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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2253.
Published online 2008 November 8. doi:  10.1107/S1600536808034855
PMCID: PMC2960082

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

Abstract

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

Related literature

For the insecticidal activity of the title compound, see: Anadón et al. (2006 [triangle]). For the synthesis, see: Whittle (1991 [triangle]).

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Object name is e-64-o2253-scheme1.jpg

Experimental

Crystal data

  • C23H19ClF3NO3
  • M r = 449.84
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2253-efi1.jpg
  • a = 34.7685 (13) Å
  • b = 7.0159 (3) Å
  • c = 18.6075 (7) Å
  • β = 102.113 (1)°
  • V = 4437.9 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.927, T max = 0.957
  • 18537 measured reflections
  • 4361 independent reflections
  • 2721 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.174
  • S = 1.03
  • 4361 reflections
  • 282 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.31 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034855/cs2097sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034855/cs2097Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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].

Experimental

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

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.

Figures

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.
Fig. 2.
Part of the crystal structure showing the short C—H···O distances as dashed lines.

Crystal data

C23H19ClF3NO3F000 = 1856
Mr = 449.84Dx = 1.347 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4557 reflections
a = 34.7685 (13) Åθ = 2.2–23.4º
b = 7.0159 (3) ŵ = 0.22 mm1
c = 18.6075 (7) ÅT = 298 (2) K
β = 102.113 (1)ºBlock, light blue
V = 4437.9 (3) Å30.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer4361 independent reflections
Radiation source: fine focus sealed Siemens Mo tube2721 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
T = 298(2) Kθmax = 26.0º
0.3° wide ω exposures scansθmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2001)h = −42→35
Tmin = 0.927, Tmax = 0.957k = −8→8
18537 measured reflectionsl = −22→22

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.174  w = 1/[σ2(Fo2) + (0.1013P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
4361 reflectionsΔρmax = 0.31 e Å3
282 parametersΔρmin = −0.31 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2097).

References

  • Anadón, A., Martínez, M., Martínez, M. A., Díaz, M. J. & Martínez-Larranga, M. R. (2006). Toxicol. Lett.165, 47–49. [PubMed]
  • Bruker (2001). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
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