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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o796.
Published online 2009 March 19. doi:  10.1107/S1600536809009064
PMCID: PMC2968980

Methyl 2-[2-((Z)-{1-trans-[2-(4-fluoro-3-methyl­phen­yl)-2-methyl­cyclo­prop­yl]ethyl­idene}amino­oxymeth­yl)phen­yl]-2-[(E)-methoxy­imino]­acetate

Abstract

The title compound, C24H27FN2O4, is an important inter­mediate in the synthesis of fungicidal strobilurin-type compounds. In the crystal structure, the oxime bond attached to the cyclo­propane ring adopts a Z configuration, while the oxime bond attached to the benzene ring adopts an E configuration. The fluoro­methyl­phenyl group adopts a trans configuration with respect to the remainder of the mol­ecule, and its mean plane forms a dihedral angle of 56.1 (1)° with the plane of the cyclo­propane ring.

Related literature

For synthesis details and related literature, see: Li et al. (2008 [triangle]); Ross et al. (2001 [triangle]).

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Object name is e-65-0o796-scheme1.jpg

Experimental

Crystal data

  • C24H27FN2O4
  • M r = 426.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o796-efi1.jpg
  • a = 7.819 (3) Å
  • b = 10.901 (4) Å
  • c = 14.565 (5) Å
  • α = 105.134 (4)°
  • β = 92.014 (4)°
  • γ = 104.718 (4)°
  • V = 1152.3 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.34 × 0.30 × 0.24 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.754, T max = 0.979
  • 6297 measured reflections
  • 4026 independent reflections
  • 2977 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.140
  • S = 1.05
  • 4026 reflections
  • 285 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009064/bi2355sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009064/bi2355Isup2.hkl

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

supplementary crystallographic information

Comment

Some cyclopropyl-containing Strobilurin-type compounds have been reported as a new class of fungicides characterized by their broad spectrum and high levels of fungicidal activity (Ross et al., 2001; Li et al., 2008). The title compound is an intermediate for preparing such compounds and the crystal structure is important to identify the configuration of possible products.

Experimental

The title compound was prepared according to a published procedure (Li et al., 2008) as follows: trans 2-(4-fluoro-3-methylphenyl)-2-methyl-1-acetylcyclopropane (26.8 g, 13 mmol) and methyl E-2-(aminooxymethyl)phenyl glyoxylate O-methyloxime (34.0 g, 14.3 mmol) were added into methanol (500 ml) and acetic acid (0.7 ml). The mixture was stirred for 14 h and washed with water and brine, dried by anhydrous magnesium sulfate, then evaporated to give an oily product. This product was seperated with silica gel chromatography to give major product A (90%) and minor product B (10%). The product B was dissolved in acetone and left to stand at room temperature. Block crystals suitable for X-ray analyses were obtained.

1H NMR(CDCl3): δ 7.78–7.81 (m, 1H), 7.523–7.492 (m, 1H), 7.412–7.382 (m, 2H), 7.212–7.195 (m, 1H), 7.177–7.035 (m, 2H), 6.785–6.753 (t, 1H), 5.044–5.038 (d, 2H), 3.948 (s, 3H), 3.705 (s, 3H), 2.055–1.986 (m, 4H), 1.868 (s, 3H), 1.205–1.189 (m, 4H).

Refinement

Although all H atoms were visible in difference Fourier maps, they were finally placed in geometrically calculated positions, with C—H distances in the range 0.93–0.98 Å, and included in the final refinement in the riding model approximation, with Uiso(H) = 1.2 or 1.5Ueq(C).

Figures

Fig. 1.
Molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms.

Crystal data

C24H27FN2O4Z = 2
Mr = 426.48F(000) = 452
Triclinic, P1Dx = 1.229 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.819 (3) ÅCell parameters from 2258 reflections
b = 10.901 (4) Åθ = 2.7–25.2°
c = 14.565 (5) ŵ = 0.09 mm1
α = 105.134 (4)°T = 293 K
β = 92.014 (4)°Block, colorless
γ = 104.718 (4)°0.34 × 0.30 × 0.24 mm
V = 1152.3 (7) Å3

Data collection

Bruker APEXII CCD diffractometer4026 independent reflections
Radiation source: fine-focus sealed tube2977 reflections with I > 2σ(I)
graphiteRint = 0.015
[var phi] and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −9→9
Tmin = 0.754, Tmax = 0.979k = −9→12
6297 measured reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0682P)2 + 0.2537P] where P = (Fo2 + 2Fc2)/3
4026 reflections(Δ/σ)max < 0.001
285 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.15 e Å3

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 (Å2)

xyzUiso*/Ueq
F11.35756 (18)0.82907 (15)0.97952 (11)0.0942 (5)
O10.56929 (18)0.50914 (14)0.67273 (10)0.0625 (4)
O20.6063 (2)0.39143 (18)0.88366 (11)0.0903 (6)
O30.33762 (19)0.25037 (15)0.86384 (10)0.0680 (4)
O40.41061 (16)0.08197 (13)0.59611 (9)0.0600 (4)
N10.4299 (2)0.55373 (18)0.63920 (12)0.0604 (4)
N20.37516 (19)0.14127 (15)0.68779 (10)0.0509 (4)
C11.0499 (3)0.9394 (2)0.8529 (2)0.0836 (7)
H11.03991.01720.84110.100*
C21.1977 (3)0.9404 (2)0.9074 (2)0.0879 (8)
H21.28751.01830.93250.105*
C31.2108 (3)0.8262 (2)0.92420 (16)0.0680 (6)
C41.0856 (3)0.7074 (2)0.88688 (14)0.0588 (5)
C51.1107 (4)0.5818 (3)0.9027 (2)0.0895 (8)
H5A1.20180.55630.86580.134*
H5B1.00120.51310.88290.134*
H5C1.14520.59580.96930.134*
C60.9380 (3)0.7098 (2)0.83200 (14)0.0558 (5)
H60.85060.63090.80530.067*
C70.9156 (3)0.8237 (2)0.81544 (15)0.0590 (5)
C80.7563 (3)0.8232 (2)0.75450 (16)0.0637 (5)
C90.7882 (4)0.8208 (4)0.6527 (2)0.1044 (10)
H9A0.88370.89600.65230.157*
H9B0.68210.82350.61890.157*
H9C0.81920.74130.62190.157*
C100.6289 (3)0.8960 (3)0.8011 (2)0.0918 (8)
H10A0.65420.94000.86910.110*
H10B0.57440.94110.76420.110*
C110.5746 (3)0.7483 (2)0.77037 (15)0.0624 (5)
H110.57440.70770.82300.075*
C120.4369 (3)0.6710 (2)0.68858 (15)0.0609 (5)
C130.2966 (3)0.7290 (3)0.65974 (19)0.0849 (7)
H13A0.34900.79670.63020.127*
H13B0.24470.76640.71530.127*
H13C0.20610.66100.61520.127*
C140.5777 (3)0.3937 (2)0.60237 (15)0.0659 (6)
H14A0.60490.41410.54270.079*
H14B0.46430.32710.59100.079*
C150.7210 (3)0.34381 (19)0.63878 (14)0.0552 (5)
C160.8912 (3)0.3751 (2)0.61019 (18)0.0790 (7)
H160.91560.42780.56880.095*
C171.0237 (3)0.3291 (3)0.6423 (2)0.0924 (9)
H171.13610.35050.62190.111*
C180.9913 (3)0.2521 (3)0.7040 (2)0.0822 (8)
H181.08070.22050.72510.099*
C190.8259 (3)0.2222 (2)0.73409 (16)0.0629 (5)
H190.80410.17150.77700.075*
C200.6902 (2)0.26630 (17)0.70163 (13)0.0482 (4)
C210.5128 (2)0.22899 (18)0.73554 (12)0.0460 (4)
C220.4921 (3)0.3000 (2)0.83565 (13)0.0536 (5)
C230.3080 (4)0.3151 (3)0.95956 (16)0.0839 (7)
H23A0.39900.31281.00460.126*
H23B0.19370.27020.97350.126*
H23C0.31160.40520.96420.126*
C240.2488 (3)−0.0023 (2)0.54163 (15)0.0660 (6)
H24A0.1929−0.06440.57490.099*
H24B0.2740−0.04910.48030.099*
H24C0.17070.04990.53290.099*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0727 (9)0.0917 (10)0.1010 (10)0.0112 (7)−0.0317 (8)0.0138 (8)
O10.0619 (8)0.0581 (8)0.0631 (8)0.0179 (7)−0.0104 (7)0.0099 (7)
O20.0780 (11)0.0935 (12)0.0624 (9)−0.0017 (10)0.0000 (8)−0.0159 (9)
O30.0682 (9)0.0725 (10)0.0519 (8)0.0143 (8)0.0142 (7)0.0015 (7)
O40.0439 (7)0.0660 (9)0.0507 (7)0.0069 (6)0.0036 (6)−0.0089 (6)
N10.0528 (10)0.0679 (12)0.0589 (10)0.0149 (8)−0.0040 (8)0.0179 (9)
N20.0423 (8)0.0574 (9)0.0468 (8)0.0151 (7)0.0040 (7)0.0025 (7)
C10.0752 (16)0.0552 (13)0.111 (2)0.0105 (12)−0.0123 (14)0.0179 (13)
C20.0710 (16)0.0578 (15)0.113 (2)0.0013 (12)−0.0212 (14)0.0066 (14)
C30.0567 (12)0.0704 (15)0.0662 (13)0.0114 (11)−0.0096 (10)0.0086 (11)
C40.0593 (12)0.0604 (12)0.0536 (11)0.0124 (10)0.0020 (9)0.0150 (9)
C50.0882 (18)0.0775 (17)0.1009 (19)0.0139 (14)−0.0201 (15)0.0343 (15)
C60.0532 (11)0.0544 (12)0.0532 (11)0.0056 (9)0.0018 (9)0.0133 (9)
C70.0538 (11)0.0591 (12)0.0617 (12)0.0129 (9)0.0047 (9)0.0152 (10)
C80.0556 (12)0.0641 (13)0.0752 (14)0.0126 (10)0.0068 (10)0.0293 (11)
C90.0740 (17)0.153 (3)0.0969 (19)0.0095 (17)0.0048 (14)0.074 (2)
C100.0781 (16)0.0698 (16)0.118 (2)0.0295 (13)−0.0085 (15)0.0025 (15)
C110.0602 (12)0.0647 (13)0.0608 (12)0.0187 (10)0.0047 (10)0.0138 (10)
C120.0527 (11)0.0747 (15)0.0586 (12)0.0183 (10)0.0055 (9)0.0231 (11)
C130.0769 (16)0.107 (2)0.0785 (16)0.0456 (15)0.0001 (13)0.0204 (14)
C140.0794 (15)0.0581 (13)0.0561 (12)0.0167 (11)−0.0040 (10)0.0123 (10)
C150.0523 (11)0.0469 (11)0.0556 (11)0.0063 (8)0.0017 (9)0.0035 (9)
C160.0671 (15)0.0739 (15)0.0773 (15)−0.0045 (12)0.0139 (12)0.0112 (12)
C170.0399 (12)0.096 (2)0.111 (2)0.0015 (12)0.0135 (13)−0.0070 (17)
C180.0427 (12)0.0842 (17)0.105 (2)0.0210 (12)−0.0052 (12)−0.0011 (15)
C190.0465 (11)0.0586 (12)0.0778 (14)0.0172 (9)−0.0082 (10)0.0082 (10)
C200.0395 (9)0.0443 (10)0.0517 (10)0.0107 (8)−0.0021 (8)−0.0005 (8)
C210.0400 (9)0.0493 (10)0.0470 (10)0.0164 (8)−0.0018 (8)0.0071 (8)
C220.0516 (11)0.0551 (11)0.0494 (10)0.0159 (9)−0.0017 (9)0.0061 (9)
C230.1056 (19)0.0876 (18)0.0553 (13)0.0333 (15)0.0254 (13)0.0059 (12)
C240.0537 (12)0.0676 (13)0.0585 (12)0.0052 (10)−0.0089 (9)−0.0006 (10)

Geometric parameters (Å, °)

F1—C31.368 (2)C10—C111.496 (3)
O1—C141.418 (2)C10—H10A0.970
O1—N11.421 (2)C10—H10B0.970
O2—C221.192 (2)C11—C121.487 (3)
O3—C221.319 (2)C11—H110.980
O3—C231.445 (3)C12—C131.496 (3)
O4—N21.3944 (19)C13—H13A0.960
O4—C241.425 (2)C13—H13B0.960
N1—C121.279 (3)C13—H13C0.960
N2—C211.278 (2)C14—C151.501 (3)
C1—C21.375 (3)C14—H14A0.970
C1—C71.385 (3)C14—H14B0.970
C1—H10.930C15—C201.388 (3)
C2—C31.358 (3)C15—C161.394 (3)
C2—H20.930C16—C171.376 (4)
C3—C41.371 (3)C16—H160.930
C4—C61.390 (3)C17—C181.371 (4)
C4—C51.505 (3)C17—H170.930
C5—H5A0.960C18—C191.368 (3)
C5—H5B0.960C18—H180.930
C5—H5C0.960C19—C201.387 (3)
C6—C71.377 (3)C19—H190.930
C6—H60.930C20—C211.483 (3)
C7—C81.502 (3)C21—C221.497 (3)
C8—C101.500 (3)C23—H23A0.960
C8—C91.507 (3)C23—H23B0.960
C8—C111.508 (3)C23—H23C0.960
C9—H9A0.960C24—H24A0.960
C9—H9B0.960C24—H24B0.960
C9—H9C0.960C24—H24C0.960
C14—O1—N1107.55 (14)C8—C11—H11114.3
C22—O3—C23116.14 (17)N1—C12—C11123.38 (19)
N2—O4—C24109.21 (14)N1—C12—C13116.2 (2)
C12—N1—O1111.23 (16)C11—C12—C13120.5 (2)
C21—N2—O4111.21 (14)C12—C13—H13A109.5
C2—C1—C7120.8 (2)C12—C13—H13B109.5
C2—C1—H1119.6H13A—C13—H13B109.5
C7—C1—H1119.6C12—C13—H13C109.5
C3—C2—C1119.1 (2)H13A—C13—H13C109.5
C3—C2—H2120.4H13B—C13—H13C109.5
C1—C2—H2120.4O1—C14—C15107.78 (16)
C2—C3—F1118.4 (2)O1—C14—H14A110.2
C2—C3—C4123.2 (2)C15—C14—H14A110.2
F1—C3—C4118.4 (2)O1—C14—H14B110.2
C3—C4—C6116.2 (2)C15—C14—H14B110.2
C3—C4—C5121.4 (2)H14A—C14—H14B108.5
C6—C4—C5122.4 (2)C20—C15—C16117.8 (2)
C4—C5—H5A109.5C20—C15—C14121.82 (18)
C4—C5—H5B109.5C16—C15—C14120.4 (2)
H5A—C5—H5B109.5C17—C16—C15121.1 (3)
C4—C5—H5C109.5C17—C16—H16119.5
H5A—C5—H5C109.5C15—C16—H16119.5
H5B—C5—H5C109.5C18—C17—C16120.5 (2)
C7—C6—C4122.83 (19)C18—C17—H17119.7
C7—C6—H6118.6C16—C17—H17119.7
C4—C6—H6118.6C19—C18—C17119.2 (2)
C6—C7—C1117.8 (2)C19—C18—H18120.4
C6—C7—C8121.80 (19)C17—C18—H18120.4
C1—C7—C8120.3 (2)C18—C19—C20121.0 (2)
C10—C8—C7118.3 (2)C18—C19—H19119.5
C10—C8—C9118.5 (2)C20—C19—H19119.5
C7—C8—C9114.35 (19)C19—C20—C15120.29 (18)
C10—C8—C1159.65 (15)C19—C20—C21118.64 (18)
C7—C8—C11118.65 (18)C15—C20—C21121.07 (16)
C9—C8—C11116.8 (2)N2—C21—C20126.38 (16)
C8—C9—H9A109.5N2—C21—C22116.44 (16)
C8—C9—H9B109.5C20—C21—C22117.18 (15)
H9A—C9—H9B109.5O2—C22—O3124.65 (18)
C8—C9—H9C109.5O2—C22—C21122.16 (19)
H9A—C9—H9C109.5O3—C22—C21113.20 (16)
H9B—C9—H9C109.5O3—C23—H23A109.5
C11—C10—C860.42 (15)O3—C23—H23B109.5
C11—C10—H10A117.7H23A—C23—H23B109.5
C8—C10—H10A117.7O3—C23—H23C109.5
C11—C10—H10B117.7H23A—C23—H23C109.5
C8—C10—H10B117.7H23B—C23—H23C109.5
H10A—C10—H10B114.9O4—C24—H24A109.5
C12—C11—C10122.1 (2)O4—C24—H24B109.5
C12—C11—C8121.18 (19)H24A—C24—H24B109.5
C10—C11—C859.93 (16)O4—C24—H24C109.5
C12—C11—H11114.3H24A—C24—H24C109.5
C10—C11—H11114.3H24B—C24—H24C109.5
C14—O1—N1—C12−166.73 (18)C10—C11—C12—N1154.4 (2)
C24—O4—N2—C21−172.57 (17)C8—C11—C12—N182.6 (3)
C7—C1—C2—C30.0 (4)C10—C11—C12—C13−25.6 (3)
C1—C2—C3—F1−179.2 (2)C8—C11—C12—C13−97.4 (3)
C1—C2—C3—C42.0 (4)N1—O1—C14—C15−178.28 (16)
C2—C3—C4—C6−1.9 (4)O1—C14—C15—C2082.5 (2)
F1—C3—C4—C6179.34 (18)O1—C14—C15—C16−97.2 (2)
C2—C3—C4—C5176.4 (3)C20—C15—C16—C170.8 (3)
F1—C3—C4—C5−2.4 (3)C14—C15—C16—C17−179.4 (2)
C3—C4—C6—C7−0.3 (3)C15—C16—C17—C18−0.5 (4)
C5—C4—C6—C7−178.6 (2)C16—C17—C18—C19−0.6 (4)
C4—C6—C7—C12.2 (3)C17—C18—C19—C201.3 (3)
C4—C6—C7—C8178.95 (19)C18—C19—C20—C15−1.0 (3)
C2—C1—C7—C6−2.1 (4)C18—C19—C20—C21179.03 (19)
C2—C1—C7—C8−178.9 (2)C16—C15—C20—C19−0.1 (3)
C6—C7—C8—C10115.1 (2)C14—C15—C20—C19−179.79 (17)
C1—C7—C8—C10−68.2 (3)C16—C15—C20—C21179.88 (17)
C6—C7—C8—C9−98.0 (3)C14—C15—C20—C210.1 (3)
C1—C7—C8—C978.7 (3)O4—N2—C21—C20−0.3 (3)
C6—C7—C8—C1146.2 (3)O4—N2—C21—C22−179.87 (15)
C1—C7—C8—C11−137.1 (2)C19—C20—C21—N2−104.2 (2)
C7—C8—C10—C11−108.4 (2)C15—C20—C21—N275.9 (3)
C9—C8—C10—C11106.1 (2)C19—C20—C21—C2275.4 (2)
C8—C10—C11—C12−110.1 (2)C15—C20—C21—C22−104.5 (2)
C10—C8—C11—C12111.6 (3)C23—O3—C22—O21.0 (3)
C7—C8—C11—C12−140.6 (2)C23—O3—C22—C21−179.41 (17)
C9—C8—C11—C122.7 (3)N2—C21—C22—O2−173.2 (2)
C7—C8—C11—C10107.8 (2)C20—C21—C22—O27.2 (3)
C9—C8—C11—C10−108.8 (3)N2—C21—C22—O37.2 (2)
O1—N1—C12—C11−0.1 (3)C20—C21—C22—O3−172.41 (16)
O1—N1—C12—C13179.85 (18)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2355).

References

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