1,2-Bis(dibromo­meth­yl)benzene

Fang, S.-K.; Lin, H.-Y.; Chen, K.-Y.

doi:10.1107/S1600536811050616

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o5

doi:10.1107/S1600536811050616

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1,2-Bis(dibromomethyl)benzene

Sin-Kai Fang,^a Hong-Yi Lin ^a and Kew-Yu Chen ^a ^*

^aDepartment of Chemical Engineering, Feng Chia University, 40724 Taichung, Taiwan
^*Correspondence e-mail: kyuchen@fcu.edu.tw

(Received 29 September 2011; accepted 25 November 2011; online 3 December 2011)

In the title compound, C₈H₆Br₄, intramolecular C—H⋯Br hydrogen bonds generate two S(6) rings. The two geminal bromine-atom substituents point to opposite sides of the aromatic ring system. In the crystal, molecules are linked by intermolecular π–π interactions with centroid–centroid distances of 3.727 (9) and 3.858 (9) Å.

Related literature

For the preparation of the title compound, see: Ghorbani-Vaghei et al. (2009 ). For its applications, see: Chen et al. (2002 , 2006 , 2007 ); Chow et al. (2005 ); Jansen et al. (2010 ); Pandithavidana et al. (2009 ); Swartz et al. (2005 ). For related structures, see: Kuś & Jones (2003); Qin et al. (2005 ); Sim et al. (2001 ). For graph-set theory, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₆Br₄
M_r = 421.77
Triclinic, $[P \overline 1]$
a = 7.0222 (8) Å
b = 7.7313 (9) Å
c = 10.5927 (12) Å
α = 108.473 (10)°
β = 97.108 (9)°
γ = 90.394 (9)°
V = 540.61 (11) Å³
Z = 2
Mo Kα radiation
μ = 14.83 mm⁻¹
T = 297 K
0.58 × 0.48 × 0.36 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.122, T_max = 1.000
4575 measured reflections
2469 independent reflections
1297 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.091
wR(F²) = 0.258
S = 1.04
2469 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 1.62 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Br1	0.98	2.64	3.364 (16)	131
C8—H8A⋯Br2	0.98	2.78	3.420 (16)	124

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811050616/aa2031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811050616/aa2031Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811050616/aa2031Isup3.cml

checkCIF report

Comment top

The title compound and its derivatives are useful reagents to build a naphthalene ring (Chen et al., 2002, 2006, 2007; Chow et al., 2005; Jansen et al., 2010; Pandithavidana et al., 2009). In addition, they have been prepared as potential precursors to pentacene derivatives (Swartz et al., 2005).

The ORTEP diagram of the title compound is shown in Fig. 1. Two intramolecular C—H···Br hydrogen bonds (see Table 1) generate two S(6) ring motifs (Bernstein et al., 1995). The two geminal bromine substituents point to opposite sides of the aromatic ring system. In the crystal structure (Fig. 2), the molecules are stabilized by intermolecular π–π interactions. Cg1···Cg1ⁱ distance is 3.727 (9)Å, symmetry code: (i) -1 - x, -y, 1 - z; Cg1···Cg1ⁱⁱ distance is 3.858 (9)Å, symmetry code: (ii) -x, -y, 1 - z; Cg1 is the centroid of the C2/C7 ring).

Related literature top

For the preparation of the title compound, see: Ghorbani-Vaghei et al. (2009). For its applications, see: Chen et al. (2002, 2006, 2007); Chow et al. (2005); Jansen et al. (2010); Pandithavidana et al. (2009); Swartz et al. (2005). For related structures, see: Kuś & Jones (2003); Qin et al. (2005); Sim et al. (2001). For graph-set theory, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by bromination of o-xylene with N,N,N',N'- tetrabromobenzene-1,3-disulfonamide in CCl₄, according to the literature method (Ghorbani-Vaghei et al., 2009). Colorless crystals suitable for the crystallographic studies were isolated over a period of four weeks by slow evaporation from the chloroform solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. A section of the crystal packing of the title compound, viewed along the a axis. H atoms have been omitted for clarity.

1,2-Bis(dibromomethyl)benzene top

Crystal data top

C₈H₆Br₄	Z = 2
M_r = 421.77	F(000) = 388
Triclinic, P1	D_x = 2.591 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0222 (8) Å	Cell parameters from 1856 reflections
b = 7.7313 (9) Å	θ = 2.8–29.1°
c = 10.5927 (12) Å	µ = 14.83 mm⁻¹
α = 108.473 (10)°	T = 297 K
β = 97.108 (9)°	Parallelepiped, colorless
γ = 90.394 (9)°	0.58 × 0.48 × 0.36 mm
V = 540.61 (11) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2469 independent reflections
Radiation source: fine-focus sealed tube	1297 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ω scans	θ_max = 29.2°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.122, T_max = 1.000	k = −10→10
4575 measured reflections	l = −14→14

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)] = 0.091	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.258	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0875P)² + 18.1246P] where P = (F_o² + 2F_c²)/3
2469 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 1.62 e Å⁻³
0 restraints	Δρ_min = −1.27 e Å⁻³

Crystal data top

C₈H₆Br₄	γ = 90.394 (9)°
M_r = 421.77	V = 540.61 (11) Å³
Triclinic, P1	Z = 2
a = 7.0222 (8) Å	Mo Kα radiation
b = 7.7313 (9) Å	µ = 14.83 mm⁻¹
c = 10.5927 (12) Å	T = 297 K
α = 108.473 (10)°	0.58 × 0.48 × 0.36 mm
β = 97.108 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2469 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1297 reflections with I > 2σ(I)
T_min = 0.122, T_max = 1.000	R_int = 0.073
4575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.091	0 restraints
wR(F²) = 0.258	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0875P)² + 18.1246P] where P = (F_o² + 2F_c²)/3
2469 reflections	Δρ_max = 1.62 e Å⁻³
109 parameters	Δρ_min = −1.27 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	1.0868 (3)	0.1807 (3)	0.90582 (19)	0.0434 (6)
Br2	0.6361 (3)	0.1787 (3)	0.9231 (2)	0.0492 (6)
Br3	0.5867 (3)	0.5842 (3)	0.7641 (2)	0.0488 (6)
Br4	1.0292 (3)	0.5783 (3)	0.7275 (2)	0.0478 (6)
C1	0.832 (3)	0.078 (3)	0.8116 (17)	0.036 (4)
H1A	0.8311	−0.0533	0.8003	0.043*
C2	0.796 (2)	0.094 (2)	0.6741 (16)	0.030 (4)
C3	0.769 (2)	−0.070 (3)	0.5681 (18)	0.035 (4)
H3A	0.7804	−0.1803	0.5862	0.042*
C4	0.725 (2)	−0.073 (2)	0.4342 (17)	0.033 (4)
H4A	0.7044	−0.1821	0.3639	0.040*
C5	0.714 (2)	0.097 (3)	0.4101 (16)	0.032 (4)
H5A	0.6924	0.1004	0.3224	0.039*
C6	0.735 (2)	0.255 (2)	0.5136 (16)	0.031 (4)
H6A	0.7183	0.3644	0.4954	0.037*
C7	0.781 (2)	0.261 (2)	0.6455 (15)	0.024 (3)
C8	0.821 (2)	0.436 (2)	0.7532 (17)	0.033 (4)
H8A	0.8533	0.4123	0.8387	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0330 (10)	0.0605 (15)	0.0388 (10)	0.0108 (9)	−0.0006 (8)	0.0207 (10)
Br2	0.0364 (11)	0.0769 (17)	0.0443 (11)	0.0028 (10)	0.0117 (9)	0.0313 (11)
Br3	0.0386 (11)	0.0406 (13)	0.0671 (14)	0.0169 (9)	0.0072 (9)	0.0165 (11)
Br4	0.0406 (11)	0.0372 (13)	0.0653 (14)	−0.0084 (8)	0.0102 (9)	0.0148 (10)
C1	0.047 (10)	0.027 (10)	0.041 (10)	−0.009 (8)	0.002 (8)	0.024 (8)
C2	0.019 (7)	0.033 (11)	0.033 (9)	0.003 (7)	0.000 (6)	0.008 (8)
C3	0.016 (8)	0.038 (11)	0.051 (11)	0.004 (7)	0.006 (7)	0.014 (9)
C4	0.040 (10)	0.026 (10)	0.033 (9)	0.005 (7)	0.017 (8)	0.003 (8)
C5	0.024 (8)	0.042 (11)	0.025 (8)	0.015 (7)	0.008 (7)	−0.001 (8)
C6	0.042 (10)	0.015 (9)	0.029 (8)	0.006 (7)	0.009 (7)	−0.003 (7)
C7	0.019 (7)	0.026 (9)	0.032 (8)	0.003 (6)	0.007 (6)	0.013 (7)
C8	0.032 (9)	0.030 (11)	0.038 (9)	−0.011 (7)	0.003 (7)	0.014 (8)

Geometric parameters (Å, º) top

Br1—C1	1.965 (17)	C3—H3A	0.9300
Br2—C1	1.932 (19)	C4—C5	1.42 (3)
Br3—C8	2.003 (18)	C4—H4A	0.9300
Br4—C8	1.922 (15)	C5—C6	1.35 (2)
C1—C2	1.49 (2)	C5—H5A	0.9300
C1—H1A	0.9800	C6—C7	1.38 (2)
C2—C7	1.42 (2)	C6—H6A	0.9300
C2—C3	1.40 (2)	C7—C8	1.47 (2)
C3—C4	1.41 (2)	C8—H8A	0.9800

C2—C1—Br2	113.8 (12)	C6—C5—C4	120.4 (16)
C2—C1—Br1	112.7 (11)	C6—C5—H5A	119.8
Br2—C1—Br1	110.0 (9)	C4—C5—H5A	119.8
C2—C1—H1A	106.6	C5—C6—C7	122.7 (17)
Br2—C1—H1A	106.6	C5—C6—H6A	118.6
Br1—C1—H1A	106.6	C7—C6—H6A	118.6
C7—C2—C3	119.0 (16)	C6—C7—C2	118.7 (15)
C7—C2—C1	124.9 (15)	C6—C7—C8	120.6 (15)
C3—C2—C1	116.0 (16)	C2—C7—C8	120.7 (14)
C4—C3—C2	121.2 (17)	C7—C8—Br4	112.8 (11)
C4—C3—H3A	119.4	C7—C8—Br3	110.0 (11)
C2—C3—H3A	119.4	Br4—C8—Br3	108.1 (9)
C5—C4—C3	117.9 (16)	C7—C8—H8A	108.6
C5—C4—H4A	121.1	Br4—C8—H8A	108.6
C3—C4—H4A	121.1	Br3—C8—H8A	108.6

Br2—C1—C2—C7	61.2 (18)	C5—C6—C7—C8	174.1 (15)
Br1—C1—C2—C7	−65.0 (19)	C3—C2—C7—C6	2 (2)
Br2—C1—C2—C3	−117.0 (14)	C1—C2—C7—C6	−176.1 (15)
Br1—C1—C2—C3	116.9 (14)	C3—C2—C7—C8	−175.9 (14)
C7—C2—C3—C4	−1 (2)	C1—C2—C7—C8	6 (2)
C1—C2—C3—C4	177.2 (14)	C6—C7—C8—Br4	−58.1 (18)
C2—C3—C4—C5	2 (2)	C2—C7—C8—Br4	119.7 (14)
C3—C4—C5—C6	−3 (2)	C6—C7—C8—Br3	62.6 (16)
C4—C5—C6—C7	5 (3)	C2—C7—C8—Br3	−119.6 (13)
C5—C6—C7—C2	−4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br1	0.98	2.64	3.364 (16)	131
C8—H8A···Br2	0.98	2.78	3.420 (16)	124

Experimental details

Crystal data
Chemical formula	C₈H₆Br₄
M_r	421.77
Crystal system, space group	Triclinic, P1
Temperature (K)	297
a, b, c (Å)	7.0222 (8), 7.7313 (9), 10.5927 (12)
α, β, γ (°)	108.473 (10), 97.108 (9), 90.394 (9)
V (Å³)	540.61 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	14.83
Crystal size (mm)	0.58 × 0.48 × 0.36

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.122, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4575, 2469, 1297
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.091, 0.258, 1.04
No. of reflections	2469
No. of parameters	109
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0875P)² + 18.1246P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.62, −1.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br1	0.98	2.64	3.364 (16)	131
C8—H8A···Br2	0.98	2.78	3.420 (16)	124

Acknowledgements

This work was supported by the National Science Council (NSC 99–2113-M-035–001-MY2) and Feng Chia University in Taiwan.

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