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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1921.
Published online 2008 September 13. doi:  10.1107/S1600536808028602
PMCID: PMC2959417

2,3,4,5,6-Penta­bromo­phenol

Abstract

The title compound, C6HBr5O, is the perbrominated derivative of phenol. The mol­ecule shows non-crystallographic mirror symmetry. Bond lengths between the C and Br atoms are normal. In the crystal structure, O—H(...)O hydrogen bonds connect the mol­ecules into infinite strands. Dispersive Br(...)Br contacts are observed. No significant π–π stacking is obvious.

Related literature

For the structure of the perfluorinated derivative of phenol, see: Das et al. (2006 [triangle]); Gdaniec (2007 [triangle]). For the structure of 2,3,4,5,6-penta­chloro­phenol, see: Sakurai (1962 [triangle]).

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Object name is e-64-o1921-scheme1.jpg

Experimental

Crystal data

  • C6HBr5O
  • M r = 488.57
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1921-efi1.jpg
  • a = 32.3058 (15) Å
  • b = 3.9957 (2) Å
  • c = 16.1887 (8) Å
  • β = 112.118 (3)°
  • V = 1935.93 (17) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 20.70 mm−1
  • T = 200 (2) K
  • 0.28 × 0.08 × 0.05 mm

Data collection

  • Nonius Kappa CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.062, T max = 0.355
  • 13465 measured reflections
  • 2219 independent reflections
  • 1930 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.074
  • S = 1.03
  • 2219 reflections
  • 111 parameters
  • H-atom parameters constrained
  • Δρmax = 0.88 e Å−3
  • Δρmin = −1.02 e Å−3

Data collection: COLLECT (Nonius, 2004 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor 1997 [triangle]); data reduction: DENZO (Otwinowski & Minor 1997 [triangle]) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028602/rk2109sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028602/rk2109Isup2.hkl

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

Acknowledgments

The authors thank Dr Peter Mayer for professional support.

supplementary crystallographic information

Comment

During efforts to obtain tetraaryloxy derivatives of orthocarbonic acid it was interesting to determine the influence of bonding to one central carbon atom on geometric parameters of the ligands. Thus the crystal structure of 2,3,4,5,6-pentabromophenol was determined.

In the molecule (Fig. 1), C—C—C angles adopt values covering a range from 119.1 (3)° on the C atom bonded to the hydroxy group to 120.7 (3)° on one of the C atoms in ortho-position to the hydroxy group. The alterations between the C—C—C angles thus are less pronounced than in the perfluorinated derivative of phenol, where the angle on the C atom bearing the hydroxy group was found at a value slightly above 116° (Gdaniec, 2007). The values more closely resemble the ones apparent in the molecular structure of the perchlorinated derivative, yet the smallest C—C—C angle is not present on the C atom bearing the hydroxy group in that compound (Sakurai, 1962).

In the crystal structure H-bonds connect the molecules to infinite strands along [010] (Fig. 2). A bifurcation of the hydrogen bond between oxygen and one of the halogen atoms in ortho-position was not observed. This is in contrast to 2,3,4,5,6–pentachlorophenol, where the presence of such a bifurcated hydrogen bond was substantiated upon nuclear quadrupole resonance spectra for the Cl atoms (Sakurai, 1962). Additionally, dispersive Br···Br interactions between the Br atoms in both meta-positions to the hydroxy group are observed. The range of these interactions falls by about 0.1 Å below the sum of van der Waals radii of the respective atoms. These connect the molecules to chains along [001]. No significant π-stacking is apparent in the crystal structure. The molecular packing is shown in Fig. 3.

Experimental

The compound was obtained commercially from Aldrich. Crystals suitable for X-ray diffraction were obtained upon recrystallization of the compound from boiling toluene.

Refinement

The H atom was located in a difference map and refined as riding on its parent O atom with an Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound, with atom labels. The displacement ellipsoids are drawn at 50% probability level. H atom is presented as a small sphere of arbitrary radius.
Fig. 2.
The crystal packing diagram, viewed along [010].

Crystal data

C6HBr5OF(000) = 1760
Mr = 488.57Dx = 3.353 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8265 reflections
a = 32.3058 (15) Åθ = 3.1–27.5°
b = 3.9957 (2) ŵ = 20.70 mm1
c = 16.1887 (8) ÅT = 200 K
β = 112.118 (3)°Rod, colourless
V = 1935.93 (17) Å30.28 × 0.08 × 0.05 mm
Z = 8

Data collection

Nonius Kappa CCD diffractometer2219 independent reflections
Radiation source: Rotating anode1930 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray opticsRint = 0.054
Rotation images; thick slices scansθmax = 27.6°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)h = −41→41
Tmin = 0.062, Tmax = 0.355k = −4→5
13465 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: FullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.075w = 1/[σ2(Fo2) + (0.0374P)2 + 5.8817P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2219 reflectionsΔρmax = 0.88 e Å3
111 parametersΔρmin = −1.02 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00087 (8)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
Br10.204848 (13)0.51248 (10)0.41077 (2)0.03029 (14)
Br20.096769 (13)0.38703 (10)0.36125 (2)0.02821 (13)
Br30.024427 (13)0.61492 (11)0.16493 (3)0.03106 (14)
Br40.060474 (12)0.97946 (11)0.02144 (2)0.02709 (13)
Br50.169251 (13)1.09979 (10)0.07733 (2)0.02651 (13)
O10.22213 (8)0.8423 (7)0.26447 (18)0.0289 (6)
H10.22710.96430.22700.043*
C10.17732 (11)0.7978 (9)0.2394 (2)0.0213 (7)
C20.16196 (12)0.6421 (9)0.2996 (2)0.0216 (7)
C30.11662 (12)0.5889 (9)0.2773 (2)0.0211 (7)
C40.08601 (11)0.6883 (9)0.1945 (2)0.0213 (7)
C50.10107 (12)0.8416 (8)0.1339 (2)0.0209 (7)
C60.14663 (12)0.8957 (8)0.1567 (2)0.0197 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0248 (2)0.0387 (3)0.0229 (2)0.00504 (16)0.00385 (16)0.00541 (16)
Br20.0300 (2)0.0331 (2)0.0244 (2)−0.00243 (15)0.01352 (16)0.00349 (14)
Br30.0171 (2)0.0443 (3)0.0318 (2)−0.00324 (15)0.00924 (16)0.00412 (16)
Br40.0201 (2)0.0377 (2)0.0212 (2)0.00309 (15)0.00524 (15)0.00423 (14)
Br50.0238 (2)0.0331 (2)0.0255 (2)−0.00301 (14)0.01252 (16)0.00230 (14)
O10.0160 (12)0.0393 (16)0.0315 (14)0.0005 (11)0.0091 (11)0.0025 (12)
C10.0146 (16)0.0222 (16)0.0260 (17)−0.0013 (14)0.0066 (13)−0.0031 (14)
C20.0188 (18)0.0236 (18)0.0201 (16)0.0003 (14)0.0048 (13)−0.0015 (13)
C30.0237 (19)0.0211 (16)0.0208 (17)−0.0001 (13)0.0110 (14)−0.0028 (13)
C40.0146 (16)0.0261 (17)0.0244 (17)−0.0029 (14)0.0087 (13)−0.0038 (14)
C50.0196 (17)0.0237 (17)0.0184 (15)−0.0001 (14)0.0061 (13)−0.0027 (13)
C60.0213 (17)0.0215 (17)0.0207 (16)−0.0026 (14)0.0129 (13)−0.0009 (13)

Geometric parameters (Å, °)

Br1—C21.884 (3)C1—C61.389 (5)
Br2—C31.888 (4)C1—C21.395 (5)
Br3—C41.886 (3)C2—C31.387 (5)
Br4—C51.882 (3)C3—C41.391 (5)
Br5—C61.886 (4)C4—C51.390 (5)
O1—C11.360 (4)C5—C61.393 (5)
O1—H10.8400
C1—O1—H1109.5C5—C4—C3119.7 (3)
O1—C1—C6122.9 (3)C5—C4—Br3120.4 (2)
O1—C1—C2117.9 (3)C3—C4—Br3120.0 (3)
C6—C1—C2119.1 (3)C4—C5—C6119.8 (3)
C3—C2—C1120.3 (3)C4—C5—Br4120.7 (3)
C3—C2—Br1122.1 (3)C6—C5—Br4119.5 (3)
C1—C2—Br1117.6 (3)C1—C6—C5120.7 (3)
C2—C3—C4120.4 (3)C1—C6—Br5117.4 (3)
C2—C3—Br2119.3 (3)C5—C6—Br5121.9 (3)
C4—C3—Br2120.3 (3)
O1—C1—C2—C3−179.7 (3)C3—C4—C5—C6−0.2 (5)
C6—C1—C2—C3−0.6 (5)Br3—C4—C5—C6179.7 (3)
O1—C1—C2—Br10.7 (4)C3—C4—C5—Br4−179.9 (3)
C6—C1—C2—Br1179.8 (3)Br3—C4—C5—Br40.1 (4)
C1—C2—C3—C40.4 (5)O1—C1—C6—C5179.4 (3)
Br1—C2—C3—C4180.0 (3)C2—C1—C6—C50.4 (5)
C1—C2—C3—Br2−178.5 (3)O1—C1—C6—Br5−0.2 (5)
Br1—C2—C3—Br21.1 (4)C2—C1—C6—Br5−179.2 (3)
C2—C3—C4—C50.0 (5)C4—C5—C6—C10.0 (5)
Br2—C3—C4—C5178.9 (3)Br4—C5—C6—C1179.7 (3)
C2—C3—C4—Br3−179.9 (3)C4—C5—C6—Br5179.6 (3)
Br2—C3—C4—Br3−1.1 (4)Br4—C5—C6—Br5−0.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O1i0.842.192.844 (4)134

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2109).

References

  • Das, D., Banerjee, R., Mondal, R., Howard, J. A. K., Boese, R. & Desiraju, G. R. (2006). Chem. Commun. pp. 555–557. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Gdaniec, M. (2007). CrystEngComm, 9, 286–288.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Nonius (2004). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sakurai, T. (1962). Acta Cryst.15, 1164–1173.
  • Sheldrick, G. M. (2001). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography