18—H18113.5
C8—C7—O1119.6 (2)C17—C19—H19A109.5
C12—C7—O1119.0 (2)C17—C19—H19B109.5
C7—C8—C9119.2 (2)H19A—C19—H19B109.5
C7—C8—H8120.4C17—C19—H19C109.5
C9—C8—H8120.4H19A—C19—H19C109.5
C8—C9—C10120.7 (2)H19B—C19—H19C109.5
C8—C9—H9119.6C17—C20—H20A109.5
C10—C9—H9119.6C17—C20—H20B109.5
C9—C10—C11120.2 (2)H20A—C20—H20B109.5
C9—C10—H10119.9C17—C20—H20C109.5
C11—C10—H10119.9H20A—C20—H20C109.5
C12—C11—C10118.9 (2)H20B—C20—H20C109.5
C12—C11—C13122.4 (2)C22—C21—C18124.9 (2)
C10—C11—C13118.7 (2)C22—C21—H21117.5
C11—C12—C7119.7 (2)C18—C21—H21117.5
C11—C12—H12120.2C21—C22—C23124.1 (2)
C7—C12—H12120.2C21—C22—Cl1123.29 (19)
C14—C13—O2109.9 (2)C23—C22—Cl1112.62 (18)
C14—C13—C11114.0 (2)F1—C23—F2106.1 (2)
O2—C13—C11109.65 (17)F1—C23—F3106.1 (2)
C14—C13—H13107.7F2—C23—F3106.3 (3)
O2—C13—H13107.7F1—C23—C22113.3 (2)
C11—C13—H13107.7F2—C23—C22112.6 (2)
N1—C14—C13179.0 (4)F3—C23—C22111.9 (2)
O3—C15—O2122.07 (19)C1—O1—C7118.18 (16)
O3—C15—C16127.24 (19)C15—O2—C13115.04 (15)
C6—C1—C2—C30.5 (3)C15—C16—C17—C20142.7 (2)
O1—C1—C2—C3−179.9 (2)C18—C16—C17—C20−107.0 (2)
C1—C2—C3—C4−0.9 (4)C19—C17—C18—C211.4 (3)
C2—C3—C4—C51.0 (4)C16—C17—C18—C21111.6 (2)
C3—C4—C5—C6−0.8 (4)C20—C17—C18—C21−143.6 (2)
C4—C5—C6—C10.4 (4)C19—C17—C18—C16−110.2 (2)
C2—C1—C6—C5−0.3 (3)C20—C17—C18—C16104.8 (2)
O1—C1—C6—C5−179.9 (2)C15—C16—C18—C21−3.2 (3)
C12—C7—C8—C9−1.6 (3)C17—C16—C18—C21−112.8 (2)
O1—C7—C8—C9176.0 (2)C15—C16—C18—C17109.7 (2)
C7—C8—C9—C102.0 (4)C17—C18—C21—C22121.1 (3)
C8—C9—C10—C11−0.8 (4)C16—C18—C21—C22−165.3 (2)
C9—C10—C11—C12−0.8 (3)C18—C21—C22—C23175.5 (2)
C9—C10—C11—C13175.9 (2)C18—C21—C22—Cl1−3.1 (3)
C10—C11—C12—C71.2 (3)C21—C22—C23—F1127.1 (3)
C13—C11—C12—C7−175.40 (18)Cl1—C22—C23—F1−54.1 (3)
C8—C7—C12—C110.0 (3)C21—C22—C23—F2−112.6 (3)
O1—C7—C12—C11−177.66 (17)Cl1—C22—C23—F266.2 (3)
C12—C11—C13—C146.9 (3)C21—C22—C23—F37.1 (3)
C10—C11—C13—C14−169.7 (2)Cl1—C22—C23—F3−174.13 (19)
C12—C11—C13—O2−116.8 (2)C2—C1—O1—C71.3 (3)
C10—C11—C13—O266.6 (3)C6—C1—O1—C7−179.1 (2)
O3—C15—C16—C1743.6 (4)C8—C7—O1—C190.7 (2)
O2—C15—C16—C17−135.4 (2)C12—C7—O1—C1−91.6 (2)
O3—C15—C16—C18−26.5 (4)O3—C15—O2—C13−4.7 (3)
O2—C15—C16—C18154.5 (2)C16—C15—O2—C13174.40 (18)
C15—C16—C17—C18−110.3 (2)C14—C13—O2—C1582.4 (3)
C15—C16—C17—C19−0.7 (3)C11—C13—O2—C15−151.59 (19)
C18—C16—C17—C19109.6 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O3i0.982.393.218 (3)142
C21—H21···O30.932.342.984 (3)126
C19—H19C···O30.962.393.037 (3)124
C21—H21···F30.932.372.716 (2)102
C5—H5···Cg1ii0.932.943.721 (1)143 (1)
C9—H9···Cg1iii0.93?3.768 (1)134 (1)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O3i0.982.393.218 (3)142
C21—H21···O30.932.342.984 (3)126
C19—H19C···O30.962.393.037 (3)124
C21—H21···F30.932.372.716 (2)102
C5—H5···Cg1ii0.932.943.721 (1)143 (1)
C9—H9···Cg1iii0.93?3.768 (1)134 (1)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y−1, z.
Acknowledgements top

The authors are grateful to Wuhan Science and Technology program (No. 200760423155) financial support.

references
References top

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