supplementary materials


Acta Cryst. (2009). E65, o305    [ doi:10.1107/S1600536809000956 ]

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

T. Tang, L. Gao, H.-S. Jia, Y.-M. Wu and H.-F. Ma

Abstract top

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.

Comment top

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.

Related literature top

For related literature on the synthesis of the title molecule, see: Chen (2008).

Experimental top

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 top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A packing diagram for (I). C—H···O hydrogen bonds are shown as dashed lines.
Ethyl 1-[(4-acetyl-2-methoxyphenoxy)methyl]cyclopropane-1-carboxylate top
Crystal data top
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 top
Enraf–Nonius CAD-4
diffractometer
1473 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
graphiteθmax = 25.3°, θmin = 1.7°
ω/2θ scansh = 014
Absorption correction: ψ scan
(North et al., 1968)
k = 010
Tmin = 0.981, Tmax = 0.991l = 1717
2874 measured reflections3 standard reflections every 200 reflections
2732 independent reflections intensity decay: 1%
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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H-atom parameters constrained
S = 0.93 w = 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
Crystal data top
C16H20O5V = 1509.0 (5) Å3
Mr = 292.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.663 (3) ŵ = 0.10 mm1
b = 8.5020 (17) ÅT = 298 K
c = 14.676 (3) Å0.20 × 0.10 × 0.10 mm
β = 107.25 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1473 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.039
Tmin = 0.981, Tmax = 0.991θmax = 25.3°
2874 measured reflections3 standard reflections every 200 reflections
2732 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.168Δρmax = 0.22 e Å3
S = 0.93Δρmin = 0.20 e Å3
2732 reflectionsAbsolute structure: ?
193 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
O50.0032 (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)
H9A0.18610.15620.52590.085*
H9B0.22560.00220.58490.085*
H9C0.31150.13340.58170.085*
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)
H12A0.23120.09790.14530.068*
H12B0.10010.06530.09300.068*
C130.2038 (3)0.0959 (5)0.0513 (2)0.0590 (11)
H13A0.14710.12680.00640.071*
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)
H15A0.06100.38430.17770.090*
H15B0.01130.47560.26750.090*
C160.0033 (4)0.5888 (6)0.1448 (4)0.0806 (14)
H16A0.06610.64900.14850.121*
H16B0.01230.56050.07970.121*
H16C0.06260.65060.16870.121*
Atomic displacement parameters (Å2) top
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, °) top
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—C87.6 (5)C6—C7—C8—C30.3 (5)
O1—C2—C3—C49.0 (5)C6—O3—C10—C11173.7 (3)
C1—C2—C3—C4170.0 (3)O3—C10—C11—C1474.4 (4)
C8—C3—C4—C50.8 (5)O3—C10—C11—C1274.2 (4)
C2—C3—C4—C5178.5 (3)O3—C10—C11—C13140.7 (3)
C9—O2—C5—C43.6 (5)C14—C11—C12—C13104.1 (4)
C9—O2—C5—C6177.7 (3)C10—C11—C12—C13106.1 (4)
C3—C4—C5—O2178.9 (3)C14—C11—C13—C12106.0 (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—C5175.5 (3)C15—O4—C14—C11179.3 (3)
O2—C5—C6—O31.2 (4)C10—C11—C14—O5173.6 (4)
C4—C5—C6—O3179.9 (3)C12—C11—C14—O524.2 (6)
O2—C5—C6—C7178.1 (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—C81.0 (5)C13—C11—C14—O4139.3 (3)
C4—C3—C8—C70.6 (5)C14—O4—C15—C1696.6 (4)
Hydrogen-bond geometry (Å, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
C7—H7A···O1i0.932.563.329 (4)140
Symmetry codes: (i) x, −y+1/2, z−1/2.
Acknowledgements top

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

references
References top

Chen, G. P. (2008). Advenchen Laboratorties, 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.