Ethyl 3-(2,4-difluoro­phen­oxy)-2-(4-methoxy­phen­yl)acrylate

Chen, W.; Cui, Y.-M.; Pan, F..; Xia, D.-S.; Zeng, Q.-F.

doi:10.1107/S1600536808036945

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2374

doi:10.1107/S1600536808036945

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Ethyl 3-(2,4-difluorophenoxy)-2-(4-methoxyphenyl)acrylate

Wu Chen,^a Yong-Ming Cui,^a Fei Pan,^a Dong-Sheng Xia ^a and Qing-Fu Zeng ^a ^*

^aEngineering Research Center for Clean Production of Textile Printing, Ministry of Education, Wuhan University of Science & Engineering, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: qingfu_zeng@163.com

(Received 20 October 2008; accepted 10 November 2008; online 20 November 2008)

In the title molecule, C₁₈H₁₆F₂O₄, the two benzene rings form a dihedral angle of 55.2 (2)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains propagating along the c axis.

Related literature

For a related crystal structure, see Fang et al. (2007 ). For the properties of phenylacetate and styrene derivatives, see: Huang et al. (2007 ); Li et al. (2007 ).

Experimental

Crystal data

C₁₈H₁₆F₂O₄
M_r = 334.31
Monoclinic, P 2₁ /c
a = 17.295 (3) Å
b = 7.294 (2) Å
c = 14.233 (2) Å
β = 113.73 (3)°
V = 1643.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 (2) K
0.31 × 0.30 × 0.28 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.967, T_max = 0.970
3340 measured reflections
3198 independent reflections
1959 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.173
S = 1.03
3198 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.93	2.52	3.280 (2)	140
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036945/cv2469sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036945/cv2469Isup2.hkl

checkCIF report

Comment top

Phenylacetate and styrene derivatives are important in view of their extensive biological activities. Recently, many of such compounds with good activities were synthesized (Huang et al., 2007; Li et al., 2007). We report in this paper the title new compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related compound (Fang et al., 2007). The dihedral angles between C1—C6 and C7—C12 benzene rings is 55.2 (2)°. The O4/C13—C15/O1/O2 plane forms dihedral angles of 5.9 (2)° and 50.2 (2)°, respectively, with C1—C6 and C7—C12 benzene rings. In the crystal, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into chains propagated along c axis.

Related literature top

For a related crystal structure, see Fang et al. (2007). For the properties of phenylacetate and styrene derivatives, see: Huang et al. (2007); Li et al. (2007).

Experimental top

Ethyl 3-bromo-2-(2,4-difluorophenyl)acrylate (0.1 mmol) and 4-methoxyphenol (0.1 mmol) were reacted in chloroform (20 ml) for 12 h, giving a clear colorless solution. Crytals of the compound were formed by gradual evaporation of the solution.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Ethyl 3-(2,4-difluorophenoxy)-2-(4-methoxyphenyl)acrylate top

Crystal data top

C₁₈H₁₆F₂O₄	F(000) = 696
M_r = 334.31	D_x = 1.351 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1232 reflections
a = 17.295 (3) Å	θ = 2.3–24.5°
b = 7.294 (2) Å	µ = 0.11 mm⁻¹
c = 14.233 (2) Å	T = 298 K
β = 113.73 (3)°	Block, colorless
V = 1643.7 (7) Å³	0.31 × 0.30 × 0.28 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3198 independent reflections
Radiation source: fine-focus sealed tube	1959 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 26.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −21→19
T_min = 0.967, T_max = 0.970	k = −8→0
3340 measured reflections	l = 0→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.173	w = 1/[σ²(F_o²) + (0.0671P)² + 1.0598P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3198 reflections	Δρ_max = 0.43 e Å⁻³
220 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (2)

Crystal data top

C₁₈H₁₆F₂O₄	V = 1643.7 (7) Å³
M_r = 334.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.295 (3) Å	µ = 0.11 mm⁻¹
b = 7.294 (2) Å	T = 298 K
c = 14.233 (2) Å	0.31 × 0.30 × 0.28 mm
β = 113.73 (3)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3198 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1959 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.970	R_int = 0.017
3340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.03	Δρ_max = 0.43 e Å⁻³
3198 reflections	Δρ_min = −0.31 e Å⁻³
220 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
F1	−0.10160 (10)	0.2759 (3)	0.53359 (13)	0.0659 (6)
F2	−0.21582 (12)	0.0299 (3)	0.20055 (15)	0.0819 (7)
O1	0.11843 (13)	0.3874 (4)	0.73642 (16)	0.0643 (7)
O2	0.25578 (13)	0.4637 (3)	0.80903 (15)	0.0544 (6)
O3	0.52673 (12)	0.3660 (3)	0.63131 (16)	0.0587 (6)
O4	0.05420 (13)	0.2906 (4)	0.53932 (19)	0.0709 (7)
C1	−0.01146 (16)	0.2255 (4)	0.4503 (2)	0.0429 (7)
C2	−0.09183 (17)	0.2176 (4)	0.4484 (2)	0.0469 (7)
C3	−0.16113 (18)	0.1544 (5)	0.3667 (2)	0.0565 (9)
H3	−0.2144	0.1520	0.3682	0.068*
C4	−0.14818 (19)	0.0949 (5)	0.2827 (2)	0.0562 (8)
C5	−0.0706 (2)	0.0975 (5)	0.2794 (2)	0.0585 (9)
H5	−0.0637	0.0558	0.2215	0.070*
C6	−0.00211 (18)	0.1628 (5)	0.3632 (2)	0.0524 (8)
H6	0.0510	0.1649	0.3612	0.063*
C7	0.28913 (16)	0.3613 (4)	0.6413 (2)	0.0411 (7)
C8	0.35658 (17)	0.2736 (4)	0.7170 (2)	0.0457 (7)
H8	0.3479	0.2147	0.7699	0.055*
C9	0.43628 (17)	0.2708 (4)	0.7167 (2)	0.0485 (8)
H9	0.4803	0.2108	0.7686	0.058*
C10	0.45029 (17)	0.3582 (4)	0.6383 (2)	0.0440 (7)
C11	0.38402 (17)	0.4463 (4)	0.5619 (2)	0.0490 (8)
H11	0.3928	0.5041	0.5087	0.059*
C12	0.30513 (17)	0.4491 (4)	0.5639 (2)	0.0460 (7)
H12	0.2615	0.5109	0.5124	0.055*
C13	0.13631 (16)	0.3039 (4)	0.5529 (2)	0.0450 (7)
H13	0.1485	0.2747	0.4967	0.054*
C14	0.20244 (17)	0.3551 (4)	0.6398 (2)	0.0427 (7)
C15	0.18686 (18)	0.4008 (4)	0.7308 (2)	0.0476 (7)
C16	0.2474 (2)	0.5001 (6)	0.9039 (2)	0.0755 (11)
H16A	0.2254	0.3927	0.9251	0.091*
H16B	0.2085	0.6009	0.8950	0.091*
C17	0.3315 (3)	0.5472 (6)	0.9827 (3)	0.0840 (12)
H17A	0.3700	0.4482	0.9896	0.126*
H17B	0.3273	0.5675	1.0472	0.126*
H17C	0.3517	0.6565	0.9626	0.126*
C18	0.59573 (18)	0.2753 (5)	0.7078 (3)	0.0696 (10)
H18A	0.6035	0.3215	0.7741	0.104*
H18B	0.6460	0.2967	0.6962	0.104*
H18C	0.5846	0.1460	0.7049	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0494 (10)	0.1005 (16)	0.0561 (11)	0.0024 (10)	0.0299 (9)	−0.0084 (11)
F2	0.0591 (12)	0.1104 (18)	0.0587 (12)	−0.0114 (12)	0.0053 (10)	−0.0136 (12)
O1	0.0527 (13)	0.0918 (19)	0.0608 (14)	−0.0086 (12)	0.0358 (11)	−0.0089 (13)
O2	0.0562 (13)	0.0704 (16)	0.0429 (11)	−0.0079 (11)	0.0267 (10)	−0.0086 (11)
O3	0.0403 (11)	0.0748 (16)	0.0661 (14)	0.0039 (11)	0.0267 (10)	0.0059 (12)
O4	0.0547 (13)	0.0828 (18)	0.0761 (17)	−0.0016 (13)	0.0272 (12)	−0.0027 (14)
C1	0.0374 (14)	0.0455 (17)	0.0454 (16)	0.0002 (13)	0.0162 (13)	0.0024 (14)
C2	0.0463 (16)	0.0555 (19)	0.0440 (17)	0.0047 (14)	0.0235 (14)	0.0027 (15)
C3	0.0394 (16)	0.070 (2)	0.056 (2)	−0.0007 (16)	0.0150 (14)	0.0078 (18)
C4	0.0479 (18)	0.064 (2)	0.0462 (18)	−0.0024 (16)	0.0084 (15)	0.0012 (16)
C5	0.061 (2)	0.072 (2)	0.0460 (18)	0.0042 (18)	0.0242 (16)	−0.0044 (17)
C6	0.0447 (16)	0.067 (2)	0.0501 (18)	−0.0004 (15)	0.0239 (14)	−0.0033 (16)
C7	0.0401 (15)	0.0405 (17)	0.0440 (16)	−0.0023 (13)	0.0184 (13)	−0.0062 (13)
C8	0.0460 (16)	0.0496 (18)	0.0452 (16)	0.0030 (14)	0.0220 (13)	0.0043 (14)
C9	0.0431 (15)	0.053 (2)	0.0453 (17)	0.0089 (14)	0.0136 (13)	0.0044 (15)
C10	0.0392 (15)	0.0469 (18)	0.0484 (17)	0.0003 (13)	0.0201 (13)	−0.0052 (14)
C11	0.0462 (16)	0.058 (2)	0.0468 (17)	0.0006 (15)	0.0232 (14)	0.0080 (15)
C12	0.0409 (15)	0.0530 (19)	0.0424 (16)	0.0041 (14)	0.0151 (13)	0.0049 (15)
C13	0.0394 (15)	0.0490 (18)	0.0511 (17)	0.0018 (13)	0.0230 (13)	0.0003 (14)
C14	0.0417 (15)	0.0436 (17)	0.0470 (17)	−0.0008 (13)	0.0220 (13)	0.0003 (14)
C15	0.0500 (17)	0.0467 (18)	0.0510 (18)	−0.0026 (14)	0.0256 (15)	0.0012 (15)
C16	0.085 (3)	0.104 (3)	0.0470 (19)	−0.005 (2)	0.0371 (19)	−0.005 (2)
C17	0.109 (3)	0.090 (3)	0.047 (2)	−0.014 (3)	0.025 (2)	−0.006 (2)
C18	0.0424 (17)	0.086 (3)	0.077 (2)	0.0103 (18)	0.0202 (17)	0.003 (2)

