2,6-Dichloro­phen­yl 4-chloro­benzoate

Abdoh, M.M.M.; Srinivasa Murthy, V.; Manjunath, B.C.; Shashikanth, S.; Lokanath, N.K.

doi:10.1107/S1600536812047204

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3449

doi:10.1107/S1600536812047204

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2,6-Dichlorophenyl 4-chlorobenzoate

M. M. M Abdoh,^a V. Srinivasa Murthy,^b B. C. Manjunath,^c S. Shashikanth ^b and N. K. Lokanath ^c ^*

^aDepartment of Physics, Faculty of Science, An Najah National University, Nabtus West Bank, Palestine, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore, 570 006, India
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

(Received 2 November 2012; accepted 16 November 2012; online 24 November 2012)

In the title compound, C₁₃H₇Cl₃O₂, the dihedral angle between the benzene rings is 82.1 (2)°. The dihedral angle between the CO₂ group and its carbon-bonded ring is 14.50 (19)° In the crystal, aromatic π–π stacking interactions [minimum ring centroid separation = 3.604 (2) Å] occur.

Related literature

For background to benzophenones, see: Khanum et al. (2004 , 2009 ). For a related structure, see: Gowda et al. (2008 ).

Experimental

Crystal data

C₁₃H₇Cl₃O₂
M_r = 301.54
Triclinic, $[P \overline 1]$
a = 7.1584 (10) Å
b = 8.1183 (13) Å
c = 11.5338 (16) Å
α = 95.352 (11)°
β = 99.852 (10)°
γ = 105.854 (10)°
V = 628.30 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 103 K
0.32 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer
8510 measured reflections
2278 independent reflections
1738 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.158
S = 1.08
2278 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: Mercury.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047204/hb6981sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047204/hb6981Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047204/hb6981Isup3.cml

checkCIF report

Comment top

The benzophenone analogues find a unique place in medicinal chemistry and play a significant role with various pharmacological properties (Khanum et al., 2004). In addition, they are reported to possess antifungal activity (Khanum et al., 2009).

In the title molecule, C₁₃H₇Cl₃O₂ (Fig. 1.), dihedral angle between the terminal benzene rings bridged by corboxylate group is 82.1 (2) °, with the conformation of the chlorobenzene ring influenced by the presence of an intramolecular C11—H···O7 interaction [2.715 (4) Å]. The overall geometry of the title compound is similar to 2,6-dichlorophenyl 4-methylbenzoate (Gowda et al., 2008).

The crystal structure (Fig. 2.) features π···π and C—Cl···π interactions. The distance between Cg(1): C1/C2/C3/C4/C5/C6 and Cg(1) is 3.604 (2) Å [-x + 1,-y,-z + 2] and 3.645 (2) Å [-x, -y, -z + 2].

Related literature top

For background to benzophenones, see: Khanum et al. (2004, 2009). For a related structure, see: Gowda et al. (2008).

Experimental top

To a stirred mixture of 2,6-dichlorophenol (1 g, 6.13 mM) and 4-chlorobenzoyl chloride (0.96 g, 5.52 mM, 0.9 eq), 20 ml of 10% aqueous sodium hydroxide was added dropwise at room temperature. The reaction mass was stirred for 1 h. The separated solid was filtered and dissolved in 2 ml diethyl ether. The organic layer was washed with water (3 × 15 ml) and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to afford 2, 6-dichlorophenyl-4- chrolobenzoate (1.52 g, 82%, M. P = 98°C) as a white solid, which was recrystallized as colourless blocks using ethyl alcohol.

IR: 1760 cm^-1(COO). ¹H NMR:600Mhz (CDCl₃) δ 7.17–7.21(1H,t), 7.39–7.41 (2H,d), 7.41–7.51 (2H,d), 8.18–8.20 (2H,d)

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: Mercury (Macrae et al., 2006).

Figures top

	Fig. 1. ORTEP diagram of the title compound showing 50% probability ellipsoids.
	Fig. 2. Packing diagram of the title compound, viewed along the crystallographic a axis.

2,6-Dichlorophenyl 4-chlorobenzoate top

Crystal data top

C₁₃H₇Cl₃O₂	Z = 2
M_r = 301.54	F(000) = 304
Triclinic, P1	D_x = 1.594 Mg m⁻³
Hall symbol: -P 1	Melting point: 371 K
a = 7.1584 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1183 (13) Å	Cell parameters from 2278 reflections
c = 11.5338 (16) Å	θ = 1.8–26.0°
α = 95.352 (11)°	µ = 0.72 mm⁻¹
β = 99.852 (10)°	T = 103 K
γ = 105.854 (10)°	Block, colourless
V = 628.30 (17) Å³	0.32 × 0.20 × 0.18 mm

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	1738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 26.0°, θ_min = 1.8°
Detector resolution: 16.0839 pixels mm^-1	h = −8→8
ω scans	k = −10→10
8510 measured reflections	l = −14→14
2278 independent 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0961P)² + 0.2256P] where P = (F_o² + 2F_c²)/3
2278 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₃H₇Cl₃O₂	γ = 105.854 (10)°
M_r = 301.54	V = 628.30 (17) Å³
Triclinic, P1	Z = 2
a = 7.1584 (10) Å	Mo Kα radiation
b = 8.1183 (13) Å	µ = 0.72 mm⁻¹
c = 11.5338 (16) Å	T = 103 K
α = 95.352 (11)°	0.32 × 0.20 × 0.18 mm
β = 99.852 (10)°

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	1738 reflections with I > 2σ(I)
8510 measured reflections	R_int = 0.045
2278 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.08	Δρ_max = 0.84 e Å⁻³
2278 reflections	Δρ_min = −0.60 e Å⁻³
163 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.32525 (12)	−0.00436 (13)	0.72254 (8)	0.0296 (3)
Cl2	0.35105 (14)	−0.85956 (14)	0.44115 (9)	0.0354 (3)
Cl3	0.19259 (12)	−0.30913 (13)	1.10648 (8)	0.0322 (3)
O7	0.2686 (3)	−0.2891 (3)	0.8624 (2)	0.0248 (8)
O9	−0.0500 (3)	−0.3628 (4)	0.7612 (2)	0.0271 (8)
C1	0.2821 (5)	0.0096 (5)	0.8663 (3)	0.0248 (10)
C2	0.2782 (5)	0.1655 (5)	0.9231 (3)	0.0269 (11)
C3	0.2488 (5)	0.1744 (6)	1.0399 (3)	0.0289 (11)
C4	0.2242 (5)	0.0298 (5)	1.0965 (3)	0.0290 (13)
C5	0.2260 (4)	−0.1256 (5)	1.0378 (3)	0.0235 (10)
C6	0.2533 (4)	−0.1378 (5)	0.9200 (3)	0.0224 (10)
C8	0.1124 (5)	−0.3822 (5)	0.7724 (3)	0.0223 (10)
C10	0.1749 (5)	−0.5020 (5)	0.6946 (3)	0.0227 (10)
C11	0.3746 (5)	−0.4855 (5)	0.6964 (3)	0.0264 (11)
C12	0.4286 (5)	−0.5932 (5)	0.6183 (3)	0.0283 (11)
C13	0.2838 (5)	−0.7194 (5)	0.5378 (3)	0.0272 (11)
C14	0.0830 (5)	−0.7394 (5)	0.5340 (3)	0.0272 (11)
C15	0.0296 (5)	−0.6312 (5)	0.6119 (3)	0.0281 (11)
H2	0.29510	0.26470	0.88370	0.0320*
H3	0.24570	0.28060	1.08060	0.0350*
H4	0.20590	0.03730	1.17630	0.0350*
H11	0.47420	−0.39890	0.75230	0.0320*
H12	0.56480	−0.58090	0.61970	0.0340*
H14	−0.01560	−0.82690	0.47810	0.0330*
H15	−0.10690	−0.64390	0.61000	0.0340*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0248 (5)	0.0392 (6)	0.0206 (5)	0.0065 (4)	0.0017 (3)	−0.0027 (4)
Cl2	0.0410 (6)	0.0383 (7)	0.0287 (5)	0.0173 (4)	0.0097 (4)	−0.0077 (5)
Cl3	0.0255 (5)	0.0408 (7)	0.0250 (5)	0.0041 (4)	0.0029 (4)	−0.0004 (5)
O7	0.0182 (12)	0.0304 (16)	0.0218 (12)	0.0080 (10)	−0.0010 (9)	−0.0090 (12)
O9	0.0186 (12)	0.0338 (17)	0.0259 (13)	0.0086 (10)	0.0015 (10)	−0.0080 (13)
C1	0.0126 (16)	0.038 (2)	0.0202 (17)	0.0080 (14)	−0.0015 (13)	−0.0065 (17)
C2	0.0133 (16)	0.028 (2)	0.034 (2)	0.0049 (14)	−0.0012 (14)	−0.0074 (19)
C3	0.0155 (17)	0.034 (2)	0.030 (2)	0.0072 (14)	−0.0022 (14)	−0.0186 (18)
C4	0.0131 (16)	0.046 (3)	0.0215 (18)	0.0067 (15)	−0.0005 (13)	−0.0130 (19)
C5	0.0130 (16)	0.035 (2)	0.0175 (17)	0.0040 (14)	0.0001 (12)	−0.0064 (17)
C6	0.0125 (15)	0.030 (2)	0.0190 (17)	0.0049 (13)	−0.0020 (12)	−0.0112 (17)
C8	0.0175 (17)	0.025 (2)	0.0192 (17)	0.0012 (14)	0.0013 (13)	−0.0029 (16)
C10	0.0191 (17)	0.028 (2)	0.0186 (17)	0.0066 (14)	0.0022 (13)	−0.0046 (17)
C11	0.0200 (17)	0.030 (2)	0.0233 (18)	0.0033 (14)	0.0006 (14)	−0.0059 (17)
C12	0.0182 (17)	0.039 (2)	0.0259 (19)	0.0082 (15)	0.0051 (14)	−0.0045 (18)
C13	0.033 (2)	0.028 (2)	0.0235 (19)	0.0140 (16)	0.0087 (15)	−0.0016 (18)
C14	0.0249 (18)	0.029 (2)	0.0235 (19)	0.0070 (15)	−0.0008 (14)	−0.0038 (18)
C15	0.0173 (17)	0.032 (2)	0.029 (2)	0.0055 (15)	−0.0012 (14)	−0.0094 (19)

Geometric parameters (Å, º) top

Cl1—C1	1.737 (4)	C10—C11	1.395 (5)
Cl2—C13	1.737 (4)	C10—C15	1.403 (5)
Cl3—C5	1.731 (4)	C11—C12	1.372 (5)
O7—C6	1.381 (4)	C12—C13	1.378 (5)
O7—C8	1.376 (4)	C13—C14	1.394 (5)
O9—C8	1.202 (4)	C14—C15	1.371 (5)
C1—C2	1.379 (5)	C2—H2	0.9500
C1—C6	1.380 (5)	C3—H3	0.9500
C2—C3	1.397 (5)	C4—H4	0.9500
C3—C4	1.380 (6)	C11—H11	0.9500
C4—C5	1.379 (5)	C12—H12	0.9500
C5—C6	1.404 (5)	C14—H14	0.9500
C8—C10	1.471 (5)	C15—H15	0.9500

C6—O7—C8	117.2 (3)	C11—C12—C13	119.5 (4)
Cl1—C1—C2	119.7 (3)	Cl2—C13—C12	119.8 (3)
Cl1—C1—C6	118.1 (3)	Cl2—C13—C14	119.1 (3)
C2—C1—C6	122.2 (3)	C12—C13—C14	121.2 (3)
C1—C2—C3	118.5 (4)	C13—C14—C15	119.1 (3)
C2—C3—C4	120.4 (4)	C10—C15—C14	120.5 (3)
C3—C4—C5	120.3 (3)	C1—C2—H2	121.00
Cl3—C5—C4	121.1 (3)	C3—C2—H2	121.00
Cl3—C5—C6	118.7 (3)	C2—C3—H3	120.00
C4—C5—C6	120.2 (3)	C4—C3—H3	120.00
O7—C6—C1	120.4 (3)	C3—C4—H4	120.00
O7—C6—C5	121.1 (3)	C5—C4—H4	120.00
C1—C6—C5	118.3 (3)	C10—C11—H11	120.00
O7—C8—O9	122.9 (3)	C12—C11—H11	120.00
O7—C8—C10	110.6 (3)	C11—C12—H12	120.00
O9—C8—C10	126.5 (3)	C13—C12—H12	120.00
C8—C10—C11	121.9 (3)	C13—C14—H14	120.00
C8—C10—C15	119.0 (3)	C15—C14—H14	120.00
C11—C10—C15	119.0 (3)	C10—C15—H15	120.00
C10—C11—C12	120.7 (3)	C14—C15—H15	120.00

C8—O7—C6—C1	−76.3 (4)	C4—C5—C6—O7	175.7 (3)
C8—O7—C6—C5	109.5 (4)	C4—C5—C6—C1	1.3 (5)
C6—O7—C8—O9	−18.4 (5)	O7—C8—C10—C11	−15.5 (5)
C6—O7—C8—C10	160.7 (3)	O7—C8—C10—C15	167.8 (3)
Cl1—C1—C2—C3	−178.2 (3)	O9—C8—C10—C11	163.6 (4)
C6—C1—C2—C3	1.6 (6)	O9—C8—C10—C15	−13.1 (6)
Cl1—C1—C6—O7	3.2 (5)	C8—C10—C11—C12	−176.4 (3)
Cl1—C1—C6—C5	177.6 (3)	C15—C10—C11—C12	0.3 (5)
C2—C1—C6—O7	−176.6 (3)	C8—C10—C15—C14	176.7 (3)
C2—C1—C6—C5	−2.2 (5)	C11—C10—C15—C14	−0.1 (6)
C1—C2—C3—C4	−0.1 (6)	C10—C11—C12—C13	−0.4 (6)
C2—C3—C4—C5	−0.8 (6)	C11—C12—C13—Cl2	−178.4 (3)
C3—C4—C5—Cl3	−179.3 (3)	C11—C12—C13—C14	0.2 (6)
C3—C4—C5—C6	0.1 (5)	Cl2—C13—C14—C15	178.7 (3)
Cl3—C5—C6—O7	−4.9 (4)	C12—C13—C14—C15	0.0 (6)
Cl3—C5—C6—C1	−179.3 (3)	C13—C14—C15—C10	−0.1 (6)

Experimental details

Crystal data
Chemical formula	C₁₃H₇Cl₃O₂
M_r	301.54
Crystal system, space group	Triclinic, P1
Temperature (K)	103
a, b, c (Å)	7.1584 (10), 8.1183 (13), 11.5338 (16)
α, β, γ (°)	95.352 (11), 99.852 (10), 105.854 (10)
V (Å³)	628.30 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.32 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8510, 2278, 1738
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.158, 1.08
No. of reflections	2278
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.60

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

References

Gowda, B. T., Foro, S., Babitha, K. S. & Fuess, H. (2008). Acta Cryst. E64, o843. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Khanum, S. A., Venu, T. D., Shasikanth, S. & Firdous, A. (2004). Bioorg. Med. Chem. Lett. 14, 5351–5355. Web of Science CrossRef PubMed CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar