PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1970.
Published online 2008 September 20. doi:  10.1107/S1600536808029541
PMCID: PMC2959309

Methyl 2,5-dichloro­benzoate

Abstract

In the mol­ecule of the title compound, C8H6Cl2O2, the benzene ring is oriented with respect to the planar ester group at a dihedral angle of 39.22 (3)°.

Related literature

For general background, see: Zheng et al. (2003 [triangle]); Al-Talib et al. (1990 [triangle]); Yousif et al. (1986 [triangle]); Ahmad et al. (2001 [triangle]); Al-Soud et al. (2004 [triangle]); El-Emam et al. (2004 [triangle]); Weinstock et al. (1991 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]); and of MOGUL, see: Bruno et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1970-scheme1.jpg

Experimental

Crystal data

  • C8H6Cl2O2
  • M r = 205.03
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1970-efi1.jpg
  • a = 3.8452 (3) Å
  • b = 7.0158 (4) Å
  • c = 15.8510 (10) Å
  • α = 77.189 (6)°
  • β = 89.130 (7)°
  • γ = 83.741 (5)°
  • V = 414.46 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.73 mm−1
  • T = 150 (1) K
  • 0.68 × 0.11 × 0.06 mm

Data collection

  • Bruker–Nonius Kappa CCD area-detector diffractometer
  • Absorption correction: Gaussian (Coppens, 1970 [triangle]) T min = 0.864, T max = 0.971
  • 5966 measured reflections
  • 1840 independent reflections
  • 1455 reflections with I > 2σ(I)
  • R int = 0.110

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.146
  • S = 1.09
  • 1840 reflections
  • 109 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.57 e Å−3

Data collection: COLLECT (Hooft, 1998 [triangle])and DENZO (Otwin­owski & Minor, 1997 [triangle]); cell refinement: DIRAX/LSQ (Duisenberg, 1992) [triangle]); data reduction: EvalCCD (Duisenberg, 1992) [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808029541/hk2533sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029541/hk2533Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan, and also thank the Ministry of Education of the Czech Republic for financial support (project No. VZ0021627501).

supplementary crystallographic information

Comment

The title compound is a lachrymator and a drug intermediate. Methyl 2,5-di- chlorobenzoate is widely employed in synthetic organic chemistry for example, 2,5-dichlorobenzohydrazide, 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, and report herein its crystal structure.

In the molecule of the title compound, (Fig. 1), the bond lengths and angles are generally within normal ranges (Cambridge Structural Database, Version 5.28, November 2006; Mogul Version 1.1; Allen, 2002, Bruno et al., 2004). The benzene ring (C1-C6) is oriented with respect to the planar ester group (O1/O2/C1/C7/C8) at a dihedral angle of 39.22 (3)°.

Experimental

For the preparation of the title compound, the mixture of 2,5-dichlorobenzoic acid (2.05 g, 10 mmol) and absolute methanol (50 ml) in the presence of a few drops of suphuric acid was refluxed for 5 h. The excess of solvent was removed by distillation. The solid residue for filltered off, washed with water and recystallized from ethanol (30%) to give the title compound (yied; 88%, m.p. 319-321 K). Suitable single crystals of the title compound were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Reaction scheme.

Crystal data

C8H6Cl2O2Z = 2
Mr = 205.03F(000) = 208
Triclinic, P1Dx = 1.643 Mg m3
Hall symbol: -P 1Melting point: 319(2) K
a = 3.8452 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.0158 (4) ÅCell parameters from 6024 reflections
c = 15.851 (1) Åθ = 1–27.5°
α = 77.189 (6)°µ = 0.73 mm1
β = 89.130 (7)°T = 150 K
γ = 83.741 (5)°Needle, colorless
V = 414.46 (5) Å30.68 × 0.11 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer1840 independent reflections
Radiation source: fine-focus sealed tube1455 reflections with I > 2σ(I)
graphiteRint = 0.110
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.6°
[var phi] and ω scansh = −4→4
Absorption correction: gaussian (Coppens, 1970)k = −9→8
Tmin = 0.864, Tmax = 0.971l = −20→20
5966 measured reflections

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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 1.10w = 1/[σ2(Fo2) + (0.0527P)2 + 0.5264P] where P = (Fo2 + 2Fc2)/3
1840 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = −0.57 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*/Ueq
Cl10.6965 (2)0.52269 (12)0.70713 (5)0.0309 (2)
Cl21.3585 (2)−0.28182 (13)0.92310 (5)0.0361 (3)
O10.6439 (7)−0.0150 (4)0.62680 (14)0.0347 (6)
O20.8542 (6)0.2744 (4)0.57949 (13)0.0288 (5)
C10.9066 (8)0.1286 (5)0.72871 (18)0.0220 (6)
C20.8841 (8)0.2952 (5)0.76262 (19)0.0235 (6)
C31.0100 (9)0.2857 (5)0.8458 (2)0.0278 (7)
H30.99540.39830.86800.033*
C41.1574 (9)0.1080 (5)0.89485 (19)0.0286 (7)
H41.24350.10060.95010.034*
C51.1755 (8)−0.0580 (5)0.8613 (2)0.0257 (7)
C61.0489 (8)−0.0510 (5)0.77933 (19)0.0245 (6)
H61.0581−0.16480.75810.029*
C70.7825 (8)0.1206 (5)0.64006 (18)0.0229 (6)
C80.7421 (9)0.2749 (5)0.49289 (19)0.0294 (7)
H8A0.85090.15930.47610.035*
H8B0.80890.38980.45360.035*
H8C0.49240.27570.49140.035*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0411 (5)0.0249 (4)0.0250 (4)0.0029 (3)−0.0044 (3)−0.0047 (3)
Cl20.0429 (5)0.0328 (5)0.0276 (4)0.0027 (4)−0.0115 (3)0.0014 (3)
O10.0496 (16)0.0344 (14)0.0231 (11)−0.0124 (11)−0.0066 (10)−0.0089 (10)
O20.0368 (13)0.0354 (13)0.0137 (10)−0.0082 (10)−0.0056 (8)−0.0017 (9)
C10.0214 (15)0.0287 (16)0.0156 (13)−0.0036 (12)−0.0005 (10)−0.0039 (11)
C20.0233 (15)0.0256 (16)0.0205 (14)−0.0043 (12)−0.0010 (11)−0.0021 (12)
C30.0331 (18)0.0295 (18)0.0230 (15)−0.0050 (13)−0.0007 (12)−0.0096 (13)
C40.0336 (18)0.0348 (18)0.0172 (14)−0.0055 (14)−0.0045 (12)−0.0042 (12)
C50.0233 (16)0.0303 (17)0.0206 (14)−0.0028 (12)−0.0014 (11)0.0003 (12)
C60.0302 (17)0.0236 (16)0.0205 (14)−0.0008 (12)−0.0026 (11)−0.0073 (12)
C70.0257 (15)0.0265 (16)0.0166 (13)0.0004 (12)−0.0013 (11)−0.0062 (11)
C80.0367 (19)0.0368 (19)0.0141 (13)0.0003 (14)−0.0047 (12)−0.0061 (12)

Geometric parameters (Å, °)

Cl1—C21.728 (3)C3—H30.9300
Cl2—C51.737 (3)C4—C31.382 (5)
O1—C71.199 (4)C4—C51.378 (5)
O2—C71.326 (4)C4—H40.9300
O2—C81.444 (3)C5—C61.384 (4)
C1—C21.385 (5)C6—H60.9301
C1—C61.395 (4)C8—H8A0.9600
C1—C71.505 (4)C8—H8B0.9600
C2—C31.396 (4)C8—H8C0.9600
C7—O2—C8115.5 (3)C4—C5—Cl2119.7 (2)
C2—C1—C6119.3 (3)C6—C5—Cl2118.9 (3)
C2—C1—C7125.6 (3)C5—C6—C1119.3 (3)
C6—C1—C7115.1 (3)C5—C6—H6120.4
C1—C2—Cl1123.1 (2)C1—C6—H6120.2
C1—C2—C3120.7 (3)O1—C7—O2124.7 (3)
C3—C2—Cl1116.3 (3)O1—C7—C1122.4 (3)
C4—C3—C2119.7 (3)O2—C7—C1112.9 (3)
C4—C3—H3120.1O2—C8—H8A109.4
C2—C3—H3120.3O2—C8—H8B109.5
C5—C4—C3119.5 (3)H8A—C8—H8B109.5
C5—C4—H4120.3O2—C8—H8C109.5
C3—C4—H4120.2H8A—C8—H8C109.5
C4—C5—C6121.4 (3)H8B—C8—H8C109.5

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2533).

References

  • Ahmad, R., Iqbal, R., Akhtar, R. H., Haq, Z. U., Duddeck, H., Stefaniak, L. & Sitkowski, J. (2001). Nucleosides Nucleotides Nucleic Acids, 20, 1671–1682. [PubMed]
  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Al-Soud, Y. A., Al-Deeri, M. N. & Al-Mosoudi, N. A. (2004). Farmaco, 59, 775–783. [PubMed]
  • Al-Talib, M., Tastoush, H. & Odeh, N. (1990). Synth. Commun.20, 1811–1814.
  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst 27, 435-436.
  • 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. [PubMed]
  • Coppens, P. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 255–270. Copenhagen: Munksgaard.
  • Duisenberg, A. J. M. (1992). J. Appl. Cryst.25, 92–96.
  • El-Emam, A. A., Al-Deeb, O. A., Al-Omar, M. & Lehmann, J. (2004). Bioorg. Med. Chem.12, 5107–5113. [PubMed]
  • Hooft, R. (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Weinstock, J. et al. (1991). J. Med. Chem.34, 1514–1517. [PubMed]
  • 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.

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