Geometric parameters (Å, º) top

F1—C2	1.358 (3)	C8—C9	1.380 (4)
F2—C4	1.364 (3)	C8—H8	0.9300
O1—C15	1.222 (3)	C9—C10	1.388 (4)
O2—C15	1.343 (3)	C9—H9	0.9300
O2—C16	1.440 (4)	C10—C11	1.381 (4)
O3—C10	1.366 (3)	C11—C12	1.376 (4)
O3—C18	1.415 (4)	C11—H11	0.9300
O4—C13	1.357 (3)	C12—H12	0.9300
O4—C1	1.401 (3)	C13—C14	1.356 (4)
C1—C2	1.380 (4)	C13—H13	0.9300
C1—C6	1.391 (4)	C14—C15	1.464 (4)
C2—C3	1.370 (4)	C16—C17	1.475 (5)
C3—C4	1.373 (4)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C5	1.362 (4)	C17—H17A	0.9600
C5—C6	1.384 (4)	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
C6—H6	0.9300	C18—H18A	0.9600
C7—C8	1.385 (4)	C18—H18B	0.9600
C7—C12	1.395 (4)	C18—H18C	0.9600
C7—C14	1.491 (4)

C15—O2—C16	116.8 (2)	C12—C11—C10	120.4 (3)
C10—O3—C18	117.7 (2)	C12—C11—H11	119.8
C13—O4—C1	125.0 (2)	C10—C11—H11	119.8
C2—C1—C6	116.5 (3)	C11—C12—C7	121.5 (3)
C2—C1—O4	118.4 (3)	C11—C12—H12	119.2
C6—C1—O4	125.1 (2)	C7—C12—H12	119.2
F1—C2—C3	118.8 (3)	C14—C13—O4	126.9 (3)
F1—C2—C1	117.1 (3)	C14—C13—H13	116.6
C3—C2—C1	124.1 (3)	O4—C13—H13	116.6
C2—C3—C4	116.8 (3)	C13—C14—C15	118.8 (2)
C2—C3—H3	121.6	C13—C14—C7	119.7 (2)
C4—C3—H3	121.6	C15—C14—C7	121.5 (3)
C5—C4—F2	119.5 (3)	O1—C15—O2	122.2 (3)
C5—C4—C3	122.3 (3)	O1—C15—C14	124.6 (3)
F2—C4—C3	118.2 (3)	O2—C15—C14	113.2 (2)
C4—C5—C6	119.3 (3)	O2—C16—C17	108.4 (3)
C4—C5—H5	120.4	O2—C16—H16A	110.0
C6—C5—H5	120.4	C17—C16—H16A	110.0
C5—C6—C1	121.0 (3)	O2—C16—H16B	110.0
C5—C6—H6	119.5	C17—C16—H16B	110.0
C1—C6—H6	119.5	H16A—C16—H16B	108.4
C8—C7—C12	117.0 (2)	C16—C17—H17A	109.5
C8—C7—C14	121.6 (3)	C16—C17—H17B	109.5
C12—C7—C14	121.3 (3)	H17A—C17—H17B	109.5
C9—C8—C7	122.3 (3)	C16—C17—H17C	109.5
C9—C8—H8	118.9	H17A—C17—H17C	109.5
C7—C8—H8	118.9	H17B—C17—H17C	109.5
C8—C9—C10	119.6 (3)	O3—C18—H18A	109.5
C8—C9—H9	120.2	O3—C18—H18B	109.5
C10—C9—H9	120.2	H18A—C18—H18B	109.5
O3—C10—C11	116.3 (3)	O3—C18—H18C	109.5
O3—C10—C9	124.4 (3)	H18A—C18—H18C	109.5
C11—C10—C9	119.3 (3)	H18B—C18—H18C	109.5

C13—O4—C1—C2	179.1 (3)	C8—C9—C10—C11	−0.1 (5)
C13—O4—C1—C6	0.8 (5)	O3—C10—C11—C12	−178.6 (3)
C6—C1—C2—F1	179.1 (3)	C9—C10—C11—C12	0.6 (5)
O4—C1—C2—F1	0.6 (4)	C10—C11—C12—C7	−1.1 (5)
C6—C1—C2—C3	−0.6 (5)	C8—C7—C12—C11	1.0 (4)
O4—C1—C2—C3	−179.1 (3)	C14—C7—C12—C11	−176.3 (3)
F1—C2—C3—C4	−179.2 (3)	C1—O4—C13—C14	−175.5 (3)
C1—C2—C3—C4	0.4 (5)	O4—C13—C14—C15	0.6 (5)
C2—C3—C4—C5	0.0 (5)	O4—C13—C14—C7	179.7 (3)
C2—C3—C4—F2	179.5 (3)	C8—C7—C14—C13	−128.4 (3)
F2—C4—C5—C6	−179.7 (3)	C12—C7—C14—C13	48.7 (4)
C3—C4—C5—C6	−0.2 (6)	C8—C7—C14—C15	50.7 (4)
C4—C5—C6—C1	0.0 (5)	C12—C7—C14—C15	−132.1 (3)
C2—C1—C6—C5	0.4 (5)	C16—O2—C15—O1	5.3 (5)
O4—C1—C6—C5	178.7 (3)	C16—O2—C15—C14	−175.9 (3)
C12—C7—C8—C9	−0.4 (4)	C13—C14—C15—O1	3.9 (5)
C14—C7—C8—C9	176.8 (3)	C7—C14—C15—O1	−175.2 (3)
C7—C8—C9—C10	0.0 (5)	C13—C14—C15—O2	−174.9 (3)
C18—O3—C10—C11	−179.3 (3)	C7—C14—C15—O2	6.0 (4)
C18—O3—C10—C9	1.5 (4)	C15—O2—C16—C17	173.7 (3)
C8—C9—C10—O3	179.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.52	3.280 (2)	140

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆F₂O₄
M_r	334.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	17.295 (3), 7.294 (2), 14.233 (2)
β (°)	113.73 (3)
V (Å³)	1643.7 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.967, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	3340, 3198, 1959
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.173, 1.03
No. of reflections	3198
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.31

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.52	3.280 (2)	140

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by Program in the National Science & Technology of China (No. 2006BAC02A11), Key Technologies R&D Program in the Educational Commission of Hubei Province of China (No. Z20081701), Technologies R&D Program in Hubei Province of China (No. 2007AA301B62).

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