2,3,5-Trimethyl-1,4-hydro­quinone

Dai, J.; Xie, M.-H.; Liu, Y.-L.; Zou, P.; Wu, H.

doi:10.1107/S1600536810000140

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o303

https://doi.org/10.1107/S1600536810000140

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2,3,5-Trimethyl-1,4-hydroquinone

Jun Dai,^a Min-Hao Xie,^a Ya-Ling Liu,^a Pei Zou ^a and Hao Wu ^a ^*

^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 ); Mulhauser & Chabardes (1986 ); Yao & Han (1999 ).

Experimental

Crystal data

C₉H₁₂O₂
M_r = 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 ) 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[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
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 I, global. DOI: https://doi.org/10.1107/S1600536810000140/hg2613sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000140/hg2613Isup2.hkl

checkCIF report

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).

Structure description top

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

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

	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.

2,3,5-Trimethyl-1,4-hydroquinone top

Crystal data top

C₉H₁₂O₂	F(000) = 164
M_r = 152.19	D_x = 1.277 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 442(2) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.035 (4) Å	Cell parameters from 930 reflections
b = 4.696 (2) Å	θ = 3.1–27.5°
c = 10.503 (5) Å	µ = 0.09 mm⁻¹
β = 92.813 (5)°	T = 93 K
V = 395.8 (3) Å³	Platelet, colorless
Z = 2	0.50 × 0.23 × 0.05 mm

Data collection top

Rigaku SPIDER diffractometer	905 independent reflections
Radiation source: Rotating Anode	667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: ψ scan (North et al., 1968)	h = −10→10
T_min = 0.957, T_max = 0.996	k = −6→6
3724 measured reflections	l = −13→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0146P)² + 0.186P] where P = (F_o² + 2F_c²)/3
905 reflections	(Δ/σ)_max < 0.001
62 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₉H₁₂O₂	V = 395.8 (3) Å³
M_r = 152.19	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.035 (4) Å	µ = 0.09 mm⁻¹
b = 4.696 (2) Å	T = 93 K
c = 10.503 (5) Å	0.50 × 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)
T_min = 0.957, T_max = 0.996	R_int = 0.031
3724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.17 e Å⁻³
905 reflections	Δρ_min = −0.11 e Å⁻³
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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.26338 (14)	0.4290 (2)	0.68009 (10)	0.0409 (3)
C1	0.38434 (19)	0.4579 (3)	0.58997 (12)	0.0326 (3)
C2	0.34638 (18)	0.6452 (3)	0.48939 (13)	0.0326 (3)
C3	0.46482 (19)	0.6852 (3)	0.39874 (12)	0.0325 (3)
H2'	0.2427	0.7424	0.4831	0.039*	0.100 (3)
H3'	0.4422	0.8107	0.3291	0.039*	0.401 (3)
C4	0.1823 (2)	0.8010 (4)	0.47751 (16)	0.0414 (5)	0.900 (3)
H4A	0.1143	0.7487	0.5489	0.050*	0.4501 (15)
H4B	0.1233	0.7487	0.3970	0.050*	0.4501 (15)
H4C	0.2025	1.0068	0.4790	0.050*	0.4501 (15)
H4D	0.1791	0.9207	0.4010	0.050*	0.4501 (15)
H4E	0.1701	0.9207	0.5529	0.050*	0.4501 (15)
H4F	0.0909	0.6627	0.4709	0.050*	0.4501 (15)
C5	0.4153 (3)	0.8844 (5)	0.2919 (2)	0.0353 (7)	0.599 (3)
H5A	0.2957	0.8652	0.2707	0.042*	0.599 (3)
H5B	0.4779	0.8375	0.2169	0.042*	0.599 (3)
H5C	0.4400	1.0808	0.3182	0.042*	0.599 (3)
H1O	0.273 (2)	0.263 (5)	0.7202 (18)	0.072 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0545 (7)	0.0301 (6)	0.0389 (6)	0.0038 (5)	0.0109 (5)	0.0004 (5)
C1	0.0468 (9)	0.0222 (7)	0.0290 (7)	−0.0009 (6)	0.0030 (6)	−0.0044 (5)
C2	0.0429 (8)	0.0217 (7)	0.0326 (7)	0.0022 (6)	−0.0034 (6)	−0.0049 (5)
C3	0.0493 (9)	0.0201 (7)	0.0276 (7)	0.0017 (6)	−0.0033 (6)	−0.0012 (5)
C4	0.0475 (11)	0.0346 (9)	0.0417 (9)	0.0054 (8)	−0.0014 (8)	0.0013 (7)
C5	0.0434 (14)	0.0308 (13)	0.0314 (12)	−0.0034 (11)	−0.0004 (10)	0.0051 (10)

Geometric parameters (Å, º) top

O1—C1	1.3961 (17)	C4—H4A	0.9800
O1—H1O	0.89 (2)	C4—H4B	0.9800
C1—C3ⁱ	1.386 (2)	C4—H4C	0.9800
C1—C2	1.3968 (19)	C4—H4D	0.9800
C2—C3	1.392 (2)	C4—H4E	0.9800
C2—C4	1.508 (2)	C4—H4F	0.9800
C2—H2'	0.9498	C5—H3'	0.5575
C3—C1ⁱ	1.386 (2)	C5—H5A	0.9800
C3—C5	1.500 (3)	C5—H5B	0.9800
C3—H3'	0.9500	C5—H5C	0.9800
C4—H2'	0.5584

C1—O1—H1O	111.0 (12)	H4A—C4—H4C	109.5
C3ⁱ—C1—O1	122.01 (13)	H4B—C4—H4C	109.5
C3ⁱ—C1—C2	121.85 (13)	C2—C4—H4D	109.5
O1—C1—C2	116.13 (13)	H2'—C4—H4D	110.8
C3—C2—C1	118.12 (13)	H4A—C4—H4D	141.1
C3—C2—C4	120.17 (13)	H4B—C4—H4D	56.3
C1—C2—C4	121.72 (14)	H4C—C4—H4D	56.3
C3—C2—H2'	121.0	C2—C4—H4E	109.5
C1—C2—H2'	120.9	H2'—C4—H4E	108.6
C4—C2—H2'	0.8	H4A—C4—H4E	56.3
C1ⁱ—C3—C2	120.04 (12)	H4B—C4—H4E	141.1
C1ⁱ—C3—C5	124.41 (15)	H4C—C4—H4E	56.3
C2—C3—C5	115.54 (15)	H4D—C4—H4E	109.5
C1ⁱ—C3—H3'	120.0	C2—C4—H4F	109.5
C2—C3—H3'	120.0	H2'—C4—H4F	109.0
C5—C3—H3'	4.5	H4A—C4—H4F	56.3
C2—C4—H2'	1.4	H4B—C4—H4F	56.3
C2—C4—H4A	109.5	H4C—C4—H4F	141.1
H2'—C4—H4A	108.1	H4D—C4—H4F	109.5
C2—C4—H4B	109.5	H4E—C4—H4F	109.5
H2'—C4—H4B	110.3	C3—C5—H3'	7.7
H4A—C4—H4B	109.5	H3'—C5—H5A	116.4
C2—C4—H4C	109.5	H3'—C5—H5B	103.1
H2'—C4—H4C	109.9	H3'—C5—H5C	108.7

C3ⁱ—C1—C2—C3	0.3 (2)	C1—C2—C3—C1ⁱ	−0.3 (2)
O1—C1—C2—C3	178.66 (12)	C4—C2—C3—C1ⁱ	179.88 (13)
C3ⁱ—C1—C2—C4	−179.88 (13)	C1—C2—C3—C5	178.88 (14)
O1—C1—C2—C4	−1.48 (19)	C4—C2—C3—C5	−1.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1ⁱⁱ	0.89 (2)	1.92 (2)	2.7833 (14)	164.9 (18)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₂O₂
M_r	152.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	93
a, b, c (Å)	8.035 (4), 4.696 (2), 10.503 (5)
β (°)	92.813 (5)
V (Å³)	395.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.23 × 0.05

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.957, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	3724, 905, 667
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.081, 1.00
No. of reflections	905
No. of parameters	62
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1ⁱ	0.89 (2)	1.92 (2)	2.7833 (14)	164.9 (18)

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

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

References

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