organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

2,6-Di­chloro­phen­yl 4-chloro­benzoate

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 ππ stacking inter­actions [minimum ring centroid separation = 3.604 (2) Å] occur.

Related literature

For background to benzophenones, see: Khanum et al. (2004[Khanum, S. A., Venu, T. D., Shasikanth, S. & Firdous, A. (2004). Bioorg. Med. Chem. Lett. 14, 5351-5355.], 2009[Khanum, S. A., Shashikanth, S., Sathyanarayana, S. G., Lokesh, S. & Deepak, S. A. (2009). Pest Manag. Sci. 65, 776-780.]). For a related structure, see: Gowda et al. (2008[Gowda, B. T., Foro, S., Babitha, K. S. & Fuess, H. (2008). Acta Cryst. E64, o843.]).

[Scheme 1]

Experimental

Crystal data
  • C13H7Cl3O2

  • Mr = 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)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.158

  • S = 1.08

  • 2278 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 0.84 e Å−3

  • Δρmin = −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[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2006[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.]); software used to prepare material for publication: Mercury.

Supporting information


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)

Refinement top

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

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
[Figure 1] Fig. 1. ORTEP diagram of the title compound showing 50% probability ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the title compound, viewed along the crystallographic a axis.
2,6-Dichlorophenyl 4-chlorobenzoate top
Crystal data top
C13H7Cl3O2Z = 2
Mr = 301.54F(000) = 304
Triclinic, P1Dx = 1.594 Mg m3
Hall symbol: -P 1Melting point: 371 K
a = 7.1584 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.1183 (13) ÅCell parameters from 2278 reflections
c = 11.5338 (16) Åθ = 1.8–26.0°
α = 95.352 (11)°µ = 0.72 mm1
β = 99.852 (10)°T = 103 K
γ = 105.854 (10)°Block, colourless
V = 628.30 (17) Å30.32 × 0.20 × 0.18 mm
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 26.0°, θmin = 1.8°
Detector resolution: 16.0839 pixels mm-1h = 88
ω scansk = 1010
8510 measured reflectionsl = 1414
2278 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-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 parametersΔρmax = 0.84 e Å3
0 restraintsΔρmin = 0.60 e Å3
Crystal data top
C13H7Cl3O2γ = 105.854 (10)°
Mr = 301.54V = 628.30 (17) Å3
Triclinic, P1Z = 2
a = 7.1584 (10) ÅMo Kα radiation
b = 8.1183 (13) ŵ = 0.72 mm1
c = 11.5338 (16) ÅT = 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 reflectionsRint = 0.045
2278 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 1.08Δρmax = 0.84 e Å3
