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

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

doi:10.1107/S1600536809000956

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o305

doi:10.1107/S1600536809000956

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

Ting Tang,^a Lei Gao,^a Hong-Sheng Jia,^b Ya-Ming Wu ^c and Hong-Fei Ma ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, ^bDepartment of Chemical Engineering, Chien-shlung Institute of Technology, Taicang 215411, People's Republic of China, and ^cDepartment of Applied Chemistry, Nanjing College of Chemical Technology, No. 625 Geguan Road, Dachang, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: mhf2356@yahoo.com.cn

(Received 9 December 2008; accepted 8 January 2009; online 14 January 2009)

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 ).

Experimental

Crystal data

C₁₆H₂₀O₅
M_r = 292.32
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.062
wR(F²) = 0.168
S = 0.93
2732 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1ⁱ	0.93	2.56	3.329 (4)	140
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; 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.

Supporting information

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

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

checkCIF report

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.

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

	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.

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

Crystal data top

C₁₆H₂₀O₅	F(000) = 624
M_r = 292.32	D_x = 1.287 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.663 (3) Å	θ = 9–13°
b = 8.5020 (17) Å	µ = 0.10 mm⁻¹
c = 14.676 (3) Å	T = 298 K
β = 107.25 (3)°	Plate, colorless
V = 1509.0 (5) Å³	0.20 × 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 tube	R_int = 0.039
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.981, T_max = 0.991	l = −17→17
2874 measured reflections	3 standard reflections every 200 reflections
2732 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.06P)² + 1.15P] where P = (F_o² + 2F_c²)/3
2732 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³
0 constraints

Crystal data top

C₁₆H₂₀O₅	V = 1509.0 (5) Å³
M_r = 292.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.663 (3) Å	µ = 0.10 mm⁻¹
b = 8.5020 (17) Å	T = 298 K
c = 14.676 (3) Å	0.20 × 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)	R_int = 0.039
T_min = 0.981, T_max = 0.991	3 standard reflections every 200 reflections
2874 measured reflections	intensity decay: 1%
2732 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 0.93	Δρ_max = 0.22 e Å⁻³
2732 reflections	Δρ_min = −0.20 e Å⁻³
193 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.5800 (2)	0.2003 (4)	0.7367 (2)	0.0809 (10)
C1	0.7006 (3)	0.3398 (5)	0.6698 (3)	0.0673 (13)
H1A	0.7445	0.3495	0.7353	0.101*
H1B	0.6823	0.4426	0.6428	0.101*
H1C	0.7418	0.2838	0.6348	0.101*
O2	0.26250 (19)	−0.0087 (3)	0.46428 (15)	0.0472 (6)
C2	0.5977 (3)	0.2525 (5)	0.6646 (3)	0.0522 (10)
O3	0.27923 (17)	0.1243 (3)	0.31287 (15)	0.0431 (6)
C3	0.5143 (3)	0.2248 (4)	0.5700 (2)	0.0403 (8)
O4	0.1020 (2)	0.3513 (3)	0.20147 (19)	0.0602 (8)
C4	0.4262 (3)	0.1219 (4)	0.5639 (2)	0.0417 (9)
H4A	0.4197	0.0740	0.6189	0.050*
C5	0.3492 (3)	0.0907 (4)	0.4776 (2)	0.0360 (8)
O5	−0.0032 (2)	0.2019 (4)	0.0853 (2)	0.0883 (11)
C6	0.3593 (3)	0.1627 (4)	0.3945 (2)	0.0375 (8)
C7	0.4462 (3)	0.2622 (4)	0.3995 (2)	0.0415 (9)
H7A	0.4534	0.3086	0.3442	0.050*
C8	0.5237 (3)	0.2938 (4)	0.4871 (3)	0.0464 (9)
H8A	0.5823	0.3616	0.4901	0.056*
C9	0.2450 (3)	−0.0810 (5)	0.5458 (3)	0.0565 (11)
H9A	0.1861	−0.1562	0.5259	0.085*
H9B	0.2256	−0.0022	0.5849	0.085*
H9C	0.3115	−0.1334	0.5817	0.085*
C10	0.2902 (3)	0.1857 (4)	0.2248 (2)	0.0413 (9)
H10A	0.3545	0.1404	0.2118	0.050*
H10B	0.2994	0.2990	0.2292	0.050*
C11	0.1888 (3)	0.1450 (4)	0.1471 (2)	0.0414 (8)
C12	0.1746 (3)	−0.0231 (5)	0.1132 (3)	0.0567 (11)
H12A	0.2312	−0.0979	0.1453	0.068*
H12B	0.1001	−0.0653	0.0930	0.068*
C13	0.2038 (3)	0.0959 (5)	0.0513 (2)	0.0590 (11)
H13A	0.1471	0.1268	−0.0064	0.071*
H13B	0.2784	0.0942	0.0461	0.071*
C14	0.0850 (3)	0.2319 (5)	0.1393 (3)	0.0497 (10)
C15	0.0056 (4)	0.4466 (6)	0.2022 (3)	0.0750 (14)
H15A	−0.0610	0.3843	0.1777	0.090*
H15B	0.0113	0.4756	0.2675	0.090*
C16	−0.0033 (4)	0.5888 (6)	0.1448 (4)	0.0806 (14)
H16A	−0.0661	0.6490	0.1485	0.121*
H16B	−0.0123	0.5605	0.0797	0.121*
H16C	0.0626	0.6506	0.1687	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0617 (18)	0.131 (3)	0.0465 (16)	0.0004 (19)	0.0099 (14)	−0.0115 (18)
C1	0.052 (2)	0.071 (3)	0.068 (3)	−0.009 (2)	0.001 (2)	−0.023 (2)
O2	0.0434 (13)	0.0557 (16)	0.0413 (13)	−0.0115 (13)	0.0106 (10)	0.0021 (12)
C2	0.048 (2)	0.057 (3)	0.045 (2)	0.007 (2)	0.0029 (18)	−0.015 (2)
O3	0.0417 (13)	0.0481 (15)	0.0364 (12)	−0.0089 (12)	0.0065 (10)	0.0034 (12)
C3	0.0379 (19)	0.043 (2)	0.0363 (18)	0.0070 (17)	0.0048 (15)	−0.0084 (17)
O4	0.0503 (15)	0.0526 (17)	0.0738 (18)	0.0038 (14)	0.0125 (13)	−0.0084 (15)
C4	0.0370 (18)	0.046 (2)	0.042 (2)	0.0080 (17)	0.0112 (15)	−0.0006 (17)
C5	0.0375 (18)	0.0311 (18)	0.0394 (18)	0.0050 (16)	0.0113 (15)	−0.0037 (15)
O5	0.0523 (18)	0.089 (2)	0.101 (2)	0.0043 (17)	−0.0115 (17)	−0.026 (2)
C6	0.0354 (18)	0.036 (2)	0.0351 (18)	−0.0015 (16)	0.0019 (14)	−0.0046 (15)
C7	0.045 (2)	0.035 (2)	0.044 (2)	0.0015 (17)	0.0112 (16)	0.0007 (17)
C8	0.041 (2)	0.035 (2)	0.058 (2)	−0.0016 (17)	0.0063 (17)	−0.0061 (18)
C9	0.058 (2)	0.061 (3)	0.057 (2)	−0.006 (2)	0.0264 (19)	0.010 (2)
C10	0.045 (2)	0.041 (2)	0.0385 (19)	−0.0018 (17)	0.0129 (15)	0.0033 (16)
C11	0.050 (2)	0.037 (2)	0.0351 (18)	−0.0027 (17)	0.0087 (15)	0.0003 (16)
C12	0.066 (3)	0.043 (2)	0.056 (2)	−0.002 (2)	0.0093 (19)	−0.0094 (19)
C13	0.071 (3)	0.066 (3)	0.037 (2)	−0.005 (2)	0.0111 (18)	−0.005 (2)
C14	0.042 (2)	0.051 (2)	0.047 (2)	−0.0062 (19)	0.0001 (18)	0.005 (2)
C15	0.061 (3)	0.069 (3)	0.102 (4)	0.020 (2)	0.034 (3)	0.010 (3)
C16	0.060 (3)	0.071 (3)	0.112 (4)	0.007 (3)	0.026 (3)	0.002 (3)

Geometric parameters (Å, º) top

O1—C2	1.227 (4)	C8—H8A	0.9300
C1—C2	1.482 (5)	C9—H9A	0.9600
C1—H1A	0.9600	C9—H9B	0.9600
C1—H1B	0.9600	C9—H9C	0.9600
C1—H1C	0.9600	C10—C11	1.483 (4)
O2—C5	1.352 (4)	C10—H10A	0.9700
O2—C9	1.419 (4)	C10—H10B	0.9700
C2—C3	1.493 (5)	C11—C14	1.482 (5)
O3—C6	1.360 (3)	C11—C12	1.506 (5)
O3—C10	1.438 (4)	C11—C13	1.532 (5)
C3—C8	1.387 (5)	C12—C13	1.478 (5)
C3—C4	1.399 (5)	C12—H12A	0.9700
O4—C14	1.339 (4)	C12—H12B	0.9700
O4—C15	1.468 (4)	C13—H13A	0.9700
C4—C5	1.376 (4)	C13—H13B	0.9700
C4—H4A	0.9300	C15—C16	1.459 (6)
C5—C6	1.405 (5)	C15—H15A	0.9700
O5—C14	1.189 (4)	C15—H15B	0.9700
C6—C7	1.373 (4)	C16—H16A	0.9600
C7—C8	1.393 (5)	C16—H16B	0.9600
C7—H7A	0.9300	C16—H16C	0.9600

C2—C1—H1A	109.5	C11—C10—H10A	110.0
C2—C1—H1B	109.5	O3—C10—H10B	110.0
H1A—C1—H1B	109.5	C11—C10—H10B	110.0
C2—C1—H1C	109.5	H10A—C10—H10B	108.4
H1A—C1—H1C	109.5	C14—C11—C10	119.3 (3)
H1B—C1—H1C	109.5	C14—C11—C12	115.5 (3)
C5—O2—C9	118.1 (3)	C10—C11—C12	117.9 (3)
O1—C2—C1	121.3 (3)	C14—C11—C13	114.4 (3)
O1—C2—C3	119.0 (4)	C10—C11—C13	117.0 (3)
C1—C2—C3	119.7 (4)	C12—C11—C13	58.2 (2)
C6—O3—C10	117.3 (2)	C13—C12—C11	61.7 (2)
C8—C3—C4	118.9 (3)	C13—C12—H12A	117.6
C8—C3—C2	121.8 (3)	C11—C12—H12A	117.6
C4—C3—C2	119.3 (3)	C13—C12—H12B	117.6
C14—O4—C15	117.2 (3)	C11—C12—H12B	117.6
C5—C4—C3	120.9 (3)	H12A—C12—H12B	114.7
C5—C4—H4A	119.5	C12—C13—C11	60.0 (2)
C3—C4—H4A	119.5	C12—C13—H13A	117.8
O2—C5—C4	125.3 (3)	C11—C13—H13A	117.8
O2—C5—C6	115.2 (3)	C12—C13—H13B	117.8
C4—C5—C6	119.5 (3)	C11—C13—H13B	117.8
O3—C6—C7	124.9 (3)	H13A—C13—H13B	114.9
O3—C6—C5	115.1 (3)	O5—C14—O4	123.1 (4)
C7—C6—C5	120.0 (3)	O5—C14—C11	125.5 (4)
C6—C7—C8	120.1 (3)	O4—C14—C11	111.4 (3)
C6—C7—H7A	119.9	C16—C15—O4	112.0 (4)
C8—C7—H7A	119.9	C16—C15—H15A	109.2
C3—C8—C7	120.5 (3)	O4—C15—H15A	109.2
C3—C8—H8A	119.7	C16—C15—H15B	109.2
C7—C8—H8A	119.7	O4—C15—H15B	109.2
O2—C9—H9A	109.5	H15A—C15—H15B	107.9
O2—C9—H9B	109.5	C15—C16—H16A	109.5
H9A—C9—H9B	109.5	C15—C16—H16B	109.5
O2—C9—H9C	109.5	H16A—C16—H16B	109.5
H9A—C9—H9C	109.5	C15—C16—H16C	109.5
H9B—C9—H9C	109.5	H16A—C16—H16C	109.5
O3—C10—C11	108.3 (3)	H16B—C16—H16C	109.5
O3—C10—H10A	110.0

O1—C2—C3—C8	173.4 (4)	C2—C3—C8—C7	178.2 (3)
C1—C2—C3—C8	−7.6 (5)	C6—C7—C8—C3	0.3 (5)
O1—C2—C3—C4	−9.0 (5)	C6—O3—C10—C11	−173.7 (3)
C1—C2—C3—C4	170.0 (3)	O3—C10—C11—C14	74.4 (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—C4	3.6 (5)	C14—C11—C12—C13	104.1 (4)
C9—O2—C5—C6	−177.7 (3)	C10—C11—C12—C13	−106.1 (4)
C3—C4—C5—O2	178.9 (3)	C14—C11—C13—C12	−106.0 (4)
C3—C4—C5—C6	0.2 (5)	C10—C11—C13—C12	107.5 (4)
C10—O3—C6—C7	3.6 (5)	C15—O4—C14—O5	0.7 (6)
C10—O3—C6—C5	−175.5 (3)	C15—O4—C14—C11	−179.3 (3)
O2—C5—C6—O3	1.2 (4)	C10—C11—C14—O5	−173.6 (4)
C4—C5—C6—O3	179.9 (3)	C12—C11—C14—O5	−24.2 (6)
O2—C5—C6—C7	−178.1 (3)	C13—C11—C14—O5	40.7 (5)
C4—C5—C6—C7	0.7 (5)	C10—C11—C14—O4	6.4 (5)
O3—C6—C7—C8	179.9 (3)	C12—C11—C14—O4	155.8 (3)
C5—C6—C7—C8	−1.0 (5)	C13—C11—C14—O4	−139.3 (3)
C4—C3—C8—C7	0.6 (5)	C14—O4—C15—C16	−96.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1ⁱ	0.93	2.56	3.329 (4)	140
C15—H15A···O5	0.97	2.32	2.678 (6)	101

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₀O₅
M_r	292.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.663 (3), 8.5020 (17), 14.676 (3)
β (°)	107.25 (3)
V (Å³)	1509.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.981, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2874, 2732, 1473
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.168, 0.93
No. of reflections	2732
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1ⁱ	0.9300	2.5600	3.329 (4)	140.00

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

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

References

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