Bis[2-bromo-4-(2-hy­droxy­eth­yl)phenol] monohydrate

Jing Zhu; Wen-ge Yang; Lu-lu Wang; Kai Wang; Yong-hong Hu

doi:10.1107/S160053681101066X

. 2011 Apr 13;67(Pt 5):o1109. doi: 10.1107/S160053681101066X

Bis[2-bromo-4-(2-hydroxyethyl)phenol] monohydrate

Jing Zhu ^a, Wen-ge Yang ^a,^*, Lu-lu Wang ^a, Kai Wang ^a, Yong-hong Hu ^b

PMCID: PMC3089086 PMID: 21754427

Abstract

In the title compound, 2C₈H₉BrO₂·H₂O, the O—C—C—C torsion angles for the hydroxyethyl group and the Br—C—C—O torsion angles involving bromo and phenol groups are 61.7 (11) and 0.7 (12)°, respectively, in one independent molecule and 61.5 (11) and 0.2 (11)°, respectively, in the other. In the crystal, molecules are linked through O—H⋯O and O—H⋯Br hydrogen bonds, forming a polymeric chain.

Related literature

For synthesis of the title compound and background information, see: Bovicelli et al. (2007 ▶). For a related structure, see: Mewett et al. (2009 ▶).

Experimental

Crystal data

2C₈H₉BrO₂·H₂O
M _r = 452.14
Monoclinic,
a = 5.9790 (12) Å
b = 18.396 (4) Å
c = 16.801 (3) Å
β = 98.83 (3)°
V = 1826.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.46 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (ψ-scans; North et al., 1968 ▶) T _min = 0.469, T _max = 0.664
3585 measured reflections
1827 independent reflections
1302 reflections with I > 2σ(I)
R _int = 0.045
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.095
S = 1.01
1827 reflections
208 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.45 e Å⁻³
Absolute structure: Flack (1983 ▶), 746 Friedel pairs
Flack parameter: 0.00 (2)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101066X/pv2391sup1.cif

e-67-o1109-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101066X/pv2391Isup2.hkl

e-67-o1109-Isup2.hkl^{(90KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW—HWA⋯Br1	0.89	2.86	3.537 (8)	134
OW—HWA⋯O2	0.89	2.00	2.820 (10)	151
O1—H1A⋯O4	0.82	1.84	2.633 (9)	163
OW—HWB⋯O1ⁱ	0.88	2.07	2.745 (10)	133
O2—H2A⋯Br1	0.85	2.56	3.026 (6)	115
O2—H2A⋯OW	0.85	2.18	2.820 (9)	131
O3—H3A⋯O2ⁱⁱ	0.82	1.80	2.592 (9)	162
O4—H4B⋯Br2	0.85	2.57	3.039 (7)	116
O4—H4B⋯OWⁱⁱⁱ	0.85	2.21	2.804 (10)	127

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This research work was supported financially by the Department of Science and Technology of Jiangsu Province (BE200830457) and the ‘863′ project (2007 A A02Z211) of the Ministry of Science and Technology of China.

supplementary crystallographic information

Comment

The title compound is used as the key intermediate in the synthesis of hydroxytyrosol (Bovicelli et al., 2007). As a part of our studies on the synthesis of hydroxytyrosol we report herein the crystal structure of the title compound.

In the molecules of the title compound, (Fig. 1), the bond lengths and angles agree very well with the corresponding bond lengths and angles reporeted in a structure containing the title compound as its fragment (Mewett et al., 2009).

In the crystal structure, O—H···O and O—H···Br type hydrogen bonding interactions (Table 1) link the molecules into ribbons extended along the a-axis (Fig. 2). The two molecules of the title compound in the asymmetric unit are identical. The torsion angles O1/C1/C2/C3 and C1/C2/C3/C8 are 61.7 (12) and -100.6 (11)°, respectively, in one molecule. The corresponding torion angles in the other molecule are 61.5 (11) and -101.5 (11)° (for O3/C9/C10/C11 and C9/C10/C11/C12, respectively).

Experimental

To a solution of 4-hydroxyphenethyl alcohol (217.4 mmol, 30 g) and NaBr (217.4 mmol, 22.17 g) in acetone (600 ml), a solution of oxone (200 g) in water (1 L) was added dropwise at 263 K within 3 h. The progress of the reaction was monitored by thin-layer chromatography (TLC, hexane/ethyl acetate 6:4), and when the reaction was over (complete consumption of the substrate), AcOEt (500 ml) was added to the mixture. The organic layer was separated, and the aqueous phase was extracted with two 300 mL portions of AcOEt. The combined organic solutions were washed with water (300 ml), dried over anhydrous Na₂SO₄ (100 g), and evaporated. The monobrominated product, obtained in almost quantitative yield (47.1 g), appeared to be spectroscopically pure, white solid (Bovicelli et al., 2007). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.