3,3′-Di-tert-butyl-5,5′-dimethoxy­biphenyl-2,2′-diol

Du, Z.-X.; Wang, L.-Z.

doi:10.1107/S1600536809023071

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1664

doi:10.1107/S1600536809023071

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3,3′-Di-tert-butyl-5,5′-dimethoxybiphenyl-2,2′-diol

Zhong-Xiang Du ^a ^* and Ling-Zhi Wang ^b

^aDepartment of Chemistry, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China, and ^bEquipment Department, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
^*Correspondence e-mail: dzx6281@126.com

(Received 13 June 2009; accepted 16 June 2009; online 24 June 2009)

The title compound, C₂₂H₃₀O₄, displays twofold rotational symmetry. The two benzene rings are almost perpendicular to each other, forming a dihedral angle of 89.8 (6)°. In the crystal, molecules are linked into an extended one-dimensional chain structure via intermolecular O—H⋯O hydrogen bonds.

Related literature

For the various methods of preparing di-BHA [a dimer of 3-tert-butyl-4-hydroxyanisole], see: Hewgill & Hewitt (1967 ); Jarl et al. (2004 ); Masahiro et al. (2005 ); Seiichiro et al. (2004 ).

Experimental

Crystal data

C₂₂H₃₀O₄
M_r = 358.46
Tetragonal, I 4₁ /a
a = 13.4289 (8) Å
c = 23.127 (3) Å
V = 4170.5 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.49 × 0.49 × 0.38 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.963, T_max = 0.972
13638 measured reflections
1938 independent reflections
1542 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.112
S = 1.04
1938 reflections
123 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	2.08	2.7592 (15)	140
Symmetry code: (i) $[x, y-{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023071/at2819sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023071/at2819Isup2.hkl

checkCIF report

Comment top

In the previous literatures, several methods for preparing di-BHA [a dimer of 3-tert-butyl-4-hydroxyanisole (BHA)] have been reported (Hewgill & Hewitt, 1967; Masahiro et al., 2005; Jarl et al., 2004; Seiichiro et al., 2004), but its single-crystal and precise molecular structure has not been investigated so far. Here we describe the structure of the title compound, (I), (Fig. 1).

Di-BHA shows 2-fold rotational symmetry characters, where the 2-fold rotation axis is perpendicular to the C6—C6A bond. The oxygen atoms are almost coplanar with their own benzene ring-the largest deviation from the least-squares plane was found for O1 (or O1A), with an atom-plane distance of 0.017 Å. The two benzene rings have a dihedral angle of 89.8°, indicating that they are almost perpendicular to each other. The phenolic hydroxyl donor and methoxyl acceptor are involved in intermolecular hydrogen bonds and they extend di-BHA molecules into a one-dimensional chain structure along the b axis (Table 1, Fig.2), thus stabilizing di-BHA in the solid state.

Related literature top

For the several methods of preparing di-BHA [a dimer of 3-tert-butyl-4-hydroxyanisole], see: Hewgill & Hewitt (1967); Jarl et al. (2004); Masahiro et al. (2005); Seiichiro et al. (2004).

Experimental top

An easy preparation method improved by Jarl et al. (2004) was adopted in our experiment. A solution of [K₃Fe(CN)₆] (0.1 mol, 3.29 g) and KOH (0.1 mol, 5.61 g) in water (100 ml) was prepared and was added dropwise to a solution of 3-tert-butyl-4-hydroxyanisole (0.1 mol, 1.80 g) in acetone (10 ml) over 3 h at room temperature. After vigorous agitation, yellow rice-shaped precipitate was obtained and filtered. Then the solid product was extracted with CH₂Cl₂ (3 × 50 ml), and the organic phase was dried over Na₂SO₄. After removal of CH₂Cl₂ under vacuum, a light brown solid was obtained. It turned into white crystal substance after washed with anhydrous ethanol(3 × 50 ml). Dissolve the white crystal substance in CH₂Cl₂ and filter the solution. About 4 days later, colourless block-shaped crystals suitable for X-ray diffraction analysis were appeared by slow evaporation in a yield of 63%. m. p. 510-511 K. Analysis, found: C 73.57, H 8.44%; C₂₂H₃₀O₄ requires: C 73.65, H 8.37%. IR (KBr, ν, cm^-1): 3412.6(ν O—H), 1594.2, 1455.6(ν (C₆H₆), skeleton), 1396.2, 1365.4(ν (CH₃)₃-C, skeleton), 1215.3, 1138.8(νC-O), 784.1(γ(C=C—H)).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), with displacement ellipsoids drawn at the 25% probability level. Atoms with suffix A are at the symmetry position (-x, -y + 3/2, z).
	Fig. 2. The crystal packing of (I), showing hydrogen bonds as dashed lines along b axis. H atoms on C atoms have been omitted.

3,3'-Di-tert-butyl-5,5'-dimethoxybiphenyl-2,2'-diol top

Crystal data top

C₂₂H₃₀O₄	D_x = 1.142 Mg m⁻³
M_r = 358.46	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 3994 reflections
Hall symbol: -I 4ad	θ = 3.0–25.5°
a = 13.4289 (8) Å	µ = 0.08 mm⁻¹
c = 23.127 (3) Å	T = 291 K
V = 4170.5 (6) Å³	Block, colourless
Z = 8	0.49 × 0.49 × 0.38 mm
F(000) = 1552

Data collection top

Bruker APEXII CCD area-detector diffractometer	1938 independent reflections
Radiation source: fine-focus sealed tube	1542 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
T_min = 0.963, T_max = 0.972	k = −15→16
13638 measured reflections	l = −28→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0476P)² + 2.3626P] where P = (F_o² + 2F_c²)/3
1938 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₂H₃₀O₄	Z = 8
M_r = 358.46	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.08 mm⁻¹
a = 13.4289 (8) Å	T = 291 K
c = 23.127 (3) Å	0.49 × 0.49 × 0.38 mm
V = 4170.5 (6) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1938 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1542 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.972	R_int = 0.025
13638 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.04	Δρ_max = 0.14 e Å⁻³
1938 reflections	Δρ_min = −0.13 e Å⁻³
123 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

	x	y	z	U_iso*/U_eq
C1	0.11953 (11)	0.79586 (10)	0.02439 (6)	0.0416 (4)
C2	0.18758 (11)	0.87570 (10)	0.02195 (6)	0.0416 (4)
C3	0.16557 (11)	0.95179 (11)	−0.01654 (6)	0.0431 (4)
H3	0.2085	1.0060	−0.0188	0.052*
C4	0.08231 (11)	0.95010 (10)	−0.05172 (6)	0.0408 (3)
C5	0.01714 (11)	0.87114 (10)	−0.04926 (6)	0.0417 (4)
H5	−0.0385	0.8696	−0.0732	0.050*
C6	0.03503 (10)	0.79350 (10)	−0.01059 (6)	0.0387 (3)
C7	0.28338 (12)	0.87786 (13)	0.05857 (7)	0.0546 (4)
C8	0.34307 (17)	0.97382 (18)	0.04844 (11)	0.0950 (8)
H8A	0.3018	1.0305	0.0566	0.142*
H8B	0.3647	0.9764	0.0089	0.142*
H8C	0.4001	0.9746	0.0735	0.142*
C9	0.34957 (16)	0.78944 (19)	0.04258 (11)	0.0878 (7)
H9A	0.4062	0.7876	0.0679	0.132*
H9B	0.3718	0.7964	0.0033	0.132*
H9C	0.3123	0.7288	0.0465	0.132*
C10	0.25901 (15)	0.87337 (17)	0.12326 (8)	0.0725 (6)
H10A	0.2230	0.9322	0.1342	0.109*
H10B	0.3197	0.8695	0.1451	0.109*
H10C	0.2190	0.8157	0.1310	0.109*
C11	0.00097 (17)	1.02543 (14)	−0.13233 (9)	0.0733 (6)
H11A	0.0167	0.9698	−0.1567	0.110*
H11B	0.0028	1.0856	−0.1547	0.110*
H11C	−0.0644	1.0168	−0.1163	0.110*
O1	0.07070 (9)	1.03143 (8)	−0.08749 (5)	0.0586 (3)
O2	0.13978 (10)	0.72001 (8)	0.06230 (6)	0.0665 (4)
H2	0.0997	0.6747	0.0574	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0462 (8)	0.0351 (7)	0.0437 (8)	−0.0028 (6)	−0.0020 (6)	0.0010 (6)
C2	0.0421 (8)	0.0389 (8)	0.0438 (8)	−0.0058 (6)	−0.0027 (6)	−0.0030 (6)
C3	0.0453 (8)	0.0369 (8)	0.0470 (8)	−0.0119 (6)	0.0005 (7)	−0.0021 (6)
C4	0.0483 (8)	0.0313 (7)	0.0427 (8)	−0.0033 (6)	−0.0002 (6)	0.0021 (6)
C5	0.0409 (8)	0.0403 (8)	0.0440 (8)	−0.0042 (6)	−0.0047 (6)	−0.0015 (6)
C6	0.0393 (8)	0.0338 (7)	0.0428 (8)	−0.0048 (6)	0.0025 (6)	−0.0024 (6)
C7	0.0491 (9)	0.0582 (10)	0.0565 (10)	−0.0083 (8)	−0.0133 (8)	−0.0002 (8)
C8	0.0763 (14)	0.1044 (17)	0.1042 (18)	−0.0472 (13)	−0.0422 (13)	0.0238 (14)
C9	0.0574 (12)	0.1129 (18)	0.0930 (16)	0.0194 (12)	−0.0211 (11)	−0.0159 (14)
C10	0.0739 (13)	0.0843 (14)	0.0595 (11)	−0.0043 (10)	−0.0228 (10)	−0.0031 (10)
C11	0.0946 (15)	0.0568 (11)	0.0686 (12)	−0.0020 (10)	−0.0309 (11)	0.0131 (9)
O1	0.0791 (8)	0.0406 (6)	0.0562 (7)	−0.0134 (5)	−0.0178 (6)	0.0115 (5)
O2	0.0759 (9)	0.0465 (7)	0.0770 (9)	−0.0174 (6)	−0.0289 (7)	0.0210 (6)

Geometric parameters (Å, º) top

C1—O2	1.3711 (18)	C8—H8A	0.9600
C1—C6	1.394 (2)	C8—H8B	0.9600
C1—C2	1.410 (2)	C8—H8C	0.9600
C2—C3	1.387 (2)	C9—H9A	0.9600
C2—C7	1.541 (2)	C9—H9B	0.9600
C3—C4	1.383 (2)	C9—H9C	0.9600
C3—H3	0.9300	C10—H10A	0.9600
C4—C5	1.3761 (19)	C10—H10B	0.9600
C4—O1	1.3788 (17)	C10—H10C	0.9600
C5—C6	1.395 (2)	C11—O1	1.400 (2)
C5—H5	0.9300	C11—H11A	0.9600
C6—C6ⁱ	1.500 (3)	C11—H11B	0.9600
C7—C9	1.529 (3)	C11—H11C	0.9600
C7—C10	1.533 (3)	O2—H2	0.8200
C7—C8	1.535 (3)

O2—C1—C6	121.03 (13)	C7—C8—H8B	109.5
O2—C1—C2	117.52 (13)	H8A—C8—H8B	109.5
C6—C1—C2	121.45 (13)	C7—C8—H8C	109.5
C3—C2—C1	116.61 (13)	H8A—C8—H8C	109.5
C3—C2—C7	121.12 (13)	H8B—C8—H8C	109.5
C1—C2—C7	122.25 (13)	C7—C9—H9A	109.5
C4—C3—C2	122.53 (13)	C7—C9—H9B	109.5
C4—C3—H3	118.7	H9A—C9—H9B	109.5
C2—C3—H3	118.7	C7—C9—H9C	109.5
C5—C4—O1	124.28 (13)	H9A—C9—H9C	109.5
C5—C4—C3	120.16 (13)	H9B—C9—H9C	109.5
O1—C4—C3	115.55 (12)	C7—C10—H10A	109.5
C4—C5—C6	119.54 (13)	C7—C10—H10B	109.5
C4—C5—H5	120.2	H10A—C10—H10B	109.5
C6—C5—H5	120.2	C7—C10—H10C	109.5
C1—C6—C5	119.70 (12)	H10A—C10—H10C	109.5
C1—C6—C6ⁱ	121.90 (13)	H10B—C10—H10C	109.5
C5—C6—C6ⁱ	118.31 (12)	O1—C11—H11A	109.5
C9—C7—C10	109.25 (17)	O1—C11—H11B	109.5
C9—C7—C8	108.15 (18)	H11A—C11—H11B	109.5
C10—C7—C8	107.07 (16)	O1—C11—H11C	109.5
C9—C7—C2	109.75 (14)	H11A—C11—H11C	109.5
C10—C7—C2	110.95 (14)	H11B—C11—H11C	109.5
C8—C7—C2	111.58 (14)	C4—O1—C11	118.33 (12)
C7—C8—H8A	109.5	C1—O2—H2	109.5

O2—C1—C2—C3	−179.81 (14)	O2—C1—C6—C6ⁱ	−2.8 (2)
C6—C1—C2—C3	0.6 (2)	C2—C1—C6—C6ⁱ	176.75 (13)
O2—C1—C2—C7	1.9 (2)	C4—C5—C6—C1	−1.1 (2)
C6—C1—C2—C7	−177.67 (14)	C4—C5—C6—C6ⁱ	−177.55 (13)
C1—C2—C3—C4	−1.0 (2)	C3—C2—C7—C9	−117.04 (18)
C7—C2—C3—C4	177.31 (14)	C1—C2—C7—C9	61.1 (2)
C2—C3—C4—C5	0.3 (2)	C3—C2—C7—C10	122.12 (17)
C2—C3—C4—O1	179.81 (14)	C1—C2—C7—C10	−59.7 (2)
O1—C4—C5—C6	−178.71 (14)	C3—C2—C7—C8	2.8 (2)
C3—C4—C5—C6	0.7 (2)	C1—C2—C7—C8	−179.02 (17)
O2—C1—C6—C5	−179.17 (14)	C5—C4—O1—C11	−13.7 (2)
C2—C1—C6—C5	0.4 (2)	C3—C4—O1—C11	166.78 (16)

Symmetry code: (i) −x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.82	2.08	2.7592 (15)	140

Symmetry code: (ii) x, y−1/2, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₃₀O₄
M_r	358.46
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	291
a, c (Å)	13.4289 (8), 23.127 (3)
V (Å³)	4170.5 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.49 × 0.49 × 0.38

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.963, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	13638, 1938, 1542
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.04
No. of reflections	1938
No. of parameters	123
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	2.08	2.7592 (15)	139.7

Symmetry code: (i) x, y−1/2, −z.

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (No. 20771054).

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