Ethyl 3,5-bis­(all­yloxy)-4-bromo­benzoate

Kirsop, P.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S1600536807002383

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 2| February 2007| Pages o833-o835

https://doi.org/10.1107/S1600536807002383

Ethyl 3,5-bis(allyloxy)-4-bromobenzoate

Peter Kirsop,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 16 January 2007; accepted 16 January 2007; online 24 January 2007)

The asymmetric molecular conformation of the title compound, C₁₅H₁₇BrO₄, may be be influenced by an intramolecular C—H⋯O interaction. The molecules form π–π stacks in the crystal structure.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our studies to determine the philicity of aryl radicals by competitive cyclization reactions (Kirsop et al., 2004 ).

Compound (I) possesses normal geometrical parameters. The dihedral angle between the mean plane of the C1–C6 benzene ring and the plane of the C7/O1/O2 group is 6.0 (5)°. The two —O—CH₂—CH=CH₂ side chains have very different conformations (Fig. 1), which may be attributable, at least in part, to an intramolecular C12—H12A⋯O3 interaction (Table 1). The molecules form π–π stacks in the crystal structure (Fig. 2), with alternating centroid-to-centroid separations between benzene rings [Cg⋯Cgⁱ = 3.626 (2), Cg⋯Cgⁱⁱ = 3.466 (2) Å; symmetry codes: (i) x, −y, 1 − z; (ii) x, 1 − y, 1 − z]. The stacking interactions give rise to columns of molecules along [010] (Fig. 3).

Figure 1
The molecular structure of (I)

, showing 50% displacement ellipsoids for non-H atoms. The intramolecular C—H⋯O interaction referred to in the Comment is indicated by a dashed line.

Figure 2
Part of a π–π stacked column of molecules (30% displacement ellipsoids and H atoms omitted). [Symmetry codes: (i) x, −y, 1 − z; (ii) x, 1 − y, 1 − z.]

Figure 3
Unit-cell contents of (I)

, viewed down [010] (50% displacement ellipsoids and H atoms omitted).

Experimental

4-Bromo-3,5-dihydroxybenzoic acid (6.8 g, 0.03 mol) was added to 100 ml of ethanol. Concentrated H₂SO₄ (1 ml) was added and the mixture was refluxed for 14 h. After cooling, the solvent was removed at reduced pressure to give a pale yellow oil. Diethyl ether (100 ml) was added and the mixture was neutralized by careful addition of a saturated NaHCO₃ solution (100 ml). The mixture was transferred to a separating funnel and the product extracted with diethyl ether (4 × 100 ml). The combined extracts were dried over anhydrous MgSO₄ and evaporated under reduced pressure to give 4-bromo-3,5-dihydroxybenzoic acid ethyl ester as a white powder (7.5 g, 96%). Ethyl 4-bromo-3,5-dihydroxybenzoate (3.00 g, 0.011 mol), allyl bromide (1.30 g, 0.011 mol) and K₂CO₃ (8.00 g, 0.0579 mol) were added to 100 ml of dry acetone. The mixture was stirred at room temperature under a nitrogen atmosphere for 14 h, then filtered and the solvent removed at reduced pressure to give a dark brown oil. Thin layer chromatography (4:1 hexane–ethyl acetate eluent) showed the title compound as a sharp spot at R_F = 0.52. The crude product was purified by flash column chromatography to yield a white powder (1.42 g, 38%). A sample of this powder was recrystallized from hot hexane to give translucent needles of (I) (m.p. 315–317 K).

Crystal data

C₁₅H₁₇BrO₄
M_r = 341.20
Orthorhombic, C 222₁
a = 22.1421 (2) Å
b = 7.0559 (13) Å
c = 19.5604 (11) Å
V = 3056.0 (6) Å³
Z = 8
D_x = 1.483 Mg m⁻³
Mo Kα radiation
μ = 2.70 mm⁻¹
T = 120 (2) K
Needle, colourless
0.22 × 0.04 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.588, T_max = 0.948
10933 measured reflections
3495 independent reflections
2604 reflections with I > 2σ(I)
R_int = 0.084
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.084
S = 1.01
3495 reflections
183 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0143P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Absolute structure: Flack (1983 ), 1500 Friedel pairs
Flack parameter: 0.106 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O3	0.95	2.39	2.715 (6)	100

H atoms were placed in idealized locations (C—H = 0.95–0.99 Å) and refined as riding atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807002383/bi2149sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807002383/bi2149Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Ethyl 3,5-bis(allyloxy)-4-bromobenzoate top

Crystal data top

C₁₅H₁₇BrO₄	F(000) = 1392
M_r = 341.20	D_x = 1.483 Mg m⁻³
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 1957 reflections
a = 22.1421 (2) Å	θ = 2.9–27.5°
b = 7.0559 (13) Å	µ = 2.70 mm⁻¹
c = 19.5604 (11) Å	T = 120 K
V = 3056.0 (6) Å³	Needle, colourless
Z = 8	0.22 × 0.04 × 0.02 mm

Data collection top

Nonius KappaCCD diffractometer	3495 independent reflections
Radiation source: fine-focus sealed tube	2604 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
ω and φ scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −20→28
T_min = 0.588, T_max = 0.948	k = −9→9
10933 measured reflections	l = −24→25

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0143P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3495 reflections	Δρ_max = 0.47 e Å⁻³
183 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1500 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.106 (13)

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
C1	0.4754 (2)	0.3097 (5)	0.4289 (2)	0.0184 (11)
C2	0.5137 (2)	0.2603 (5)	0.4827 (2)	0.0185 (10)
C3	0.4891 (2)	0.2071 (5)	0.5457 (2)	0.0173 (10)
H3	0.5145	0.1745	0.5829	0.021*
C4	0.4267 (2)	0.2030 (6)	0.5526 (2)	0.0159 (10)
C5	0.3893 (2)	0.2505 (6)	0.4987 (2)	0.0171 (10)
H5	0.3467	0.2467	0.5046	0.021*
C6	0.4132 (2)	0.3035 (6)	0.4364 (2)	0.0184 (11)
C7	0.3970 (2)	0.1440 (6)	0.6178 (2)	0.0215 (11)
C8	0.4125 (2)	0.0183 (7)	0.7297 (2)	0.0278 (12)
H8A	0.4379	−0.0848	0.7484	0.033*
H8B	0.3713	−0.0323	0.7227	0.033*
C9	0.4103 (2)	0.1796 (7)	0.7799 (2)	0.0360 (14)
H9A	0.3918	0.1362	0.8226	0.054*
H9B	0.3863	0.2835	0.7607	0.054*
H9C	0.4514	0.2244	0.7891	0.054*
C10	0.6157 (2)	0.2438 (7)	0.5223 (2)	0.0246 (12)
H10A	0.6095	0.1206	0.5454	0.030*
H10B	0.6102	0.3462	0.5563	0.030*
C11	0.6776 (2)	0.2528 (7)	0.4924 (3)	0.0313 (12)
H11	0.7105	0.2476	0.5236	0.038*
C12	0.6911 (2)	0.2671 (7)	0.4278 (3)	0.0360 (13)
H12A	0.6598	0.2728	0.3946	0.043*
H12B	0.7321	0.2719	0.4138	0.043*
C13	0.3152 (2)	0.3480 (7)	0.3880 (2)	0.0235 (11)
H13A	0.3021	0.4327	0.4255	0.028*
H13B	0.3020	0.2174	0.3988	0.028*
C14	0.2884 (2)	0.4107 (6)	0.3224 (2)	0.0274 (12)
H14	0.2995	0.5312	0.3048	0.033*
C15	0.2503 (2)	0.3082 (7)	0.2876 (3)	0.0383 (15)
H15A	0.2385	0.1871	0.3042	0.046*
H15B	0.2343	0.3545	0.2458	0.046*
O1	0.34357 (14)	0.1487 (5)	0.62781 (15)	0.0253 (8)
O2	0.43720 (12)	0.0814 (4)	0.66439 (15)	0.0216 (7)
O3	0.57368 (14)	0.2653 (4)	0.46792 (16)	0.0251 (8)
O4	0.37974 (13)	0.3545 (4)	0.38091 (14)	0.0220 (7)
Br1	0.509124 (19)	0.38018 (6)	0.34421 (2)	0.02348 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.023 (3)	0.017 (2)	0.015 (2)	−0.0058 (18)	0.001 (2)	0.0005 (18)
C2	0.017 (3)	0.014 (2)	0.025 (3)	0.003 (2)	0.001 (2)	−0.0052 (17)
C3	0.024 (3)	0.0149 (19)	0.013 (2)	0.0015 (19)	−0.004 (2)	−0.0008 (16)
C4	0.017 (3)	0.016 (2)	0.014 (3)	0.0011 (18)	0.001 (2)	−0.0034 (18)
C5	0.016 (3)	0.018 (2)	0.017 (3)	0.0009 (19)	−0.001 (2)	−0.001 (2)
C6	0.021 (3)	0.019 (3)	0.016 (3)	−0.0008 (18)	0.003 (2)	−0.0041 (19)
C7	0.027 (3)	0.015 (2)	0.023 (3)	−0.006 (2)	0.002 (2)	−0.006 (2)
C8	0.032 (3)	0.037 (3)	0.014 (3)	0.005 (2)	0.002 (2)	0.005 (2)
C9	0.036 (3)	0.052 (4)	0.021 (3)	0.000 (2)	−0.003 (3)	−0.009 (2)
C10	0.023 (3)	0.029 (3)	0.022 (3)	0.003 (2)	−0.003 (2)	−0.004 (2)
C11	0.023 (3)	0.033 (3)	0.038 (3)	0.005 (2)	−0.002 (3)	0.002 (3)
C12	0.020 (3)	0.041 (3)	0.046 (4)	0.001 (2)	0.008 (3)	0.001 (3)
C13	0.019 (3)	0.025 (3)	0.026 (3)	0.004 (2)	−0.001 (2)	0.001 (2)
C14	0.023 (3)	0.024 (3)	0.035 (3)	−0.004 (2)	−0.010 (2)	0.002 (2)
C15	0.038 (4)	0.038 (3)	0.040 (4)	0.002 (2)	−0.015 (3)	0.002 (3)
O1	0.0175 (19)	0.033 (2)	0.0253 (18)	0.0034 (16)	0.0019 (14)	0.0034 (16)
O2	0.0218 (17)	0.0273 (17)	0.0157 (17)	0.0050 (12)	−0.0004 (14)	0.0030 (15)
O3	0.019 (2)	0.0346 (19)	0.0217 (19)	−0.0019 (14)	−0.0013 (17)	−0.0002 (16)
O4	0.0168 (18)	0.0308 (18)	0.0184 (17)	0.0035 (16)	−0.0010 (13)	0.0049 (15)
Br1	0.0254 (2)	0.0274 (2)	0.0176 (2)	−0.0024 (2)	0.0027 (2)	0.0011 (2)

Geometric parameters (Å, º) top

C1—C6	1.386 (6)	C9—H9B	0.980
C1—C2	1.395 (6)	C9—H9C	0.980
C1—Br1	1.884 (4)	C10—O3	1.421 (5)
C2—O3	1.361 (5)	C10—C11	1.492 (6)
C2—C3	1.397 (6)	C10—H10A	0.990
C3—C4	1.389 (6)	C10—H10B	0.990
C3—H3	0.950	C11—C12	1.303 (6)
C4—C5	1.381 (6)	C11—H11	0.950
C4—C7	1.494 (6)	C12—H12A	0.950
C5—C6	1.381 (6)	C12—H12B	0.950
C5—H5	0.950	C13—O4	1.436 (5)
C6—O4	1.363 (5)	C13—C14	1.481 (6)
C7—O1	1.200 (5)	C13—H13A	0.990
C7—O2	1.348 (5)	C13—H13B	0.990
C8—O2	1.459 (5)	C14—C15	1.303 (6)
C8—C9	1.504 (6)	C14—H14	0.950
C8—H8A	0.990	C15—H15A	0.950
C8—H8B	0.990	C15—H15B	0.950
C9—H9A	0.980

C6—C1—C2	121.0 (4)	C8—C9—H9C	109.5
C6—C1—Br1	119.7 (3)	H9A—C9—H9C	109.5
C2—C1—Br1	119.2 (3)	H9B—C9—H9C	109.5
O3—C2—C1	115.2 (4)	O3—C10—C11	107.7 (4)
O3—C2—C3	125.1 (4)	O3—C10—H10A	110.2
C1—C2—C3	119.7 (4)	C11—C10—H10A	110.2
C4—C3—C2	118.6 (4)	O3—C10—H10B	110.2
C4—C3—H3	120.7	C11—C10—H10B	110.2
C2—C3—H3	120.7	H10A—C10—H10B	108.5
C5—C4—C3	121.1 (4)	C12—C11—C10	126.3 (5)
C5—C4—C7	117.1 (4)	C12—C11—H11	116.8
C3—C4—C7	121.7 (4)	C10—C11—H11	116.8
C4—C5—C6	120.6 (4)	C11—C12—H12A	120.0
C4—C5—H5	119.7	C11—C12—H12B	120.0
C6—C5—H5	119.7	H12A—C12—H12B	120.0
O4—C6—C5	124.5 (4)	O4—C13—C14	107.8 (4)
O4—C6—C1	116.6 (4)	O4—C13—H13A	110.1
C5—C6—C1	118.9 (4)	C14—C13—H13A	110.1
O1—C7—O2	123.4 (4)	O4—C13—H13B	110.1
O1—C7—C4	124.4 (4)	C14—C13—H13B	110.1
O2—C7—C4	112.3 (4)	H13A—C13—H13B	108.5
O2—C8—C9	110.6 (4)	C15—C14—C13	123.1 (5)
O2—C8—H8A	109.5	C15—C14—H14	118.5
C9—C8—H8A	109.5	C13—C14—H14	118.5
O2—C8—H8B	109.5	C14—C15—H15A	120.0
C9—C8—H8B	109.5	C14—C15—H15B	120.0
H8A—C8—H8B	108.1	H15A—C15—H15B	120.0
C8—C9—H9A	109.5	C7—O2—C8	116.4 (3)
C8—C9—H9B	109.5	C2—O3—C10	118.5 (3)
H9A—C9—H9B	109.5	C6—O4—C13	117.1 (3)

C6—C1—C2—O3	177.6 (3)	C5—C4—C7—O1	−5.7 (6)
Br1—C1—C2—O3	−1.0 (5)	C3—C4—C7—O1	175.3 (4)
C6—C1—C2—C3	−1.2 (6)	C5—C4—C7—O2	173.3 (4)
Br1—C1—C2—C3	−179.7 (3)	C3—C4—C7—O2	−5.6 (6)
O3—C2—C3—C4	−177.9 (3)	O3—C10—C11—C12	−3.5 (7)
C1—C2—C3—C4	0.7 (5)	O4—C13—C14—C15	123.9 (5)
C2—C3—C4—C5	−0.1 (6)	O1—C7—O2—C8	−0.3 (6)
C2—C3—C4—C7	178.8 (4)	C4—C7—O2—C8	−179.3 (3)
C3—C4—C5—C6	0.0 (7)	C9—C8—O2—C7	−91.1 (5)
C7—C4—C5—C6	−179.0 (4)	C1—C2—O3—C10	171.0 (4)
C4—C5—C6—O4	−179.3 (4)	C3—C2—O3—C10	−10.3 (6)
C4—C5—C6—C1	−0.5 (6)	C11—C10—O3—C2	179.5 (3)
C2—C1—C6—O4	180.0 (4)	C5—C6—O4—C13	−1.4 (6)
Br1—C1—C6—O4	−1.5 (5)	C1—C6—O4—C13	179.8 (4)
C2—C1—C6—C5	1.1 (6)	C14—C13—O4—C6	179.3 (3)
Br1—C1—C6—C5	179.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O3	0.95	2.39	2.715 (6)	100

Acknowledgements

We thank the EPSRC UK National Crystallography Service (University of Southampton) for the data collection.

References

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