2278 reflectionsΔρmin = 0.60 e Å3
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
xyzUiso*/Ueq
Cl10.32525 (12)0.00436 (13)0.72254 (8)0.0296 (3)
Cl20.35105 (14)0.85956 (14)0.44115 (9)0.0354 (3)
Cl30.19259 (12)0.30913 (13)1.10648 (8)0.0322 (3)
O70.2686 (3)0.2891 (3)0.8624 (2)0.0248 (8)
O90.0500 (3)0.3628 (4)0.7612 (2)0.0271 (8)
C10.2821 (5)0.0096 (5)0.8663 (3)0.0248 (10)
C20.2782 (5)0.1655 (5)0.9231 (3)0.0269 (11)
C30.2488 (5)0.1744 (6)1.0399 (3)0.0289 (11)
C40.2242 (5)0.0298 (5)1.0965 (3)0.0290 (13)
C50.2260 (4)0.1256 (5)1.0378 (3)0.0235 (10)
C60.2533 (4)0.1378 (5)0.9200 (3)0.0224 (10)
C80.1124 (5)0.3822 (5)0.7724 (3)0.0223 (10)
C100.1749 (5)0.5020 (5)0.6946 (3)0.0227 (10)
C110.3746 (5)0.4855 (5)0.6964 (3)0.0264 (11)
C120.4286 (5)0.5932 (5)0.6183 (3)0.0283 (11)
C130.2838 (5)0.7194 (5)0.5378 (3)0.0272 (11)
C140.0830 (5)0.7394 (5)0.5340 (3)0.0272 (11)
C150.0296 (5)0.6312 (5)0.6119 (3)0.0281 (11)
H20.295100.264700.883700.0320*
H30.245700.280601.080600.0350*
H40.205900.037301.176300.0350*
H110.474200.398900.752300.0320*
H120.564800.580900.619700.0340*
H140.015600.826900.478100.0330*
H150.106900.643900.610000.0340*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0248 (5)0.0392 (6)0.0206 (5)0.0065 (4)0.0017 (3)0.0027 (4)
Cl20.0410 (6)0.0383 (7)0.0287 (5)0.0173 (4)0.0097 (4)0.0077 (5)
Cl30.0255 (5)0.0408 (7)0.0250 (5)0.0041 (4)0.0029 (4)0.0004 (5)
O70.0182 (12)0.0304 (16)0.0218 (12)0.0080 (10)0.0010 (9)0.0090 (12)
O90.0186 (12)0.0338 (17)0.0259 (13)0.0086 (10)0.0015 (10)0.0080 (13)
C10.0126 (16)0.038 (2)0.0202 (17)0.0080 (14)0.0015 (13)0.0065 (17)
C20.0133 (16)0.028 (2)0.034 (2)0.0049 (14)0.0012 (14)0.0074 (19)
C30.0155 (17)0.034 (2)0.030 (2)0.0072 (14)0.0022 (14)0.0186 (18)
C40.0131 (16)0.046 (3)0.0215 (18)0.0067 (15)0.0005 (13)0.0130 (19)
C50.0130 (16)0.035 (2)0.0175 (17)0.0040 (14)0.0001 (12)0.0064 (17)
C60.0125 (15)0.030 (2)0.0190 (17)0.0049 (13)0.0020 (12)0.0112 (17)
C80.0175 (17)0.025 (2)0.0192 (17)0.0012 (14)0.0013 (13)0.0029 (16)
C100.0191 (17)0.028 (2)0.0186 (17)0.0066 (14)0.0022 (13)0.0046 (17)
C110.0200 (17)0.030 (2)0.0233 (18)0.0033 (14)0.0006 (14)0.0059 (17)
C120.0182 (17)0.039 (2)0.0259 (19)0.0082 (15)0.0051 (14)0.0045 (18)
C130.033 (2)0.028 (2)0.0235 (19)0.0140 (16)0.0087 (15)0.0016 (18)
C140.0249 (18)0.029 (2)0.0235 (19)0.0070 (15)0.0008 (14)0.0038 (18)
C150.0173 (17)0.032 (2)0.029 (2)0.0055 (15)0.0012 (14)0.0094 (19)
Geometric parameters (Å, º) top
Cl1—C11.737 (4)C10—C111.395 (5)
Cl2—C131.737 (4)C10—C151.403 (5)
Cl3—C51.731 (4)C11—C121.372 (5)
O7—C61.381 (4)C12—C131.378 (5)
O7—C81.376 (4)C13—C141.394 (5)
O9—C81.202 (4)C14—C151.371 (5)
C1—C21.379 (5)C2—H20.9500
C1—C61.380 (5)C3—H30.9500
C2—C31.397 (5)C4—H40.9500
C3—C41.380 (6)C11—H110.9500
C4—C51.379 (5)C12—H120.9500
C5—C61.404 (5)C14—H140.9500
C8—C101.471 (5)C15—H150.9500
C6—O7—C8117.2 (3)C11—C12—C13119.5 (4)
Cl1—C1—C2119.7 (3)Cl2—C13—C12119.8 (3)
Cl1—C1—C6118.1 (3)Cl2—C13—C14119.1 (3)
C2—C1—C6122.2 (3)C12—C13—C14121.2 (3)
C1—C2—C3118.5 (4)C13—C14—C15119.1 (3)
C2—C3—C4120.4 (4)C10—C15—C14120.5 (3)
C3—C4—C5120.3 (3)C1—C2—H2121.00
Cl3—C5—C4121.1 (3)C3—C2—H2121.00
Cl3—C5—C6118.7 (3)C2—C3—H3120.00
C4—C5—C6120.2 (3)C4—C3—H3120.00
O7—C6—C1120.4 (3)C3—C4—H4120.00
O7—C6—C5121.1 (3)C5—C4—H4120.00
C1—C6—C5118.3 (3)C10—C11—H11120.00
O7—C8—O9122.9 (3)C12—C11—H11120.00
O7—C8—C10110.6 (3)C11—C12—H12120.00
O9—C8—C10126.5 (3)C13—C12—H12120.00
C8—C10—C11121.9 (3)C13—C14—H14120.00
C8—C10—C15119.0 (3)C15—C14—H14120.00
C11—C10—C15119.0 (3)C10—C15—H15120.00
C10—C11—C12120.7 (3)C14—C15—H15120.00
C8—O7—C6—C176.3 (4)C4—C5—C6—O7175.7 (3)
C8—O7—C6—C5109.5 (4)C4—C5—C6—C11.3 (5)
C6—O7—C8—O918.4 (5)O7—C8—C10—C1115.5 (5)
C6—O7—C8—C10160.7 (3)O7—C8—C10—C15167.8 (3)
Cl1—C1—C2—C3178.2 (3)O9—C8—C10—C11163.6 (4)
C6—C1—C2—C31.6 (6)O9—C8—C10—C1513.1 (6)
Cl1—C1—C6—O73.2 (5)C8—C10—C11—C12176.4 (3)
Cl1—C1—C6—C5177.6 (3)C15—C10—C11—C120.3 (5)
C2—C1—C6—O7176.6 (3)C8—C10—C15—C14176.7 (3)
C2—C1—C6—C52.2 (5)C11—C10—C15—C140.1 (6)
C1—C2—C3—C40.1 (6)C10—C11—C12—C130.4 (6)
C2—C3—C4—C50.8 (6)C11—C12—C13—Cl2178.4 (3)
C3—C4—C5—Cl3179.3 (3)C11—C12—C13—C140.2 (6)
C3—C4—C5—C60.1 (5)Cl2—C13—C14—C15178.7 (3)
Cl3—C5—C6—O74.9 (4)C12—C13—C14—C150.0 (6)
Cl3—C5—C6—C1179.3 (3)C13—C14—C15—C100.1 (6)

Experimental details

Crystal data
Chemical formulaC13H7Cl3O2
Mr301.54
Crystal system, space groupTriclinic, 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)
V3)628.30 (17)
Z2
Radiation typeMo Kα
µ (mm1)0.72
Crystal size (mm)0.32 × 0.20 × 0.18
Data collection
DiffractometerOxford Diffraction Xcalibur CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8510, 2278, 1738
Rint0.045
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.158, 1.08
No. of reflections2278
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.84, 0.60

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

 

References

First citationGowda, B. T., Foro, S., Babitha, K. S. & Fuess, H. (2008). Acta Cryst. E64, o843.  Web of Science CSD CrossRef IUCr Journals
First citationKhanum, S. A., Shashikanth, S., Sathyanarayana, S. G., Lokesh, S. & Deepak, S. A. (2009). Pest Manag. Sci. 65, 776–780.  Web of Science CrossRef PubMed CAS
First citationKhanum, S. A., Venu, T. D., Shasikanth, S. & Firdous, A. (2004). Bioorg. Med. Chem. Lett. 14, 5351–5355.  Web of Science CrossRef PubMed CAS
First citationMacrae, 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
First citationOxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds