2,3,4,5,6-Penta­bromo­phenol

Betz, R.; Klüfers, P.; Mayer, P.

doi:10.1107/S1600536808028602

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1921

doi:10.1107/S1600536808028602

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2,3,4,5,6-Pentabromophenol

Richard Betz,^a Peter Klüfers ^a ^* and Peter Mayer ^a

^aDepartment Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstrasse 5–13 (Haus D), 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 3 September 2008; accepted 6 September 2008; online 13 September 2008)

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 ); Gdaniec (2007 ). For the structure of 2,3,4,5,6-pentachlorophenol, see: Sakurai (1962 ).

Experimental

Crystal data

C₆HBr₅O
M_r = 488.57
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.030
wR(F²) = 0.074
S = 1.03
2219 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.88 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.84	2.19	2.844 (4)	134
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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

Computing details top

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

Figures top

	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].

2,3,4,5,6-Pentabromophenol top

Crystal data top

C₆HBr₅O	F(000) = 1760
M_r = 488.57	D_x = 3.353 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8265 reflections
a = 32.3058 (15) Å	θ = 3.1–27.5°
b = 3.9957 (2) Å	µ = 20.70 mm⁻¹
c = 16.1887 (8) Å	T = 200 K
β = 112.118 (3)°	Rod, colourless
V = 1935.93 (17) Å³	0.28 × 0.08 × 0.05 mm
Z = 8

Data collection top

Nonius Kappa CCD diffractometer	2219 independent reflections
Radiation source: Rotating anode	1930 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray optics monochromator	R_int = 0.054
Rotation images; thick slices scans	θ_max = 27.6°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −41→41
T_min = 0.062, T_max = 0.355	k = −4→5
13465 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: Full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0374P)² + 5.8817P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2219 reflections	Δρ_max = 0.88 e Å⁻³
111 parameters	Δρ_min = −1.02 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00087 (8)

Crystal data top

C₆HBr₅O	V = 1935.93 (17) Å³
M_r = 488.57	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 32.3058 (15) Å	µ = 20.70 mm⁻¹
b = 3.9957 (2) Å	T = 200 K
c = 16.1887 (8) Å	0.28 × 0.08 × 0.05 mm
β = 112.118 (3)°

Data collection top

Nonius Kappa CCD diffractometer	2219 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1930 reflections with I > 2σ(I)
T_min = 0.062, T_max = 0.355	R_int = 0.054
13465 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.03	Δρ_max = 0.88 e Å⁻³
2219 reflections	Δρ_min = −1.02 e Å⁻³
111 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.204848 (13)	0.51248 (10)	0.41077 (2)	0.03029 (14)
Br2	0.096769 (13)	0.38703 (10)	0.36125 (2)	0.02821 (13)
Br3	0.024427 (13)	0.61492 (11)	0.16493 (3)	0.03106 (14)
Br4	0.060474 (12)	0.97946 (11)	0.02144 (2)	0.02709 (13)
Br5	0.169251 (13)	1.09979 (10)	0.07733 (2)	0.02651 (13)
O1	0.22213 (8)	0.8423 (7)	0.26447 (18)	0.0289 (6)
H1	0.2271	0.9643	0.2270	0.043*
C1	0.17732 (11)	0.7978 (9)	0.2394 (2)	0.0213 (7)
C2	0.16196 (12)	0.6421 (9)	0.2996 (2)	0.0216 (7)
C3	0.11662 (12)	0.5889 (9)	0.2773 (2)	0.0211 (7)
C4	0.08601 (11)	0.6883 (9)	0.1945 (2)	0.0213 (7)
C5	0.10107 (12)	0.8416 (8)	0.1339 (2)	0.0209 (7)
C6	0.14663 (12)	0.8957 (8)	0.1567 (2)	0.0197 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0248 (2)	0.0387 (3)	0.0229 (2)	0.00504 (16)	0.00385 (16)	0.00541 (16)
Br2	0.0300 (2)	0.0331 (2)	0.0244 (2)	−0.00243 (15)	0.01352 (16)	0.00349 (14)
Br3	0.0171 (2)	0.0443 (3)	0.0318 (2)	−0.00324 (15)	0.00924 (16)	0.00412 (16)
Br4	0.0201 (2)	0.0377 (2)	0.0212 (2)	0.00309 (15)	0.00524 (15)	0.00423 (14)
Br5	0.0238 (2)	0.0331 (2)	0.0255 (2)	−0.00301 (14)	0.01252 (16)	0.00230 (14)
O1	0.0160 (12)	0.0393 (16)	0.0315 (14)	0.0005 (11)	0.0091 (11)	0.0025 (12)
C1	0.0146 (16)	0.0222 (16)	0.0260 (17)	−0.0013 (14)	0.0066 (13)	−0.0031 (14)
C2	0.0188 (18)	0.0236 (18)	0.0201 (16)	0.0003 (14)	0.0048 (13)	−0.0015 (13)
C3	0.0237 (19)	0.0211 (16)	0.0208 (17)	−0.0001 (13)	0.0110 (14)	−0.0028 (13)
C4	0.0146 (16)	0.0261 (17)	0.0244 (17)	−0.0029 (14)	0.0087 (13)	−0.0038 (14)
C5	0.0196 (17)	0.0237 (17)	0.0184 (15)	−0.0001 (14)	0.0061 (13)	−0.0027 (13)
C6	0.0213 (17)	0.0215 (17)	0.0207 (16)	−0.0026 (14)	0.0129 (13)	−0.0009 (13)

Geometric parameters (Å, º) top

Br1—C2	1.884 (3)	C1—C6	1.389 (5)
Br2—C3	1.888 (4)	C1—C2	1.395 (5)
Br3—C4	1.886 (3)	C2—C3	1.387 (5)
Br4—C5	1.882 (3)	C3—C4	1.391 (5)
Br5—C6	1.886 (4)	C4—C5	1.390 (5)
O1—C1	1.360 (4)	C5—C6	1.393 (5)
O1—H1	0.8400

C1—O1—H1	109.5	C5—C4—C3	119.7 (3)
O1—C1—C6	122.9 (3)	C5—C4—Br3	120.4 (2)
O1—C1—C2	117.9 (3)	C3—C4—Br3	120.0 (3)
C6—C1—C2	119.1 (3)	C4—C5—C6	119.8 (3)
C3—C2—C1	120.3 (3)	C4—C5—Br4	120.7 (3)
C3—C2—Br1	122.1 (3)	C6—C5—Br4	119.5 (3)
C1—C2—Br1	117.6 (3)	C1—C6—C5	120.7 (3)
C2—C3—C4	120.4 (3)	C1—C6—Br5	117.4 (3)
C2—C3—Br2	119.3 (3)	C5—C6—Br5	121.9 (3)
C4—C3—Br2	120.3 (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—C6	179.7 (3)
O1—C1—C2—Br1	0.7 (4)	C3—C4—C5—Br4	−179.9 (3)
C6—C1—C2—Br1	179.8 (3)	Br3—C4—C5—Br4	0.1 (4)
C1—C2—C3—C4	0.4 (5)	O1—C1—C6—C5	179.4 (3)
Br1—C2—C3—C4	180.0 (3)	C2—C1—C6—C5	0.4 (5)
C1—C2—C3—Br2	−178.5 (3)	O1—C1—C6—Br5	−0.2 (5)
Br1—C2—C3—Br2	1.1 (4)	C2—C1—C6—Br5	−179.2 (3)
C2—C3—C4—C5	0.0 (5)	C4—C5—C6—C1	0.0 (5)
Br2—C3—C4—C5	178.9 (3)	Br4—C5—C6—C1	179.7 (3)
C2—C3—C4—Br3	−179.9 (3)	C4—C5—C6—Br5	179.6 (3)
Br2—C3—C4—Br3	−1.1 (4)	Br4—C5—C6—Br5	−0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	2.19	2.844 (4)	134

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

Experimental details

Crystal data
Chemical formula	C₆HBr₅O
M_r	488.57
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	32.3058 (15), 3.9957 (2), 16.1887 (8)
β (°)	112.118 (3)
V (Å³)	1935.93 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	20.70
Crystal size (mm)	0.28 × 0.08 × 0.05

Data collection
Diffractometer	Nonius Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.062, 0.355
No. of measured, independent and observed [I > 2σ(I)] reflections	13465, 2219, 1930
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.03
No. of reflections	2219
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −1.02

Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	2.19	2.844 (4)	134.1

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

Acknowledgements

The authors thank Dr Peter Mayer for professional support.

References

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