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ISSN: 2056-9890

2,3,5-Tri­methyl-1,4-hydro­quinone

aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
*Correspondence e-mail: haijiaoyiya@sina.com

(Received 27 November 2009; accepted 4 January 2010; online 9 January 2010)

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[Close, R. E. & Oroshnik, W. (1977). US Patent No. 4055575]); Mulhauser & Chabardes (1986[Mulhauser, M. & Chabardes, P. (1986). Eur. Patent No. 0177398]); Yao & Han (1999[Yao, X. F. & Han, H. (1999). Hunan Huagong, A29, 14-16.]).

[Scheme 1]

Experimental

Crystal data
  • C9H12O2

  • Mr = 152.19

  • Monoclinic, P 21 /n

  • 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.957, Tmax = 0.996

  • 3724 measured reflections

  • 905 independent reflections

  • 667 reflections with I > 2σ(I)

  • Rint = 0.031

  • Standard reflections: 0

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O1i 0.89 (2) 1.92 (2) 2.7833 (14) 164.9 (18)
Symmetry code: (i) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: RAPID-AUTO (Rigaku, 2004[Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 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
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
[Figure 2] Fig. 2. Presentation of the two-dimensional hydrogen-bonded network. Hydrogen bonds are shown as dashed lines.
2,3,5-Trimethyl-1,4-hydroquinone top
Crystal data top
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 top
Rigaku SPIDER
diffractometer
905 independent reflections
Radiation source: Rotating Anode667 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: ψ scan
(North et al., 1968)
h = 1010
Tmin = 0.957, Tmax = 0.996k = 66
3724 measured reflectionsl = 1313
Refinement top
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 = 1.00 w = 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
Crystal data top
C9H12O2V = 395.8 (3) Å3
Mr = 152.19Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.035 (4) ŵ = 0.09 mm1
b = 4.696 (2) ÅT = 93 K
c = 10.503 (5) Å0.50 × 0.23 × 0.05 mm
β = 92.813 (5)°
Data collection top
Rigaku SPIDER
diffractometer
905 independent reflections
Absorption correction: ψ scan
(North et al., 1968)
667 reflections with I > 2σ(I)
Tmin = 0.957, Tmax = 0.996Rint = 0.031
3724 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0401 restraint
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.17 e Å3
905 reflectionsΔρmin = 0.11 e Å3
62 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
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) top
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, º) top
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—C1i0.3 (2)
O1—C1—C2—C3178.66 (12)C4—C2—C3—C1i179.88 (13)
C3i—C1—C2—C4179.88 (13)C1—C2—C3—C5178.88 (14)
O1—C1—C2—C41.48 (19)C4—C2—C3—C51.0 (2)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O1ii0.89 (2)1.92 (2)2.7833 (14)164.9 (18)
Symmetry code: (ii) x+1/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC9H12O2
Mr152.19
Crystal system, space groupMonoclinic, P21/n
Temperature (K)93
a, b, c (Å)8.035 (4), 4.696 (2), 10.503 (5)
β (°) 92.813 (5)
V3)395.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.23 × 0.05
Data collection
DiffractometerRigaku SPIDER
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.957, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
3724, 905, 667
Rint0.031
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.081, 1.00
No. of reflections905
No. of parameters62
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.11

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O1i0.89 (2)1.92 (2)2.7833 (14)164.9 (18)
Symmetry code: (i) x+1/2, y1/2, z+3/2.
 

Acknowledgements

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

References

First citationClose, R. E. & Oroshnik, W. (1977). US Patent No. 4055575
First citationMulhauser, M. & Chabardes, P. (1986). Eur. Patent No. 0177398
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science
First citationRigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationYao, X. F. & Han, H. (1999). Hunan Huagong, A29, 14–16.

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ISSN: 2056-9890
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