organic compounds
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
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
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Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell 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
10.1107/S1600536812047204/hb6981sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047204/hb6981Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812047204/hb6981Isup3.cml
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)
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).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
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).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. |
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 |
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 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 |
C13H7Cl3O2 | γ = 105.854 (10)° |
Mr = 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)° |
Oxford Diffraction Xcalibur CCD diffractometer | 1738 reflections with I > 2σ(I) |
8510 measured reflections | Rint = 0.045 |
2278 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.84 e Å−3 |
2278 reflections | Δρmin = −0.60 e Å−3 |
163 parameters |
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. |
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* |
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) |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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
Khanum, 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 Google Scholar
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
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.
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].