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Acta Cryst. (2007). E63, o3027    [ doi:10.1107/S1600536807025238 ]

Methyl 2,6-dimethoxybenzoate

G. Qadeer, N. H. Rama, M. A. Malik and M. Helliwell

Abstract top

The title compound, C10H12O4, is an important intermediate for the synthesis of biologically active heterocyclic compounds. The planar ester group is oriented with respect to the benzene ring at a dihedral angle of 81.46 (3)°.

Comment top

The title compound, (I), is a lachrymator and a drug intermediate. It is widely employed in synthetic organic chemistry for example; 2,6-dimehthoxybenzohydr- azide (Qadeer et al., 2007), 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In addition, methyl 4-(bromomethyl)benzoate has been used in the synthesis of 1-(carboxybenzyl)imidazole-5-acrylic acids, which are potent and selective angiotensin II receptor antagonists (Weinstock et al., 1991). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure.

The title molecule (Fig. 1) shows no unusual features when compared with the Mogul norms (Bruno et al., 2004). The dihedral angle between the planar ester group and benzene ring is 81.46 (3)°.

As can be seen from the packing diagram (Fig. 2), the molecules of (I) are stacked along the a axis and elongated along the b axis. Dipole-dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For general background, see: Qadeer et al. (2007); Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Ahmad et al. (2001); Al-Soud et al. (2004); El-Emam et al. (2004); Weinstock et al. (1991); Bruno et al. (2004).

Experimental top

For the preparation of (I), a mixture of methyl-2,6-dimethoxybenzoate (1.96 g, 10 mmol) and hydrazine hydrate (80%, 15 ml) in absolute ethanol (50 ml) was refluxed for 5 h at 413–423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol (30%) to give the title compound (yield: 91%). Colorless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement top

H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for aromatic H atoms.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I).
[Figure 3] Fig. 3. The synthesis route for the formation of the title compound.
methyl 2,6-dimethoxybenzoate top
Crystal data top
C10H12O4Dx = 1.317 Mg m−3
Mr = 196.20Melting point: 450(1) K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1609 reflections
a = 7.2306 (9) Åθ = 2.9–23.6°
b = 14.1058 (17) ŵ = 0.10 mm−1
c = 19.403 (2) ÅT = 100 K
V = 1978.9 (4) Å3Block, colourless
Z = 80.40 × 0.30 × 0.30 mm
F(000) = 832
Data collection top
Bruker APEXII
diffractometer		2033 independent reflections
Radiation source: fine-focus sealed tube1271 reflections with I > 2σ(I)
graphiteRint = 0.064
φ and ω scansθmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→9
Tmin = 0.960, Tmax = 0.970k = −17→15
10579 measured reflectionsl = −24→22
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-atom parameters constrained
S = 0.85 w = 1/[σ2(Fo2) + (0.0303P)2]
where P = (Fo2 + 2Fc2)/3
2033 reflections(Δ/σ)max < 0.001
130 parametersΔρmax = 0.17 e Å−3
0 restraintsΔρmin = −0.17 e Å−3
Crystal data top
C10H12O4V = 1978.9 (4) Å3
Mr = 196.20Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.2306 (9) ŵ = 0.10 mm−1
b = 14.1058 (17) ÅT = 100 K
c = 19.403 (2) Å0.40 × 0.30 × 0.30 mm
Data collection top
Bruker APEXII
diffractometer		1271 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.064
Tmin = 0.960, Tmax = 0.970θmax = 26.4°
10579 measured reflectionsStandard reflections: none
2033 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.076Δρmax = 0.17 e Å−3
S = 0.85Δρmin = −0.17 e Å−3
2033 reflectionsAbsolute structure: ?
130 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
O10.32641 (14)0.23587 (7)0.03432 (5)0.0274 (3)
O20.52183 (14)0.26194 (7)0.12196 (5)0.0305 (3)
O30.57947 (15)0.04433 (7)0.08234 (5)0.0343 (3)
O40.07719 (14)0.21697 (7)0.16359 (5)0.0272 (3)
C10.3235 (2)0.12555 (11)0.12428 (7)0.0230 (4)
C20.4173 (2)0.03933 (11)0.11826 (7)0.0276 (4)
C30.3440 (2)−0.04231 (11)0.14695 (8)0.0323 (4)
H30.4061−0.10130.14220.039*
C40.1787 (2)−0.03647 (12)0.18270 (8)0.0344 (4)
H40.1288−0.09240.20260.041*
C50.0838 (2)0.04769 (11)0.19046 (7)0.0303 (4)
H5−0.02870.05000.21570.036*
C60.1568 (2)0.12911 (11)0.16044 (7)0.0245 (4)
C70.4041 (2)0.21447 (10)0.09467 (7)0.0226 (4)
C80.3873 (2)0.32382 (11)0.00241 (8)0.0297 (4)
H8A0.36640.37670.03430.045*
H8B0.31710.3346−0.04010.045*
H8C0.51940.3195−0.00850.045*
C90.6844 (2)−0.04143 (12)0.07533 (9)0.0462 (5)
H9A0.7218−0.06390.12100.069*
H9B0.7948−0.02910.04740.069*
H9C0.6084−0.08990.05280.069*
C10−0.0943 (2)0.22482 (12)0.20085 (8)0.0341 (4)
H10A−0.18400.17960.18210.051*
H10B−0.14290.28940.19620.051*
H10C−0.07280.21090.24970.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0275 (6)0.0282 (7)0.0267 (5)−0.0047 (5)−0.0031 (5)0.0051 (5)
O20.0282 (6)0.0268 (7)0.0364 (6)−0.0056 (5)−0.0072 (5)0.0012 (5)
O30.0338 (7)0.0246 (7)0.0446 (7)0.0085 (5)0.0067 (6)0.0003 (5)
O40.0242 (6)0.0274 (7)0.0301 (6)0.0005 (5)0.0052 (5)0.0022 (5)
C10.0247 (9)0.0221 (9)0.0221 (8)−0.0016 (7)−0.0039 (7)−0.0006 (6)
C20.0288 (10)0.0266 (10)0.0273 (8)−0.0016 (8)−0.0045 (8)−0.0004 (7)
C30.0395 (11)0.0221 (10)0.0352 (9)0.0000 (8)−0.0078 (8)−0.0005 (7)
C40.0421 (11)0.0263 (10)0.0350 (9)−0.0121 (8)−0.0094 (8)0.0057 (8)
C50.0300 (10)0.0320 (10)0.0289 (8)−0.0085 (8)−0.0013 (7)0.0037 (7)
C60.0257 (9)0.0242 (9)0.0237 (8)−0.0030 (7)−0.0047 (7)−0.0006 (7)
C70.0198 (8)0.0221 (9)0.0260 (8)0.0044 (7)0.0012 (7)−0.0039 (7)
C80.0292 (10)0.0279 (10)0.0320 (9)0.0000 (8)0.0035 (7)0.0091 (7)
C90.0456 (12)0.0309 (11)0.0622 (12)0.0143 (9)0.0069 (10)−0.0013 (9)
C100.0269 (9)0.0396 (11)0.0358 (9)0.0027 (8)0.0091 (7)0.0041 (8)
Geometric parameters (Å, °) top
O1—C71.3335 (16)C4—C51.379 (2)
O1—C81.4548 (17)C4—H40.9500
O2—C71.2055 (17)C5—C61.392 (2)
O3—C21.3658 (18)C5—H50.9500
O3—C91.4345 (17)C8—H8A0.9800
O4—C61.3680 (17)C8—H8B0.9800
O4—C101.4397 (17)C8—H8C0.9800
C1—C61.3951 (19)C9—H9A0.9800
C1—C21.398 (2)C9—H9B0.9800
C1—C71.498 (2)C9—H9C0.9800
C2—C31.384 (2)C10—H10A0.9800
C3—C41.385 (2)C10—H10B0.9800
C3—H30.9500C10—H10C0.9800
C7—O1—C8116.06 (12)O2—C7—O1123.88 (14)
C2—O3—C9117.32 (12)O2—C7—C1124.86 (13)
C6—O4—C10117.04 (12)O1—C7—C1111.25 (13)
C6—C1—C2119.51 (14)O1—C8—H8A109.5
C6—C1—C7119.94 (13)O1—C8—H8B109.5
C2—C1—C7120.50 (14)H8A—C8—H8B109.5
O3—C2—C3125.22 (15)O1—C8—H8C109.5
O3—C2—C1114.49 (14)H8A—C8—H8C109.5
C3—C2—C1120.29 (15)H8B—C8—H8C109.5
C4—C3—C2118.84 (16)O3—C9—H9A109.5
C4—C3—H3120.6O3—C9—H9B109.5
C2—C3—H3120.6H9A—C9—H9B109.5
C5—C4—C3122.38 (16)O3—C9—H9C109.5
C5—C4—H4118.8H9A—C9—H9C109.5
C3—C4—H4118.8H9B—C9—H9C109.5
C4—C5—C6118.39 (16)O4—C10—H10A109.5
C4—C5—H5120.8O4—C10—H10B109.5
C6—C5—H5120.8H10A—C10—H10B109.5
O4—C6—C5124.68 (14)O4—C10—H10C109.5
O4—C6—C1114.74 (13)H10A—C10—H10C109.5
C5—C6—C1120.57 (15)H10B—C10—H10C109.5
C9—O3—C2—C3−1.7 (2)C4—C5—C6—O4179.56 (13)
C9—O3—C2—C1178.89 (13)C4—C5—C6—C1−0.9 (2)
C6—C1—C2—O3−179.47 (12)C2—C1—C6—O4179.59 (13)
C7—C1—C2—O3−1.9 (2)C7—C1—C6—O42.00 (19)
C6—C1—C2—C31.1 (2)C2—C1—C6—C50.0 (2)
C7—C1—C2—C3178.67 (13)C7—C1—C6—C5−177.57 (13)
O3—C2—C3—C4179.34 (13)C8—O1—C7—O2−2.0 (2)
C1—C2—C3—C4−1.3 (2)C8—O1—C7—C1176.88 (12)
C2—C3—C4—C50.4 (2)C6—C1—C7—O296.75 (18)
C3—C4—C5—C60.7 (2)C2—C1—C7—O2−80.82 (19)
C10—O4—C6—C50.1 (2)C6—C1—C7—O1−82.08 (16)
C10—O4—C6—C1−179.47 (12)C2—C1—C7—O1100.35 (16)
Acknowledgements top

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan, and also thank Javeed Akhtar for useful discussion of the crystal data.

references
References top

Ahmad, R., Iqbal, R., Akhtar, R. H., Haq, Z. U., Duddeck, H., Stefaniak, L. & Sitkowski, J. (2001). Nucleosides Nucleotides Nucleic Acids, 20, 1671–1682.

Al-Soud, Y. A., Al-Deeri, M. N. & Al-Mosoudi, N. A. (2004). Il Farmaco, 59, 775–783.

Al-Talib, M., Tastoush, H. & Odeh, N. (1990). Synth. Commun. 20, 1811–1814.

Bruker (1998). SMART. Version 5.630. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT (Version 6.36a) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004). J. Chem. Inf. Comput. Sci. 44, 2133–2144.

El-Emam, A. A., Al-Deeb, O. A., Al-Omar, M. & Lehmann, J. (2004). Bioorg. Med. Chem. 12, 5107–5113.

Qadeer, G., Rama, N. H. & Wong, W. Y. (2007). Acta Cryst. E63, o2892–?. [These authors do not match published paper - please check]

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Weinstock, J., Keenan, R. M., Samanen, J., Hempel, J., Finkelstein, J. A., Franz, R. G., Gaitanopoulos, D. E., Girard, G. R., Gleason, J. G., Hill, D. T., Morgan, T. M., Peishoff, C. E., Aiyar, N., Brooks, D. P., Fredrickson, T. A., Ohlstein, E. H., Ruffolo, R. R., Stack, E. J., Sulpizio, A. C., Weidley, E. F. & Edwards, R. M. (1991). J. Med. Chem. 34, 1514–1517.

Yousif, M. Y., Ismail, A. M., Elman, A. A. & El-Kerdawy, M. M. (1986). J. Chem. Soc. Pak. 8, 183–187.

Zheng, X., Li, Z., Wang, Y., Chen, W., Huang, Q., Liu, C. & Song, G. (2003). J. Fluorine Chem. 117, 163–169.