Dimethyl 2,6-dihydroxy­benzene-1,4-dicarboxyl­ate

Zhao, D.; Wang, K.; Zhang, J.; Jin, N.

doi:10.1107/S1600536810011074

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o981

doi:10.1107/S1600536810011074

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Dimethyl 2,6-dihydroxybenzene-1,4-dicarboxylate

Deming Zhao,^a ^* Kun Wang,^a Jianting Zhang ^a and Ningren Jin ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: dmzhao@zjut.edu.cn

(Received 3 February 2010; accepted 24 March 2010; online 31 March 2010)

The title compound, C₁₀H₁₀O₆, was obtained from an esterification reaction of 2,6-dihydroxyterephthalic acid and methanol. In the molecular structure, all of the C atoms are nearly coplanar. The two hydroxy groups have C2 symmetry. Intramolecular O—H⋯O hydrogen bonds are observed. In the crystal, weak O—H⋯O interactions link the molecules.

Related literature

For general background to terephthalate derivatives, see: Brunner (1928 ); Teruhiko et al. (1998 ). For a related structure, see: Dai et al. (2005 ).

Experimental

Crystal data

C₁₀H₁₀O₆
M_r = 226.18
Monoclinic, P 2₁ /c
a = 11.6462 (8) Å
b = 7.0925 (3) Å
c = 13.5745 (10) Å
β = 114.327 (9)°
V = 1021.70 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.34 × 0.26 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.865, T_max = 1.000
4572 measured reflections
2083 independent reflections
1161 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.178
S = 1.09
2083 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.84	2.567 (3)	147
O4—H4⋯O1	0.82	1.89	2.593 (3)	144
O4—H4⋯O3ⁱ	0.82	2.58	3.099 (3)	123
Symmetry code: (i) x, y+1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011074/gw2078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810011074/gw2078Isup2.hkl

checkCIF report

Comment top

The title compound as one of terephthalate derivatives, is an important pharmacological and material intermediate (Brunner, 1928; Teruhiko et al., 1998). There is almost no report about crystal structure. As part of our ongoing studies, we now describe the synthesis and the crystal structure of the title compound. In this paper, the crystal structure of it was determined (Fig. 1). The molecule contains benzene ring, dihydroxygroup and dimethyl group. All of atoms except the hydrogen atoms are nearly coplanar. The terminal dimethyl group are centrosymmetric. The dihydroxy group are axisymmetric. In the crystal structure, intramolecular O—H···O hydrogen bonds are observed.

Related literature top

For general background to terephthalate derivatives, see: Brunner (1928); Teruhiko et al. (1998). For a related structure, see: Dai et al. (2005).

Experimental top

2,6-dihydroxyterephthalic acid (15 mmol) was dissolved in methanol (45 ml), thionyl dichloride (3 ml) was slowly added to the methanol solution afterward, and the mixture was stired at reflux temperature for 72 hours (monitored by TLC). Then the solvent was distilled under vacuum, and the residue was poured into water (50 ml). The pH of the solution was adjusted with sodium bicarbonate to pH = 7.0. The resulting white solid was filtered off, washed with water. The obtained solid was dissolved in methanol. Single crystals were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The asymmetric unit of the structure of the title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecule packing of the title compound showing O—H···O interactions.

Dimethyl 2,6-dihydroxybenzene-1,4-dicarboxylate top

Crystal data top

C₁₀H₁₀O₆	F(000) = 472
M_r = 226.18	D_x = 1.470 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1855 reflections
a = 11.6462 (8) Å	θ = 2.9–29.2°
b = 7.0925 (3) Å	µ = 0.12 mm⁻¹
c = 13.5745 (10) Å	T = 293 K
β = 114.327 (9)°	Block, white
V = 1021.70 (11) Å³	0.34 × 0.26 × 0.20 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer	2083 independent reflections
Radiation source: fine-focus sealed tube	1161 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 16.0395 pixels mm^-1	θ_max = 26.4°, θ_min = 3.3°
ω scans	h = −14→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→8
T_min = 0.865, T_max = 1.000	l = −16→15
4572 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0906P)² + 0.0929P] where P = (F_o² + 2F_c²)/3
2083 reflections	(Δ/σ)_max = 0.002
149 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₀O₆	V = 1021.70 (11) Å³
M_r = 226.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6462 (8) Å	µ = 0.12 mm⁻¹
b = 7.0925 (3) Å	T = 293 K
c = 13.5745 (10) Å	0.34 × 0.26 × 0.20 mm
β = 114.327 (9)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer	2083 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1161 reflections with I > 2σ(I)
T_min = 0.865, T_max = 1.000	R_int = 0.023
4572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.09	Δρ_max = 0.26 e Å⁻³
2083 reflections	Δρ_min = −0.21 e Å⁻³
149 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	1.10292 (17)	0.3212 (3)	0.65789 (15)	0.0531 (6)
O2	1.16658 (17)	0.0296 (3)	0.71430 (17)	0.0594 (6)
O3	1.00830 (17)	−0.2437 (3)	0.65185 (18)	0.0588 (6)
H3	1.0760	−0.1914	0.6860	0.088*
O4	0.8686 (2)	0.3940 (3)	0.5366 (2)	0.0694 (7)
H4	0.9419	0.4218	0.5747	0.104*
O5	0.48877 (19)	−0.0097 (4)	0.36441 (19)	0.0809 (8)
O6	0.55844 (19)	−0.2972 (3)	0.42310 (17)	0.0622 (6)
C1	1.2310 (3)	0.3910 (5)	0.7143 (3)	0.0605 (9)
H1A	1.2712	0.3957	0.6652	0.091*
H1C	1.2773	0.3082	0.7733	0.091*
H1B	1.2290	0.5152	0.7417	0.091*
C2	1.0826 (2)	0.1371 (4)	0.6627 (2)	0.0418 (6)
C3	0.9508 (2)	0.0794 (3)	0.6008 (2)	0.0370 (6)
C4	0.9197 (2)	−0.1122 (3)	0.5979 (2)	0.0393 (6)
C5	0.7983 (2)	−0.1768 (4)	0.5401 (2)	0.0395 (6)
H5	0.7798	−0.3044	0.5397	0.047*
C6	0.7048 (2)	−0.0498 (4)	0.4829 (2)	0.0391 (6)
C7	0.7314 (2)	0.1397 (4)	0.4830 (2)	0.0449 (7)
H7	0.6675	0.2237	0.4438	0.054*
C8	0.8531 (2)	0.2059 (3)	0.5412 (2)	0.0430 (7)
C9	0.5725 (3)	−0.1122 (4)	0.4170 (2)	0.0476 (7)
C10	0.4355 (3)	−0.3758 (5)	0.3582 (3)	0.0769 (11)
H10A	0.4105	−0.3402	0.2840	0.115*
H10B	0.3752	−0.3286	0.3835	0.115*
H10C	0.4392	−0.5108	0.3641	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0335 (11)	0.0493 (12)	0.0635 (13)	−0.0079 (9)	0.0067 (10)	−0.0032 (10)
O2	0.0326 (10)	0.0563 (12)	0.0718 (14)	0.0062 (9)	0.0039 (10)	0.0043 (11)
O3	0.0360 (11)	0.0445 (11)	0.0775 (14)	0.0103 (9)	0.0048 (10)	0.0115 (11)
O4	0.0480 (13)	0.0347 (11)	0.0953 (18)	0.0029 (9)	−0.0010 (12)	0.0016 (11)
O5	0.0340 (11)	0.0803 (17)	0.0952 (19)	0.0052 (12)	−0.0068 (12)	0.0146 (14)
O6	0.0367 (11)	0.0582 (14)	0.0749 (15)	−0.0086 (10)	0.0062 (10)	−0.0071 (11)
C1	0.0382 (16)	0.070 (2)	0.0634 (19)	−0.0148 (15)	0.0108 (15)	−0.0065 (17)
C2	0.0343 (14)	0.0434 (16)	0.0428 (15)	0.0023 (12)	0.0111 (12)	−0.0003 (13)
C3	0.0298 (13)	0.0377 (14)	0.0389 (14)	0.0039 (11)	0.0094 (11)	−0.0029 (11)
C4	0.0333 (14)	0.0376 (15)	0.0430 (15)	0.0079 (11)	0.0116 (12)	0.0029 (12)
C5	0.0341 (15)	0.0331 (13)	0.0464 (15)	0.0031 (11)	0.0116 (13)	−0.0024 (12)
C6	0.0312 (14)	0.0421 (15)	0.0390 (14)	0.0021 (11)	0.0096 (12)	−0.0025 (11)
C7	0.0298 (14)	0.0459 (17)	0.0460 (16)	0.0130 (12)	0.0026 (12)	0.0021 (13)
C8	0.0366 (15)	0.0346 (15)	0.0498 (16)	0.0029 (11)	0.0097 (13)	−0.0027 (12)
C9	0.0322 (15)	0.0552 (19)	0.0487 (17)	0.0008 (14)	0.0098 (13)	−0.0040 (14)
C10	0.0425 (19)	0.090 (3)	0.084 (2)	−0.0231 (18)	0.0110 (18)	−0.024 (2)

Geometric parameters (Å, º) top

O1—C2	1.334 (3)	C2—C3	1.472 (4)
O1—C1	1.454 (3)	C3—C4	1.403 (3)
O2—C2	1.210 (3)	C3—C8	1.413 (3)
O3—C4	1.360 (3)	C4—C5	1.382 (3)
O3—H3	0.8200	C5—C6	1.379 (3)
O4—C8	1.351 (3)	C5—H5	0.9300
O4—H4	0.8200	C6—C7	1.379 (4)
O5—C9	1.190 (3)	C6—C9	1.495 (4)
O6—C9	1.329 (3)	C7—C8	1.389 (4)
O6—C10	1.449 (3)	C7—H7	0.9300
C1—H1A	0.9600	C10—H10A	0.9600
C1—H1C	0.9600	C10—H10B	0.9600
C1—H1B	0.9600	C10—H10C	0.9600

C2—O1—C1	118.1 (2)	C6—C5—H5	120.4
C4—O3—H3	109.5	C4—C5—H5	120.4
C8—O4—H4	109.5	C7—C6—C5	120.8 (2)
C9—O6—C10	117.3 (3)	C7—C6—C9	117.7 (2)
O1—C1—H1A	109.5	C5—C6—C9	121.6 (2)
O1—C1—H1C	109.5	C6—C7—C8	120.4 (2)
H1A—C1—H1C	109.5	C6—C7—H7	119.8
O1—C1—H1B	109.5	C8—C7—H7	119.8
H1A—C1—H1B	109.5	O4—C8—C7	115.6 (2)
H1C—C1—H1B	109.5	O4—C8—C3	124.2 (2)
O2—C2—O1	121.8 (2)	C7—C8—C3	120.3 (2)
O2—C2—C3	124.1 (2)	O5—C9—O6	123.3 (3)
O1—C2—C3	114.1 (2)	O5—C9—C6	124.5 (3)
C4—C3—C8	117.4 (2)	O6—C9—C6	112.2 (2)
C4—C3—C2	118.8 (2)	O6—C10—H10A	109.5
C8—C3—C2	123.8 (2)	O6—C10—H10B	109.5
O3—C4—C5	116.8 (2)	H10A—C10—H10B	109.5
O3—C4—C3	121.3 (2)	O6—C10—H10C	109.5
C5—C4—C3	121.9 (2)	H10A—C10—H10C	109.5
C6—C5—C4	119.3 (2)	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.84	2.567 (3)	147
O4—H4···O1	0.82	1.89	2.593 (3)	144
O4—H4···O3ⁱ	0.82	2.58	3.099 (3)	123

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀O₆
M_r	226.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.6462 (8), 7.0925 (3), 13.5745 (10)
β (°)	114.327 (9)
V (Å³)	1021.70 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.34 × 0.26 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.865, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4572, 2083, 1161
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.178, 1.09
No. of reflections	2083
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.84	2.567 (3)	147.0
O4—H4···O1	0.82	1.89	2.593 (3)	143.8
O4—H4···O3ⁱ	0.82	2.58	3.099 (3)	122.5

Symmetry code: (i) x, y+1, z.

Acknowledgements

This work was supported by the Key Science and Technology Research Program of Jiangsu Province (BE 2006077) and the Academic Foundation of Zhejiang University of Technology (No. 20090101).

References

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