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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o303.
Published online 2010 January 9. doi:  10.1107/S1600536810000140
PMCID: PMC2979790

2,3,5-Trimethyl-1,4-hydro­quinone

Abstract

The mol­ecule of the title compound, C9H12O2, is approximately planar (mean atomic deviation = 0.0346 Å) and disposed about a crystallographic centre of symmetry. The H atom of the benzene ring is disordered over four orientations, with occupancies of 0.100 (3) and 0.401 (3) at the C atoms in the 2- and 3-positions and the same at their symmetric location. The H atoms of methyl group at the 2-position are disordered over two positions of equal occupancy. In the crystal structure, adjacent mol­ecules are linked through O—H(...)O hydrogen bonds, forming a two-dimensional network.

Related literature

The title compound is an important inter­mediate for the preparation of vitamin E, see: Close & Oroshnik (1977 [triangle]); Mulhauser & Chabardes (1986 [triangle]); Yao & Han (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o303-scheme1.jpg

Experimental

Crystal data

  • C9H12O2
  • M r = 152.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o303-efi1.jpg
  • a = 8.035 (4) Å
  • b = 4.696 (2) Å
  • c = 10.503 (5) Å
  • β = 92.813 (5)°
  • V = 395.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 93 K
  • 0.50 × 0.23 × 0.05 mm

Data collection

  • Rigaku SPIDER diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.957, T max = 0.996
  • 3724 measured reflections
  • 905 independent reflections
  • 667 reflections with I > 2σ(I)
  • R int = 0.031
  • Standard reflections: 0

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.081
  • S = 1.00
  • 905 reflections
  • 62 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.11 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 I, global. DOI: 10.1107/S1600536810000140/hg2613sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000140/hg2613Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the Jiangsu Institute of Nuclear Medicine.

supplementary crystallographic information

Comment

The molecule of the title compound (Fig.1) is useful as an important intermediate for the preparation of vitamin E (Close et al., 1977; Mulhauser et al., 1986; Yao et al., 1999;). We report here the crystal structure of the title compound. The crystal data show that the molecule is approximately planar and and disposed about a crystallographic centre of symmetry. Two hydroxy groups are attached at C1 and C1a of the benzene ring. The only one hydrogen of the benzene ring can be found in other four positions. The occupancies of hydrogen atom(H2') and methyl group(C4) are 0.100 (3) and 0.900 (3) at C2 and the same of its symmetric location(C2a). And the occupancies of H3' and C5 are 0.401 (3) and 0.599 (3) at C3 and C3a. Also the H atoms of methyl group(C4) are disordered over two positions by rotation about its C—C δ bond with equal occupancies.In the crystal structure, adjacent molecules are linked through O—H···O hydrogen bonds to form a two-dimensional hydrogen-bonded network parallel to the [1 0 1] crystallographic plane (Tab 1 and Fig. 2).

Experimental

A sample of commercial 2,3,5-trimethyl-1,4-hydroquinone(Aldrich) was crystalized by slow evaporation of a solution in benzene: colourless platelet-shaped crystals were formed after several days. 1H-NMR (400 MHz; CDCl3) δ: 2.145, 2.172, 2.181 (s, 9H, 3×CH3), 4.194, 4.213 (s, 2H, 2×OH), 6.453 (s, 1H, Ph—H); 13C-NMR(400 MHz; CDCl3) δ: 11.94, 12.28, 15.90(3×CH3), 114.33 (Ph-H), 120.82, 121.02, 123.48 (3×Ph-CH3), 145.90, 146.94 (2×Ph-OH).

Refinement

The H atom of the benzene ring is disordered over four positions, the occupancies are 0.100 (3),0.401 (3) and the same of their symmetric location. In the case of methyl group(C4), H atoms are disordered over two sites of equal occupancy by rotation about the C—C bonds. The hydroxyl hydrogen was located by difference Fourier synthesis. Other H atoms were placed in geometry calculated positions, taking full account of the disordered noted above, with C—H set to 0.95 Å and 0.98 Å for benzene and methyl H atoms respectively, and refined with a riding model, with Uiso(H) = 1.2Ueq(C) in all cases.

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
Fig. 2.
Presentation of the two-dimensional hydrogen-bonded network. Hydrogen bonds are shown as dashed lines.

Crystal data

C9H12O2F(000) = 164
Mr = 152.19Dx = 1.277 Mg m3
Monoclinic, P21/nMelting point: 442(2) K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.035 (4) ÅCell parameters from 930 reflections
b = 4.696 (2) Åθ = 3.1–27.5°
c = 10.503 (5) ŵ = 0.09 mm1
β = 92.813 (5)°T = 93 K
V = 395.8 (3) Å3Platelet, colorless
Z = 20.50 × 0.23 × 0.05 mm

Data collection

Rigaku SPIDER diffractometer905 independent reflections
Radiation source: Rotating Anode667 reflections with I > 2σ(I)
graphiteRint = 0.031
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: ψ scan (North et al., 1968)h = −10→10
Tmin = 0.957, Tmax = 0.996k = −6→6
3724 measured reflectionsl = −13→13

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0146P)2 + 0.186P] where P = (Fo2 + 2Fc2)/3
905 reflections(Δ/σ)max < 0.001
62 parametersΔρmax = 0.17 e Å3
1 restraintΔρmin = −0.11 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 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)

xyzUiso*/UeqOcc. (<1)
O10.26338 (14)0.4290 (2)0.68009 (10)0.0409 (3)
C10.38434 (19)0.4579 (3)0.58997 (12)0.0326 (3)
C20.34638 (18)0.6452 (3)0.48939 (13)0.0326 (3)
C30.46482 (19)0.6852 (3)0.39874 (12)0.0325 (3)
H2'0.24270.74240.48310.039*0.100 (3)
H3'0.44220.81070.32910.039*0.401 (3)
C40.1823 (2)0.8010 (4)0.47751 (16)0.0414 (5)0.900 (3)
H4A0.11430.74870.54890.050*0.4501 (15)
H4B0.12330.74870.39700.050*0.4501 (15)
H4C0.20251.00680.47900.050*0.4501 (15)
H4D0.17910.92070.40100.050*0.4501 (15)
H4E0.17010.92070.55290.050*0.4501 (15)
H4F0.09090.66270.47090.050*0.4501 (15)
C50.4153 (3)0.8844 (5)0.2919 (2)0.0353 (7)0.599 (3)
H5A0.29570.86520.27070.042*0.599 (3)
H5B0.47790.83750.21690.042*0.599 (3)
H5C0.44001.08080.31820.042*0.599 (3)
H1O0.273 (2)0.263 (5)0.7202 (18)0.072 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0545 (7)0.0301 (6)0.0389 (6)0.0038 (5)0.0109 (5)0.0004 (5)
C10.0468 (9)0.0222 (7)0.0290 (7)−0.0009 (6)0.0030 (6)−0.0044 (5)
C20.0429 (8)0.0217 (7)0.0326 (7)0.0022 (6)−0.0034 (6)−0.0049 (5)
C30.0493 (9)0.0201 (7)0.0276 (7)0.0017 (6)−0.0033 (6)−0.0012 (5)
C40.0475 (11)0.0346 (9)0.0417 (9)0.0054 (8)−0.0014 (8)0.0013 (7)
C50.0434 (14)0.0308 (13)0.0314 (12)−0.0034 (11)−0.0004 (10)0.0051 (10)

Geometric parameters (Å, °)

O1—C11.3961 (17)C4—H4A0.9800
O1—H1O0.89 (2)C4—H4B0.9800
C1—C3i1.386 (2)C4—H4C0.9800
C1—C21.3968 (19)C4—H4D0.9800
C2—C31.392 (2)C4—H4E0.9800
C2—C41.508 (2)C4—H4F0.9800
C2—H2'0.9498C5—H3'0.5575
C3—C1i1.386 (2)C5—H5A0.9800
C3—C51.500 (3)C5—H5B0.9800
C3—H3'0.9500C5—H5C0.9800
C4—H2'0.5584
C1—O1—H1O111.0 (12)H4A—C4—H4C109.5
C3i—C1—O1122.01 (13)H4B—C4—H4C109.5
C3i—C1—C2121.85 (13)C2—C4—H4D109.5
O1—C1—C2116.13 (13)H2'—C4—H4D110.8
C3—C2—C1118.12 (13)H4A—C4—H4D141.1
C3—C2—C4120.17 (13)H4B—C4—H4D56.3
C1—C2—C4121.72 (14)H4C—C4—H4D56.3
C3—C2—H2'121.0C2—C4—H4E109.5
C1—C2—H2'120.9H2'—C4—H4E108.6
C4—C2—H2'0.8H4A—C4—H4E56.3
C1i—C3—C2120.04 (12)H4B—C4—H4E141.1
C1i—C3—C5124.41 (15)H4C—C4—H4E56.3
C2—C3—C5115.54 (15)H4D—C4—H4E109.5
C1i—C3—H3'120.0C2—C4—H4F109.5
C2—C3—H3'120.0H2'—C4—H4F109.0
C5—C3—H3'4.5H4A—C4—H4F56.3
C2—C4—H2'1.4H4B—C4—H4F56.3
C2—C4—H4A109.5H4C—C4—H4F141.1
H2'—C4—H4A108.1H4D—C4—H4F109.5
C2—C4—H4B109.5H4E—C4—H4F109.5
H2'—C4—H4B110.3C3—C5—H3'7.7
H4A—C4—H4B109.5H3'—C5—H5A116.4
C2—C4—H4C109.5H3'—C5—H5B103.1
H2'—C4—H4C109.9H3'—C5—H5C108.7
C3i—C1—C2—C30.3 (2)C1—C2—C3—C1i−0.3 (2)
O1—C1—C2—C3178.66 (12)C4—C2—C3—C1i179.88 (13)
C3i—C1—C2—C4−179.88 (13)C1—C2—C3—C5178.88 (14)
O1—C1—C2—C4−1.48 (19)C4—C2—C3—C5−1.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O···O1ii0.89 (2)1.92 (2)2.7833 (14)164.9 (18)

Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2613).

References

  • Close, R. E. & Oroshnik, W. (1977). US Patent No. 4055575
  • Mulhauser, M. & Chabardes, P. (1986). Eur. Patent No. 0177398
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yao, X. F. & Han, H. (1999). Hunan Huagong, A29, 14–16.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography