1-Bromo-2,6-di­hydroxy­benzene containing R44(8) rings and C(2) helices

Kirsop, P.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S0108270104006882

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 5| May 2004| Pages o353-o355

doi:10.1107/S0108270104006882

1-Bromo-2,6-dihydroxybenzene containing R₄⁴(8) rings and C(2) helices

Peter Kirsop,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 22 March 2004; accepted 23 March 2004; online 21 April 2004)

Molecules of the title compound (also known as 2-bromoresorcinol), C₆H₅BrO₂, are essentially planar and possess normal geometrical parameters. The crystal packing is influenced by O—H⋯O and O—H⋯O/Br hydrogen bonds and π–π stacking interactions, resulting in a distinctive high-symmetry structure containing R $[{_4^4}]$ (8) rings and helical C(2) chains.

Comment

The title compound, (I) (Fig. 1), also known as 2-bromoresorcinol, arose during our studies to determine the philicity of aryl radicals by competitive cyclization (Kirsop et al., 2004 ).

Compound (I) possesses normal geometrical parameters [mean C—C = 1.386 (2) Å, C1—Br1 = 1.885 (2) Å and mean C—O = 1.373 (3) Å] and, as expected, is essentially planar (for the non-H atoms, the r.m.s deviation from the best least-squares plane is 0.008 Å).

As well as van der Waals forces, the crystal packing is strongly influenced by hydrogen bonding (Table 1). A hydrogen bond involving atom H2 is bifurcated to an intermolecular O and an intramolecular Br acceptor species, and the donor–acceptor bond-angle sum about atom H2 is 360°. The situation involving atom H1 is less clear cut. As well as an intermolecular O1—H1⋯O1ⁱ bond (see Table 1 for symmetry code), there is also a possible, very long, intermolecular O1—H1⋯Br1ⁱ contact with an H⋯Br distance of 3.13 Å, although this was flagged as being of questionable significance in a PLATON (Spek, 2003 ) analysis of (I). However, the donor–acceptor bond-angle sum for atoms O1, O1ⁱ and Br1ⁱ about H1 is 358°, which suggests that this interaction may have some significance beyond being merely a packing contact.

The hydrogen-bonding scheme in (I) results in two distinctive submotifs to the unit-cell packing. In the first of these, the $[\overline 4]$ axis along [001] at x = $[{1 \over 2}]$ , y = $[{1 \over 4}]$ , with the inversion point at z = $[{3 \over 8}]$ , and equivalent locations, generates a closed ring of four molecules of (I) by way of four O1—H1⋯O1 bonds (Fig. 2), thus characterized by an R $[{_4^4}]$ (8) motif (Bernstein et al., 1995 ).

In the second submotif, the 4₁ screw axis at x = $[{1 \over 4}]$ , y = $[{1 \over 2}]$ generates helical chains of molecules of (I) linked by O2—H2⋯O2 hydrogen bonds, forming C(2) chains (Fig. 3). Space-group symmetry results in an equal number of clockwise and anticlockwise helices, by way of the alternating (with respect to both [100] and [010]) array of 4₁ and 4₃ axes.

Finally, π–π stacking interactions are present in (I). The inversion centre at ( $[{1 \over 4}]$ , $[{1 \over 4}]$ , $[{1 \over 4}]$ ) and equivalent locations generates pairs of molecules of (I), with a Cg⋯Cgⁱⁱⁱ separation of 3.6397 (12) Å [Cg is the centroid of the C1–C6 ring at (0.3348, 0.2915, 0.7669); symmetry code: (iii) $[{1 \over 2}]$ − x, $[{1 \over 2}]$ − y, $[{3 \over 2}]$ − z]. The best least-squares ring planes for Cg and Cgⁱⁱⁱ are exactly parallel (dihedral angle = 0.0°) and are separated by 3.470 Å. The lateral displacement of Cgⁱⁱⁱ relative to the normal from the Cg best least-squares plane at Cg to the Cgⁱⁱⁱ best least-squares plane is 1.098 Å. The unit-cell packing of (I) is shown in Fig. 4.

Although the local hydrogen-bonding motifs are similar, the structure of (I) is entirely different to that of 1,3,5-tribromo-2,6-dihydroxybenzene (Kirsop et al., 2004), which contains chain-like associations of molecules and is chiral by way of the molecular packing.

Figure 1
The asymmetric unit of (I

), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii and the intramolecular hydrogen bond is shown as a dashed line.

Figure 2
Part of the crystal structure of (I

), showing a hydrogen-bonded R $[{_4^4}]$ (8) ring and a close π–π contact (ring centroids linked by an open line) [symmetry codes: (i) $[{3 \over 4}]$ − y, x − $[{1 \over 4}]$ , $[{3 \over 4}]$ − z; (ii) $[{1 \over 4}]$ + y, $[{3 \over 4}]$ − x, $[{3 \over 4}]$ − z; (iii) 1 − x, $[{1 \over 2}]$ − y, z; (iv) $[{1 \over 2}]$ − x, $[{1 \over 2}]$ − y, $[{3 \over 2}]$ − z]. H atoms bonded to C atoms and the unit-cell box have been omitted for clarity.

Figure 3
Part of the crystal structure of (I

), showing a hydrogen-bonded helical chain of O2—H2⋯O2 bonds [symmetry codes: (i) y − $[{1 \over 4}]$ , $[{3 \over 4}]$ − x, z − $[{1 \over 4}]$ ; (ii) $[{1 \over 2}]$ − x, 1 − y, z − $[{1 \over 2}]$ ; (iii) $[{3 \over 4}]$ − y, $[{1 \over 4}]$ + x, z − $[{3 \over 4}]$ ; (iv) x, y, 1 − z]. Atom H1, C-bound H atoms and the intramolecular O2—H2⋯Br1 hydrogen bond have been omitted for clarity, as has the unit-cell box.

Figure 4
The unit-cell packing in (I

), viewed down [001], with C-bound H atoms omitted for clarity. The hydrogen bonds forming the R $[{_4^4}]$ (8) loops are indicated by thin lines and the hydrogen bonds forming the helical chains are indicated by dashed lines. The ring centroids are indicated by small spheres and the π–π interactions by open lines. The cell orientation corresponds to that given for the second setting of I4₁/a in International Tables for X-ray Crystallography (1983, Vol. A).

Experimental

A solution of Na₂SO₄ (3.04 g, 0.024 mol) and NaOH (0.96 g, 0.024 mol) in distilled water (36 ml) was added to a suspension of 1,3,5-tribromo-2,6-dihydroxybenzene (Kirsop et al., 2004; 4.16 g, 0.012 mol) in a 1:5 mixture of methanol and water (50 ml). The resulting mixture was stirred at 293 K for 1 h, after which time the suspension had disappeared, leaving a pale-yellow liquid. The solution was acidified with 1 M HCl (4 ml) and extracted with diethyl ether (4 × 50 ml), and the extract was dried over anhydrous MgSO₄ for 10 min. The MgSO₄ was removed by filtration and the solvent was removed at reduced pressure to give a pale-cream powder (yield 1.86 g, 82%). A sample of this powder was recrystallized from hot ethyl acetate to give large colourless needles of (I) [m.p. 373 K; literature value (Rice, 1926 ) 375.5 K]. ¹H NMR (CDCl₃): δ 5.37 (2H, s, OH), 6.60 (2H, d, J = 8 Hz, Ar-H), 7.10 (1H, t, J = 9 Hz, Ar-H); ¹³C NMR (CDCl₃): δ 99.4, 108.1, 129.0, 152.9; IR (ν_max, cm⁻¹): 3330, 1460, 1295, 1035.

Crystal data

C₆H₅BrO₂
M_r = 189.01
Tetragonal, I4₁/a
a = 19.2497 (10) Å
c = 6.9209 (4) Å
V = 2564.5 (2) Å³
Z = 16
D_x = 1.958 Mg m⁻³
Mo Kα radiation
Cell parameters from 3773 reflections
θ = 3.0–29.6°
μ = 6.32 mm⁻¹
T = 293 (2) K
Shard, colourless
0.41 × 0.39 × 0.18 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.118, T_max = 0.321
10 408 measured reflections
1869 independent reflections
1395 reflections with I > 2σ(I)
R_int = 0.041
θ_max = 30.0°
h = −23 → 27
k = −27 → 19
l = −9 → 9

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.064
S = 0.97
1869 reflections
83 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0357P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.00240 (17)

Table 1
Geometry of hydrogen bonds and short intramolecular contacts (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.86	1.95	2.773 (2)	160
O1—H1⋯Br1ⁱ	0.86	3.13	3.7451 (16)	131
O2—H2⋯O2ⁱⁱ	0.88	2.20	2.9233 (17)	139
O2—H2⋯Br1	0.88	2.60	3.1137 (15)	118
Symmetry codes: (i) $[{\script{3\over 4}}-y,x-{\script{1\over 4}},{\script{3\over 4}}-z]$ ; (ii) $[y-{\script{1\over 4}},{\script{3\over 4}}-x,z-{\script{1\over 4}}]$ .

H atoms bound to O atoms were located from difference maps and refined as riding. H atoms bound to C atoms were placed geometrically and refined as riding. For all H atoms, the constraint U_iso(H) = 1.2U_eq(parent atom) was applied.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270104006882/gd1314sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104006882/gd1314Isup2.hkl

Comment top

The title compound, (I) (Fig. 1), also known as bromoresorcinol, arose during our studies to determine the philicity of aryl radicals by competitive cyclization (Kirsop et al., 2004). \sch

Compound (I) possesses normal geometrical parameters [mean C—C bond 1.386 (2), C1—Br1 1.885 (2) and mean C—O bond 1.373 (3) Å] and, as expected, is essentially planar [for the non-H atoms, the r.m.s deviation from the best least-squares plane is 0.008 Å].

As well as van der Waals' forces, the crystal packing is strongly influenced by hydrogen bonds (Table 1). The hydrogen bond involving atom H2 is bifurcated to an intermolecular O and an intramolecular Br acceptor species, and the donor-acceptor bond-angle sum about atom H2 is 360°. The situation involving atom H1 is less clear cut. As well as the intermolecular O1—H1···O1ⁱ bond (see Table 1 for symmetry code), there is also a possible, very long, intermolecular O1—H1···Br1ⁱ contact with H···Br 3.13 Å, although this was flagged as being of questionable significance in a PLATON (Spek, 2003) analysis of (I). However, the donor-acceptor bond-angle sum for atoms O1, O1ⁱ and Br1ⁱ about H1 is 358°, which suggests that this interaction may have some significance beyond being merely a packing contact.

The hydrogen-bonding scheme in (I) results in two distinctive sub-motifs to the unit-cell packing. In the first of these, the 4 axis along [001] at (x = 1/2, y = 1/4) with the inversion point at z = 3/8, and equivalent locations, generates a closed ring of four molecules of (I) by way of four O1—H1···O1 bonds (Fig. 2), thus characterized by an R₄⁴(8) motif (Bernstein et al., 1995).

In the second sub-motif, the 4₁ screw axis at (x = 1/4, y = 1/2) generates helical chains of molecules of (I) linked by O2—H2···O2 hydrogen bonds, forming C(2) chains (Fig. 3). Space-group symmetry results in an equal number of clockwise and anticlockwise helices, by way of the alternating (with respect to both [100] and [010]) array of 4₁ and 4₃ axes.

Finally, π–π stacking interactions are present in (I). The inversion centre at (1/4, 1/4, 1/4) and equivalent locations generates pairs of molecules of (I), with a Cg···Cgⁱⁱⁱ separation of 3.6397 (12) Å [Cg is the centroid of the C1—C6 ring at (0.3348, 0.2915, 0.7669); symmetry code: (iii) 1/2 − x, 1/2 − y, 3/2 − z]. The best least-squares ring planes for Cg and Cgⁱⁱⁱ are exactly parallel (dihedral angle 0.0°) and are separated by 3.470 Å. The lateral displacement of Cgⁱⁱⁱ relative to the normal from the Cg best least-squares plane at Cg to the Cgⁱⁱⁱ best least squares plane is 1.098 Å. The unit-cell packing of (I) is shown in Fig. 4.

Although the local hydrogen-bonding motifs are similar, the structure of (I) is entirely different to that of 1,3,5-tribromo-2,6-dihydroxy benzene (Kirsop et al., 2004), which contains chain-like associations of molecules and is chiral by way of the molecular packing.

Table 1. Geometry of hydrogen bonds and short intramolecular contacts (Å, °)

Experimental top

A solution of Na₂SO₄ (3.04 g, 0.024 mol) and NaOH (0.96 g, 0.024 mol) in distilled water (36 ml) was added to a suspension of 1,3,5-tribromo-2,6-dihydroxybenzene (Kirsop et al., 2004; 4.16 g, 0.012 mol) in a 1:5 mixture of methanol and water (50 ml). The mixture was stirred at 293 K for 1 h, after which the suspension had disappeared, leaving a pale-yellow liquid. The solution was acidified with 1M HCl (4 ml) and extracted with diethyl ether (4 × 50 ml), and the extract was dried over anhydrous MgSO₄ for 10 min. The MgSO₄ was removed by filtration and the solvent removed at reduced pressure to give a pale-cream powder (1.86 g, 82%). A sample of this powder was recrystallized from hot ethyl acetate to give large colourless needles of (I) [m.p 373 K; literature value (Rice, 1926) 375.5 K]. 1H NMR (CDCl₃, δ, p.p.m.): 5.37 (2H, s, OH), 6.60 (2H, d, J = 8 Hz, Ar—H), 7.10 (1H, t, J = 9 Hz, Ar—H); ¹³C NMR (CDCl₃, δ, p.p.m.): 99.4, 108.1, 129.0, 152.9; IR (ν_max, cm⁻¹): 3330, 1460, 1295, 1035.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii and the intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. Part of the crystal structure of (I), showing a hydrogen-bonded R₄⁴(8) ring and a close π–π contact (ring centroids linked by an open line). Symmetry codes: (i) 3/4 − y, x − 1/4, 3/4 − z; (ii) 1/4 + y, 3/4 − x, 3/4 − z; (iii) 1 − x, 1/2 − y, z; (iv) 1/2 − x, 1/2 − y, 3/2 − z. H atoms bonded to C atoms and the unit-cell box have been omitted for clarity.
	Fig. 3. Part of the crystal structure of (I), showing a hydrogen-bonded helical chain of O2—H2···O2 bonds. Symmetry codes: (i) y − 1/4, 3/4 − x, z − 1/4; (ii) 1/2 − x, 1 − y, z − 1/2; (iii) 3/4 − y, 1/4 + x, z − 3/4; (iv) x, y, 1 − z. Atom H1 and C-bound H atoms, and the intramolecular O2—H2···Br1 hydrogen bond, have been omitted for clarity, as has the unit-cell box.
	Fig. 4. The unit-cell packing in (I), viewed down [001], with C-bound H atoms omitted for clarity. The hydrogen bonds forming the R₄⁴(8) loops are indicated by thin lines, and the hydrogen bonds forming the helical chains are indicated by dashed lines. The ring centroids are indicated by small spheres and the π–π interactions by open lines. The cell orientation corresponds to that given for the second setting of I4₁/a in International Tables, Vol. A.

1-Bromo-2,6-dihydroxybenzene top

Crystal data top

C₆H₅BrO₂	D_x = 1.958 Mg m⁻³
M_r = 189.01	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 3773 reflections
Hall symbol: -I 4ad	θ = 3.0–29.6°
a = 19.2497 (10) Å	µ = 6.32 mm⁻¹
c = 6.9209 (4) Å	T = 293 K
V = 2564.5 (2) Å³	Shard, colourless
Z = 16	0.41 × 0.39 × 0.18 mm
F(000) = 1472

Data collection top

Bruker SMART1000 CCD area-detector diffractometer	1869 independent reflections
Radiation source: fine-focus sealed tube	1395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 30.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −23→27
T_min = 0.118, T_max = 0.321	k = −27→19
10408 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (C-H)
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0357P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
1869 reflections	Δρ_max = 0.48 e Å⁻³
83 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00240 (17)

Crystal data top

C₆H₅BrO₂	Z = 16
M_r = 189.01	Mo Kα radiation
Tetragonal, I4₁/a	µ = 6.32 mm⁻¹
a = 19.2497 (10) Å	T = 293 K
c = 6.9209 (4) Å	0.41 × 0.39 × 0.18 mm
V = 2564.5 (2) Å³

Data collection top

Bruker SMART1000 CCD area-detector diffractometer	1869 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1395 reflections with I > 2σ(I)
T_min = 0.118, T_max = 0.321	R_int = 0.041
10408 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 0.97	Δρ_max = 0.48 e Å⁻³
1869 reflections	Δρ_min = −0.43 e Å⁻³
83 parameters

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
C1	0.33307 (10)	0.33911 (10)	0.6176 (3)	0.0309 (4)
C2	0.36916 (10)	0.27674 (11)	0.5953 (3)	0.0352 (4)
C3	0.37147 (11)	0.22959 (11)	0.7465 (4)	0.0438 (5)
H3	0.3964	0.1884	0.7341	0.053*
C4	0.33656 (12)	0.24419 (12)	0.9151 (3)	0.0454 (6)
H4	0.3375	0.2121	1.0156	0.055*
C5	0.29995 (11)	0.30584 (12)	0.9383 (3)	0.0403 (5)
H5	0.2768	0.3151	1.0534	0.048*
C6	0.29828 (10)	0.35326 (10)	0.7883 (3)	0.0330 (4)
O1	0.40242 (8)	0.26601 (8)	0.4230 (2)	0.0468 (4)
H1	0.4196	0.2255	0.4054	0.056*
O2	0.26280 (8)	0.41440 (8)	0.8179 (2)	0.0422 (4)
H2	0.2508	0.4299	0.7034	0.051*
Br1	0.332289 (12)	0.403689 (11)	0.41277 (3)	0.04201 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0294 (10)	0.0304 (10)	0.0329 (10)	−0.0052 (8)	−0.0018 (7)	0.0001 (7)
C2	0.0311 (10)	0.0325 (11)	0.0421 (12)	−0.0029 (8)	0.0028 (9)	−0.0038 (9)
C3	0.0413 (12)	0.0302 (11)	0.0601 (15)	0.0016 (9)	−0.0017 (11)	0.0036 (10)
C4	0.0510 (14)	0.0400 (13)	0.0452 (13)	−0.0033 (11)	−0.0059 (11)	0.0114 (10)
C5	0.0410 (12)	0.0459 (13)	0.0341 (12)	−0.0037 (9)	−0.0019 (9)	0.0027 (9)
C6	0.0301 (10)	0.0327 (10)	0.0361 (11)	−0.0004 (8)	−0.0025 (8)	−0.0031 (8)
O1	0.0494 (10)	0.0347 (8)	0.0563 (10)	0.0032 (7)	0.0188 (8)	−0.0064 (7)
O2	0.0489 (9)	0.0423 (9)	0.0354 (9)	0.0117 (7)	0.0029 (7)	−0.0023 (6)
Br1	0.05029 (16)	0.04044 (15)	0.03530 (14)	0.00434 (10)	0.00310 (9)	0.00424 (9)

Geometric parameters (Å, º) top

C1—C6	1.385 (3)	C4—C5	1.389 (3)
C1—C2	1.396 (3)	C4—H4	0.9300
C1—Br1	1.885 (2)	C5—C6	1.383 (3)
C2—O1	1.369 (3)	C5—H5	0.9300
C2—C3	1.386 (3)	C6—O2	1.376 (2)
C3—C4	1.376 (3)	O1—H1	0.8558
C3—H3	0.9300	O2—H2	0.8779

C6—C1—C2	120.28 (19)	C3—C4—H4	119.3
C6—C1—Br1	120.51 (15)	C5—C4—H4	119.3
C2—C1—Br1	119.21 (15)	C6—C5—C4	119.3 (2)
O1—C2—C3	122.9 (2)	C6—C5—H5	120.4
O1—C2—C1	117.31 (19)	C4—C5—H5	120.4
C3—C2—C1	119.7 (2)	O2—C6—C5	117.64 (19)
C4—C3—C2	119.4 (2)	O2—C6—C1	122.38 (18)
C4—C3—H3	120.3	C5—C6—C1	119.95 (19)
C2—C3—H3	120.3	C2—O1—H1	116.2
C3—C4—C5	121.4 (2)	C6—O2—H2	106.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.86	1.95	2.773 (2)	160
O1—H1···Br1ⁱ	0.86	3.13	3.7451 (16)	131
O2—H2···O2ⁱⁱ	0.88	2.20	2.9233 (17)	139
O2—H2···Br1	0.88	2.60	3.1137 (15)	118

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y−1/4, −x+3/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₆H₅BrO₂
M_r	189.01
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	19.2497 (10), 6.9209 (4)
V (Å³)	2564.5 (2)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	6.32
Crystal size (mm)	0.41 × 0.39 × 0.18

Data collection
Diffractometer	Bruker SMART1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.118, 0.321
No. of measured, independent and observed [I > 2σ(I)] reflections	10408, 1869, 1395
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.064, 0.97
No. of reflections	1869
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.43

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.86	1.95	2.773 (2)	160
O1—H1···Br1ⁱ	0.86	3.13	3.7451 (16)	131
O2—H2···O2ⁱⁱ	0.88	2.20	2.9233 (17)	139
O2—H2···Br1	0.88	2.60	3.1137 (15)	118

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y−1/4, −x+3/4, z−1/4.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–565. CrossRef CAS IUCr Journals Google Scholar
Kirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o222–o224. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rice, G. P. (1926). J. Am. Chem. Soc. 48, 3125–3130. CrossRef Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 60| Part 5| May 2004| Pages o353-o355

doi:10.1107/S0108270104006882

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