(3,6-Dibromo-o-phenyl­ene)dimethanol

Li, Q.; Xue, W.

doi:10.1107/S1600536811001206

organic compounds

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Volume 67| Part 2| February 2011| Page o400

doi:10.1107/S1600536811001206

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(3,6-Dibromo-o-phenylene)dimethanol

Qi Li ^a and Wei-jian Xue ^a ^*

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: liqi20100906@163.com

(Received 15 December 2010; accepted 9 January 2011; online 15 January 2011)

The title compound, C₈H₈Br₂O₂, was synthesized from the hydrolysis of 1,4-dibromo-2,3-bis(bromomethyl)benzene. One intramolecular O—H⋯O and two intramolecular C—H⋯Br interactions occur. In the crystal, molecules are linked into a chain running parallel to [010]. Adjacent chains are linked into a two-dimensional layer by a combination of intermolecular O—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For the preparation of the title compound, see: Abad (2005 ); Lai & Yap, (1993 ).

Experimental

Crystal data

C₈H₈Br₂O₂
M_r = 295.96
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.482 (2) Å
b = 9.123 (5) Å
c = 22.819 (11) Å
V = 933.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 8.64 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.277, T_max = 0.479
11471 measured reflections
2300 independent reflections
1795 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.111
S = 1.05
2300 reflections
115 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.60 e Å⁻³
Absolute structure: Flack (1983 ), 918 Friedel pairs
Flack parameter: 0.03 (2)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Br2	0.97	2.61	3.192 (6)	119
C7—H7B⋯Br1	0.97	2.66	3.169 (5)	114
O2—H2⋯O1ⁱ	0.82 (6)	1.92 (3)	2.703 (6)	160 (7)
O1—H1⋯O2	0.81 (6)	1.95 (4)	2.703 (6)	152 (7)
C8—H8B⋯Cg1ⁱⁱ	0.97	3.01	3.63(5)	123
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001206/om2391sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001206/om2391Isup2.hkl

checkCIF report

Comment top

Benzyl alcohol derivatives are important compounds as preservatives, dyes, fibers, and nylons. In our work, the hydrolysis of 1,4-dibromo-2,3-bis(bromomethyl)benzene gave rise to the dimethanol product reported here. The molecules of (3,6-dibromo-1,2-phenylene)dimethanol (Figure 1) are linked into a one-dimensional chain running parallel to the [010] direction by intra- and intermolecular O-H···O hydrogen bond interactions. The adjacent chains are linked into a two-dimensional layer by the combination of the O2—H2···O1(1 - x, y - 1/2, 1/2 - z) (Table 1) hydrogen bonds and C—H···π interaction (H8B (1+x,y,z)···Cg1 = 3.01 (1) Å, C8—H8B···Cg1 = 122.9°, Cg1 is the centroid defined by atoms C1—C6.)

Related literature top

For the preparation of the title compound, see: Abad et al. (2005); Lai et al. (1993).

Experimental top

The title compound was synthesized according to the reported literature (Abad et al., 2005 and Lai et al., 1993). The reaction of 1,4-dibromo-2,3-dimethylbenzene with N-bromosuccinimide in carbon tetrachloride in the presence of benzoyl peroxide under illumination and reflux gave 1,4-dibromo-2,3-bis(bromomethyl)benzene. Then 1,4-dibromo-2,3-bis(bromomethyl)benzene with NaOH in water at room temperature gave rise to (3,6-dibromo-1,2-phenylene)dimethanol . Crystals suitable for X-ray diffraction were grown by slow evaporation of a chloroform-methanol (5:1) solution of the title compound at room temperature.

Computing details top

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

Figures top

Fig. 1. A view of the title compound, showing the atom labelling scheme, with displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity.

(3,6-Dibromo-o-phenylene)dimethanol top

Crystal data top

C₈H₈Br₂O₂	F(000) = 568
M_r = 295.96	D_x = 2.107 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3167 reflections
a = 4.482 (2) Å	θ = 2.4–24.1°
b = 9.123 (5) Å	µ = 8.64 mm⁻¹
c = 22.819 (11) Å	T = 298 K
V = 933.0 (8) Å³	Needle, colorless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	2300 independent reflections
Radiation source: fine-focus sealed tube	1795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −5→5
T_min = 0.277, T_max = 0.479	k = −12→12
11471 measured reflections	l = −30→30

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0525P)² + 0.6273P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.004
2300 reflections	Δρ_max = 1.17 e Å⁻³
115 parameters	Δρ_min = −0.60 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 918 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (2)

Crystal data top

C₈H₈Br₂O₂	V = 933.0 (8) Å³
M_r = 295.96	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.482 (2) Å	µ = 8.64 mm⁻¹
b = 9.123 (5) Å	T = 298 K
c = 22.819 (11) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	2300 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	1795 reflections with I > 2σ(I)
T_min = 0.277, T_max = 0.479	R_int = 0.040
11471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	Δρ_max = 1.17 e Å⁻³
S = 1.05	Δρ_min = −0.60 e Å⁻³
2300 reflections	Absolute structure: Flack (1983), 918 Friedel pairs
115 parameters	Absolute structure parameter: 0.03 (2)
2 restraints

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	0.30061 (15)	0.81127 (6)	0.06905 (3)	0.0657 (2)
Br2	0.8120 (2)	0.15549 (7)	0.12029 (4)	0.0930 (3)
C1	0.4665 (11)	0.6246 (5)	0.0868 (2)	0.0422 (11)
C2	0.6474 (10)	0.6045 (5)	0.13420 (19)	0.0380 (10)
C3	0.7599 (11)	0.4622 (5)	0.14561 (19)	0.0443 (11)
C4	0.6766 (13)	0.3496 (5)	0.1078 (2)	0.0518 (12)
C5	0.4952 (14)	0.3730 (7)	0.0605 (2)	0.0593 (14)
H5	0.4439	0.2955	0.0360	0.071*
C6	0.3902 (13)	0.5100 (7)	0.0495 (2)	0.0532 (13)
H6	0.2683	0.5270	0.0172	0.064*
C7	0.7251 (12)	0.7281 (5)	0.17504 (19)	0.0466 (11)
H7A	0.9324	0.7197	0.1868	0.056*
H7B	0.7003	0.8209	0.1549	0.056*
C8	0.9546 (13)	0.4374 (7)	0.1983 (2)	0.0566 (13)
H8A	1.0251	0.3369	0.1982	0.068*
H8B	1.1273	0.5013	0.1960	0.068*
O1	0.5374 (9)	0.7250 (4)	0.22612 (15)	0.0555 (9)
H1	0.582 (16)	0.651 (5)	0.244 (3)	0.083*
O2	0.7969 (9)	0.4656 (4)	0.25204 (16)	0.0610 (9)
H2	0.680 (14)	0.397 (6)	0.250 (3)	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0672 (3)	0.0603 (3)	0.0697 (3)	0.0117 (3)	0.0053 (3)	0.0190 (3)
Br2	0.1119 (6)	0.0401 (3)	0.1269 (6)	0.0091 (4)	0.0183 (5)	0.0023 (3)
C1	0.042 (3)	0.042 (3)	0.043 (2)	−0.004 (2)	0.006 (2)	0.0020 (19)
C2	0.031 (2)	0.040 (2)	0.042 (2)	−0.0079 (18)	0.0103 (19)	−0.0006 (18)
C3	0.041 (3)	0.046 (2)	0.046 (2)	−0.006 (2)	0.013 (2)	0.0019 (19)
C4	0.054 (3)	0.039 (2)	0.062 (3)	−0.005 (2)	0.010 (3)	0.002 (2)
C5	0.070 (4)	0.053 (3)	0.056 (3)	−0.014 (3)	−0.001 (3)	−0.015 (2)
C6	0.052 (3)	0.067 (3)	0.041 (2)	−0.010 (2)	−0.004 (2)	0.001 (2)
C7	0.047 (3)	0.043 (2)	0.050 (2)	−0.006 (2)	0.004 (2)	−0.0046 (19)
C8	0.045 (3)	0.060 (3)	0.065 (3)	0.002 (3)	0.000 (3)	0.009 (3)
O1	0.066 (2)	0.049 (2)	0.052 (2)	−0.0007 (19)	0.0113 (19)	−0.0068 (16)
O2	0.062 (2)	0.069 (2)	0.0515 (18)	−0.007 (2)	−0.004 (2)	0.0116 (18)

Geometric parameters (Å, º) top

Br1—C1	1.902 (5)	C5—H5	0.9300
Br2—C4	1.894 (5)	C6—H6	0.9300
C1—C2	1.365 (6)	C7—O1	1.438 (5)
C1—C6	1.391 (7)	C7—H7A	0.9700
C2—C3	1.417 (7)	C7—H7B	0.9700
C2—C7	1.504 (6)	C8—O2	1.439 (7)
C3—C4	1.392 (7)	C8—H8A	0.9700
C3—C8	1.502 (7)	C8—H8B	0.9700
C4—C5	1.368 (8)	O1—H1	0.81 (6)
C5—C6	1.359 (9)	O2—H2	0.82 (6)

C2—C1—C6	122.0 (5)	C5—C6—H6	120.2
C2—C1—Br1	121.4 (4)	C1—C6—H6	120.2
C6—C1—Br1	116.5 (4)	O1—C7—C2	110.6 (4)
C1—C2—C3	118.7 (4)	O1—C7—H7A	109.5
C1—C2—C7	121.9 (4)	C2—C7—H7A	109.5
C3—C2—C7	119.4 (4)	O1—C7—H7B	109.5
C4—C3—C2	117.8 (4)	C2—C7—H7B	109.5
C4—C3—C8	122.7 (4)	H7A—C7—H7B	108.1
C2—C3—C8	119.4 (4)	O2—C8—C3	111.7 (4)
C5—C4—C3	122.3 (5)	O2—C8—H8A	109.3
C5—C4—Br2	117.0 (4)	C3—C8—H8A	109.3
C3—C4—Br2	120.7 (4)	O2—C8—H8B	109.3
C6—C5—C4	119.7 (5)	C3—C8—H8B	109.3
C6—C5—H5	120.2	H8A—C8—H8B	107.9
C4—C5—H5	120.2	C7—O1—H1	107 (5)
C5—C6—C1	119.5 (5)	C8—O2—H2	98 (5)

C6—C1—C2—C3	−0.1 (7)	C8—C3—C4—Br2	−1.0 (6)
Br1—C1—C2—C3	178.9 (3)	C3—C4—C5—C6	−0.1 (8)
C6—C1—C2—C7	−178.9 (4)	Br2—C4—C5—C6	179.8 (4)
Br1—C1—C2—C7	0.1 (6)	C4—C5—C6—C1	−0.6 (8)
C1—C2—C3—C4	−0.6 (6)	C2—C1—C6—C5	0.7 (8)
C7—C2—C3—C4	178.2 (4)	Br1—C1—C6—C5	−178.4 (4)
C1—C2—C3—C8	−178.8 (4)	C1—C2—C7—O1	98.1 (5)
C7—C2—C3—C8	0.0 (6)	C3—C2—C7—O1	−80.7 (5)
C2—C3—C4—C5	0.7 (7)	C4—C3—C8—O2	−114.8 (5)
C8—C3—C4—C5	178.9 (5)	C2—C3—C8—O2	63.3 (6)
C2—C3—C4—Br2	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br2	0.97	2.61	3.192 (6)	119
C7—H7B···Br1	0.97	2.66	3.169 (5)	114
O2—H2···O1ⁱ	0.82 (6)	1.92 (3)	2.703 (6)	160 (7)
O1—H1···O2	0.81 (6)	1.95 (4)	2.703 (6)	152 (7)
C8—H8B···Cg1ⁱⁱ	0.97	3.01	3.63 (5)	123

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

Experimental details

Crystal data
Chemical formula	C₈H₈Br₂O₂
M_r	295.96
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	4.482 (2), 9.123 (5), 22.819 (11)
V (Å³)	933.0 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.64
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.277, 0.479
No. of measured, independent and observed [I > 2σ(I)] reflections	11471, 2300, 1795
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.111, 1.05
No. of reflections	2300
No. of parameters	115
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.17, −0.60
Absolute structure	Flack (1983), 918 Friedel pairs
Absolute structure parameter	0.03 (2)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br2	0.97	2.61	3.192 (6)	119
C7—H7B···Br1	0.97	2.66	3.169 (5)	114
O2—H2···O1ⁱ	0.82 (6)	1.92 (3)	2.703 (6)	160 (7)
O1—H1···O2	0.81 (6)	1.95 (4)	2.703 (6)	152 (7)
C8—H8B···Cg1ⁱⁱ	0.97	3.01	3.63 (5)	123

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

Acknowledgements

The authors are grateful to Xianggao Meng for the data collection.

References

Abad, A. (2005). Synthesis, 19, 3355–3361. Web of Science CrossRef Google Scholar
Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lai, Y.-H. & Yap, A. H.-T. (1993). J. Chem. Soc. Perkin Trans. 2, pp. 1373–1377. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o400

doi:10.1107/S1600536811001206

Open

access