1-Allyl­oxy-2-bromo-3-(3-phenyl­allyl­oxy)­benzene

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

doi:10.1107/S1600536804013133

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 60| Part 7| July 2004| Pages o1147-o1148

https://doi.org/10.1107/S1600536804013133

1-Allyloxy-2-bromo-3-(3-phenylallyloxy)benzene

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 24 May 2004; accepted 1 June 2004; online 12 June 2004)

The title compound, C₁₈H₁₇BrO₂, possesses normal geometrical parameters. A possible intramolecular C—H⋯O interaction is present. The crystal packing is influenced by π–π stacking.

Comment

The title compound, (I) (Fig. 1), arose during our studies to determine the philicity of aryl radicals by competitive cyclization (Kirsop et al., 2004a ,b).

Compound (I) possesses normal geometrical parameters. A PLATON (Spek, 2003 ) analysis of (I) indicated that an intramolecular C—H⋯O interaction (Table 1) may occur between an exo methylene C1—H1A group and acceptor O1, which may help to stabilize an essentially planar arrangement of the atoms C1, C2, C3 and O1 [C1—C2—C3—O1 = −3.0 (6)°]. The acute C—H⋯O bond angle of 100° is consistent with the intramolecular nature of this interaction.

As well as van der Waals forces, the crystal packing in (I) is influenced by π–π stacking interactions. Inversion symmetry results in dimeric associations of molecules of (I) with a C_g⋯C_gⁱ separation of 3.767 (3) Å [C_g is the geometric centroid of atoms C13–C18; symmetry code: (i) −1 − x, 2 − y, −z]. The ring planes are exactly parallel and separated by 3.55 (3) Å. The lateral displacement of C_gⁱ relative to the perpendicular from C_g to the mean plane for the atoms C13ⁱ–C18ⁱ is 1.25 (8) Å. The packing of (I) is shown in Fig. 2.

Figure 1
The molecular structure of (I

) (30% displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius and the possible intramolecular C—H⋯O interaction is shown as a dashed lines.

Figure 2
The packing in (I

) projected on to (100), with π–π stacking interactions involving the C13–C18 phenyl rings indicated by dashed lines and all C—H H atoms omitted for clarity (30% displacement ellipsoids).

Experimental

2-Bromobenzene-1,3-diol (Kirsop et al., 2004b ; 5.00 g, 0.026 mol), allyl bromide (3.20 g, 0.026 mol) and potassium carbonate (8.00 g, 0.0579 mol) were added to 100 ml of dry acetone. The mixture was stirred at reflux under a nitrogen atmosphere for 3 h. After cooling, the mixture was filtered and the solvent removed at reduced pressure to give a dark brown oil (4.64 g, 78%). Thin-layer chromatography (4:1 hexane–ethyl acetate) showed three sharp spots: at R_F = 0.24 was unreacted starting material, at R_F = 0.38 was 3-allyloxy-2-bromophenol, and at R_F = 0.52 was 1,3-bis(allyloxy)-2-bromobenzene. These compounds were separated using flash column chromatography to give 3-allyloxy-2-bromophenol as a clear oil (1.85 g, 31%). ¹H NMR: δ_H (CDCl₃) 4.58 (2H, d, J = 4.9 Hz, CH₂), 5.30 (1H, d, J = 10.7 Hz, CH), 5.47 (1H, d J = 17.1 Hz, CH) 5.74 (1H, s, OH), 6.05 (1H, m, CH), 6.45 (1H, d, J = 8.2 Hz, Ar-H), 6.66 (1H, d, J = 9.8 Hz, Ar-H), 7.12 (1H, t, J = 8.2 Hz, Ar-H). ¹³C NMR: δ_C 69.8, 100.6, 105.0, 108.6, 117.8, 128.6, 132.6, 153.6, 155.5. ν_max (KBr)/cm⁻¹: 3497, 2912, 1595, 1463, 1269, 1192, 1064, 767.

A mixture of 3-allyloxy-2-bromophenol (2.00 g, 0.009 mol), cinnamyl bromide (2.06 g, 0.011 mol) and potassium carbonate (8.0 g, 0.058 mol) was added to dry acetone (100 ml). The mixture was stirred at reflux under a nitrogen atmosphere for 12 h. After cooling, the mixture was filtered and the solvent removed at reduced pressure to give a dark brown oil (1.92 g, 68%). Thin-layer chromatography (4:1 hexane–ethyl acetate) showed 1-allyloxy-2-bromo-3-(3-phenyl-allyloxy) benzene (I) as a sharp spot at R_F = 0.33. The crude product was purified by flash column chromatography to give (I) as a white powder (1.56 g, 51%). A sample of this powder was recrystallized from hot hexane–ethyl acetate (20:1) to give translucent rhombs and slabs (m.p. 353–355 K). ¹H NMR: δ_H (CDCl₃) 4.58 (2H, d, J = 4.1 Hz, CH₂), 4.74 (2H, d, J = 3.9 Hz, CH₂), 5.26 (1H, d, J = 9.6 Hz, CH₂), 5.44 (1H, d, J = 17.0 Hz, CH₂), 6.01–6.08 (1H, m, CH), 6.37–6.41 (1H, m, CH), 6.53 (1H, d, J = 7.0 Hz, Ar-H), 6.58 (1H, d, J = 7.0 Hz, Ar-H), 6.75 (1H, d, J = 9.2 Hz, CH), 7.14 (1H, t, J = 8.1 Hz, CH), 7.23 (1H, d, J = 6.2 Hz, Ar-H), 7.29 (2H, t, J = 8.3 Hz, Ar-H), 7.38 (2H, d, J = 7.2 Hz, Ar-H). ¹³C NMR: δ_C 70.0, 70.1, 102.7, 106.6, 106.7, 117.8, 124.2 (2 C), 126.8, 128.1, 128.2, 128.8 (2 C), 132.9, 133.1, 136.6, 156.6 (2 C). ν_max (KBr)/cm⁻¹: 1644, 1591, 1470, 1375, 1255, 1116, 1062, 767.

Crystal data

C₁₈H₁₇BrO₂
M_r = 345.23
Monoclinic, P2₁/n
a = 7.2956 (4) Å
b = 14.8719 (8) Å
c = 14.7849 (7) Å
β = 95.171 (1)°
V = 1597.62 (14) Å³
Z = 4
D_x = 1.435 Mg m⁻³
Mo Kα radiation
Cell parameters from 3898 reflections
θ = 2.7–23.3°
μ = 2.57 mm⁻¹
T = 293 (2) K
Slab, colourless
0.47 × 0.32 × 0.18 mm

Data collection

Bruker SMART1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.362, T_max = 0.628
11903 measured reflections
3131 independent reflections
2142 reflections with I > 2σ(I)
R_int = 0.025
θ_max = 26.0°
h = −8 → 8
k = −18 → 18
l = −17 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.06
3131 reflections
190 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.058P)² + 0.1552P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1	0.93	2.39	2.715 (5)	100

All the H atoms were positioned geometrically and refined as riding on their carrier C atoms (C—H = 0.93 Å for aromatic and sp²-hybridized C atoms and C—H = 0.97 Å for sp³-hybridized C atoms) with the the constraint U_iso(H) = 1.2U_eq(carrier atom) applied.

