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

Obata, R.; Ohba, S.; Einaga, Y.; Nishiyama, S.

doi:10.1107/S2056989015006313

organic compounds

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o278-o279

https://doi.org/10.1107/S2056989015006313

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

Rika Obata,^a Shigeru Ohba,^a ^* Yasuaki Einaga ^b and Shigeru Nishiyama ^b

^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.

Keywords: crystal structure; biphenyl; axial chirality; O—H⋯π interactions.

CCDC reference: 1056738

1. Related literature

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 ).

2. Experimental

2.1. Crystal data

C₂₂H₂₈Br₂O₂
M_r = 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 ) T_min = 0.630, T_max = 0.773
9406 measured reflections
1966 independent reflections
1615 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack x determined using 621 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
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	D⋯A	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); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; 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 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1056738

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015006313/su5104sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006313/su5104Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015006313/su5104Isup3.cml

checkCIF report

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 U_iso(H) = 1.5U_eq(O). C-Bound H atoms were included in calculated positions and refined as riding: C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(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

Refinement details top

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

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	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

C₂₂H₂₈Br₂O₂	D_x = 1.472 Mg m⁻³
M_r = 484.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pba2	Cell parameters from 4121 reflections
a = 7.3680 (5) Å	θ = 2.9–23.6°
b = 22.4243 (14) Å	µ = 3.72 mm⁻¹
c = 6.6148 (4) Å	T = 299 K
V = 1092.91 (12) Å³	Prism, colourless
Z = 2	0.16 × 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 tube	R_int = 0.036
ω scans	θ_max = 25.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −8→8
T_min = 0.630, T_max = 0.773	k = −26→26
9406 measured reflections	l = −7→7
1966 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0176P)² + 0.3778P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.48 e Å⁻³
1966 reflections	Δρ_min = −0.21 e Å⁻³
123 parameters	Absolute structure: Flack x determined using 621 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.034 (9)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₂H₂₈Br₂O₂	V = 1092.91 (12) Å³
M_r = 484.24	Z = 2
Orthorhombic, Pba2	Mo Kα radiation
a = 7.3680 (5) Å	µ = 3.72 mm⁻¹
b = 22.4243 (14) Å	T = 299 K
c = 6.6148 (4) Å	0.16 × 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)
T_min = 0.630, T_max = 0.773	R_int = 0.036
9406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.065	Δρ_max = 0.48 e Å⁻³
S = 1.06	Δρ_min = −0.21 e Å⁻³
1966 reflections	Absolute structure: Flack x determined using 621 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
123 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Br1	1.18668 (8)	0.81211 (2)	0.48288 (15)	0.0681 (2)
O2	0.7528 (4)	0.98204 (13)	0.9897 (9)	0.0576 (8)
H2	0.7777	1.0166	0.9607	0.086*
C3	0.9856 (6)	0.96676 (17)	0.7429 (7)	0.0352 (10)
C4	1.0903 (6)	0.9290 (2)	0.6223 (7)	0.0388 (11)
C5	1.0536 (6)	0.8689 (2)	0.6397 (7)	0.0399 (11)
C6	0.9212 (6)	0.84644 (19)	0.7649 (7)	0.0394 (11)
H6	0.9023	0.8054	0.7685	0.047*
C7	0.8150 (6)	0.88292 (19)	0.8859 (7)	0.0360 (10)
C8	0.8518 (6)	0.94415 (19)	0.8707 (7)	0.0370 (11)
C9	1.2322 (7)	0.9538 (2)	0.4852 (15)	0.0650 (14)
H9A	1.1993	0.9460	0.3473	0.098*
H9B	1.3467	0.9353	0.5143	0.098*
H9C	1.2417	0.9960	0.5058	0.098*
C10	0.6668 (5)	0.8582 (2)	1.0234 (8)	0.0428 (15)
C11	0.6564 (7)	0.7905 (2)	1.0111 (14)	0.074 (2)
H11A	0.6243	0.7789	0.8761	0.111*
H11B	0.5661	0.7762	1.1039	0.111*
H11C	0.7722	0.7737	1.0456	0.111*
C12	0.7053 (8)	0.8746 (3)	1.2449 (9)	0.0756 (18)
H12A	0.8260	0.8623	1.2802	0.113*
H12B	0.6195	0.8548	1.3311	0.113*
H12C	0.6944	0.9170	1.2619	0.113*
C13	0.4827 (6)	0.8829 (2)	0.9625 (15)	0.0760 (17)
H13A	0.4791	0.9249	0.9894	0.114*
H13B	0.3893	0.8632	1.0387	0.114*
H13C	0.4634	0.8760	0.8208	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0866 (4)	0.0458 (3)	0.0718 (4)	0.0118 (2)	0.0311 (4)	−0.0118 (4)
O2	0.0646 (19)	0.0366 (16)	0.072 (2)	0.0049 (14)	0.018 (3)	−0.009 (3)
C3	0.040 (3)	0.030 (2)	0.036 (3)	0.0016 (19)	−0.004 (2)	0.001 (2)
C4	0.048 (3)	0.033 (3)	0.035 (3)	0.003 (2)	0.002 (2)	0.000 (2)
C5	0.048 (3)	0.035 (3)	0.037 (3)	0.009 (2)	0.003 (2)	−0.003 (2)
C6	0.046 (3)	0.028 (2)	0.045 (3)	0.002 (2)	−0.002 (2)	−0.002 (2)
C7	0.036 (3)	0.034 (2)	0.038 (2)	0.008 (2)	−0.005 (2)	−0.002 (2)
C8	0.042 (3)	0.031 (3)	0.038 (2)	0.006 (2)	0.000 (2)	−0.005 (2)
C9	0.084 (3)	0.048 (3)	0.063 (3)	0.003 (2)	0.033 (5)	−0.003 (5)
C10	0.035 (3)	0.045 (3)	0.048 (4)	−0.0010 (19)	0.008 (3)	0.003 (2)
C11	0.070 (3)	0.048 (3)	0.104 (6)	−0.013 (2)	0.036 (5)	0.008 (4)
C12	0.078 (4)	0.099 (5)	0.049 (4)	−0.021 (4)	0.010 (3)	0.002 (3)
C13	0.039 (3)	0.086 (4)	0.103 (5)	0.005 (2)	0.012 (4)	0.020 (5)

