2,4-Dibromo-6-tert-butyl­benzene-1,3-diol

Wang, X.; Niu, J.; Zhi, C.

doi:10.1107/S1600536811034866

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2618

https://doi.org/10.1107/S1600536811034866

Open

access

2,4-Dibromo-6-tert-butylbenzene-1,3-diol

Xia Wang,^a ^* Jun-long Niu ^b and Cai-xia Zhi ^b

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bDepartment of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China
^*Correspondence e-mail: wangxiawx83@yahoo.com.cn

(Received 11 June 2011; accepted 25 August 2011; online 14 September 2011)

In the title compound, C₁₀H₁₂Br₂O₂, a multiply substituted bromoarene, the C—C—C angles within the aromatic ring are in the range 115.7 (7)-122.4 (7)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, but no π–π stacking is observed.

Related literature

For similar compounds, see: Butler & Walker (1993 ); Seevers & Counsell (1982 ); Zheng et al. (2004 ).

Experimental

Crystal data

C₁₀H₁₂Br₂O₂
M_r = 324.02
Tetragonal, $[P \overline 4b 2]$
a = 11.618 (3) Å
c = 17.761 (4) Å
V = 2397.4 (9) Å³
Z = 8
Mo Kα radiation
μ = 6.74 mm⁻¹
T = 290 K
0.22 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.319, T_max = 0.346
4935 measured reflections
1367 independent reflections
775 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.059
S = 1.08
1367 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.82	2.67	3.246 (13)	129
O2—H2⋯O2ⁱⁱ	0.82	2.36	2.979 (9)	133
Symmetry codes: (i) -x+1, -y+2, z; (ii) -y+1, x, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 global, I. DOI: https://doi.org/10.1107/S1600536811034866/vm2103sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811034866/vm2103Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811034866/vm2103Isup3.cml

checkCIF report

Comment top

Bromoarenes have proven to be important and valuable precursors for the synthesis of a wide variety of target compounds by functionalization through cross-coupling reactions, and have been used as key intermediates in the synthesis of a large number of natural products and bioactive materials (Butler & Walker, 1993; Seevers & Counsell, 1982). In this paper, we synthesized the title compound and reported its crystal structure. In the title compound, C—C—C angles within the phenyl ring span a range of 115.7 (7) ° to 122.4 (7) ° with the smallest angle found on the C6 atom bearing the tert-butyl substituent, and the largest angle is found for the unsubstituted C5 atom (Fig. 1). In the crystal, molecules are linked by O—H···O hydrogen bonds (Table 1, Fig. 2). In addition, the benzene rings between the adjacent molecules are stacked in a face-to-face orientation with the distance of 3.858 Å, a distance longer than the π–π stacking distances of 3.33 - 3.53 Å reported elsewhere (Zheng et al., 2004), indicating no π–π stacking is observed for this compound.

Related literature top

For similar compounds, see: Butler & Walker (1993); Seevers & Counsell (1982); Zheng et al. (2004).

Experimental top

A mixture of 4,6-di-tert-butylbenzene-1,3-diol (111 mg, 0.5 mmol), p-toluenesulfonic acid monohydrate (285 mg, 1.5 mmol) and N-bromosuccinimide in acetonitrile (2 ml) was heated to reflux for 3 h. Subsequently, the solvent was removed under reduced pressure, and the residue was purified by preparative TLC on silica gel plates (eluent: petroleum ether/EtOAc, 4:1) to give the product as a white solid (282 mg, 87% yield). Colourless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.

Structure description top

For similar compounds, see: Butler & Walker (1993); Seevers & Counsell (1982); Zheng et al. (2004).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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. View of the title compound, showing the labeling of the 30% probability ellipsolids.
	Fig. 2. A view of the crystal packing along the c axis. Hydrogen bonds are shown as dashed lines.

2,4-Dibromo-6-tert-butylbenzene-1,3-diol top

Crystal data top

C₁₀H₁₂Br₂O₂	D_x = 1.795 Mg m⁻³
M_r = 324.02	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 1414 reflections
Hall symbol: P -4 -2ab	θ = 3.4–29.0°
a = 11.618 (3) Å	µ = 6.74 mm⁻¹
c = 17.761 (4) Å	T = 290 K
V = 2397.4 (9) Å³	Prismatic, colorless
Z = 8	0.22 × 0.20 × 0.20 mm
F(000) = 1264

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1367 independent reflections
Radiation source: fine-focus sealed tube	775 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
Detector resolution: 16.2312 pixels mm^-1	θ_max = 26.4°, θ_min = 3.4°
ω scans	h = −7→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→11
T_min = 0.319, T_max = 0.346	l = −22→11
4935 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0056P)²] where P = (F_o² + 2F_c²)/3
1367 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₀H₁₂Br₂O₂	Z = 8
M_r = 324.02	Mo Kα radiation
Tetragonal, P4b2	µ = 6.74 mm⁻¹
a = 11.618 (3) Å	T = 290 K
c = 17.761 (4) Å	0.22 × 0.20 × 0.20 mm
V = 2397.4 (9) Å³

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1367 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	775 reflections with I > 2σ(I)
T_min = 0.319, T_max = 0.346	R_int = 0.087
4935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.08	Δρ_max = 0.34 e Å⁻³
1367 reflections	Δρ_min = −0.35 e Å⁻³
132 parameters

Special details top

Experimental. CrysAlisPro (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.54152 (12)	0.82654 (10)	0.57359 (5)	0.1038 (5)
Br2	0.26935 (9)	0.44073 (9)	0.65318 (6)	0.0780 (4)
O1	0.5347 (6)	0.8647 (5)	0.7424 (3)	0.076 (2)
H1	0.5215	0.9175	0.7131	0.114*
O2	0.4052 (6)	0.6107 (6)	0.5499 (2)	0.085 (2)
H2	0.4250	0.5434	0.5444	0.128*
C1	0.4723 (7)	0.7689 (7)	0.7214 (4)	0.045 (2)
C2	0.4666 (7)	0.7357 (7)	0.6471 (4)	0.058 (2)
C3	0.4069 (7)	0.6383 (8)	0.6250 (4)	0.055 (3)
C4	0.3557 (7)	0.5756 (6)	0.6803 (5)	0.050 (2)
C5	0.3603 (7)	0.6096 (7)	0.7559 (4)	0.047 (2)
H5	0.3220	0.5655	0.7917	0.056*
C6	0.4188 (7)	0.7050 (7)	0.7788 (4)	0.046 (2)
C7	0.4255 (8)	0.7422 (9)	0.8617 (4)	0.065 (3)
C8	0.3682 (9)	0.8603 (8)	0.8714 (4)	0.090 (4)
H8A	0.2916	0.8579	0.8512	0.134*
H8B	0.4123	0.9176	0.8452	0.134*
H8C	0.3648	0.8794	0.9240	0.134*
C9	0.5530 (9)	0.7473 (11)	0.8882 (5)	0.121 (4)
H9A	0.5558	0.7698	0.9402	0.182*
H9B	0.5943	0.8024	0.8583	0.182*
H9C	0.5877	0.6728	0.8825	0.182*
C10	0.3623 (9)	0.6572 (8)	0.9131 (4)	0.093 (3)
H10A	0.3963	0.5822	0.9082	0.139*
H10B	0.2827	0.6536	0.8990	0.139*
H10C	0.3684	0.6825	0.9644	0.139*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1535 (13)	0.0852 (10)	0.0726 (6)	−0.0324 (7)	0.0515 (8)	0.0131 (6)
Br2	0.0772 (8)	0.0694 (8)	0.0875 (7)	−0.0210 (6)	0.0110 (7)	−0.0109 (6)
O1	0.080 (6)	0.068 (5)	0.079 (4)	−0.032 (5)	0.013 (3)	−0.007 (3)
O2	0.130 (7)	0.084 (6)	0.041 (3)	−0.009 (5)	0.028 (3)	−0.012 (3)
C1	0.049 (6)	0.037 (6)	0.050 (4)	−0.005 (4)	0.010 (5)	0.001 (4)
C2	0.070 (7)	0.054 (6)	0.049 (5)	−0.013 (5)	0.023 (5)	0.002 (5)
C3	0.070 (7)	0.053 (7)	0.043 (5)	−0.009 (5)	0.019 (5)	0.011 (5)
C4	0.047 (6)	0.026 (5)	0.076 (6)	−0.007 (4)	0.009 (5)	−0.004 (4)
C5	0.038 (6)	0.060 (7)	0.041 (5)	0.003 (5)	0.011 (4)	0.013 (5)
C6	0.047 (6)	0.048 (6)	0.044 (4)	−0.002 (5)	0.010 (4)	0.012 (5)
C7	0.067 (7)	0.084 (8)	0.046 (5)	−0.005 (6)	0.000 (5)	0.007 (5)
C8	0.120 (11)	0.094 (10)	0.055 (6)	0.009 (7)	0.022 (6)	−0.011 (5)
C9	0.108 (11)	0.162 (13)	0.094 (7)	−0.020 (8)	−0.047 (7)	0.023 (7)
C10	0.112 (11)	0.112 (10)	0.054 (6)	−0.013 (7)	0.006 (6)	0.009 (6)

Geometric parameters (Å, º) top

Br1—C2	1.891 (7)	C6—C7	1.536 (10)
Br2—C4	1.922 (7)	C7—C10	1.532 (11)
O1—C1	1.379 (8)	C7—C8	1.536 (11)
O1—H1	0.8200	C7—C9	1.556 (11)
O2—C3	1.373 (8)	C8—H8A	0.9600
O2—H2	0.8200	C8—H8B	0.9600
C1—C2	1.377 (9)	C8—H8C	0.9600
C1—C6	1.406 (9)	C9—H9A	0.9600
C2—C3	1.384 (10)	C9—H9B	0.9600
C3—C4	1.360 (10)	C9—H9C	0.9600
C4—C5	1.400 (9)	C10—H10A	0.9600
C5—C6	1.362 (10)	C10—H10B	0.9600
C5—H5	0.9300	C10—H10C	0.9600

C1—O1—H1	109.5	C6—C7—C8	109.7 (6)
C3—O2—H2	109.5	C10—C7—C9	107.5 (7)
C2—C1—O1	120.7 (7)	C6—C7—C9	110.4 (7)
C2—C1—C6	121.7 (7)	C8—C7—C9	110.2 (10)
O1—C1—C6	117.5 (7)	C7—C8—H8A	109.5
C1—C2—C3	121.6 (7)	C7—C8—H8B	109.5
C1—C2—Br1	118.9 (6)	H8A—C8—H8B	109.5
C3—C2—Br1	119.5 (5)	C7—C8—H8C	109.5
C4—C3—O2	124.7 (8)	H8A—C8—H8C	109.5
C4—C3—C2	117.0 (7)	H8B—C8—H8C	109.5
O2—C3—C2	118.3 (7)	C7—C9—H9A	109.5
C3—C4—C5	121.6 (7)	C7—C9—H9B	109.5
C3—C4—Br2	119.0 (6)	H9A—C9—H9B	109.5
C5—C4—Br2	119.4 (6)	C7—C9—H9C	109.5
C6—C5—C4	122.4 (7)	H9A—C9—H9C	109.5
C6—C5—H5	118.8	H9B—C9—H9C	109.5
C4—C5—H5	118.8	C7—C10—H10A	109.5
C5—C6—C1	115.7 (7)	C7—C10—H10B	109.5
C5—C6—C7	122.7 (7)	H10A—C10—H10B	109.5
C1—C6—C7	121.6 (8)	C7—C10—H10C	109.5
C10—C7—C6	111.5 (8)	H10A—C10—H10C	109.5
C10—C7—C8	107.5 (7)	H10B—C10—H10C	109.5

O1—C1—C2—C3	178.4 (9)	Br2—C4—C5—C6	−179.3 (7)
C6—C1—C2—C3	0.7 (14)	C4—C5—C6—C1	1.4 (13)
O1—C1—C2—Br1	−2.1 (12)	C4—C5—C6—C7	−179.3 (7)
C6—C1—C2—Br1	−179.8 (7)	C2—C1—C6—C5	−0.8 (13)
C1—C2—C3—C4	−1.1 (13)	O1—C1—C6—C5	−178.6 (8)
Br1—C2—C3—C4	179.4 (6)	C2—C1—C6—C7	179.9 (8)
C1—C2—C3—O2	−180.0 (8)	O1—C1—C6—C7	2.1 (12)
Br1—C2—C3—O2	0.5 (12)	C5—C6—C7—C10	1.8 (12)
O2—C3—C4—C5	−179.5 (7)	C1—C6—C7—C10	−178.9 (8)
C2—C3—C4—C5	1.7 (12)	C5—C6—C7—C8	−117.2 (10)
O2—C3—C4—Br2	−2.2 (12)	C1—C6—C7—C8	62.1 (11)
C2—C3—C4—Br2	179.0 (7)	C5—C6—C7—C9	121.2 (10)
C3—C4—C5—C6	−2.0 (13)	C1—C6—C7—C9	−59.5 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	2.67	3.246 (13)	129
O2—H2···O2ⁱⁱ	0.82	2.36	2.979 (9)	133

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂Br₂O₂
M_r	324.02
Crystal system, space group	Tetragonal, P4b2
Temperature (K)	290
a, c (Å)	11.618 (3), 17.761 (4)
V (Å³)	2397.4 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.74
Crystal size (mm)	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.319, 0.346
No. of measured, independent and observed [I > 2σ(I)] reflections	4935, 1367, 775
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.059, 1.08
No. of reflections	1367
No. of parameters	132
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.35

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), 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	2.67	3.246 (13)	129.2
O2—H2···O2ⁱⁱ	0.82	2.36	2.979 (9)	133.1

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

Acknowledgements

The authors thank Professors Hong-Wei Hou and Yu Zhu of Zhengzhou University for their help.

References

Butler, A. & Walker, J.-V. (1993). Chem. Rev. 93, 1937–1944. CrossRef CAS Web of Science Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Seevers, R.-H. & Counsell, R.-E. (1982). Chem. Rev. 82, 575–590. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, S.-L., Yang, J.-H., Yu, X.-L., Chen, X.-M. & Wong, W.-T. (2004). Inorg. Chem. 43, 830–838. Web of Science CSD CrossRef PubMed CAS Google Scholar