(E)-Methyl 3-{3-[(4-bromo­phen­oxy)­methyl]phen­yl}acrylate

Abstract

In the mol­ecule of the title compound, C₁₇H₁₅BrO₃, the rings make a dihedral angle of 75.54 (17)°. In the crystal structure, inter­molecular C—H⋯O hydrogen bonds link the mol­ecules into centrosymmetric dimers, and the π-stacked dimers inter­act with neighbouring dimers via C—H⋯π stacking inter­actions.

Related literature

For general background, see: de Fraine et al. (1991 ▶); Zhang & Ji (1992 ▶); Janiak (2000 ▶). For related literature, see: Ren et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₇H₁₅BrO₃

• M _r = 347.20

• Orthorhombic,

• a = 15.5226 (9) Å

• b = 5.9390 (3) Å

• c = 34.775 (2) Å

• V = 3205.9 (3) ų

• Z = 8

• Mo Kα radiation

• μ = 2.57 mm⁻¹

• T = 292 (2) K

• 0.20 × 0.10 × 0.10 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2001a ▶) T _min = 0.627, T _max = 0.783

• 30716 measured reflections

• 3147 independent reflections

• 1604 reflections with I > 2σ(I)

• R _int = 0.061

Refinement

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.162

• S = 1.02

• 3147 reflections

• 191 parameters

• H-atom parameters constrained

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2001b ▶).

Supplementary Material

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

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

Cg2 is the centroid of the ring C1–C6.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2i	0.93	2.45	3.370 (6)	172
C12—H12⋯Cg2ii	0.93	2.99	3.677 (3)	132

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Phenyl acrylate and its derivatives are important compounds because of their agrochemical and medical applications (de Fraine et al., 1991; Zhang & Ji, 1992). We report herein the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C1—C6) and B (C8—C13) are, of course, planar, and they are oriented at a dihedral angle of A/B = 75.54 (17)°.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2) and the π-stacked dimers interact with neighbouring dimers via C–H/π stacking interactions (Table 1) (Janiak, 2000), in which both of them seem to be effective in the stabilization of the structure.

Experimental

(E)-methyl 3-(3-(bromomethyl)phenyl)acrylate, (II), was firstly synthesized, (yield; 52.8%), according to a literature method (Ren et al., 2007). For the preparation of the title compound, (I), 4-bromophenol (2.0 mmol) and potassium carbonate (1.2 mmol) was added to a solution of compound (II) (2.0 mmol) in acetone (30 ml). The mixture was stirred at 329 K for 5 h, the solvent was removed under reduced pressure, and the residue was purified by chromatography (silica gel with 5% ethyl acetate in petroleum ether). Colorless crystals of (I) suitable for X-ray analysis were grown from methanol.

Refinement

H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

Fig. 1.

The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Fig. 3.

The formation of the title compound.

Crystal data

C17H15BrO3	F000 = 1408
Mr = 347.20	Dx = 1.439 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3230 reflections
a = 15.5226 (9) Å	θ = 2.3–18.7º
b = 5.9390 (3) Å	µ = 2.57 mm−1
c = 34.775 (2) Å	T = 292 (2) K
V = 3205.9 (3) Å3	Block, colorless
Z = 8	0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3147 independent reflections
Radiation source: fine-focus sealed tube	1604 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.061
T = 292(2) K	θmax = 26.0º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001a)	h = −19→19
Tmin = 0.627, Tmax = 0.783	k = −7→7
30716 measured reflections	l = −39→42

