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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1664.
Published online 2009 June 24. doi:  10.1107/S1600536809023071
PMCID: PMC2969421

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

Abstract

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 [triangle]); Jarl et al. (2004 [triangle]); Masahiro et al. (2005 [triangle]); Seiichiro et al. (2004 [triangle]).

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Object name is e-65-o1664-scheme1.jpg

Experimental

Crystal data

  • C22H30O4
  • M r = 358.46
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-65-o1664-efi2.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.112
  • S = 1.04
  • 1938 reflections
  • 123 parameters
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.13 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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)).

Refinement

H atoms bonded to C were positioned geometrically with C—H distance of 0.93–0.96 Å, and treated as riding atoms, with Uiso(H)=1.2 or 1.5Ueq(C). The O—H hydrogen atom was located in a difference Fourier map and the applied restraint of the O—H distance was 0.820 Å, with Uiso(H)=1.5Ueq(O).

Figures

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.

Crystal data

C22H30O4Dx = 1.142 Mg m3
Mr = 358.46Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3994 reflections
Hall symbol: -I 4adθ = 3.0–25.5°
a = 13.4289 (8) ŵ = 0.08 mm1
c = 23.127 (3) ÅT = 291 K
V = 4170.5 (6) Å3Block, colourless
Z = 80.49 × 0.49 × 0.38 mm
F(000) = 1552

Data collection

Bruker APEXII CCD area-detector diffractometer1938 independent reflections
Radiation source: fine-focus sealed tube1542 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −16→15
Tmin = 0.963, Tmax = 0.972k = −15→16
13638 measured reflectionsl = −28→27

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0476P)2 + 2.3626P] where P = (Fo2 + 2Fc2)/3
1938 reflections(Δ/σ)max < 0.001
123 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = −0.13 e Å3

Special details

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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)

xyzUiso*/Ueq
C10.11953 (11)0.79586 (10)0.02439 (6)0.0416 (4)
C20.18758 (11)0.87570 (10)0.02195 (6)0.0416 (4)
C30.16557 (11)0.95179 (11)−0.01654 (6)0.0431 (4)
H30.20851.0060−0.01880.052*
C40.08231 (11)0.95010 (10)−0.05172 (6)0.0408 (3)
C50.01714 (11)0.87114 (10)−0.04926 (6)0.0417 (4)
H5−0.03850.8696−0.07320.050*
C60.03503 (10)0.79350 (10)−0.01059 (6)0.0387 (3)
C70.28338 (12)0.87786 (13)0.05857 (7)0.0546 (4)
C80.34307 (17)0.97382 (18)0.04844 (11)0.0950 (8)
H8A0.30181.03050.05660.142*
H8B0.36470.97640.00890.142*
H8C0.40010.97460.07350.142*
C90.34957 (16)0.78944 (19)0.04258 (11)0.0878 (7)
H9A0.40620.78760.06790.132*
H9B0.37180.79640.00330.132*
H9C0.31230.72880.04650.132*
C100.25901 (15)0.87337 (17)0.12326 (8)0.0725 (6)
H10A0.22300.93220.13420.109*
H10B0.31970.86950.14510.109*
H10C0.21900.81570.13100.109*
C110.00097 (17)1.02543 (14)−0.13233 (9)0.0733 (6)
H11A0.01670.9698−0.15670.110*
H11B0.00281.0856−0.15470.110*
H11C−0.06441.0168−0.11630.110*
O10.07070 (9)1.03143 (8)−0.08749 (5)0.0586 (3)
O20.13978 (10)0.72001 (8)0.06230 (6)0.0665 (4)
H20.09970.67470.05740.100*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0462 (8)0.0351 (7)0.0437 (8)−0.0028 (6)−0.0020 (6)0.0010 (6)
C20.0421 (8)0.0389 (8)0.0438 (8)−0.0058 (6)−0.0027 (6)−0.0030 (6)
C30.0453 (8)0.0369 (8)0.0470 (8)−0.0119 (6)0.0005 (7)−0.0021 (6)
C40.0483 (8)0.0313 (7)0.0427 (8)−0.0033 (6)−0.0002 (6)0.0021 (6)
C50.0409 (8)0.0403 (8)0.0440 (8)−0.0042 (6)−0.0047 (6)−0.0015 (6)
C60.0393 (8)0.0338 (7)0.0428 (8)−0.0048 (6)0.0025 (6)−0.0024 (6)
C70.0491 (9)0.0582 (10)0.0565 (10)−0.0083 (8)−0.0133 (8)−0.0002 (8)
C80.0763 (14)0.1044 (17)0.1042 (18)−0.0472 (13)−0.0422 (13)0.0238 (14)
C90.0574 (12)0.1129 (18)0.0930 (16)0.0194 (12)−0.0211 (11)−0.0159 (14)
C100.0739 (13)0.0843 (14)0.0595 (11)−0.0043 (10)−0.0228 (10)−0.0031 (10)
C110.0946 (15)0.0568 (11)0.0686 (12)−0.0020 (10)−0.0309 (11)0.0131 (9)
O10.0791 (8)0.0406 (6)0.0562 (7)−0.0134 (5)−0.0178 (6)0.0115 (5)
O20.0759 (9)0.0465 (7)0.0770 (9)−0.0174 (6)−0.0289 (7)0.0210 (6)

Geometric parameters (Å, °)

C1—O21.3711 (18)C8—H8A0.9600
C1—C61.394 (2)C8—H8B0.9600
C1—C21.410 (2)C8—H8C0.9600
C2—C31.387 (2)C9—H9A0.9600
C2—C71.541 (2)C9—H9B0.9600
C3—C41.383 (2)C9—H9C0.9600
C3—H30.9300C10—H10A0.9600
C4—C51.3761 (19)C10—H10B0.9600
C4—O11.3788 (17)C10—H10C0.9600
C5—C61.395 (2)C11—O11.400 (2)
C5—H50.9300C11—H11A0.9600
C6—C6i1.500 (3)C11—H11B0.9600
C7—C91.529 (3)C11—H11C0.9600
C7—C101.533 (3)O2—H20.8200
C7—C81.535 (3)
O2—C1—C6121.03 (13)C7—C8—H8B109.5
O2—C1—C2117.52 (13)H8A—C8—H8B109.5
C6—C1—C2121.45 (13)C7—C8—H8C109.5
C3—C2—C1116.61 (13)H8A—C8—H8C109.5
C3—C2—C7121.12 (13)H8B—C8—H8C109.5
C1—C2—C7122.25 (13)C7—C9—H9A109.5
C4—C3—C2122.53 (13)C7—C9—H9B109.5
C4—C3—H3118.7H9A—C9—H9B109.5
C2—C3—H3118.7C7—C9—H9C109.5
C5—C4—O1124.28 (13)H9A—C9—H9C109.5
C5—C4—C3120.16 (13)H9B—C9—H9C109.5
O1—C4—C3115.55 (12)C7—C10—H10A109.5
C4—C5—C6119.54 (13)C7—C10—H10B109.5
C4—C5—H5120.2H10A—C10—H10B109.5
C6—C5—H5120.2C7—C10—H10C109.5
C1—C6—C5119.70 (12)H10A—C10—H10C109.5
C1—C6—C6i121.90 (13)H10B—C10—H10C109.5
C5—C6—C6i118.31 (12)O1—C11—H11A109.5
C9—C7—C10109.25 (17)O1—C11—H11B109.5
C9—C7—C8108.15 (18)H11A—C11—H11B109.5
C10—C7—C8107.07 (16)O1—C11—H11C109.5
C9—C7—C2109.75 (14)H11A—C11—H11C109.5
C10—C7—C2110.95 (14)H11B—C11—H11C109.5
C8—C7—C2111.58 (14)C4—O1—C11118.33 (12)
C7—C8—H8A109.5C1—O2—H2109.5
O2—C1—C2—C3−179.81 (14)O2—C1—C6—C6i−2.8 (2)
C6—C1—C2—C30.6 (2)C2—C1—C6—C6i176.75 (13)
O2—C1—C2—C71.9 (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—C4177.31 (14)C1—C2—C7—C961.1 (2)
C2—C3—C4—C50.3 (2)C3—C2—C7—C10122.12 (17)
C2—C3—C4—O1179.81 (14)C1—C2—C7—C10−59.7 (2)
O1—C4—C5—C6−178.71 (14)C3—C2—C7—C82.8 (2)
C3—C4—C5—C60.7 (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—C50.4 (2)C3—C4—O1—C11166.78 (16)

Symmetry codes: (i) −x, −y+3/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.822.082.7592 (15)140

Symmetry codes: (ii) x, y−1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2819).

References

  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hewgill, F. R. & Hewitt, D. G. (1967). J. Chem. Soc. C, pp. 726–730.
  • Jarl, I. V., Alison, C. H., Samuel, N., Rafael, S., Allison, M. M., Martin, L., Anthony, L. S., Christian, M. & Dieter, V. (2004). Adv. Synth. Catal.346, 993–1003.
  • Masahiro, O., Kanae, T. S., Takao, K., Kentaro, O., Masako, S., Shiro, U., Keiichi, H. & Toyoshige, E. (2005). Biol. Pharm. Bull.28, 1120–1122. [PubMed]
  • Seiichiro, F., Mariko, I. & Ichiro, Y. (2004). Internet J. Mol. Des. pp. 241–246.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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