(E)-1,2-Bis(3-bromo-4-methyl­phen­yl)ethene

Boeré, R.T.; Robbins, S.J.

doi:10.1107/S1600536807067645

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o363

doi:10.1107/S1600536807067645

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(E)-1,2-Bis(3-bromo-4-methylphenyl)ethene

René T. Boeré ^a ^* and Steven J. Robbins ^a

^aDepartment of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, AB, Canada T1K 3M4
^*Correspondence e-mail: boere@uleth.ca

(Received 15 December 2007; accepted 19 December 2007; online 4 January 2008)

In the structure of the title compound, C₁₆H₁₄Br₂, the central C=C bond length is 1.329 (4) Å and the two benzene rings are approximately coplanar with the double bond, with twist angles of 7.5 (2) and 13.6 (2)°.

Related literature

For related literature, see: Daik et al. (1998 ); Harada & Ogawa et al. (2004 ); Ogawa et al. (1992 ); Mallory et al. (2001 ).

Experimental

Crystal data

C₁₆H₁₄Br₂
M_r = 366.09
Monoclinic, P 2₁ /c
a = 6.3301 (4) Å
b = 7.6499 (5) Å
c = 28.164 (2) Å
β = 91.208 (1)°
V = 1363.55 (16) Å³
Z = 4
Mo Kα radiation
μ = 5.92 mm⁻¹
T = 173 (2) K
0.27 × 0.19 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.303, T_max = 0.578
14025 measured reflections
2793 independent reflections
2393 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.054
S = 1.08
2793 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2003 ); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067645/pv2061sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067645/pv2061Isup2.hkl

checkCIF report

Comment top

The title compound, (I) (Fig. 1), was prepared by a Ti catalyzed McMurray coupling (Mallory et al., 2001) with 99% E selectivity. The almost-planar molecules pack (Fig. 2) in slipped stacks with T-contacts typical for aromatic molecules. The only other isomeric stilbene for which a structure has been reported is Z-1,2-bis-(4-bromophenyl)-1,2-dimethylethene (Daik et al., 1998) for which C=C is 1.330 (10) and 1.344 (10)Å (for two independent molecules in an asymmetric unit). Unlike in I, the phenyl rings in this compound are twisted almost orthogonal to the double bond, perhaps because of steric interactions between methyl and phenyl groups. More structurally comparable alkenes include E-1,2-bis-(2,4-dimethylphenyl)ethene and E-1,2-bis-(2,4,5-trimethylphenyl)ethene (Ogawa et al., 1992) for which C=C are 1.320 (4) and 1.327 (3) Å, respectively. A detailed study of geometric distortions in trans-stilbene has recently been published (Harada & Ogawa, 2004).

Related literature top

For related literature, see: Daik et al. (1998); Harada & Ogawa et al. (2004); Ogawa et al. (1992); Mallory et al. (2001).

Experimental top

At 273 K under N₂, 0.18 ml (1.6 mmol) of TiCl₄ was stirred with 0.18 g (2.8 mmol) Zn dust in 25 ml of dry THF. To this mixture was added 0.25 g (1.3 mmol) of 3-bromo-4-methylbenzaldehyde and refluxed for 4 h before being quenched with 25 ml of 1.0 M HCl. After extracting with hexanes the organic phase was washed with brine solution and dried over MgSO₄. Removal of solvent resulted in a white powder that was recrystallized from ethyl acetate to give 0.11 g (yield = 58%) of the desired product as colorless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 2003); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. A view of (I) plotted with displacement ellipsoids at 50% probability level.
	Fig. 2. Unit-cell contents of (I) showing the herringbone arrangement of slipped-stacks with T-contacts between registers.

(E)-1,2-Bis(3-bromo-4-methylphenyl)ethene top

Crystal data top

C₁₆H₁₄Br₂	Z = 4
M_r = 366.09	F(000) = 720
Monoclinic, P2₁/c	D_x = 1.783 Mg m⁻³
Hall symbol: -P2ybc	Melting point: 424.75 K
a = 6.3301 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6499 (5) Å	µ = 5.92 mm⁻¹
c = 28.164 (2) Å	T = 173 K
β = 91.208 (1)°	Prism, colourless
V = 1363.55 (16) Å³	0.27 × 0.19 × 0.10 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2793 independent reflections
Radiation source: fine-focus sealed tube, Bruker D8	2393 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→7
T_min = 0.303, T_max = 0.578	k = −9→9
14025 measured reflections	l = −35→35

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0179P)² + 1.6865P] where P = (F_o² + 2F_c²)/3
2793 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₆H₁₄Br₂	V = 1363.55 (16) Å³
M_r = 366.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3301 (4) Å	µ = 5.92 mm⁻¹
b = 7.6499 (5) Å	T = 173 K
c = 28.164 (2) Å	0.27 × 0.19 × 0.10 mm
β = 91.208 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2793 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2393 reflections with I > 2σ(I)
T_min = 0.303, T_max = 0.578	R_int = 0.027
14025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.054	H-atom parameters constrained
S = 1.09	Δρ_max = 0.43 e Å⁻³
2793 reflections	Δρ_min = −0.32 e Å⁻³
165 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
Br1	0.08255 (4)	0.93057 (4)	0.562520 (9)	0.02689 (8)
C1	0.0145 (4)	0.8529 (3)	0.62456 (8)	0.0197 (5)
C2	−0.1806 (4)	0.7739 (3)	0.63183 (9)	0.0217 (5)
C3	−0.2158 (4)	0.7151 (3)	0.67779 (10)	0.0241 (6)
H3	−0.3476	0.6620	0.6844	0.029*
C4	−0.0673 (4)	0.7309 (3)	0.71400 (9)	0.0237 (6)
H4	−0.0972	0.6867	0.7446	0.028*
C5	0.1280 (4)	0.8119 (3)	0.70600 (9)	0.0213 (6)
C6	0.1650 (4)	0.8749 (3)	0.66049 (9)	0.0212 (5)
H6	0.2939	0.9332	0.6541	0.025*
C7	0.2912 (4)	0.8315 (4)	0.74343 (9)	0.0241 (6)
H7	0.4101	0.9015	0.7361	0.029*
C8	−0.3452 (4)	0.7506 (4)	0.59307 (10)	0.0282 (6)
H8A	−0.2872	0.6792	0.5676	0.034*
H8B	−0.3865	0.8653	0.5804	0.034*
H8C	−0.4693	0.6922	0.6060	0.034*
Br2	0.44176 (4)	0.73105 (4)	0.971236 (9)	0.02871 (8)
C11	0.5297 (4)	0.7870 (3)	0.90906 (9)	0.0205 (5)
C12	0.7254 (4)	0.8675 (3)	0.90274 (9)	0.0218 (5)
C13	0.7768 (4)	0.9044 (3)	0.85612 (10)	0.0243 (6)
H13	0.9102	0.9558	0.8501	0.029*
C14	0.6420 (4)	0.8695 (4)	0.81816 (9)	0.0253 (6)
H14	0.6834	0.8991	0.7869	0.030*
C15	0.4454 (4)	0.7913 (3)	0.82503 (9)	0.0218 (6)
C16	0.3931 (4)	0.7476 (3)	0.87155 (9)	0.0224 (6)
H16	0.2629	0.6906	0.8774	0.027*
C17	0.2894 (4)	0.7613 (4)	0.78658 (9)	0.0250 (6)
H17	0.1761	0.6842	0.7932	0.030*
C18	0.8708 (4)	0.9153 (4)	0.94351 (10)	0.0279 (6)
H18A	0.8014	1.0011	0.9638	0.033*
H18B	1.0011	0.9656	0.9313	0.033*
H18C	0.9047	0.8104	0.9621	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02994 (15)	0.03138 (16)	0.01930 (14)	−0.00196 (12)	−0.00088 (10)	0.00574 (11)
C1	0.0243 (14)	0.0192 (13)	0.0157 (12)	0.0034 (11)	0.0018 (10)	0.0006 (10)
C2	0.0207 (13)	0.0217 (14)	0.0226 (13)	0.0025 (11)	−0.0021 (10)	−0.0016 (11)
C3	0.0214 (13)	0.0219 (14)	0.0291 (15)	0.0000 (11)	0.0031 (11)	0.0012 (11)
C4	0.0295 (15)	0.0221 (14)	0.0196 (13)	0.0031 (11)	0.0033 (11)	−0.0001 (11)
C5	0.0252 (14)	0.0196 (13)	0.0190 (13)	0.0025 (11)	0.0001 (11)	−0.0042 (10)
C6	0.0193 (13)	0.0224 (14)	0.0218 (13)	−0.0019 (11)	0.0014 (10)	−0.0017 (11)
C7	0.0253 (14)	0.0256 (15)	0.0213 (14)	0.0010 (11)	0.0001 (11)	−0.0028 (11)
C8	0.0247 (14)	0.0314 (16)	0.0283 (15)	−0.0022 (12)	−0.0052 (11)	−0.0001 (12)
Br2	0.03120 (16)	0.03709 (17)	0.01781 (14)	−0.00261 (12)	−0.00030 (11)	0.00279 (12)
C11	0.0259 (14)	0.0184 (13)	0.0172 (13)	0.0044 (11)	0.0003 (10)	0.0014 (10)
C12	0.0221 (13)	0.0169 (13)	0.0262 (14)	0.0042 (10)	−0.0029 (11)	−0.0014 (11)
C13	0.0192 (13)	0.0218 (14)	0.0321 (15)	0.0008 (11)	0.0027 (11)	0.0016 (11)
C14	0.0298 (15)	0.0249 (14)	0.0213 (14)	0.0026 (12)	0.0030 (11)	0.0018 (11)
C15	0.0251 (14)	0.0185 (13)	0.0217 (13)	0.0028 (11)	−0.0017 (11)	−0.0011 (10)
C16	0.0216 (13)	0.0216 (14)	0.0240 (14)	−0.0008 (11)	−0.0008 (10)	0.0009 (11)
C17	0.0287 (15)	0.0243 (14)	0.0218 (14)	−0.0022 (12)	−0.0013 (11)	−0.0023 (11)
C18	0.0272 (15)	0.0248 (15)	0.0314 (15)	−0.0020 (12)	−0.0052 (12)	−0.0019 (12)

Geometric parameters (Å, º) top

Br1—C1	1.904 (2)	Br2—C11	1.898 (3)
C1—C6	1.386 (3)	C11—C16	1.385 (4)
C1—C2	1.393 (4)	C11—C12	1.398 (4)
C2—C3	1.393 (4)	C12—C13	1.389 (4)
C2—C8	1.504 (4)	C12—C18	1.502 (4)
C3—C4	1.378 (4)	C13—C14	1.380 (4)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.405 (4)	C14—C15	1.398 (4)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.394 (4)	C15—C16	1.399 (4)
C5—C7	1.468 (4)	C15—C17	1.468 (4)
C6—H6	0.9500	C16—H16	0.9500
C7—C17	1.329 (4)	C17—H17	0.9500
C7—H7	0.9500	C18—H18A	0.9800
C8—H8A	0.9800	C18—H18B	0.9800
C8—H8B	0.9800	C18—H18C	0.9800
C8—H8C	0.9800

C6—C1—C2	122.9 (2)	C16—C11—C12	122.7 (2)
C6—C1—Br1	117.82 (19)	C16—C11—Br2	117.7 (2)
C2—C1—Br1	119.25 (19)	C12—C11—Br2	119.67 (19)
C3—C2—C1	115.9 (2)	C13—C12—C11	115.9 (2)
C3—C2—C8	120.9 (2)	C13—C12—C18	121.4 (2)
C1—C2—C8	123.2 (2)	C11—C12—C18	122.7 (2)
C4—C3—C2	122.6 (3)	C14—C13—C12	122.7 (3)
C4—C3—H3	118.7	C14—C13—H13	118.7
C2—C3—H3	118.7	C12—C13—H13	118.7
C3—C4—C5	120.6 (2)	C13—C14—C15	120.9 (2)
C3—C4—H4	119.7	C13—C14—H14	119.6
C5—C4—H4	119.7	C15—C14—H14	119.6
C6—C5—C4	117.7 (2)	C14—C15—C16	117.5 (2)
C6—C5—C7	119.7 (2)	C14—C15—C17	123.5 (2)
C4—C5—C7	122.6 (2)	C16—C15—C17	119.0 (2)
C1—C6—C5	120.2 (2)	C11—C16—C15	120.4 (2)
C1—C6—H6	119.9	C11—C16—H16	119.8
C5—C6—H6	119.9	C15—C16—H16	119.8
C17—C7—C5	126.6 (3)	C7—C17—C15	126.4 (3)
C17—C7—H7	116.7	C7—C17—H17	116.8
C5—C7—H7	116.7	C15—C17—H17	116.8
C2—C8—H8A	109.5	C12—C18—H18A	109.5
C2—C8—H8B	109.5	C12—C18—H18B	109.5
H8A—C8—H8B	109.5	H18A—C18—H18B	109.5
C2—C8—H8C	109.5	C12—C18—H18C	109.5
H8A—C8—H8C	109.5	H18A—C18—H18C	109.5
H8B—C8—H8C	109.5	H18B—C18—H18C	109.5

Br2—C11—C12—C18	−1.0 (3)	C6—C5—C7—C17	−171.7 (3)
Br1—C1—C2—C8	−1.7 (4)	C16—C15—C17—C7	162.7 (3)
C4—C5—C7—C17	8.2 (4)	C5—C7—C17—C15	−175.4 (2)
C14—C15—C17—C7	−14.1 (4)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Br₂
M_r	366.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.3301 (4), 7.6499 (5), 28.164 (2)
β (°)	91.208 (1)
V (Å³)	1363.55 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.92
Crystal size (mm)	0.27 × 0.19 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.303, 0.578
No. of measured, independent and observed [I > 2σ(I)] reflections	14025, 2793, 2393
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.054, 1.09
No. of reflections	2793
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.32

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2006), SHELXS97 (Sheldrick, 1990), SHELXTL (Sheldrick, 2003), Mercury (Macrae et al., 2006), publCIF (Westrip, 2008).

Acknowledgements

Support provided by Dr Peter Dibble and the Natural Sciences and Engineering Research Council of Canada (NSERC) is gratefully acknowledged. The diffractometer was purchased with the help of NSERC and the University of Lethbridge.

References

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