Refinement

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)] = 0.054	H-atom parameters constrained
wR(F2) = 0.162	w = 1/[σ2(Fo2) + (0.0796P)2 + 0.4215P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3147 reflections	Δρmax = 0.43 e Å−3
191 parameters	Δρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Br1	0.40930 (5)	0.23555 (10)	0.518514 (16)	0.1544 (4)
O1	0.36979 (14)	0.7793 (4)	0.66326 (7)	0.0701 (7)
O2	0.3798 (2)	0.5459 (6)	0.87722 (9)	0.1199 (11)
O3	0.3379 (2)	0.8260 (5)	0.91548 (8)	0.1118 (10)
C1	0.3993 (3)	0.4150 (7)	0.56360 (11)	0.0898 (12)
C2	0.3295 (3)	0.3823 (7)	0.58702 (11)	0.0857 (11)
H2	0.2876	0.2765	0.5807	0.103*
C3	0.3223 (2)	0.5087 (6)	0.62015 (10)	0.0757 (10)
H3	0.2749	0.4882	0.6362	0.091*
C4	0.3841 (2)	0.6647 (6)	0.62979 (10)	0.0619 (8)
C5	0.4538 (3)	0.6952 (7)	0.60590 (11)	0.0824 (11)
H5	0.4959	0.8008	0.6120	0.099*
C6	0.4606 (3)	0.5678 (8)	0.57284 (12)	0.1048 (14)
H6	0.5079	0.5872	0.5567	0.126*
C7	0.4336 (2)	0.9377 (6)	0.67551 (10)	0.0679 (9)
H7A	0.4406	1.0551	0.6564	0.082*
H7B	0.4886	0.8629	0.6790	0.082*
C8	0.40363 (19)	1.0367 (5)	0.71267 (10)	0.0596 (8)
C9	0.41060 (19)	0.9171 (5)	0.74654 (10)	0.0588 (8)
H9	0.4367	0.7761	0.7462	0.071*
C10	0.37953 (19)	1.0021 (5)	0.78124 (10)	0.0573 (8)
C11	0.3427 (2)	1.2169 (5)	0.78140 (11)	0.0649 (9)
H11	0.3227	1.2787	0.8043	0.078*
C12	0.3361 (2)	1.3359 (6)	0.74792 (11)	0.0711 (9)
H12	0.3110	1.4781	0.7481	0.085*
C13	0.3661 (2)	1.2477 (6)	0.71394 (12)	0.0702 (9)
H13	0.3612	1.3313	0.6914	0.084*
C14	0.3823 (2)	0.8606 (6)	0.81570 (10)	0.0678 (9)
H14	0.4047	0.7168	0.8122	0.081*
C15	0.3574 (2)	0.9096 (6)	0.85094 (10)	0.0782 (10)
H15	0.3378	1.0539	0.8566	0.094*
C16	0.3602 (2)	0.7391 (8)	0.88138 (12)	0.0839 (11)
C17	0.3380 (4)	0.6729 (10)	0.94758 (13)	0.1363 (19)
H17A	0.2947	0.5598	0.9437	0.204*
H17B	0.3259	0.7545	0.9708	0.204*
H17C	0.3935	0.6024	0.9496	0.204*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.2067 (8)	0.1611 (7)	0.0952 (5)	−0.0426 (5)	0.0403 (4)	−0.0565 (4)
O1	0.0677 (14)	0.0822 (16)	0.0602 (14)	−0.0103 (13)	0.0043 (11)	−0.0070 (12)
O2	0.153 (3)	0.111 (2)	0.095 (2)	0.054 (2)	0.0227 (19)	0.028 (2)
O3	0.146 (3)	0.125 (2)	0.0641 (18)	0.019 (2)	0.0085 (17)	0.0156 (17)
C1	0.122 (3)	0.083 (3)	0.065 (2)	−0.012 (3)	0.011 (2)	−0.012 (2)
C2	0.101 (3)	0.086 (3)	0.070 (2)	−0.020 (2)	−0.002 (2)	−0.003 (2)
C3	0.073 (2)	0.093 (3)	0.061 (2)	−0.012 (2)	0.0019 (17)	−0.004 (2)
C4	0.068 (2)	0.066 (2)	0.051 (2)	0.0013 (18)	−0.0010 (16)	0.0095 (17)
C5	0.089 (3)	0.091 (3)	0.067 (2)	−0.016 (2)	0.012 (2)	−0.002 (2)
C6	0.120 (3)	0.117 (4)	0.077 (3)	−0.024 (3)	0.032 (2)	−0.014 (3)
C7	0.068 (2)	0.071 (2)	0.065 (2)	−0.0073 (18)	0.0012 (16)	0.0018 (18)
C8	0.0560 (19)	0.058 (2)	0.064 (2)	−0.0026 (16)	−0.0043 (15)	−0.0005 (17)
C9	0.0608 (19)	0.0459 (18)	0.070 (2)	0.0039 (15)	−0.0045 (16)	−0.0035 (17)
C10	0.0540 (18)	0.054 (2)	0.064 (2)	0.0023 (15)	−0.0053 (15)	−0.0004 (17)
C11	0.064 (2)	0.056 (2)	0.074 (2)	0.0021 (16)	0.0009 (17)	−0.0127 (18)
C12	0.075 (2)	0.0505 (19)	0.088 (3)	0.0072 (17)	−0.002 (2)	0.007 (2)
C13	0.074 (2)	0.062 (2)	0.075 (3)	−0.0012 (19)	−0.0049 (19)	0.0131 (19)
C14	0.070 (2)	0.070 (2)	0.064 (2)	0.0064 (18)	−0.0031 (17)	−0.0047 (19)
C15	0.090 (3)	0.076 (2)	0.068 (2)	0.017 (2)	−0.001 (2)	0.003 (2)
C16	0.080 (3)	0.104 (3)	0.067 (3)	0.021 (2)	0.003 (2)	0.009 (2)
C17	0.165 (5)	0.167 (5)	0.077 (3)	0.014 (4)	0.009 (3)	0.034 (3)

Geometric parameters (Å, °)

Br1—C1	1.902 (4)	C9—H9	0.9300
C1—C6	1.355 (6)	C10—C11	1.398 (4)
C1—C2	1.369 (5)	C10—C14	1.464 (5)
C2—C3	1.380 (5)	C11—C12	1.366 (5)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.375 (5)	C12—C13	1.374 (5)
C3—H3	0.9300	C12—H12	0.9300
C4—O1	1.367 (4)	C13—H13	0.9300
C4—C5	1.376 (5)	C14—C15	1.317 (4)
C5—C6	1.380 (5)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.466 (5)
C6—H6	0.9300	C15—H15	0.9300
C7—O1	1.431 (4)	C16—O2	1.196 (4)
C7—C8	1.494 (5)	C16—O3	1.339 (5)
C7—H7A	0.9700	C17—O3	1.440 (5)
C7—H7B	0.9700	C17—H17A	0.9600
C8—C9	1.380 (5)	C17—H17B	0.9600
C8—C13	1.382 (4)	C17—H17C	0.9600
C9—C10	1.394 (4)
C6—C1—C2	120.7 (4)	C9—C10—C11	118.4 (3)
C6—C1—Br1	120.9 (3)	C9—C10—C14	119.3 (3)
C2—C1—Br1	118.4 (3)	C11—C10—C14	122.2 (3)
C1—C2—C3	118.9 (4)	C12—C11—C10	120.0 (3)
C1—C2—H2	120.5	C12—C11—H11	120.0
C3—C2—H2	120.5	C10—C11—H11	120.0
C4—C3—C2	120.9 (3)	C11—C12—C13	120.7 (3)
C4—C3—H3	119.6	C11—C12—H12	119.7
C2—C3—H3	119.6	C13—C12—H12	119.7
O1—C4—C3	115.5 (3)	C12—C13—C8	121.0 (3)
O1—C4—C5	125.2 (3)	C12—C13—H13	119.5
C3—C4—C5	119.4 (3)	C8—C13—H13	119.5
C4—C5—C6	119.4 (4)	C15—C14—C10	128.7 (3)
C4—C5—H5	120.3	C15—C14—H14	115.6
C6—C5—H5	120.3	C10—C14—H14	115.6
C1—C6—C5	120.7 (4)	C14—C15—C16	120.7 (4)
C1—C6—H6	119.7	C14—C15—H15	119.6
C5—C6—H6	119.7	C16—C15—H15	119.6
O1—C7—C8	107.5 (3)	O2—C16—O3	122.9 (4)
O1—C7—H7A	110.2	O2—C16—C15	125.7 (4)
C8—C7—H7A	110.2	O3—C16—C15	111.4 (4)
O1—C7—H7B	110.2	O3—C17—H17A	109.5
C8—C7—H7B	110.2	O3—C17—H17B	109.5
H7A—C7—H7B	108.5	H17A—C17—H17B	109.5
C9—C8—C13	118.2 (3)	O3—C17—H17C	109.5
C9—C8—C7	120.7 (3)	H17A—C17—H17C	109.5
C13—C8—C7	121.0 (3)	H17B—C17—H17C	109.5
C8—C9—C10	121.7 (3)	C4—O1—C7	117.9 (2)
C8—C9—H9	119.2	C16—O3—C17	116.3 (4)
C10—C9—H9	119.2
C6—C1—C2—C3	0.4 (6)	C9—C10—C11—C12	1.4 (5)
Br1—C1—C2—C3	178.9 (3)	C14—C10—C11—C12	−175.3 (3)
C1—C2—C3—C4	−0.3 (6)	C10—C11—C12—C13	−0.6 (5)
C2—C3—C4—O1	−180.0 (3)	C11—C12—C13—C8	0.1 (5)
C2—C3—C4—C5	0.3 (5)	C9—C8—C13—C12	−0.4 (5)
O1—C4—C5—C6	179.9 (3)	C7—C8—C13—C12	178.0 (3)
C3—C4—C5—C6	−0.4 (6)	C9—C10—C14—C15	179.2 (3)
C2—C1—C6—C5	−0.5 (7)	C11—C10—C14—C15	−4.1 (5)
Br1—C1—C6—C5	−179.0 (3)	C10—C14—C15—C16	176.0 (3)
C4—C5—C6—C1	0.5 (6)	C14—C15—C16—O2	−4.0 (7)
O1—C7—C8—C9	77.1 (3)	C14—C15—C16—O3	175.8 (3)
O1—C7—C8—C13	−101.2 (3)	C3—C4—O1—C7	177.7 (3)
C13—C8—C9—C10	1.2 (4)	C5—C4—O1—C7	−2.7 (5)
C7—C8—C9—C10	−177.1 (3)	C8—C7—O1—C4	−179.2 (3)
C8—C9—C10—C11	−1.8 (4)	O2—C16—O3—C17	−0.5 (6)
C8—C9—C10—C14	175.1 (3)	C15—C16—O3—C17	179.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2i	0.93	2.45	3.370 (6)	172
C12—H12···Cg2ii	0.93	2.99	3.677 (3)	132

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y−1/2, z−1/2.