4,6-Dibromo-2,3-dimethyl­phenol

Liu, Q.; Wang, J.; Xue, W.; Li, Q.

doi:10.1107/S1600536811003151

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o712

doi:10.1107/S1600536811003151

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4,6-Dibromo-2,3-dimethylphenol

Qiaoru Liu,^a Jungang Wang,^b ^* Weijian Xue ^b and Qi Li ^b

^aSchool of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan 467000, People's Republic of China, and ^bKey Laboratory of Pesticide 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: qwjgq@163.com

(Received 18 January 2011; accepted 24 January 2011; online 26 February 2011)

The molecule of the title compound, C₈H₈Br₂O, is approximately planar with a maximum deviation of 0.063 (1) Å for one of the Br atoms. In the crystal, adjacent molecules are joined intermolecular O—H⋯O hydrogen bonds, forming chains parallel to [010]. The structure also features a short Br⋯Br interaction of 3.362 (1) Å.

Related literature

For the synthesis, see: Lai et al. (1993 ). For a related structure, see: Bringmann & Messer (2001 ).

Experimental

Crystal data

C₈H₈Br₂O
M_r = 279.96
Monoclinic, P 2₁
a = 7.3604 (5) Å
b = 4.4310 (6) Å
c = 14.0245 (10) Å
β = 92.482 (1)°
V = 456.96 (8) Å³
Z = 2
Mo Kα radiation
μ = 8.81 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.333, T_max = 0.473
5557 measured reflections
2250 independent reflections
1882 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.090
S = 0.99
2250 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 1275 Friedel pairs
Flack parameter: 0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.82	2.25	2.913 (4)	139
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003151/ng5106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003151/ng5106Isup2.hkl

checkCIF report

Comment top

In the title compound,C~8~H~8~Br~2Õ, the adjacent molecules are molecules are joined togethe by the O1—H1···O1 (-x, y - 1/2, 2 - z) hydrogen bond, forming a one-dimensional chain running parallel to the [010] direction(Table 1 and Figure 2). Also Br···Br interaction was observed in (I) with a distance of 3.362 (1) Å between them All the bond lengths and angles are similar to the reported compound (Bringmann et al., 2001).

Related literature top

For the synthesis, see: Lai et al. (1993). For a related structure, see: Bringmann & Messer (2001).

Experimental top

The title compound, synthesized by 2,3-dimethyl phenylamine through three steps such as bromination, diazotization-bromination-hydrolysis reaction.The operating process was based on the literarure (Lai et al., 1993) and made some improvement.

Firstly, 1-amino-4-bromo-2,3-dimethylbenzene was prepared from 2,3-dimethyl phenylamine as described in the literarure(Lai et al., 1993). Then treatment as follows: Sodiumnitrite (1.75 g, 25 mmol) in water (10 ml) was added dropwise into the rapidly stirring mixture of 40% hydrogen bromide (15 ml) containing l-amino-2,3-dimethylbenzene (5.00 g, 25 mmol). The mixture was kept in an ice-bath stiring for 2 h, while the temperature was kept below 5°C by the addition of pieces of ice. Then added 1.97 g (14 mmol) cuprous bromide which was pretreatmented by refluxing with 10 ml 40% hydrogen bromide solution for 1 h. After the addition the mixture was heated refluxing for an additional 1 h, and then cooled to room temperature, extract by methylenechloride. The organic layer was washed by water, dried by anhydrous natriumsulfate, evaporated under reduced pressure and chromatographed on silica gel with hexane as the eluent. The title compound was obtained as needle crystal solid 1.82 grams. Yield was 26%. Colorless needle-like single crystals suitable for X-ray diffraction studies were obtained by slow evaporation of a solution of the title compound in chloroform: methanol (3: 1) 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Part of the crystal packing, showing the formation of the one-dimensional chain in (I) by the O1—H1···O1(-x, y - 1/2, 2 - z) hydrogen bond.

4,6-Dibromo-2,3-dimethylphenol top

Crystal data top

C₈H₈Br₂O	F(000) = 268
M_r = 279.96	D_x = 2.035 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2355 reflections
a = 7.3604 (5) Å	θ = 2.8–24.5°
b = 4.4310 (6) Å	µ = 8.81 mm⁻¹
c = 14.0245 (10) Å	T = 298 K
β = 92.482 (1)°	Needle, colorless
V = 456.96 (8) Å³	0.16 × 0.12 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2250 independent reflections
Radiation source: fine-focus sealed tube	1882 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
phi and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.333, T_max = 0.473	k = −5→5
5557 measured reflections	l = −18→18

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0403P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
2250 reflections	Δρ_max = 0.57 e Å⁻³
102 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

Crystal data top

C₈H₈Br₂O	V = 456.96 (8) Å³
M_r = 279.96	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.3604 (5) Å	µ = 8.81 mm⁻¹
b = 4.4310 (6) Å	T = 298 K
c = 14.0245 (10) Å	0.16 × 0.12 × 0.10 mm
β = 92.482 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2250 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1882 reflections with I > 2σ(I)
T_min = 0.333, T_max = 0.473	R_int = 0.042
5557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.090	Δρ_max = 0.57 e Å⁻³
S = 0.99	Δρ_min = −0.29 e Å⁻³
2250 reflections	Absolute structure: Flack (1983), 1275 Friedel pairs
102 parameters	Absolute structure parameter: 0.02 (2)
0 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	0.87217 (5)	−0.34219 (12)	0.92038 (3)	0.05521 (15)
Br2	0.86105 (8)	0.29262 (15)	0.57447 (4)	0.0790 (2)
C1	0.5729 (5)	0.0139 (10)	0.8491 (3)	0.0436 (9)
C2	0.4789 (5)	0.2000 (10)	0.7846 (3)	0.0458 (10)
C3	0.5600 (6)	0.2866 (12)	0.6995 (3)	0.0496 (9)
C4	0.7350 (6)	0.1753 (13)	0.6843 (3)	0.0516 (9)
C5	0.8255 (5)	−0.0114 (11)	0.7471 (3)	0.0498 (10)
H5	0.9405	−0.0835	0.7342	0.060*
C6	0.7440 (5)	−0.0922 (9)	0.8300 (3)	0.0429 (9)
C7	0.2920 (6)	0.3103 (13)	0.8071 (4)	0.0621 (12)
H7A	0.2479	0.1971	0.8597	0.093*
H7B	0.2110	0.2837	0.7522	0.093*
H7C	0.2978	0.5204	0.8237	0.093*
C8	0.4589 (8)	0.4836 (14)	0.6281 (4)	0.0684 (14)
H8A	0.5442	0.5917	0.5911	0.103*
H8B	0.3849	0.6245	0.6610	0.103*
H8C	0.3828	0.3605	0.5866	0.103*
O1	0.4886 (4)	−0.0551 (8)	0.9326 (2)	0.0533 (8)
H1	0.5505	−0.1777	0.9634	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0508 (2)	0.0528 (2)	0.0620 (3)	0.0041 (2)	0.00077 (17)	−0.0045 (2)
Br2	0.0927 (4)	0.0918 (4)	0.0547 (3)	−0.0172 (3)	0.0285 (3)	−0.0037 (3)
C1	0.043 (2)	0.0419 (19)	0.046 (2)	−0.0093 (17)	0.0072 (16)	−0.0128 (19)
C2	0.047 (2)	0.042 (3)	0.049 (2)	−0.0074 (17)	0.0016 (16)	−0.0067 (17)
C3	0.061 (2)	0.044 (2)	0.043 (2)	−0.012 (2)	−0.0015 (18)	−0.007 (2)
C4	0.059 (2)	0.054 (2)	0.043 (2)	−0.015 (2)	0.0118 (16)	−0.004 (2)
C5	0.045 (2)	0.049 (2)	0.056 (3)	−0.006 (2)	0.0103 (18)	−0.014 (2)
C6	0.043 (2)	0.042 (2)	0.043 (2)	−0.0011 (17)	−0.0010 (16)	−0.0099 (18)
C7	0.046 (2)	0.066 (3)	0.074 (3)	0.004 (2)	0.007 (2)	0.001 (3)
C8	0.089 (4)	0.063 (3)	0.052 (3)	−0.001 (3)	−0.006 (3)	0.002 (3)
O1	0.0545 (17)	0.0582 (19)	0.0482 (18)	0.0023 (15)	0.0143 (13)	0.0007 (15)

Geometric parameters (Å, º) top

Br1—C6	1.903 (4)	C5—C6	1.379 (6)
Br2—C4	1.905 (4)	C5—H5	0.9300
C1—C6	1.381 (5)	C7—H7A	0.9600
C1—O1	1.383 (5)	C7—H7B	0.9600
C1—C2	1.387 (6)	C7—H7C	0.9600
C2—C3	1.411 (6)	C8—H8A	0.9600
C2—C7	1.507 (6)	C8—H8B	0.9600
C3—C4	1.404 (7)	C8—H8C	0.9600
C3—C8	1.501 (7)	O1—H1	0.8200
C4—C5	1.361 (7)

C6—C1—O1	122.4 (4)	C5—C6—Br1	119.5 (3)
C6—C1—C2	120.6 (4)	C1—C6—Br1	119.9 (3)
O1—C1—C2	117.1 (3)	C2—C7—H7A	109.5
C1—C2—C3	119.8 (4)	C2—C7—H7B	109.5
C1—C2—C7	119.4 (4)	H7A—C7—H7B	109.5
C3—C2—C7	120.9 (4)	C2—C7—H7C	109.5
C4—C3—C2	117.2 (4)	H7A—C7—H7C	109.5
C4—C3—C8	122.4 (4)	H7B—C7—H7C	109.5
C2—C3—C8	120.4 (4)	C3—C8—H8A	109.5
C5—C4—C3	122.8 (4)	C3—C8—H8B	109.5
C5—C4—Br2	116.6 (3)	H8A—C8—H8B	109.5
C3—C4—Br2	120.6 (4)	C3—C8—H8C	109.5
C4—C5—C6	119.0 (4)	H8A—C8—H8C	109.5
C4—C5—H5	120.5	H8B—C8—H8C	109.5
C6—C5—H5	120.5	C1—O1—H1	109.5
C5—C6—C1	120.6 (4)

C6—C1—C2—C3	−1.2 (6)	C2—C3—C4—Br2	−177.2 (3)
O1—C1—C2—C3	178.0 (4)	C8—C3—C4—Br2	4.2 (7)
C6—C1—C2—C7	179.6 (4)	C3—C4—C5—C6	−1.1 (7)
O1—C1—C2—C7	−1.3 (6)	Br2—C4—C5—C6	177.0 (3)
C1—C2—C3—C4	0.3 (6)	C4—C5—C6—C1	0.2 (6)
C7—C2—C3—C4	179.6 (4)	C4—C5—C6—Br1	−177.9 (3)
C1—C2—C3—C8	178.9 (4)	O1—C1—C6—C5	−178.2 (4)
C7—C2—C3—C8	−1.8 (7)	C2—C1—C6—C5	0.9 (6)
C2—C3—C4—C5	0.8 (7)	O1—C1—C6—Br1	−0.1 (5)
C8—C3—C4—C5	−177.8 (5)	C2—C1—C6—Br1	179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	2.25	2.913 (4)	139
O1—H1···Br1	0.82	2.57	3.108 (3)	124
C8—H8A···Br2	0.96	2.70	3.200 (6)	113

Symmetry code: (i) −x+1, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₈H₈Br₂O
M_r	279.96
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	7.3604 (5), 4.4310 (6), 14.0245 (10)
β (°)	92.482 (1)
V (Å³)	456.96 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.81
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.333, 0.473
No. of measured, independent and observed [I > 2σ(I)] reflections	5557, 2250, 1882
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.090, 0.99
No. of reflections	2250
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.29
Absolute structure	Flack (1983), 1275 Friedel pairs
Absolute structure parameter	0.02 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	2.25	2.913 (4)	138.7

Symmetry code: (i) −x+1, y−1/2, −z+2.

Acknowledgements

This research was supported by the Top-class Foundation of Pingdingshan University (No. 2006045).

References

Bringmann, G. & Messer, K. (2001). Phytochemistry, 56, 387–391. Web of Science CSD CrossRef PubMed CAS 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. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar