2,6-Dichloro­phen­yl 4-chloro­benzoate

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 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 ▶); 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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].

Experimental

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)

Refinement

All hydrogen atoms were located geometrically with C—H = 0.93–0.97) Å and allowed to ride on their parent atoms with U_iso(H) = 1.2U_eq(aromatic C).

Figures

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.

Crystal data

C13H7Cl3O2	Z = 2
Mr = 301.54	F(000) = 304
Triclinic, P1	Dx = 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

Oxford Diffraction Xcalibur CCD diffractometer	1738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 26.0°, θmin = 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

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(Fo2) + (0.0961P)2 + 0.2256P] where P = (Fo2 + 2Fc2)/3
2278 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.84 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)