Methyl 2,5-dichloro­benzoate

Babar, T.M.; Qadeer, G.; Rama, N.H.; Ruzicka, A.; Padelkova, Z.

doi:10.1107/S1600536808029541

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1970

doi:10.1107/S1600536808029541

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Methyl 2,5-dichlorobenzoate

Tariq Mahmood Babar,^a Ghulam Qadeer,^a Nasim Hasan Rama,^a ^* Ales Ruzicka ^b and Zdenka Padelkova ^b

^aDepartment of Chemistry, Quaid-i-Azam Univeristy, Islamabad 45320, Pakistan, and ^bDepartment of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Nam. Cs. Legii' 565, 53210 Pardubice, Czech Republic
^*Correspondence e-mail: nasimhrama@yahoo.com

(Received 15 September 2008; accepted 15 September 2008; online 20 September 2008)

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 ); 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 ). For a description of the Cambridge Structural Database, see: Allen (2002 ); and of MOGUL, see: Bruno et al. (2004 ).

Experimental

Crystal data

C₈H₆Cl₂O₂
M_r = 205.03
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.053
wR(F²) = 0.146
S = 1.09
1840 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: COLLECT (Hooft, 1998 )and DENZO (Otwinowski & Minor, 1997 ); cell refinement: DIRAX/LSQ (Duisenberg, 1992)); data reduction: EvalCCD (Duisenberg, 1992)); 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.

Supporting information

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

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

checkCIF report

Comment top

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)°.

Related literature top

For related literature, see: 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). For bond-length data, see: Allen (2002); Bruno et al. (2004).

Experimental top

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.

Computing details top

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).

Figures top

	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.

methyl 2,5-dichlorobenzoate top

Crystal data top

C₈H₆Cl₂O₂	Z = 2
M_r = 205.03	F(000) = 208
Triclinic, P1	D_x = 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

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	1840 independent reflections
Radiation source: fine-focus sealed tube	1455 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ϕ and ω scans	h = −4→4
Absorption correction: gaussian (Coppens, 1970)	k = −9→8
T_min = 0.864, T_max = 0.971	l = −20→20
5966 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0527P)² + 0.5264P] where P = (F_o² + 2F_c²)/3
1840 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₈H₆Cl₂O₂	γ = 83.741 (5)°
M_r = 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)°

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	1840 independent reflections
Absorption correction: gaussian (Coppens, 1970)	1455 reflections with I > 2σ(I)
T_min = 0.864, T_max = 0.971	R_int = 0.110
5966 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.10	Δρ_max = 0.44 e Å⁻³
1840 reflections	Δρ_min = −0.57 e Å⁻³
109 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₈H₆Cl₂O₂
M_r	205.03
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	3.8452 (3), 7.0158 (4), 15.851 (1)
α, β, γ (°)	77.189 (6), 89.130 (7), 83.741 (5)
V (Å³)	414.46 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.68 × 0.11 × 0.06

Data collection
Diffractometer	Bruker–Nonius KappaCCD area-detector diffractometer
Absorption correction	Gaussian (Coppens, 1970)
T_min, T_max	0.864, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	5966, 1840, 1455
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.146, 1.10
No. of reflections	1840
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.57

Computer programs: , COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Acknowledgements

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).

References

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