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97; 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/S1600536804013133/na6336sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804013133/na6336Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

C₁₈H₁₇BrO₂	F(000) = 704
M_r = 345.23	D_x = 1.435 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 353-355 K K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.2956 (4) Å	Cell parameters from 3898 reflections
b = 14.8719 (8) Å	θ = 2.7–23.3°
c = 14.7849 (7) Å	µ = 2.57 mm⁻¹
β = 95.171 (1)°	T = 293 K
V = 1597.62 (14) Å³	Slab, colourless
Z = 4	0.47 × 0.32 × 0.18 mm

Data collection top

Bruker SMART1000 CCD diffractometer	3131 independent reflections
Radiation source: fine-focus sealed tube	2142 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→8
T_min = 0.362, T_max = 0.628	k = −18→18
11903 measured reflections	l = −17→18

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.058P)² + 0.1552P] where P = (F_o² + 2F_c²)/3
3131 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

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	0.7164 (6)	0.9837 (4)	0.4453 (3)	0.1019 (14)
H1A	0.5955	0.9901	0.4204	0.122*
H1B	0.7707	1.0283	0.4828	0.122*
C2	0.8077 (6)	0.9138 (4)	0.4283 (3)	0.0988 (14)
H2	0.9279	0.9109	0.4550	0.119*
C3	0.7445 (5)	0.8372 (3)	0.3711 (3)	0.0866 (11)
H3A	0.8176	0.8325	0.3197	0.104*
H3B	0.7581	0.7819	0.4058	0.104*
C4	0.4709 (5)	0.7921 (2)	0.2806 (2)	0.0655 (9)
C5	0.5451 (6)	0.7111 (2)	0.2545 (3)	0.0843 (11)
H5	0.6620	0.6936	0.2782	0.101*
C6	0.4451 (6)	0.6577 (2)	0.1939 (3)	0.0904 (13)
H6	0.4964	0.6036	0.1772	0.109*
C7	0.2716 (5)	0.6796 (2)	0.1561 (3)	0.0813 (11)
H7	0.2073	0.6415	0.1147	0.098*
C8	0.1952 (5)	0.7604 (2)	0.1815 (2)	0.0651 (9)
C9	0.2946 (4)	0.81529 (19)	0.2437 (2)	0.0599 (8)
C10	−0.0783 (6)	0.7392 (2)	0.0806 (3)	0.0902 (11)
H10A	−0.1080	0.6809	0.1050	0.108*
H10B	−0.0082	0.7298	0.0287	0.108*
C11	−0.2497 (5)	0.7898 (2)	0.0529 (3)	0.0787 (10)
H11	−0.3270	0.8030	0.0978	0.094*
C12	−0.3003 (6)	0.8172 (3)	−0.0290 (3)	0.0832 (11)
H12	−0.2236	0.8021	−0.0736	0.100*
C13	−0.4657 (5)	0.8693 (2)	−0.0587 (2)	0.0714 (9)
C14	−0.6087 (5)	0.8823 (2)	−0.0051 (3)	0.0759 (10)
H14	−0.6035	0.8551	0.0517	0.091*
C15	−0.7564 (6)	0.9336 (3)	−0.0329 (3)	0.0943 (12)
H15	−0.8512	0.9407	0.0045	0.113*
C16	−0.7669 (7)	0.9751 (3)	−0.1160 (4)	0.1047 (14)
H16	−0.8677	1.0109	−0.1348	0.126*
C17	−0.6283 (9)	0.9635 (4)	−0.1706 (3)	0.1101 (17)
H17	−0.6344	0.9915	−0.2271	0.132*
C18	−0.4786 (7)	0.9101 (3)	−0.1426 (3)	0.0964 (14)
H18	−0.3856	0.9018	−0.1809	0.116*
O1	0.5548 (3)	0.85114 (16)	0.33997 (17)	0.0765 (7)
O2	0.0263 (3)	0.79109 (15)	0.14831 (17)	0.0765 (7)
Br1	0.19441 (5)	0.92522 (2)	0.27726 (3)	0.08017 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.091 (3)	0.132 (4)	0.080 (3)	−0.007 (3)	−0.005 (2)	0.003 (3)
C2	0.066 (3)	0.145 (5)	0.084 (3)	0.005 (3)	−0.002 (2)	0.021 (3)
C3	0.064 (2)	0.100 (3)	0.096 (3)	0.020 (2)	0.012 (2)	0.030 (3)
C4	0.063 (2)	0.0543 (18)	0.084 (2)	0.0068 (15)	0.0306 (18)	0.0191 (18)
C5	0.080 (2)	0.056 (2)	0.123 (3)	0.0145 (18)	0.041 (2)	0.023 (2)
C6	0.104 (3)	0.0459 (19)	0.129 (4)	0.013 (2)	0.054 (3)	0.007 (2)
C7	0.094 (3)	0.0520 (19)	0.103 (3)	−0.0017 (18)	0.038 (2)	−0.0010 (19)
C8	0.071 (2)	0.0481 (17)	0.080 (2)	0.0007 (15)	0.0282 (19)	0.0050 (17)
C9	0.065 (2)	0.0443 (16)	0.074 (2)	0.0052 (14)	0.0266 (18)	0.0068 (15)
C10	0.092 (3)	0.071 (2)	0.108 (3)	−0.011 (2)	0.012 (2)	−0.021 (2)
C11	0.084 (3)	0.071 (2)	0.083 (3)	−0.0210 (19)	0.019 (2)	−0.020 (2)
C12	0.093 (3)	0.088 (3)	0.073 (3)	−0.030 (2)	0.027 (2)	−0.029 (2)
C13	0.084 (3)	0.071 (2)	0.060 (2)	−0.0312 (18)	0.012 (2)	−0.0142 (18)
C14	0.089 (3)	0.079 (2)	0.060 (2)	−0.021 (2)	0.012 (2)	−0.0101 (19)
C15	0.092 (3)	0.097 (3)	0.094 (3)	−0.016 (2)	0.006 (3)	−0.021 (3)
C16	0.115 (4)	0.085 (3)	0.106 (4)	−0.020 (3)	−0.034 (3)	−0.018 (3)
C17	0.147 (5)	0.112 (4)	0.065 (3)	−0.056 (4)	−0.025 (3)	0.004 (3)
C18	0.113 (4)	0.115 (4)	0.062 (3)	−0.051 (3)	0.012 (2)	−0.016 (2)
O1	0.0589 (14)	0.0716 (15)	0.0984 (18)	0.0117 (11)	0.0044 (13)	0.0088 (14)
O2	0.0765 (16)	0.0618 (14)	0.0917 (17)	−0.0025 (12)	0.0096 (13)	−0.0180 (13)
Br1	0.0675 (3)	0.0665 (2)	0.1065 (3)	0.01149 (16)	0.0076 (2)	−0.0170 (2)

Geometric parameters (Å, º) top

C1—C2	1.271 (6)	C10—O2	1.430 (4)
C1—H1A	0.9300	C10—C11	1.485 (5)
C1—H1B	0.9300	C10—H10A	0.9700
C2—C3	1.467 (6)	C10—H10B	0.9700
C2—H2	0.9300	C11—C12	1.298 (5)
C3—O1	1.434 (4)	C11—H11	0.9300
C3—H3A	0.9700	C12—C13	1.468 (6)
C3—H3B	0.9700	C12—H12	0.9300
C4—O1	1.348 (4)	C13—C18	1.377 (5)
C4—C5	1.390 (5)	C13—C14	1.380 (5)
C4—C9	1.395 (4)	C14—C15	1.353 (6)
C5—C6	1.358 (6)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.371 (6)
C6—C7	1.376 (5)	C15—H15	0.9300
C6—H6	0.9300	C16—C17	1.361 (7)
C7—C8	1.389 (4)	C16—H16	0.9300
C7—H7	0.9300	C17—C18	1.383 (7)
C8—O2	1.363 (4)	C17—H17	0.9300
C8—C9	1.385 (5)	C18—H18	0.9300
C9—Br1	1.875 (3)

C2—C1—H1A	120.0	O2—C10—H10A	110.2
C2—C1—H1B	120.0	C11—C10—H10A	110.2
H1A—C1—H1B	120.0	O2—C10—H10B	110.2
C1—C2—C3	127.3 (4)	C11—C10—H10B	110.2
C1—C2—H2	116.4	H10A—C10—H10B	108.5
C3—C2—H2	116.4	C12—C11—C10	125.3 (4)
O1—C3—C2	108.5 (3)	C12—C11—H11	117.4
O1—C3—H3A	110.0	C10—C11—H11	117.4
C2—C3—H3A	110.0	C11—C12—C13	127.0 (4)
O1—C3—H3B	110.0	C11—C12—H12	116.5
C2—C3—H3B	110.0	C13—C12—H12	116.5
H3A—C3—H3B	108.4	C18—C13—C14	117.5 (4)
O1—C4—C5	125.5 (3)	C18—C13—C12	119.4 (4)
O1—C4—C9	116.2 (3)	C14—C13—C12	123.1 (4)
C5—C4—C9	118.3 (4)	C15—C14—C13	121.8 (4)
C6—C5—C4	119.4 (4)	C15—C14—H14	119.1
C6—C5—H5	120.3	C13—C14—H14	119.1
C4—C5—H5	120.3	C14—C15—C16	120.3 (5)
C5—C6—C7	123.3 (3)	C14—C15—H15	119.8
C5—C6—H6	118.3	C16—C15—H15	119.8
C7—C6—H6	118.3	C17—C16—C15	119.3 (5)
C6—C7—C8	118.1 (4)	C17—C16—H16	120.3
C6—C7—H7	120.9	C15—C16—H16	120.3
C8—C7—H7	120.9	C16—C17—C18	120.3 (4)
O2—C8—C9	116.3 (3)	C16—C17—H17	119.9
O2—C8—C7	124.3 (3)	C18—C17—H17	119.9
C9—C8—C7	119.4 (3)	C13—C18—C17	120.7 (5)
C8—C9—C4	121.5 (3)	C13—C18—H18	119.6
C8—C9—Br1	119.8 (2)	C17—C18—H18	119.6
C4—C9—Br1	118.7 (3)	C4—O1—C3	118.9 (3)
O2—C10—C11	107.6 (3)	C8—O2—C10	118.6 (3)

C1—C2—C3—O1	−3.0 (6)	C11—C12—C13—C18	165.4 (4)
O1—C4—C5—C6	179.9 (3)	C11—C12—C13—C14	−12.4 (6)
C9—C4—C5—C6	0.4 (5)	C18—C13—C14—C15	−0.4 (5)
C4—C5—C6—C7	0.2 (6)	C12—C13—C14—C15	177.4 (3)
C5—C6—C7—C8	−0.2 (6)	C13—C14—C15—C16	−0.6 (6)
C6—C7—C8—O2	178.9 (3)	C14—C15—C16—C17	0.7 (6)
C6—C7—C8—C9	−0.3 (5)	C15—C16—C17—C18	0.1 (6)
O2—C8—C9—C4	−178.3 (3)	C14—C13—C18—C17	1.2 (5)
C7—C8—C9—C4	0.9 (5)	C12—C13—C18—C17	−176.7 (3)
O2—C8—C9—Br1	−0.2 (4)	C16—C17—C18—C13	−1.1 (6)
C7—C8—C9—Br1	179.1 (2)	C5—C4—O1—C3	8.6 (5)
O1—C4—C9—C8	179.5 (3)	C9—C4—O1—C3	−171.9 (3)
C5—C4—C9—C8	−1.0 (5)	C2—C3—O1—C4	175.2 (3)
O1—C4—C9—Br1	1.3 (4)	C9—C8—O2—C10	177.0 (3)
C5—C4—C9—Br1	−179.1 (2)	C7—C8—O2—C10	−2.2 (5)
O2—C10—C11—C12	120.8 (4)	C11—C10—O2—C8	−176.8 (3)
C10—C11—C12—C13	−178.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.93	2.39	2.715 (5)	100

References

Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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