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

Abstract

In the mol­ecule of the title compound, C₁₇H₁₃ClF₂O₃, the dihedral angles formed by the aromatic rings of the chloro­benzene and difluoro­benzene groups with the plane of the acrylate unit are 48.85 (12) and 9.07 (14)°, respectively. In the crystal structure, mol­ecules are linked by weak inter­molecular C—H⋯O hydrogen-bond inter­actions, forming chains along the c axis.

Related literature

For the synthesis and crystal structures of related compounds, see: Li, Xue et al. (2008 ▶); Li, Wang & Jian (2008 ▶); Lin & Jian (2008 ▶); Liu et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₇H₁₃ClF₂O₃

• M _r = 338.72

• Monoclinic,

• a = 16.275 (3) Å

• b = 7.503 (2) Å

• c = 13.812 (3) Å

• β = 111.11 (3)°

• V = 1573.4 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.28 mm⁻¹

• T = 298 (2) K

• 0.30 × 0.10 × 0.10 mm

Data collection

• Bruker SMART 1000 CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.922, T _max = 0.973

• 2956 measured reflections

• 2823 independent reflections

• 1566 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.065

• wR(F ²) = 0.189

• S = 1.02

• 2823 reflections

• 210 parameters

• H-atom parameters constrained

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

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.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1i	0.93	2.51	3.321 (4)	146

Symmetry code: (i) .

supplementary crystallographic information

Comment

Recently, the synthesis and structure of a number of etheric compounds have been widely investigated (Li, Xue et al., 2008; Li, Wang & Jian, 2008; Lin & Jian, 2008; Liu et al., 2008). We report herein the crystal structure of the new title compound.

In the molecule of the title compound (Fig. 1), the dihedral angles between the aromatic rings of the chlorobenzene and difluorobenzene groups with the plane of the acrylate unit are 48.85 (12) and 9.07 (14)° respectively. All the bond lengths (Allen et al., 1987) and angles are not unusual. In the crystal structure, molecules are linked by weak intermolecular C—H···O hydrogen interactions forming chains along the c axis (Table 1).

Experimental

An equimolar solution of ethyl 3-bromo-2-(4-chlorophenyl)acrylate and 2,4-difluorophenol in chloroform was left to react overnight at room temperature. Block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent in air for five days.

Refinement

H atoms were included in the riding model approximation with C–H = 0.93–0.97 Å and with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms.

Figures

Fig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C17H13ClF2O3	F000 = 696
Mr = 338.72	Dx = 1.430 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1002 reflections
a = 16.275 (3) Å	θ = 2.4–24.5º
b = 7.503 (2) Å	µ = 0.28 mm−1
c = 13.812 (3) Å	T = 298 (2) K
β = 111.11 (3)º	Block, colorless
V = 1573.4 (7) Å3	0.30 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2823 independent reflections
Radiation source: fine-focus sealed tube	1566 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.027
T = 298(2) K	θmax = 25.2º
ω scans	θmin = 1.3º
Absorption correction: multi-scan(SADABS; Bruker, 2001)	h = −19→18
Tmin = 0.922, Tmax = 0.973	k = −9→10
2956 measured reflections	l = −16→16

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.065	w = 1/[σ2(Fo2) + (0.0904P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.189	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.38 e Å−3
2823 reflections	Δρmin = −0.34 e Å−3
210 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (3)
Secondary atom site location: difference Fourier map

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	1.0187 (2)	0.7796 (5)	0.9699 (3)	0.0450 (9)
C2	1.1022 (2)	0.7724 (5)	1.0453 (3)	0.0473 (9)
C3	1.1764 (2)	0.8337 (6)	1.0319 (3)	0.0581 (11)
H3	1.2315	0.8266	1.0844	0.070*
C4	1.1654 (3)	0.9066 (6)	0.9368 (3)	0.0597 (11)
C5	1.0851 (3)	0.9178 (6)	0.8598 (3)	0.0621 (12)
H5	1.0797	0.9691	0.7964	0.074*
C6	1.0121 (3)	0.8535 (6)	0.8755 (3)	0.0561 (11)
H6	0.9574	0.8596	0.8222	0.067*
C7	0.7054 (2)	0.6469 (5)	0.8670 (3)	0.0423 (9)
C8	0.6325 (2)	0.7234 (5)	0.8808 (3)	0.0540 (10)
H8	0.6376	0.7663	0.9459	0.065*
C9	0.5527 (2)	0.7366 (6)	0.7996 (3)	0.0571 (11)
H9	0.5045	0.7876	0.8100	0.069*
C10	0.5451 (2)	0.6742 (5)	0.7036 (3)	0.0543 (11)
C11	0.6147 (3)	0.5952 (6)	0.6881 (3)	0.0572 (11)
H11	0.6086	0.5513	0.6229	0.069*
C12	0.6947 (2)	0.5804 (5)	0.7696 (3)	0.0482 (10)
H12	0.7418	0.5252	0.7588	0.058*
C13	0.8635 (2)	0.7022 (5)	0.9293 (3)	0.0465 (9)
H13	0.8526	0.7373	0.8612	0.056*
C14	0.7936 (2)	0.6482 (5)	0.9511 (3)	0.0426 (9)
C15	0.8065 (2)	0.5946 (5)	1.0579 (3)	0.0483 (10)
C16	0.7414 (3)	0.4744 (6)	1.1715 (3)	0.0627 (12)
H16A	0.7580	0.5754	1.2185	0.075*
H16B	0.7858	0.3824	1.1975	0.075*
C17	0.6537 (3)	0.4055 (7)	1.1643 (3)	0.0716 (13)
H17A	0.6093	0.4922	1.1303	0.107*
H17B	0.6538	0.3831	1.2327	0.107*
H17C	0.6415	0.2968	1.1250	0.107*
Cl1	0.44478 (7)	0.69754 (19)	0.60039 (9)	0.0891 (5)
F1	1.10978 (13)	0.7012 (3)	1.13855 (15)	0.0663 (7)
F2	1.23761 (16)	0.9699 (4)	0.9209 (2)	0.0858 (9)
O3	0.94846 (18)	0.7113 (4)	0.9954 (2)	0.0723 (9)
O1	0.87704 (17)	0.6033 (4)	1.13049 (18)	0.0666 (9)
O2	0.73412 (16)	0.5282 (4)	1.06775 (17)	0.0525 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.043 (2)	0.048 (2)	0.043 (2)	−0.0032 (18)	0.0138 (16)	−0.0068 (18)
C2	0.047 (2)	0.057 (2)	0.0348 (19)	0.0045 (19)	0.0106 (16)	−0.0028 (18)
C3	0.042 (2)	0.078 (3)	0.049 (2)	−0.007 (2)	0.0090 (17)	−0.010 (2)
C4	0.053 (2)	0.070 (3)	0.062 (3)	−0.008 (2)	0.028 (2)	−0.011 (2)
C5	0.071 (3)	0.074 (3)	0.044 (2)	−0.001 (2)	0.024 (2)	0.001 (2)
C6	0.049 (2)	0.073 (3)	0.040 (2)	−0.005 (2)	0.0084 (17)	−0.002 (2)
C7	0.042 (2)	0.043 (2)	0.039 (2)	−0.0041 (17)	0.0112 (15)	0.0051 (16)
C8	0.048 (2)	0.062 (3)	0.046 (2)	0.002 (2)	0.0106 (17)	−0.004 (2)
C9	0.044 (2)	0.063 (3)	0.060 (3)	0.007 (2)	0.0137 (19)	0.004 (2)
C10	0.044 (2)	0.056 (3)	0.048 (2)	−0.003 (2)	−0.0007 (17)	0.0099 (19)
C11	0.059 (2)	0.067 (3)	0.038 (2)	−0.006 (2)	0.0081 (18)	−0.001 (2)
C12	0.048 (2)	0.054 (2)	0.041 (2)	−0.0005 (19)	0.0140 (16)	−0.0013 (18)
C13	0.045 (2)	0.055 (2)	0.0329 (18)	0.0044 (19)	0.0056 (16)	0.0002 (17)
C14	0.042 (2)	0.047 (2)	0.0327 (18)	0.0010 (17)	0.0072 (15)	−0.0008 (16)
C15	0.049 (2)	0.052 (2)	0.039 (2)	−0.0023 (19)	0.0113 (18)	−0.0016 (18)
C16	0.069 (3)	0.076 (3)	0.038 (2)	−0.006 (2)	0.0140 (19)	0.002 (2)
C17	0.075 (3)	0.084 (3)	0.057 (3)	−0.013 (3)	0.025 (2)	−0.001 (2)
Cl1	0.0572 (7)	0.1132 (11)	0.0671 (8)	0.0017 (7)	−0.0137 (5)	0.0169 (7)
F1	0.0541 (13)	0.0976 (19)	0.0380 (12)	−0.0022 (13)	0.0054 (10)	0.0107 (12)
F2	0.0689 (16)	0.119 (2)	0.0845 (18)	−0.0260 (16)	0.0462 (14)	−0.0119 (17)
O3	0.0592 (18)	0.086 (2)	0.0644 (19)	−0.0014 (17)	0.0134 (15)	−0.0021 (17)
O1	0.0509 (16)	0.099 (2)	0.0377 (15)	−0.0153 (16)	0.0018 (12)	0.0063 (15)
O2	0.0487 (15)	0.0678 (18)	0.0382 (13)	−0.0050 (14)	0.0123 (11)	0.0020 (13)

Geometric parameters (Å, °)

C1—C6	1.384 (5)	C10—C11	1.363 (5)
C1—C2	1.385 (5)	C10—Cl1	1.747 (4)
C1—O3	1.409 (4)	C11—C12	1.385 (5)
C2—F1	1.358 (4)	C11—H11	0.9300
C2—C3	1.365 (5)	C12—H12	0.9300
C3—C4	1.373 (6)	C13—C14	1.340 (5)
C3—H3	0.9300	C13—O3	1.356 (4)
C4—F2	1.357 (4)	C13—H13	0.9300
C4—C5	1.359 (5)	C14—C15	1.469 (5)
C5—C6	1.370 (5)	C15—O1	1.224 (4)
C5—H5	0.9300	C15—O2	1.331 (4)
C6—H6	0.9300	C16—O2	1.452 (4)
C7—C12	1.386 (5)	C16—C17	1.486 (5)
C7—C8	1.392 (5)	C16—H16A	0.9700
C7—C14	1.486 (4)	C16—H16B	0.9700
C8—C9	1.380 (5)	C17—H17A	0.9600
C8—H8	0.9300	C17—H17B	0.9600
C9—C10	1.368 (5)	C17—H17C	0.9600
C9—H9	0.9300
C6—C1—C2	116.5 (3)	C10—C11—C12	119.9 (4)
C6—C1—O3	125.9 (3)	C10—C11—H11	120.1
C2—C1—O3	117.6 (3)	C12—C11—H11	120.1
F1—C2—C3	118.6 (3)	C11—C12—C7	120.8 (4)
F1—C2—C1	117.2 (3)	C11—C12—H12	119.6
C3—C2—C1	124.1 (4)	C7—C12—H12	119.6
C2—C3—C4	116.6 (4)	C14—C13—O3	127.3 (3)
C2—C3—H3	121.7	C14—C13—H13	116.3
C4—C3—H3	121.7	O3—C13—H13	116.3
F2—C4—C5	119.7 (4)	C13—C14—C15	118.8 (3)
F2—C4—C3	118.2 (4)	C13—C14—C7	119.1 (3)
C5—C4—C3	122.1 (4)	C15—C14—C7	122.1 (3)
C4—C5—C6	119.8 (4)	O1—C15—O2	122.7 (3)
C4—C5—H5	120.1	O1—C15—C14	124.1 (4)
C6—C5—H5	120.1	O2—C15—C14	113.2 (3)
C5—C6—C1	120.9 (4)	O2—C16—C17	107.1 (3)
C5—C6—H6	119.6	O2—C16—H16A	110.3
C1—C6—H6	119.6	C17—C16—H16A	110.3
C12—C7—C8	117.8 (3)	O2—C16—H16B	110.3
C12—C7—C14	120.6 (3)	C17—C16—H16B	110.3
C8—C7—C14	121.4 (3)	H16A—C16—H16B	108.5
C9—C8—C7	121.1 (4)	C16—C17—H17A	109.5
C9—C8—H8	119.4	C16—C17—H17B	109.5
C7—C8—H8	119.4	H17A—C17—H17B	109.5
C10—C9—C8	119.6 (4)	C16—C17—H17C	109.5
C10—C9—H9	120.2	H17A—C17—H17C	109.5
C8—C9—H9	120.2	H17B—C17—H17C	109.5
C11—C10—C9	120.7 (3)	C13—O3—C1	124.9 (3)
C11—C10—Cl1	120.0 (3)	C15—O2—C16	116.4 (3)
C9—C10—Cl1	119.2 (3)
C6—C1—C2—F1	179.6 (3)	C10—C11—C12—C7	−0.7 (6)
O3—C1—C2—F1	−0.6 (5)	C8—C7—C12—C11	2.1 (6)
C6—C1—C2—C3	0.4 (6)	C14—C7—C12—C11	−173.4 (4)
O3—C1—C2—C3	−179.8 (4)	O3—C13—C14—C15	1.2 (6)
F1—C2—C3—C4	−179.2 (3)	O3—C13—C14—C7	−179.6 (3)
C1—C2—C3—C4	0.0 (6)	C12—C7—C14—C13	44.5 (5)
C2—C3—C4—F2	179.6 (4)	C8—C7—C14—C13	−130.9 (4)
C2—C3—C4—C5	0.1 (7)	C12—C7—C14—C15	−136.4 (4)
F2—C4—C5—C6	179.8 (4)	C8—C7—C14—C15	48.3 (5)
C3—C4—C5—C6	−0.7 (7)	C13—C14—C15—O1	3.5 (6)
C4—C5—C6—C1	1.1 (7)	C7—C14—C15—O1	−175.7 (4)
C2—C1—C6—C5	−1.0 (6)	C13—C14—C15—O2	−174.1 (3)
O3—C1—C6—C5	179.3 (4)	C7—C14—C15—O2	6.8 (5)
C12—C7—C8—C9	−1.6 (6)	C14—C13—O3—C1	−175.8 (4)
C14—C7—C8—C9	173.9 (4)	C6—C1—O3—C13	2.4 (6)
C7—C8—C9—C10	−0.2 (6)	C2—C1—O3—C13	−177.4 (4)
C8—C9—C10—C11	1.6 (6)	O1—C15—O2—C16	3.3 (6)
C8—C9—C10—Cl1	−178.1 (3)	C14—C15—O2—C16	−179.1 (3)
C9—C10—C11—C12	−1.2 (6)	C17—C16—O2—C15	179.9 (3)
Cl1—C10—C11—C12	178.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1i	0.93	2.51	3.321 (4)	146

Symmetry codes: (i) x, −y+3/2, z−1/2.