Acta Cryst. (2008). E64, o1970 [ doi:10.1107/S1600536808029541 ]
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)°.
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.
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).
Data collection: COLLECT (Hooft, 1998); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hk2533fig1thm.gif)
| 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]](./hk2533fig2thm.gif)
| Fig. 2. Reaction scheme. |
| C8H6Cl2O2 | Z = 2 |
| Mr = 205.03 | F(000) = 208 |
| Triclinic, P1 | Dx = 1.643 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 319(2) K |
| a = 3.8452 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 7.0158 (4) Å | Cell parameters from 6024 reflections |
| c = 15.851 (1) Å | θ = 1–27.5° |
| α = 77.189 (6)° | µ = 0.73 mm−1 |
| β = 89.130 (7)° | T = 150 K |
| γ = 83.741 (5)° | Needle, colorless |
| V = 414.46 (5) Å3 | 0.68 × 0.11 × 0.06 mm |
| Bruker–Nonius KappaCCD area-detector diffractometer | 1840 independent reflections |
| Radiation source: fine-focus sealed tube | 1455 reflections with I > 2σ(I) |
| graphite | Rint = 0.110 |
| Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
| φ and ω scans | h = −4→4 |
| Absorption correction: gaussian (Coppens, 1970) | k = −9→8 |
| Tmin = 0.864, Tmax = 0.971 | l = −20→20 |
| 5966 measured reflections |
| 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.146 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.5264P] where P = (Fo2 + 2Fc2)/3 |
| 1840 reflections | (Δ/σ)max < 0.001 |
| 109 parameters | Δρmax = 0.44 e Å−3 |
| 0 restraints | Δρmin = −0.57 e Å−3 |
| C8H6Cl2O2 | γ = 83.741 (5)° |
| Mr = 205.03 | V = 414.46 (5) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 3.8452 (3) Å | Mo Kα radiation |
| b = 7.0158 (4) Å | µ = 0.73 mm−1 |
| c = 15.851 (1) Å | T = 150 K |
| α = 77.189 (6)° | 0.68 × 0.11 × 0.06 mm |
| β = 89.130 (7)° |
| Bruker–Nonius KappaCCD area-detector diffractometer | 1840 independent reflections |
| Absorption correction: gaussian (Coppens, 1970) | 1455 reflections with I > 2σ(I) |
| Tmin = 0.864, Tmax = 0.971 | Rint = 0.110 |
| 5966 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.146 | Δρmax = 0.44 e Å−3 |
| S = 1.10 | Δρmin = −0.57 e Å−3 |
| 1840 reflections | Absolute structure: ? |
| 109 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.6965 (2) | 0.52269 (12) | 0.70713 (5) | 0.0309 (2) | |
| Cl2 | 1.3585 (2) | −0.28182 (13) | 0.92310 (5) | 0.0361 (3) | |
| O1 | 0.6439 (7) | −0.0150 (4) | 0.62680 (14) | 0.0347 (6) | |
| O2 | 0.8542 (6) | 0.2744 (4) | 0.57949 (13) | 0.0288 (5) | |
| C1 | 0.9066 (8) | 0.1286 (5) | 0.72871 (18) | 0.0220 (6) | |
| C2 | 0.8841 (8) | 0.2952 (5) | 0.76262 (19) | 0.0235 (6) | |
| C3 | 1.0100 (9) | 0.2857 (5) | 0.8458 (2) | 0.0278 (7) | |
| H3 | 0.9954 | 0.3983 | 0.8680 | 0.033* | |
| C4 | 1.1574 (9) | 0.1080 (5) | 0.89485 (19) | 0.0286 (7) | |
| H4 | 1.2435 | 0.1006 | 0.9501 | 0.034* | |
| C5 | 1.1755 (8) | −0.0580 (5) | 0.8613 (2) | 0.0257 (7) | |
| C6 | 1.0489 (8) | −0.0510 (5) | 0.77933 (19) | 0.0245 (6) | |
| H6 | 1.0581 | −0.1648 | 0.7581 | 0.029* | |
| C7 | 0.7825 (8) | 0.1206 (5) | 0.64006 (18) | 0.0229 (6) | |
| C8 | 0.7421 (9) | 0.2749 (5) | 0.49289 (19) | 0.0294 (7) | |
| H8A | 0.8509 | 0.1593 | 0.4761 | 0.035* | |
| H8B | 0.8089 | 0.3898 | 0.4536 | 0.035* | |
| H8C | 0.4924 | 0.2757 | 0.4914 | 0.035* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0411 (5) | 0.0249 (4) | 0.0250 (4) | 0.0029 (3) | −0.0044 (3) | −0.0047 (3) |
| Cl2 | 0.0429 (5) | 0.0328 (5) | 0.0276 (4) | 0.0027 (4) | −0.0115 (3) | 0.0014 (3) |
| O1 | 0.0496 (16) | 0.0344 (14) | 0.0231 (11) | −0.0124 (11) | −0.0066 (10) | −0.0089 (10) |
| O2 | 0.0368 (13) | 0.0354 (13) | 0.0137 (10) | −0.0082 (10) | −0.0056 (8) | −0.0017 (9) |
| C1 | 0.0214 (15) | 0.0287 (16) | 0.0156 (13) | −0.0036 (12) | −0.0005 (10) | −0.0039 (11) |
| C2 | 0.0233 (15) | 0.0256 (16) | 0.0205 (14) | −0.0043 (12) | −0.0010 (11) | −0.0021 (12) |
| C3 | 0.0331 (18) | 0.0295 (18) | 0.0230 (15) | −0.0050 (13) | −0.0007 (12) | −0.0096 (13) |
| C4 | 0.0336 (18) | 0.0348 (18) | 0.0172 (14) | −0.0055 (14) | −0.0045 (12) | −0.0042 (12) |
| C5 | 0.0233 (16) | 0.0303 (17) | 0.0206 (14) | −0.0028 (12) | −0.0014 (11) | 0.0003 (12) |
| C6 | 0.0302 (17) | 0.0236 (16) | 0.0205 (14) | −0.0008 (12) | −0.0026 (11) | −0.0073 (12) |
| C7 | 0.0257 (15) | 0.0265 (16) | 0.0166 (13) | 0.0004 (12) | −0.0013 (11) | −0.0062 (11) |
| C8 | 0.0367 (19) | 0.0368 (19) | 0.0141 (13) | 0.0003 (14) | −0.0047 (12) | −0.0061 (12) |
| Cl1—C2 | 1.728 (3) | C3—H3 | 0.9300 |
| Cl2—C5 | 1.737 (3) | C4—C3 | 1.382 (5) |
| O1—C7 | 1.199 (4) | C4—C5 | 1.378 (5) |
| O2—C7 | 1.326 (4) | C4—H4 | 0.9300 |
| O2—C8 | 1.444 (3) | C5—C6 | 1.384 (4) |
| C1—C2 | 1.385 (5) | C6—H6 | 0.9301 |
| C1—C6 | 1.395 (4) | C8—H8A | 0.9600 |
| C1—C7 | 1.505 (4) | C8—H8B | 0.9600 |
| C2—C3 | 1.396 (4) | C8—H8C | 0.9600 |
| C7—O2—C8 | 115.5 (3) | C4—C5—Cl2 | 119.7 (2) |
| C2—C1—C6 | 119.3 (3) | C6—C5—Cl2 | 118.9 (3) |
| C2—C1—C7 | 125.6 (3) | C5—C6—C1 | 119.3 (3) |
| C6—C1—C7 | 115.1 (3) | C5—C6—H6 | 120.4 |
| C1—C2—Cl1 | 123.1 (2) | C1—C6—H6 | 120.2 |
| C1—C2—C3 | 120.7 (3) | O1—C7—O2 | 124.7 (3) |
| C3—C2—Cl1 | 116.3 (3) | O1—C7—C1 | 122.4 (3) |
| C4—C3—C2 | 119.7 (3) | O2—C7—C1 | 112.9 (3) |
| C4—C3—H3 | 120.1 | O2—C8—H8A | 109.4 |
| C2—C3—H3 | 120.3 | O2—C8—H8B | 109.5 |
| C5—C4—C3 | 119.5 (3) | H8A—C8—H8B | 109.5 |
| C5—C4—H4 | 120.3 | O2—C8—H8C | 109.5 |
| C3—C4—H4 | 120.2 | H8A—C8—H8C | 109.5 |
| C4—C5—C6 | 121.4 (3) | H8B—C8—H8C | 109.5 |
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 of (project No. VZ0021627501)
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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)°.