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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o305.
Published online 2009 January 14. doi:  10.1107/S1600536809000956
PMCID: PMC2968388

Ethyl 1-[(4-acetyl-2-methoxy­phen­oxy)meth­yl]cyclo­propane-1-carboxyl­ate

Abstract

In the title compound, C16H20O5, the dihedral angle between the planar rings, viz. benzene and cyclo­propane, is 52.1 (2)°. Mol­ecules are connected in the crystal via weak inter­molecular C—H(...)O hydrogen bonds, forming chains in the [001] direction.

Related literature

For details of the synthesis, see: Chen (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o305-scheme1.jpg

Experimental

Crystal data

  • C16H20O5
  • M r = 292.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o305-efi1.jpg
  • a = 12.663 (3) Å
  • b = 8.5020 (17) Å
  • c = 14.676 (3) Å
  • β = 107.25 (3)°
  • V = 1509.0 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 (2) K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.981, T max = 0.991
  • 2874 measured reflections
  • 2732 independent reflections
  • 1473 reflections with I > 2σ(I)
  • R int = 0.039
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.168
  • S = 0.93
  • 2732 reflections
  • 193 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); 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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000956/bh2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000956/bh2213Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound, (I), is one of the most important intermediates in the synthesis of 7-[(1-aminocyclopropyl)methoxy]-N-(1H-indol-5-yl)-6-methoxyquinolin-4-amine, which has advantageous pharmacological properties and inhibits the activity of protein tyrosine kinases (Chen, 2008). We report here the crystal structure of (I).

All bond lengths and angles are within expected ranges. Both benzene and cyclopropane rings are planar, and make a dihedral angle of 52.1 (2)° (rings C3···C8 and C11···C13). Molecules are linked together via intermolecular C—H···O hydrogen bonds, which may be effective to the stabilization of the crystal structure.

Experimental

The title compound was synthesized using a method similar to that reported recently (Chen, 2008). The crystals were obtained by evaporating the acetone slowly at room temperature for about 14 d.

Refinement

H atoms were positioned geometrically, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and constrained to ride on their parent atoms, with Uiso(H) = xUeq(carrier C), where x = 1.5 for methyl groups and x = 1.2 otherwise. Methyl groups were allowed to rotate about their C—C bonds.

Figures

Fig. 1.
A drawing of the molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Intramolecular C—H···O hydrogen bond is shown as a dashed line.
Fig. 2.
A packing diagram for (I). C—H···O hydrogen bonds are shown as dashed lines.

Crystal data

C16H20O5F(000) = 624
Mr = 292.32Dx = 1.287 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 12.663 (3) Åθ = 9–13°
b = 8.5020 (17) ŵ = 0.10 mm1
c = 14.676 (3) ÅT = 298 K
β = 107.25 (3)°Plate, colorless
V = 1509.0 (5) Å30.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1473 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
graphiteθmax = 25.3°, θmin = 1.7°
ω/2θ scansh = 0→14
Absorption correction: ψ scan (North et al., 1968)k = 0→10
Tmin = 0.981, Tmax = 0.991l = −17→17
2874 measured reflections3 standard reflections every 200 reflections
2732 independent reflections intensity decay: 1%

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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H-atom parameters constrained
S = 0.93w = 1/[σ2(Fo2) + (0.06P)2 + 1.15P] where P = (Fo2 + 2Fc2)/3
2732 reflections(Δ/σ)max < 0.001
193 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.20 e Å3
0 constraints

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

xyzUiso*/Ueq
O10.5800 (2)0.2003 (4)0.7367 (2)0.0809 (10)
C10.7006 (3)0.3398 (5)0.6698 (3)0.0673 (13)
H1A0.74450.34950.73530.101*
H1B0.68230.44260.64280.101*
H1C0.74180.28380.63480.101*
O20.26250 (19)−0.0087 (3)0.46428 (15)0.0472 (6)
C20.5977 (3)0.2525 (5)0.6646 (3)0.0522 (10)
O30.27923 (17)0.1243 (3)0.31287 (15)0.0431 (6)
C30.5143 (3)0.2248 (4)0.5700 (2)0.0403 (8)
O40.1020 (2)0.3513 (3)0.20147 (19)0.0602 (8)
C40.4262 (3)0.1219 (4)0.5639 (2)0.0417 (9)
H4A0.41970.07400.61890.050*
C50.3492 (3)0.0907 (4)0.4776 (2)0.0360 (8)
O5−0.0032 (2)0.2019 (4)0.0853 (2)0.0883 (11)
C60.3593 (3)0.1627 (4)0.3945 (2)0.0375 (8)
C70.4462 (3)0.2622 (4)0.3995 (2)0.0415 (9)
H7A0.45340.30860.34420.050*
C80.5237 (3)0.2938 (4)0.4871 (3)0.0464 (9)
H8A0.58230.36160.49010.056*
C90.2450 (3)−0.0810 (5)0.5458 (3)0.0565 (11)
H9A0.1861−0.15620.52590.085*
H9B0.2256−0.00220.58490.085*
H9C0.3115−0.13340.58170.085*
C100.2902 (3)0.1857 (4)0.2248 (2)0.0413 (9)
H10A0.35450.14040.21180.050*
H10B0.29940.29900.22920.050*
C110.1888 (3)0.1450 (4)0.1471 (2)0.0414 (8)
C120.1746 (3)−0.0231 (5)0.1132 (3)0.0567 (11)
H12A0.2312−0.09790.14530.068*
H12B0.1001−0.06530.09300.068*
C130.2038 (3)0.0959 (5)0.0513 (2)0.0590 (11)
H13A0.14710.1268−0.00640.071*
H13B0.27840.09420.04610.071*
C140.0850 (3)0.2319 (5)0.1393 (3)0.0497 (10)
C150.0056 (4)0.4466 (6)0.2022 (3)0.0750 (14)
H15A−0.06100.38430.17770.090*
H15B0.01130.47560.26750.090*
C16−0.0033 (4)0.5888 (6)0.1448 (4)0.0806 (14)
H16A−0.06610.64900.14850.121*
H16B−0.01230.56050.07970.121*
H16C0.06260.65060.16870.121*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0617 (18)0.131 (3)0.0465 (16)0.0004 (19)0.0099 (14)−0.0115 (18)
C10.052 (2)0.071 (3)0.068 (3)−0.009 (2)0.001 (2)−0.023 (2)
O20.0434 (13)0.0557 (16)0.0413 (13)−0.0115 (13)0.0106 (10)0.0021 (12)
C20.048 (2)0.057 (3)0.045 (2)0.007 (2)0.0029 (18)−0.015 (2)
O30.0417 (13)0.0481 (15)0.0364 (12)−0.0089 (12)0.0065 (10)0.0034 (12)
C30.0379 (19)0.043 (2)0.0363 (18)0.0070 (17)0.0048 (15)−0.0084 (17)
O40.0503 (15)0.0526 (17)0.0738 (18)0.0038 (14)0.0125 (13)−0.0084 (15)
C40.0370 (18)0.046 (2)0.042 (2)0.0080 (17)0.0112 (15)−0.0006 (17)
C50.0375 (18)0.0311 (18)0.0394 (18)0.0050 (16)0.0113 (15)−0.0037 (15)
O50.0523 (18)0.089 (2)0.101 (2)0.0043 (17)−0.0115 (17)−0.026 (2)
C60.0354 (18)0.036 (2)0.0351 (18)−0.0015 (16)0.0019 (14)−0.0046 (15)
C70.045 (2)0.035 (2)0.044 (2)0.0015 (17)0.0112 (16)0.0007 (17)
C80.041 (2)0.035 (2)0.058 (2)−0.0016 (17)0.0063 (17)−0.0061 (18)
C90.058 (2)0.061 (3)0.057 (2)−0.006 (2)0.0264 (19)0.010 (2)
C100.045 (2)0.041 (2)0.0385 (19)−0.0018 (17)0.0129 (15)0.0033 (16)
C110.050 (2)0.037 (2)0.0351 (18)−0.0027 (17)0.0087 (15)0.0003 (16)
C120.066 (3)0.043 (2)0.056 (2)−0.002 (2)0.0093 (19)−0.0094 (19)
C130.071 (3)0.066 (3)0.037 (2)−0.005 (2)0.0111 (18)−0.005 (2)
C140.042 (2)0.051 (2)0.047 (2)−0.0062 (19)0.0001 (18)0.005 (2)
C150.061 (3)0.069 (3)0.102 (4)0.020 (2)0.034 (3)0.010 (3)
C160.060 (3)0.071 (3)0.112 (4)0.007 (3)0.026 (3)0.002 (3)

Geometric parameters (Å, °)

O1—C21.227 (4)C8—H8A0.9300
C1—C21.482 (5)C9—H9A0.9600
C1—H1A0.9600C9—H9B0.9600
C1—H1B0.9600C9—H9C0.9600
C1—H1C0.9600C10—C111.483 (4)
O2—C51.352 (4)C10—H10A0.9700
O2—C91.419 (4)C10—H10B0.9700
C2—C31.493 (5)C11—C141.482 (5)
O3—C61.360 (3)C11—C121.506 (5)
O3—C101.438 (4)C11—C131.532 (5)
C3—C81.387 (5)C12—C131.478 (5)
C3—C41.399 (5)C12—H12A0.9700
O4—C141.339 (4)C12—H12B0.9700
O4—C151.468 (4)C13—H13A0.9700
C4—C51.376 (4)C13—H13B0.9700
C4—H4A0.9300C15—C161.459 (6)
C5—C61.405 (5)C15—H15A0.9700
O5—C141.189 (4)C15—H15B0.9700
C6—C71.373 (4)C16—H16A0.9600
C7—C81.393 (5)C16—H16B0.9600
C7—H7A0.9300C16—H16C0.9600
C2—C1—H1A109.5C11—C10—H10A110.0
C2—C1—H1B109.5O3—C10—H10B110.0
H1A—C1—H1B109.5C11—C10—H10B110.0
C2—C1—H1C109.5H10A—C10—H10B108.4
H1A—C1—H1C109.5C14—C11—C10119.3 (3)
H1B—C1—H1C109.5C14—C11—C12115.5 (3)
C5—O2—C9118.1 (3)C10—C11—C12117.9 (3)
O1—C2—C1121.3 (3)C14—C11—C13114.4 (3)
O1—C2—C3119.0 (4)C10—C11—C13117.0 (3)
C1—C2—C3119.7 (4)C12—C11—C1358.2 (2)
C6—O3—C10117.3 (2)C13—C12—C1161.7 (2)
C8—C3—C4118.9 (3)C13—C12—H12A117.6
C8—C3—C2121.8 (3)C11—C12—H12A117.6
C4—C3—C2119.3 (3)C13—C12—H12B117.6
C14—O4—C15117.2 (3)C11—C12—H12B117.6
C5—C4—C3120.9 (3)H12A—C12—H12B114.7
C5—C4—H4A119.5C12—C13—C1160.0 (2)
C3—C4—H4A119.5C12—C13—H13A117.8
O2—C5—C4125.3 (3)C11—C13—H13A117.8
O2—C5—C6115.2 (3)C12—C13—H13B117.8
C4—C5—C6119.5 (3)C11—C13—H13B117.8
O3—C6—C7124.9 (3)H13A—C13—H13B114.9
O3—C6—C5115.1 (3)O5—C14—O4123.1 (4)
C7—C6—C5120.0 (3)O5—C14—C11125.5 (4)
C6—C7—C8120.1 (3)O4—C14—C11111.4 (3)
C6—C7—H7A119.9C16—C15—O4112.0 (4)
C8—C7—H7A119.9C16—C15—H15A109.2
C3—C8—C7120.5 (3)O4—C15—H15A109.2
C3—C8—H8A119.7C16—C15—H15B109.2
C7—C8—H8A119.7O4—C15—H15B109.2
O2—C9—H9A109.5H15A—C15—H15B107.9
O2—C9—H9B109.5C15—C16—H16A109.5
H9A—C9—H9B109.5C15—C16—H16B109.5
O2—C9—H9C109.5H16A—C16—H16B109.5
H9A—C9—H9C109.5C15—C16—H16C109.5
H9B—C9—H9C109.5H16A—C16—H16C109.5
O3—C10—C11108.3 (3)H16B—C16—H16C109.5
O3—C10—H10A110.0
O1—C2—C3—C8173.4 (4)C2—C3—C8—C7178.2 (3)
C1—C2—C3—C8−7.6 (5)C6—C7—C8—C30.3 (5)
O1—C2—C3—C4−9.0 (5)C6—O3—C10—C11−173.7 (3)
C1—C2—C3—C4170.0 (3)O3—C10—C11—C1474.4 (4)
C8—C3—C4—C5−0.8 (5)O3—C10—C11—C12−74.2 (4)
C2—C3—C4—C5−178.5 (3)O3—C10—C11—C13−140.7 (3)
C9—O2—C5—C43.6 (5)C14—C11—C12—C13104.1 (4)
C9—O2—C5—C6−177.7 (3)C10—C11—C12—C13−106.1 (4)
C3—C4—C5—O2178.9 (3)C14—C11—C13—C12−106.0 (4)
C3—C4—C5—C60.2 (5)C10—C11—C13—C12107.5 (4)
C10—O3—C6—C73.6 (5)C15—O4—C14—O50.7 (6)
C10—O3—C6—C5−175.5 (3)C15—O4—C14—C11−179.3 (3)
O2—C5—C6—O31.2 (4)C10—C11—C14—O5−173.6 (4)
C4—C5—C6—O3179.9 (3)C12—C11—C14—O5−24.2 (6)
O2—C5—C6—C7−178.1 (3)C13—C11—C14—O540.7 (5)
C4—C5—C6—C70.7 (5)C10—C11—C14—O46.4 (5)
O3—C6—C7—C8179.9 (3)C12—C11—C14—O4155.8 (3)
C5—C6—C7—C8−1.0 (5)C13—C11—C14—O4−139.3 (3)
C4—C3—C8—C70.6 (5)C14—O4—C15—C16−96.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7A···O1i0.932.563.329 (4)140
C15—H15A···O50.972.322.678 (6)101

Symmetry codes: (i) x, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2213).

References

  • Chen, G. P. (2008). Advenchen Laboratories, LLC, USA. WO Patent No. 2008112407.
  • Enraf–Nonius (1985). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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