Geometric parameters (Å, º) top

Br1—C5	1.913 (4)	C9—H9B	0.9600
O2—C8	1.369 (6)	C9—H9C	0.9600
O2—H2	0.8200	C10—C13	1.520 (7)
C3—C8	1.394 (6)	C10—C11	1.521 (7)
C3—C4	1.396 (6)	C10—C12	1.537 (8)
C3—C3ⁱ	1.506 (8)	C11—H11A	0.9600
C4—C5	1.379 (6)	C11—H11B	0.9600
C4—C9	1.491 (8)	C11—H11C	0.9600
C5—C6	1.375 (6)	C12—H12A	0.9600
C6—C7	1.386 (6)	C12—H12B	0.9600
C6—H6	0.9300	C12—H12C	0.9600
C7—C8	1.403 (6)	C13—H13A	0.9600
C7—C10	1.526 (6)	C13—H13B	0.9600
C9—H9A	0.9600	C13—H13C	0.9600

C8—O2—H2	109.5	C13—C10—C11	107.7 (4)
C8—C3—C4	121.1 (4)	C13—C10—C7	110.4 (5)
C8—C3—C3ⁱ	117.3 (4)	C11—C10—C7	111.5 (4)
C4—C3—C3ⁱ	121.6 (4)	C13—C10—C12	109.3 (5)
C5—C4—C3	115.9 (4)	C11—C10—C12	107.4 (5)
C5—C4—C9	123.5 (4)	C7—C10—C12	110.5 (4)
C3—C4—C9	120.5 (4)	C10—C11—H11A	109.5
C6—C5—C4	123.2 (4)	C10—C11—H11B	109.5
C6—C5—Br1	116.5 (3)	H11A—C11—H11B	109.5
C4—C5—Br1	120.3 (3)	C10—C11—H11C	109.5
C5—C6—C7	122.2 (4)	H11A—C11—H11C	109.5
C5—C6—H6	118.9	H11B—C11—H11C	109.5
C7—C6—H6	118.9	C10—C12—H12A	109.5
C6—C7—C8	115.3 (4)	C10—C12—H12B	109.5
C6—C7—C10	122.2 (4)	H12A—C12—H12B	109.5
C8—C7—C10	122.5 (4)	C10—C12—H12C	109.5
O2—C8—C3	120.0 (4)	H12A—C12—H12C	109.5
O2—C8—C7	117.6 (4)	H12B—C12—H12C	109.5
C3—C8—C7	122.4 (4)	C10—C13—H13A	109.5
C4—C9—H9A	109.5	C10—C13—H13B	109.5
C4—C9—H9B	109.5	H13A—C13—H13B	109.5
H9A—C9—H9B	109.5	C10—C13—H13C	109.5
C4—C9—H9C	109.5	H13A—C13—H13C	109.5
H9A—C9—H9C	109.5	H13B—C13—H13C	109.5
H9B—C9—H9C	109.5

C8—C3—C4—C5	−0.5 (6)	C3ⁱ—C3—C8—O2	0.0 (6)
C3ⁱ—C3—C4—C5	178.5 (4)	C4—C3—C8—C7	0.1 (7)
C8—C3—C4—C9	179.6 (5)	C3ⁱ—C3—C8—C7	−179.0 (4)
C3ⁱ—C3—C4—C9	−1.4 (7)	C6—C7—C8—O2	−178.9 (4)
C3—C4—C5—C6	0.9 (7)	C10—C7—C8—O2	1.9 (6)
C9—C4—C5—C6	−179.3 (6)	C6—C7—C8—C3	0.1 (6)
C3—C4—C5—Br1	179.9 (3)	C10—C7—C8—C3	−179.1 (4)
C9—C4—C5—Br1	−0.2 (7)	C6—C7—C10—C13	−118.6 (5)
C4—C5—C6—C7	−0.8 (7)	C8—C7—C10—C13	60.5 (6)
Br1—C5—C6—C7	−179.8 (3)	C6—C7—C10—C11	1.0 (6)
C5—C6—C7—C8	0.3 (7)	C8—C7—C10—C11	−179.8 (5)
C5—C6—C7—C10	179.4 (4)	C6—C7—C10—C12	120.4 (5)
C4—C3—C8—O2	179.0 (4)	C8—C7—C10—C12	−60.5 (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···A	D—H	H···A	D···A	D—H···A
O2—H2···Cgⁱ	0.82	2.54	3.047 (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···A	D—H	H···A	D···A	D—H···A
O2—H2···Cgⁱ	0.820	2.536	3.047 (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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o278-o279

https://doi.org/10.1107/S2056989015006313

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

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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