organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Crystal structure of 5,5′-di­bromo-3,3′-di-tert-butyl-6,6′-di­methyl­bi­phenyl-2,2′-diol

aResearch and Education Center for Natural Sciences, Keio University, Hiyoshi 4-1-1, Kohoku-ku, Yokohama 223-8521, Japan, and bDepartment of Chemistry, Faculty of Science and Technology, Keio University; and JST-CREST/ACELL, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
*Correspondence e-mail: ohba@a3.keio.jp

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 25 March 2015; accepted 28 March 2015; online 2 April 2015)

The whole mol­ecule of the title compound, C22H28Br2O2, is generated by twofold rotation symmetry. The dihedral angle of the biphenyl moiety is 85.05 (11)°. The hy­droxy groups show intra­molecular O—H⋯π inter­actions without any other hydrogen-bond acceptors. In the crystal, there are no other significant inter­molecular inter­actions present.

1. Related literature

For the synthesis of the title compound using a transition-metal catalyst, see: Kubota et al. (2012[Kubota, Y., Shirakawa, S., Inoue, T. & Maruoka, K. (2012). Tetrahedron Lett. 53, 3739-3741.]). For the determination of the absolute configuration of the corresponding (+)-chloro derivative, viz. S, see: Gutierrez et al. (2010[Gutierrez, E. G., Moorhead, E. J., Smith, E. H., Lin, V., Ackerman, L. K. G., Knezevic, C. E., Sun, V., Grant, S. & Wenzel, A. G. (2010). Eur. J. Org. Chem. pp. 3027-3031.]). For the crystal structure of a similar compound, i.e. 5,5′-dimeth­oxy-6,6′-di­methyl­biphenyl-2,2′-diol di­chloro­methane solvate, see: Guo et al. (2011[Guo, F., Konkol, L. C. & Thomson, R. J. (2011). J. Am. Chem. Soc. 133, 18-20.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C22H28Br2O2

  • Mr = 484.24

  • Orthorhombic, P b a 2

  • a = 7.3680 (5) Å

  • b = 22.4243 (14) Å

  • c = 6.6148 (4) Å

  • V = 1092.91 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 3.72 mm−1

  • T = 299 K

  • 0.16 × 0.15 × 0.10 mm

2.2. Data collection

  • Bruker D8 VENTURE diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.630, Tmax = 0.773

  • 9406 measured reflections

  • 1966 independent reflections

  • 1615 reflections with I > 2σ(I)

  • Rint = 0.036

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.065

  • S = 1.06

  • 1966 reflections

  • 123 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack x determined using 621 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: 0.034 (9)

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of benzene ring C3–C8.

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯Cgi 0.82 2.54 3.047 (5) 122
Symmetry code: (i) -x+2, -y+2, z.

Data collection: APEX2 (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL2014 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Synthesis and crystallization top

The synthesis of the title compound, (I), is described in Fig. 2. It was prepared using iodine-mediated coupling method from 4-bromo-2-tert-butyl-5-methyl­phenol. To the solution of 4-bromo-2-tert-butyl-5-methyl­phenol (0.242 g, 1 mmol) in di­chloro­methane (1 mL) was added N-iodo­succinimide (abbreviated to NIS, 0.225 g, 1 mmol) and 3% H2O2 (1 mL). After shaking (200 rpm) the reaction mixture for 24 h at room temperature, it was poured into saturated Na2S2O3 solution, and extracted with chloro­form. The organic layer was washed with saturated NaCl and dried over anhydrous Na2SO4. The mixture was evaporated and purified by silica-gel column chromatography to give title compound (I) as white solid (yield: 0.138 g, 57%). 1H-NMR (400 MHz, CDCl3) 1.32 (18H, s), 1.92 (6H, s), 4.80 (2H, s), 7.47 (2H, s). Tof-MS ES(-) Anal. 481.0357, Calcd. 481.0378 for C22H27O2Br2. The crystals were grown by slow evaporation from a toluene/n-hexane (1/4) solution.

Refinement top

Crystal data, data collection and structure refinement details are summarized in the experimental table. The hydroxyl H atom was located from a difference Fourier map but was refined as riding (AFIX 147) with Uiso(H) = 1.5Ueq(O). C-Bound H atoms were included in calculated positions and refined as riding: C—H = 0.93–0.96 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Related literature top

For the synthesis of the title compound using a transition-metal catalyst, see: Kubota et al. (2012). For the determination of the absolute configuration of the corresponding (+)-chloro derivative, viz. S, see: Gutierrez et al. (2010). For the crystal structure of a similar compound, i.e. 5,5'-dimethoxy-6,6'-dimethylbiphenyl-2,2'-diol dichloromethane solvate, see: Guo et al. (2011).

Structure description top

For the synthesis of the title compound using a transition-metal catalyst, see: Kubota et al. (2012). For the determination of the absolute configuration of the corresponding (+)-chloro derivative, viz. S, see: Gutierrez et al. (2010). For the crystal structure of a similar compound, i.e. 5,5'-dimethoxy-6,6'-dimethylbiphenyl-2,2'-diol dichloromethane solvate, see: Guo et al. (2011).

Synthesis and crystallization top

The synthesis of the title compound, (I), is described in Fig. 2. It was prepared using iodine-mediated coupling method from 4-bromo-2-tert-butyl-5-methyl­phenol. To the solution of 4-bromo-2-tert-butyl-5-methyl­phenol (0.242 g, 1 mmol) in di­chloro­methane (1 mL) was added N-iodo­succinimide (abbreviated to NIS, 0.225 g, 1 mmol) and 3% H2O2 (1 mL). After shaking (200 rpm) the reaction mixture for 24 h at room temperature, it was poured into saturated Na2S2O3 solution, and extracted with chloro­form. The organic layer was washed with saturated NaCl and dried over anhydrous Na2SO4. The mixture was evaporated and purified by silica-gel column chromatography to give title compound (I) as white solid (yield: 0.138 g, 57%). 1H-NMR (400 MHz, CDCl3) 1.32 (18H, s), 1.92 (6H, s), 4.80 (2H, s), 7.47 (2H, s). Tof-MS ES(-) Anal. 481.0357, Calcd. 481.0378 for C22H27O2Br2. The crystals were grown by slow evaporation from a toluene/n-hexane (1/4) solution.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in the experimental table. The hydroxyl H atom was located from a difference Fourier map but was refined as riding (AFIX 147) with Uiso(H) = 1.5Ueq(O). C-Bound H atoms were included in calculated positions and refined as riding: C—H = 0.93–0.96 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The synthesis of the title compound, (I).
5,5'-Dibromo-3,3'-di-tert-butyl-6,6'-dimethylbiphenyl-2,2'-diol top
Crystal data top
C22H28Br2O2Dx = 1.472 Mg m3
Mr = 484.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pba2Cell parameters from 4121 reflections
a = 7.3680 (5) Åθ = 2.9–23.6°
b = 22.4243 (14) ŵ = 3.72 mm1
c = 6.6148 (4) ÅT = 299 K
V = 1092.91 (12) Å3Prism, colourless
Z = 20.16 × 0.15 × 0.10 mm
F(000) = 492
Data collection top
Bruker D8 VENTURE
diffractometer
1615 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
ω scansθmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 88
Tmin = 0.630, Tmax = 0.773k = 2626
9406 measured reflectionsl = 77
1966 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.031 w = 1/[σ2(Fo2) + (0.0176P)2 + 0.3778P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.48 e Å3
1966 reflectionsΔρmin = 0.21 e Å3
123 parametersAbsolute structure: Flack x determined using 621 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.034 (9)
Primary atom site location: structure-invariant direct methods
Crystal data top
C22H28Br2O2V = 1092.91 (12) Å3
Mr = 484.24Z = 2
Orthorhombic, Pba2Mo Kα radiation
a = 7.3680 (5) ŵ = 3.72 mm1
b = 22.4243 (14) ÅT = 299 K
c = 6.6148 (4) Å0.16 × 0.15 × 0.10 mm
Data collection top
Bruker D8 VENTURE
diffractometer
1966 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
1615 reflections with I > 2σ(I)
Tmin = 0.630, Tmax = 0.773Rint = 0.036
9406 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.065Δρmax = 0.48 e Å3
S = 1.06Δρmin = 0.21 e Å3
1966 reflectionsAbsolute structure: Flack x determined using 621 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
123 parametersAbsolute structure parameter: 0.034 (9)
1 restraint
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.18668 (8)0.81211 (2)0.48288 (15)0.0681 (2)
O20.7528 (4)0.98204 (13)0.9897 (9)0.0576 (8)
H20.77771.01660.96070.086*
C30.9856 (6)0.96676 (17)0.7429 (7)0.0352 (10)
C41.0903 (6)0.9290 (2)0.6223 (7)0.0388 (11)
C51.0536 (6)0.8689 (2)0.6397 (7)0.0399 (11)
C60.9212 (6)0.84644 (19)0.7649 (7)0.0394 (11)
H60.90230.80540.76850.047*
C70.8150 (6)0.88292 (19)0.8859 (7)0.0360 (10)
C80.8518 (6)0.94415 (19)0.8707 (7)0.0370 (11)
C91.2322 (7)0.9538 (2)0.4852 (15)0.0650 (14)
H9A1.19930.94600.34730.098*
H9B1.34670.93530.51430.098*
H9C1.24170.99600.50580.098*
C100.6668 (5)0.8582 (2)1.0234 (8)0.0428 (15)
C110.6564 (7)0.7905 (2)1.0111 (14)0.074 (2)
H11A0.62430.77890.87610.111*
H11B0.56610.77621.10390.111*
H11C0.77220.77371.04560.111*
C120.7053 (8)0.8746 (3)1.2449 (9)0.0756 (18)
H12A0.82600.86231.28020.113*
H12B0.61950.85481.33110.113*
H12C0.69440.91701.26190.113*
C130.4827 (6)0.8829 (2)0.9625 (15)0.0760 (17)
H13A0.47910.92490.98940.114*
H13B0.38930.86321.03870.114*
H13C0.46340.87600.82080.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0866 (4)0.0458 (3)0.0718 (4)0.0118 (2)0.0311 (4)0.0118 (4)
O20.0646 (19)0.0366 (16)0.072 (2)0.0049 (14)0.018 (3)0.009 (3)
C30.040 (3)0.030 (2)0.036 (3)0.0016 (19)0.004 (2)0.001 (2)
C40.048 (3)0.033 (3)0.035 (3)0.003 (2)0.002 (2)0.000 (2)
C50.048 (3)0.035 (3)0.037 (3)0.009 (2)0.003 (2)0.003 (2)
C60.046 (3)0.028 (2)0.045 (3)0.002 (2)0.002 (2)0.002 (2)
C70.036 (3)0.034 (2)0.038 (2)0.008 (2)0.005 (2)0.002 (2)
C80.042 (3)0.031 (3)0.038 (2)0.006 (2)0.000 (2)0.005 (2)
C90.084 (3)0.048 (3)0.063 (3)0.003 (2)0.033 (5)0.003 (5)
C100.035 (3)0.045 (3)0.048 (4)0.0010 (19)0.008 (3)0.003 (2)
C110.070 (3)0.048 (3)0.104 (6)0.013 (2)0.036 (5)0.008 (4)
C120.078 (4)0.099 (5)0.049 (4)0.021 (4)0.010 (3)0.002 (3)
C130.039 (3)0.086 (4)0.103 (5)0.005 (2)0.012 (4)0.020 (5)
Geometric parameters (Å, º) top
Br1—C51.913 (4)C9—H9B0.9600
O2—C81.369 (6)C9—H9C0.9600
O2—H20.8200C10—C131.520 (7)
C3—C81.394 (6)C10—C111.521 (7)
C3—C41.396 (6)C10—C121.537 (8)
C3—C3i1.506 (8)C11—H11A0.9600
C4—C51.379 (6)C11—H11B0.9600
C4—C91.491 (8)C11—H11C0.9600
C5—C61.375 (6)C12—H12A0.9600
C6—C71.386 (6)C12—H12B0.9600
C6—H60.9300C12—H12C0.9600
C7—C81.403 (6)C13—H13A0.9600
C7—C101.526 (6)C13—H13B0.9600
C9—H9A0.9600C13—H13C0.9600
C8—O2—H2109.5C13—C10—C11107.7 (4)
C8—C3—C4121.1 (4)C13—C10—C7110.4 (5)
C8—C3—C3i117.3 (4)C11—C10—C7111.5 (4)
C4—C3—C3i121.6 (4)C13—C10—C12109.3 (5)
C5—C4—C3115.9 (4)C11—C10—C12107.4 (5)
C5—C4—C9123.5 (4)C7—C10—C12110.5 (4)
C3—C4—C9120.5 (4)C10—C11—H11A109.5
C6—C5—C4123.2 (4)C10—C11—H11B109.5
C6—C5—Br1116.5 (3)H11A—C11—H11B109.5
C4—C5—Br1120.3 (3)C10—C11—H11C109.5
C5—C6—C7122.2 (4)H11A—C11—H11C109.5
C5—C6—H6118.9H11B—C11—H11C109.5
C7—C6—H6118.9C10—C12—H12A109.5
C6—C7—C8115.3 (4)C10—C12—H12B109.5
C6—C7—C10122.2 (4)H12A—C12—H12B109.5
C8—C7—C10122.5 (4)C10—C12—H12C109.5
O2—C8—C3120.0 (4)H12A—C12—H12C109.5
O2—C8—C7117.6 (4)H12B—C12—H12C109.5
C3—C8—C7122.4 (4)C10—C13—H13A109.5
C4—C9—H9A109.5C10—C13—H13B109.5
C4—C9—H9B109.5H13A—C13—H13B109.5
H9A—C9—H9B109.5C10—C13—H13C109.5
C4—C9—H9C109.5H13A—C13—H13C109.5
H9A—C9—H9C109.5H13B—C13—H13C109.5
H9B—C9—H9C109.5
C8—C3—C4—C50.5 (6)C3i—C3—C8—O20.0 (6)
C3i—C3—C4—C5178.5 (4)C4—C3—C8—C70.1 (7)
C8—C3—C4—C9179.6 (5)C3i—C3—C8—C7179.0 (4)
C3i—C3—C4—C91.4 (7)C6—C7—C8—O2178.9 (4)
C3—C4—C5—C60.9 (7)C10—C7—C8—O21.9 (6)
C9—C4—C5—C6179.3 (6)C6—C7—C8—C30.1 (6)
C3—C4—C5—Br1179.9 (3)C10—C7—C8—C3179.1 (4)
C9—C4—C5—Br10.2 (7)C6—C7—C10—C13118.6 (5)
C4—C5—C6—C70.8 (7)C8—C7—C10—C1360.5 (6)
Br1—C5—C6—C7179.8 (3)C6—C7—C10—C111.0 (6)
C5—C6—C7—C80.3 (7)C8—C7—C10—C11179.8 (5)
C5—C6—C7—C10179.4 (4)C6—C7—C10—C12120.4 (5)
C4—C3—C8—O2179.0 (4)C8—C7—C10—C1260.5 (6)
Symmetry code: (i) x+2, y+2, z.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of benzene ring C3–C8.
D—H···AD—HH···AD···AD—H···A
O2—H2···Cgi0.822.543.047 (5)122
Symmetry code: (i) x+2, y+2, z.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of benzene ring C3–C8.
D—H···AD—HH···AD···AD—H···A
O2—H2···Cgi0.8202.5363.047 (5)122
Symmetry code: (i) x+2, y+2, z.
 

Acknowledgements

We are grateful to Nippon Soda Co. Ltd for the kind gift of 4-bromo-2-tert-butyl-5-methyl­phenol. This research was supported by grants from the Research and Education Center for Natural Sciences, Keio University (to SO), and Keio Gijuku Academic Development Funds (to RO).

References

First citationBruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGuo, F., Konkol, L. C. & Thomson, R. J. (2011). J. Am. Chem. Soc. 133, 18–20.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationGutierrez, E. G., Moorhead, E. J., Smith, E. H., Lin, V., Ackerman, L. K. G., Knezevic, C. E., Sun, V., Grant, S. & Wenzel, A. G. (2010). Eur. J. Org. Chem. pp. 3027–3031.  CSD CrossRef Google Scholar
First citationKubota, Y., Shirakawa, S., Inoue, T. & Maruoka, K. (2012). Tetrahedron Lett. 53, 3739–3741.  CrossRef CAS Google Scholar
First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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