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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

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

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 ππ 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[link]) (Fig. 1[link]), also known as 2-bromo­resorcinol, arose during our studies to determine the philicity of aryl radicals by competitive cyclization (Kirsop et al., 2004[Kirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o222-o224.]).

[Scheme 1]

Compound (I[link]) 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[link]). 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[link] 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[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]) analysis of (I[link]). 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[link]) 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[link]) by way of four O1—H1⋯O1 bonds (Fig. 2[link]), thus characterized by an R[{_4^4}](8) motif (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

In the second submotif, the 41 screw axis at x = [{1 \over 4}], y = [{1 \over 2}] generates helical chains of mol­ecules of (I[link]) linked by O2—H2⋯O2 hydrogen bonds, forming C(2) chains (Fig. 3[link]). 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, ππ stacking interactions are present in (I[link]). The inversion centre at ([{1 \over 4}], [{1 \over 4}], [{1 \over 4}]) and equivalent locations generates pairs of mol­ecules of (I[link]), with a CgCgiii 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[link]) is shown in Fig. 4[link].

Although the local hydrogen-bonding motifs are similar, the structure of (I[link]) is entirely different to that of 1,3,5-tri­bromo-2,6-di­hydroxybenzene (Kirsop et al., 2004[Kirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o222-o224.]), which contains chain-like associations of mol­ecules and is chiral by way of the molecular packing.

[Figure 1]
Figure 1
The asymmetric unit of (I[link]), 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]
Figure 2
Part of the crystal structure of (I[link]), showing a hydrogen-bonded R[{_4^4}](8) ring and a close ππ 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]
Figure 3
Part of the crystal structure of (I[link]), 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]
Figure 4
The unit-cell packing in (I[link]), 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 ππ 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[Kirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o222-o224.]; 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[link]) [m.p. 373 K; literature value (Rice, 1926[Rice, G. P. (1926). J. Am. Chem. Soc. 48, 3125-3130.]) 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 (νmax, cm−1): 3330, 1460, 1295, 1035.

Crystal data
  • C6H5BrO2

  • Mr = 189.01

  • Tetragonal, I41/a

  • a = 19.2497 (10) Å

  • c = 6.9209 (4) Å

  • V = 2564.5 (2) Å3

  • Z = 16

  • Dx = 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[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.118, Tmax = 0.321

  • 10 408 measured reflections

  • 1869 independent reflections

  • 1395 reflections with I > 2σ(I)

  • Rint = 0.041

  • θmax = 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(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.43 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • Extinction coefficient: 0.00240 (17)

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

D—H⋯A D—H H⋯A DA 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 Uiso(H) = 1.2Ueq(parent atom) was applied.

Data collection: SMART (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565-565.]); software used to prepare material for publication: SHELXL97.

Supporting information


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, ππ 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 (νmax, cm−1): 3330, 1460, 1295, 1035.

Refinement top

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 Uiso(H) = 1.2 Ueq(parent atom) was applied.

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
[Figure 1] 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.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing a hydrogen-bonded R44(8) ring and a close ππ 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.
[Figure 3] 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.
[Figure 4] 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 ππ 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
C6H5BrO2Dx = 1.958 Mg m3
Mr = 189.01Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3773 reflections
Hall symbol: -I 4adθ = 3.0–29.6°
a = 19.2497 (10) ŵ = 6.32 mm1
c = 6.9209 (4) ÅT = 293 K
V = 2564.5 (2) Å3Shard, colourless
Z = 160.41 × 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 tube1395 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scansθmax = 30.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 2327
Tmin = 0.118, Tmax = 0.321k = 2719
10408 measured reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap (O-H) and geom (C-H)
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.0357P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.001
1869 reflectionsΔρmax = 0.48 e Å3
83 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00240 (17)
Crystal data top
C6H5BrO2Z = 16
Mr = 189.01Mo Kα radiation
Tetragonal, I41/aµ = 6.32 mm1
a = 19.2497 (10) ÅT = 293 K
c = 6.9209 (4) Å0.41 × 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)
Tmin = 0.118, Tmax = 0.321Rint = 0.041
10408 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 0.97Δρmax = 0.48 e Å3
1869 reflectionsΔρmin = 0.43 e Å3
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
xyzUiso*/Ueq
C10.33307 (10)0.33911 (10)0.6176 (3)0.0309 (4)
C20.36916 (10)0.27674 (11)0.5953 (3)0.0352 (4)
C30.37147 (11)0.22959 (11)0.7465 (4)0.0438 (5)
H30.39640.18840.73410.053*
C40.33656 (12)0.24419 (12)0.9151 (3)0.0454 (6)
H40.33750.21211.01560.055*
C50.29995 (11)0.30584 (12)0.9383 (3)0.0403 (5)
H50.27680.31511.05340.048*
C60.29828 (10)0.35326 (10)0.7883 (3)0.0330 (4)
O10.40242 (8)0.26601 (8)0.4230 (2)0.0468 (4)
H10.41960.22550.40540.056*
O20.26280 (8)0.41440 (8)0.8179 (2)0.0422 (4)
H20.25080.42990.70340.051*
Br10.332289 (12)0.403689 (11)0.41277 (3)0.04201 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0294 (10)0.0304 (10)0.0329 (10)0.0052 (8)0.0018 (7)0.0001 (7)
C20.0311 (10)0.0325 (11)0.0421 (12)0.0029 (8)0.0028 (9)0.0038 (9)
C30.0413 (12)0.0302 (11)0.0601 (15)0.0016 (9)0.0017 (11)0.0036 (10)
C40.0510 (14)0.0400 (13)0.0452 (13)0.0033 (11)0.0059 (11)0.0114 (10)
C50.0410 (12)0.0459 (13)0.0341 (12)0.0037 (9)0.0019 (9)0.0027 (9)
C60.0301 (10)0.0327 (10)0.0361 (11)0.0004 (8)0.0025 (8)0.0031 (8)
O10.0494 (10)0.0347 (8)0.0563 (10)0.0032 (7)0.0188 (8)0.0064 (7)
O20.0489 (9)0.0423 (9)0.0354 (9)0.0117 (7)0.0029 (7)0.0023 (6)
Br10.05029 (16)0.04044 (15)0.03530 (14)0.00434 (10)0.00310 (9)0.00424 (9)
Geometric parameters (Å, º) top
C1—C61.385 (3)C4—C51.389 (3)
C1—C21.396 (3)C4—H40.9300
C1—Br11.885 (2)C5—C61.383 (3)
C2—O11.369 (3)C5—H50.9300
C2—C31.386 (3)C6—O21.376 (2)
C3—C41.376 (3)O1—H10.8558
C3—H30.9300O2—H20.8779
C6—C1—C2120.28 (19)C3—C4—H4119.3
C6—C1—Br1120.51 (15)C5—C4—H4119.3
C2—C1—Br1119.21 (15)C6—C5—C4119.3 (2)
O1—C2—C3122.9 (2)C6—C5—H5120.4
O1—C2—C1117.31 (19)C4—C5—H5120.4
C3—C2—C1119.7 (2)O2—C6—C5117.64 (19)
C4—C3—C2119.4 (2)O2—C6—C1122.38 (18)
C4—C3—H3120.3C5—C6—C1119.95 (19)
C2—C3—H3120.3C2—O1—H1116.2
C3—C4—C5121.4 (2)C6—O2—H2106.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1i0.861.952.773 (2)160
O1—H1···Br1i0.863.133.7451 (16)131
O2—H2···O2ii0.882.202.9233 (17)139
O2—H2···Br10.882.603.1137 (15)118
Symmetry codes: (i) y+3/4, x1/4, z+3/4; (ii) y1/4, x+3/4, z1/4.

Experimental details

Crystal data
Chemical formulaC6H5BrO2
Mr189.01
Crystal system, space groupTetragonal, I41/a
Temperature (K)293
a, c (Å)19.2497 (10), 6.9209 (4)
V3)2564.5 (2)
Z16
Radiation typeMo Kα
µ (mm1)6.32
Crystal size (mm)0.41 × 0.39 × 0.18
Data collection
DiffractometerBruker SMART1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.118, 0.321
No. of measured, independent and
observed [I > 2σ(I)] reflections
10408, 1869, 1395
Rint0.041
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.064, 0.97
No. of reflections1869
No. of parameters83
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1···O1i0.861.952.773 (2)160
O1—H1···Br1i0.863.133.7451 (16)131
O2—H2···O2ii0.882.202.9233 (17)139
O2—H2···Br10.882.603.1137 (15)118
Symmetry codes: (i) y+3/4, x1/4, z+3/4; (ii) y1/4, x+3/4, z1/4.
 

References

First citationBernstein, 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
First citationBruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565–565.  CrossRef CAS IUCr Journals Google Scholar
First citationKirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o222–o224.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationRice, G. P. (1926). J. Am. Chem. Soc. 48, 3125–3130.  CrossRef Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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