Dimethyl 4,5-dichlorobenzene-1,2-dicarboxyl­ate

Sun, Y.

doi:10.1107/S1600536812007167

organic compounds

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Volume 68| Part 3| March 2012| Page o834

doi:10.1107/S1600536812007167

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Dimethyl 4,5-dichlorobenzene-1,2-dicarboxylate

Yongling Sun ^a ^*

^aDepartment of Biology, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: sylswx@163.com

(Received 20 January 2012; accepted 17 February 2012; online 24 February 2012)

In the title compound, C₁₀H₈Cl₂O₄, the two Cl atoms and one of the methoxycarbonyl groups are almost coplanar [maximum derivation = 0.035 (2) Å] with the benzene plane, and the other methoxycarbonyl group exhibits an almost orthogonal disposition relative to the benzene plane, with a dihedral angle of 84.82 (3)° between the planes. In the crystal, the molecules are connected into a chain propagating along the [011] direction through nonclassical C—H⋯O hydrogen bonds.

Related literature

For the chemical properties and structural nature nature of some related benzenecarboxylate derivatives, see: Galešić et al. (1984 ); Liang et al. (2004 ); Mallinson et al. (2003 ); Rauf et al. (2008 ).

Experimental

Crystal data

C₁₀H₈Cl₂O₄
M_r = 263.06
Triclinic, $[P \overline 1]$
a = 7.1906 (14) Å
b = 7.8410 (17) Å
c = 10.6205 (15) Å
α = 97.779 (15)°
β = 109.040 (15)°
γ = 91.864 (18)°
V = 558.95 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 295 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.871, T_max = 0.902
3362 measured reflections
1966 independent reflections
1663 reflections with I > 2σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.03
1966 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O4ⁱ	0.93	2.37	3.278 (2)	164
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007167/rk2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007167/rk2334Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007167/rk2334Isup3.cml

checkCIF report

Comment top

Benzenecarboxylate derivatives have been extensively studied due to their excellent chemical properties and easily modified structural natures. (Mallinson et al., 2003 and Liang et al., 2004). Furthermore, the investigate on single-crystal structure of benzenecarboxylate derivatives have become increasingly important in revealing precisely the relation between their chemical properties and molecular structures (Galešić et al., 1984 and Rauf et al., 2008). As an extension of our work on benzenecarboxylate structural characterization, the title compound, I, is synthesized and characterized by X-ray diffraction, as shown in Fig. 1.

The compound I crystallizes in the triclinic system and consists of one phenyl framework, together with two chlorine atoms and two methoxycarbonyl groups linked to its peripheral position, respectively. Two chlorine atoms are co-planar with the benzene ring, companying the maximum deviation of 0.035 (2)Å from this benzene plane. Furthermore, one methoxycarbonyl group is also co-planar with this benzene plane, with the dihedral angel of 2.03 (3)° between the methoxycarbonyl plane of C9–O3–O4–C10 and the benzene plane. In contrast, the other methoxycarbonyl plane of C7–O1–O2–C8 exhibits almostly orthogonal configuration in relative to this benzene plane with the dihedral angle of 84.82 (3)° between them. As shown in Table 1, the distances of C–O (esterified hydroxyl oxygen atom) locating in the range of 1.321 (2)-1.448 (2)Å, clearly indicate their typical single-bond nature in contrast to the obviously double-bond of C═O (carbonyl oxygen atom) 1.187 (2)Å and 1.193 (2)Å, revealing the excellent flexible bridge nature of these methoxycarbonyl moieties. Furthermore, this compound molecules are connected into one-dimension chain along the [0 1 1] direction through H bond C6–H6···O4ⁱ with H6···O4ⁱ distance of 2.373 (3)°. Symmetry code: (i) x, y-1, z.

Related literature top

For the chemical properties and structural nature of many benzenecarboxylate derivatives, see: Galešić et al. (1984); Liang et al. (2004); Mallinson et al. (2003); Rauf et al. (2008).

Experimental top

To the solution of 4,5-dichloro-1,2-benzenedicarboxyl acid (466 mg, 2 mmol) in MeOH (50 ml), one drop of H₂SO₄ was added. After refluxed for five hours under N₂ atmosphere, the resulting mixture was evaporated, and the residue was chromatographed on a silica gel column using CHCl₃ as eluent. Repeated chromatography followed by recrystallization from CHCl₃ and MeOH gave the target compound as white crystals. Yield: 182 mg, 34.6%. Anal. for C₁₀H₈Cl₂O₄: Calc. C, 45.66; H, 3.07; Found: C, 45.42; H, 3.17. The No. of CCDC: 863226.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

Dimethyl 4,5-dichlorobenzene-1,2-dicarboxylate top

Crystal data top

C₁₀H₈Cl₂O₄	Z = 2
M_r = 263.06	F(000) = 268
Triclinic, P1	D_x = 1.563 Mg m⁻³
Hall symbol: -P 1	Melting point: 389 K
a = 7.1906 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8410 (17) Å	Cell parameters from 1973 reflections
c = 10.6205 (15) Å	θ = 2.4–25.0°
α = 97.779 (15)°	µ = 0.58 mm⁻¹
β = 109.040 (15)°	T = 295 K
γ = 91.864 (18)°	Block, colourless
V = 558.95 (19) Å³	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1966 independent reflections
Radiation source: fine-focus sealed tube	1663 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.871, T_max = 0.902	k = −9→8
3362 measured reflections	l = −12→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0449P)² + 0.1781P] where P = (F_o² + 2F_c²)/3
1966 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₀H₈Cl₂O₄	γ = 91.864 (18)°
M_r = 263.06	V = 558.95 (19) Å³
Triclinic, P1	Z = 2
a = 7.1906 (14) Å	Mo Kα radiation
b = 7.8410 (17) Å	µ = 0.58 mm⁻¹
c = 10.6205 (15) Å	T = 295 K
α = 97.779 (15)°	0.24 × 0.20 × 0.18 mm
β = 109.040 (15)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1966 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1663 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.902	R_int = 0.010
3362 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
1966 reflections	Δρ_min = −0.24 e Å⁻³
147 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.31371 (9)	0.97739 (8)	0.82726 (5)	0.0629 (2)
Cl2	0.25088 (11)	0.57862 (8)	0.71088 (6)	0.0693 (2)
O1	0.3423 (2)	0.70631 (19)	0.21566 (13)	0.0517 (4)
O3	0.2024 (2)	1.05587 (17)	0.22604 (14)	0.0524 (4)
C7	0.1745 (3)	0.7231 (2)	0.24061 (19)	0.0404 (4)
C9	0.2309 (3)	1.1128 (2)	0.3543 (2)	0.0414 (4)
C1	0.2123 (3)	0.7964 (2)	0.38630 (18)	0.0365 (4)
C6	0.2187 (3)	0.6771 (2)	0.47290 (19)	0.0449 (5)
H6	0.2027	0.5596	0.4397	0.054*
C3	0.2674 (3)	1.0250 (2)	0.57299 (19)	0.0401 (4)
H7	0.2835	1.1423	0.6069	0.048*
C2	0.2367 (2)	0.9725 (2)	0.43690 (18)	0.0349 (4)
C4	0.2743 (3)	0.9063 (3)	0.65837 (19)	0.0404 (4)
C5	0.2487 (3)	0.7316 (2)	0.60792 (19)	0.0431 (5)
O2	0.0140 (2)	0.6798 (2)	0.16088 (15)	0.0648 (4)
O4	0.2507 (4)	1.26184 (19)	0.39955 (19)	0.0862 (6)
C10	0.1877 (4)	1.1857 (3)	0.1392 (3)	0.0655 (7)
H13A	0.1488	1.1307	0.0470	0.098*
H13C	0.3134	1.2499	0.1630	0.098*
H13B	0.0910	1.2628	0.1499	0.098*
C8	0.3252 (4)	0.6420 (3)	0.0777 (2)	0.0654 (7)
H14C	0.2624	0.7232	0.0206	0.098*
H14A	0.2476	0.5331	0.0491	0.098*
H14B	0.4544	0.6271	0.0720	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0775 (4)	0.0733 (4)	0.0381 (3)	−0.0010 (3)	0.0256 (3)	−0.0048 (3)
Cl2	0.1004 (5)	0.0595 (4)	0.0460 (3)	−0.0028 (3)	0.0175 (3)	0.0212 (3)
O1	0.0606 (10)	0.0574 (9)	0.0324 (7)	0.0079 (7)	0.0121 (7)	−0.0017 (6)
O3	0.0733 (10)	0.0391 (8)	0.0445 (8)	0.0031 (7)	0.0171 (7)	0.0124 (6)
C7	0.0532 (12)	0.0281 (9)	0.0347 (10)	−0.0003 (8)	0.0077 (9)	0.0049 (7)
C9	0.0407 (11)	0.0328 (10)	0.0472 (11)	0.0020 (8)	0.0104 (9)	0.0056 (8)
C1	0.0370 (10)	0.0335 (9)	0.0339 (10)	0.0009 (7)	0.0062 (8)	0.0027 (7)
C6	0.0580 (13)	0.0320 (10)	0.0392 (11)	−0.0003 (8)	0.0104 (9)	0.0028 (8)
C3	0.0380 (10)	0.0352 (10)	0.0434 (11)	0.0014 (8)	0.0124 (8)	−0.0028 (8)
C2	0.0299 (9)	0.0330 (9)	0.0388 (10)	0.0016 (7)	0.0083 (8)	0.0034 (7)
C4	0.0346 (10)	0.0500 (11)	0.0343 (10)	0.0003 (8)	0.0112 (8)	0.0007 (8)
C5	0.0474 (11)	0.0428 (11)	0.0373 (10)	0.0000 (8)	0.0109 (9)	0.0089 (8)
O2	0.0618 (10)	0.0745 (11)	0.0412 (9)	−0.0148 (8)	0.0007 (8)	−0.0018 (8)
O4	0.159 (2)	0.0288 (8)	0.0697 (12)	0.0046 (9)	0.0378 (12)	0.0052 (8)
C10	0.0815 (17)	0.0585 (14)	0.0626 (15)	0.0099 (12)	0.0233 (13)	0.0313 (12)
C8	0.0928 (19)	0.0670 (15)	0.0366 (11)	0.0110 (13)	0.0243 (12)	0.0006 (10)

Geometric parameters (Å, º) top

Cl1—C4	1.7308 (19)	C6—C5	1.383 (3)
Cl2—C5	1.7260 (19)	C6—H6	0.9300
O1—C7	1.324 (2)	C3—C4	1.376 (3)
O1—C8	1.447 (2)	C3—C2	1.390 (3)
O3—C9	1.321 (2)	C3—H7	0.9300
O3—C10	1.448 (2)	C4—C5	1.385 (3)
C7—O2	1.193 (2)	C10—H13A	0.9600
C7—C1	1.508 (3)	C10—H13C	0.9600
C9—O4	1.187 (2)	C10—H13B	0.9600
C9—C2	1.490 (3)	C8—H14C	0.9600
C1—C6	1.390 (3)	C8—H14A	0.9600
C1—C2	1.396 (3)	C8—H14B	0.9600

C7—O1—C8	116.24 (17)	C1—C2—C9	124.47 (17)
C9—O3—C10	116.45 (16)	C3—C4—C5	119.57 (17)
O2—C7—O1	125.13 (18)	C3—C4—Cl1	119.55 (15)
O2—C7—C1	123.77 (19)	C5—C4—Cl1	120.87 (15)
O1—C7—C1	111.03 (16)	C6—C5—C4	120.08 (17)
O4—C9—O3	123.07 (18)	C6—C5—Cl2	118.90 (15)
O4—C9—C2	123.22 (19)	C4—C5—Cl2	121.02 (15)
O3—C9—C2	113.71 (15)	O3—C10—H13A	109.5
C6—C1—C2	119.35 (17)	O3—C10—H13C	109.5
C6—C1—C7	116.17 (16)	H13A—C10—H13C	109.5
C2—C1—C7	124.47 (16)	O3—C10—H13B	109.5
C5—C6—C1	120.58 (17)	H13A—C10—H13B	109.5
C5—C6—H6	119.7	H13C—C10—H13B	109.5
C1—C6—H6	119.7	O1—C8—H14C	109.5
C4—C3—C2	121.09 (17)	O1—C8—H14A	109.5
C4—C3—H7	119.5	H14C—C8—H14A	109.5
C2—C3—H7	119.5	O1—C8—H14B	109.5
C3—C2—C1	119.31 (17)	H14C—C8—H14B	109.5
C3—C2—C9	116.21 (16)	H14A—C8—H14B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O4ⁱ	0.93	2.37	3.278 (2)	164

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₈Cl₂O₄
M_r	263.06
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.1906 (14), 7.8410 (17), 10.6205 (15)
α, β, γ (°)	97.779 (15), 109.040 (15), 91.864 (18)
V (Å³)	558.95 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.871, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	3362, 1966, 1663
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.03
No. of reflections	1966
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.24

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O4ⁱ	0.93	2.37	3.278 (2)	164.1

Symmetry code: (i) x, y−1, z.

References

Galešić, N., Matijašić, I. & Bruvo, M. (1984). Acta Cryst. C40, 308–311. CSD CrossRef Web of Science IUCr Journals Google Scholar
Liang, M., Liao, D., Jiang, Z., Yan, S. & Cheng, P. (2004). Inorg. Chem. Commun. 7, 173-175. Web of Science CSD CrossRef CAS Google Scholar
Mallinson, P. R., Smith, G. T., Wilson, C. C., Grech, E. & Wozniak, K. (2003). J. Am. Chem. Soc. 125, 4259-4270. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rauf, M. K., Saeed, M. A., Imtiaz-ud-Din, Bolte, M., Badshah, A. & Mirz, B. (2008). J. Organomet. Chem. 693, 3043-3048. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o834

doi:10.1107/S1600536812007167

Open

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