organic compounds
2,4-Dichlorobenzyl 2-methoxybenzoate
aNational Institute of Technology-Karnataka, Department of Chemistry, Surathkal, Mangalore 575 025, India, and bNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth, 6031, South Africa
*Correspondence e-mail: richard.betz@webmail.co.za
In the title compound, C15H12Cl2O3, the aromatic rings make a dihedral angle of 10.78 (4)°. In the molecule, there is a short C—H⋯O contact. In the crystal, C—H⋯O contacts connect the molecules into C(7)C(8) chains along the b axis. The shortest intercentroid distance between two benzoic acid aromatic systems is 3.7416 (8) Å.
Related literature
For pharmacological properties of phenyl benzoates, see: Oxford et al. (2005); Ostergaard (1994). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995); Etter et al. (1990).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536813006156/ng5318sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813006156/ng5318Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813006156/ng5318Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536813006156/ng5318Isup4.cml
A mixture of 1-(bromomethyl)-2,4-dichlorobenzene (0.1 g, 0.0004 mol), potassium carbonate (0.062 g, 0.00045 mol) and 2-methoxybenzoic acid (0.068 g, 0.00045 mol) in dimethylformamide (5 ml) was stirred at 60 °C for 2 h. After completion of the reaction, the reaction mixture was poured into ice-cold water. The solid product obtained was filtered, washed with water and recrystallized from ethanol (yield: 0.120 g, 93.0%).
Carbon-bound H atoms were placed in calculated positions (C–H 0.95 Å for aromatic carbon atoms and C–H 0.99 Å for methylene groups) and were included in the
in the riding model approximation, with U(H) set to 1.2Ueq(C). The H atoms of the methyl groups were allowed to rotate with a fixed angle around the C–C bond to best fit the experimental electron density with U(H) set to 1.5Ueq(C).Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C15H12Cl2O3 | F(000) = 640 |
Mr = 311.15 | Dx = 1.519 Mg m−3 |
Monoclinic, P21/c | Melting point = 376–374 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1816 (5) Å | Cell parameters from 6565 reflections |
b = 15.2481 (6) Å | θ = 2.7–28.3° |
c = 7.4207 (4) Å | µ = 0.48 mm−1 |
β = 99.299 (2)° | T = 200 K |
V = 1360.25 (11) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.37 × 0.15 mm |
Bruker APEXII CCD diffractometer | 3379 independent reflections |
Radiation source: fine-focus sealed tube | 2868 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 28.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −16→16 |
Tmin = 0.847, Tmax = 0.982 | k = −20→20 |
12933 measured reflections | l = −9→9 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0407P)2 + 0.3593P] where P = (Fo2 + 2Fc2)/3 |
3379 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C15H12Cl2O3 | V = 1360.25 (11) Å3 |
Mr = 311.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1816 (5) Å | µ = 0.48 mm−1 |
b = 15.2481 (6) Å | T = 200 K |
c = 7.4207 (4) Å | 0.38 × 0.37 × 0.15 mm |
β = 99.299 (2)° |
Bruker APEXII CCD diffractometer | 3379 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2868 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 0.982 | Rint = 0.015 |
12933 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.26 e Å−3 |
3379 reflections | Δρmin = −0.23 e Å−3 |
182 parameters |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.83729 (2) | 0.13621 (2) | 0.22173 (5) | 0.03453 (10) | |
Cl2 | 0.93726 (3) | 0.47791 (2) | 0.20393 (6) | 0.05086 (12) | |
O1 | 0.50796 (7) | 0.23368 (5) | 0.32072 (13) | 0.0302 (2) | |
O2 | 0.42680 (8) | 0.10301 (6) | 0.32410 (15) | 0.0417 (2) | |
O3 | 0.39479 (7) | 0.37220 (5) | 0.34997 (14) | 0.0354 (2) | |
C1 | 0.60253 (9) | 0.19251 (7) | 0.26253 (17) | 0.0260 (2) | |
H1A | 0.5802 | 0.1629 | 0.1435 | 0.031* | |
H1B | 0.6354 | 0.1483 | 0.3532 | 0.031* | |
C2 | 0.42351 (9) | 0.18141 (7) | 0.34359 (16) | 0.0250 (2) | |
C3 | 0.37406 (13) | 0.46402 (9) | 0.3289 (2) | 0.0465 (4) | |
H3A | 0.4363 | 0.4920 | 0.2823 | 0.070* | |
H3B | 0.3664 | 0.4896 | 0.4473 | 0.070* | |
H3C | 0.3053 | 0.4735 | 0.2425 | 0.070* | |
C11 | 0.68490 (9) | 0.26426 (7) | 0.24577 (15) | 0.0234 (2) | |
C12 | 0.79427 (9) | 0.24488 (7) | 0.22730 (16) | 0.0244 (2) | |
C13 | 0.87222 (10) | 0.30935 (8) | 0.21331 (17) | 0.0291 (3) | |
H13 | 0.9464 | 0.2945 | 0.2012 | 0.035* | |
C14 | 0.83948 (10) | 0.39622 (8) | 0.21735 (17) | 0.0303 (3) | |
C15 | 0.73151 (10) | 0.41879 (8) | 0.23178 (18) | 0.0306 (3) | |
H15 | 0.7097 | 0.4786 | 0.2319 | 0.037* | |
C16 | 0.65539 (10) | 0.35254 (8) | 0.24611 (17) | 0.0274 (2) | |
H16 | 0.5810 | 0.3678 | 0.2564 | 0.033* | |
C21 | 0.32638 (9) | 0.22915 (7) | 0.39497 (16) | 0.0249 (2) | |
C22 | 0.31284 (9) | 0.32091 (8) | 0.39762 (16) | 0.0268 (2) | |
C23 | 0.21596 (10) | 0.35594 (9) | 0.44706 (18) | 0.0327 (3) | |
H23 | 0.2066 | 0.4177 | 0.4505 | 0.039* | |
C24 | 0.13359 (10) | 0.30135 (10) | 0.49094 (18) | 0.0355 (3) | |
H24 | 0.0686 | 0.3260 | 0.5261 | 0.043* | |
C25 | 0.14469 (10) | 0.21127 (10) | 0.48428 (18) | 0.0351 (3) | |
H25 | 0.0870 | 0.1740 | 0.5113 | 0.042* | |
C26 | 0.24091 (10) | 0.17634 (8) | 0.43777 (17) | 0.0296 (3) | |
H26 | 0.2491 | 0.1144 | 0.4349 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02915 (16) | 0.02768 (16) | 0.0483 (2) | 0.00585 (11) | 0.01086 (13) | −0.00228 (12) |
Cl2 | 0.03554 (19) | 0.03606 (19) | 0.0846 (3) | −0.00991 (14) | 0.02065 (18) | 0.00427 (17) |
O1 | 0.0219 (4) | 0.0242 (4) | 0.0472 (5) | −0.0005 (3) | 0.0138 (4) | −0.0033 (3) |
O2 | 0.0334 (5) | 0.0234 (4) | 0.0723 (7) | −0.0010 (4) | 0.0204 (5) | −0.0008 (4) |
O3 | 0.0301 (4) | 0.0218 (4) | 0.0571 (6) | 0.0015 (3) | 0.0155 (4) | 0.0014 (4) |
C1 | 0.0220 (5) | 0.0230 (5) | 0.0345 (6) | 0.0021 (4) | 0.0090 (4) | −0.0009 (5) |
C2 | 0.0220 (5) | 0.0251 (5) | 0.0280 (6) | −0.0011 (4) | 0.0040 (4) | 0.0020 (4) |
C3 | 0.0460 (8) | 0.0234 (6) | 0.0740 (11) | 0.0030 (6) | 0.0218 (8) | 0.0014 (6) |
C11 | 0.0219 (5) | 0.0261 (5) | 0.0227 (5) | 0.0005 (4) | 0.0048 (4) | 0.0003 (4) |
C12 | 0.0244 (5) | 0.0259 (5) | 0.0235 (5) | 0.0033 (4) | 0.0052 (4) | −0.0005 (4) |
C13 | 0.0218 (5) | 0.0350 (6) | 0.0318 (6) | 0.0008 (5) | 0.0086 (4) | 0.0001 (5) |
C14 | 0.0282 (6) | 0.0295 (6) | 0.0347 (6) | −0.0058 (5) | 0.0092 (5) | 0.0012 (5) |
C15 | 0.0311 (6) | 0.0252 (6) | 0.0372 (7) | 0.0006 (5) | 0.0102 (5) | 0.0013 (5) |
C16 | 0.0231 (5) | 0.0276 (6) | 0.0329 (6) | 0.0023 (4) | 0.0085 (5) | 0.0009 (5) |
C21 | 0.0220 (5) | 0.0277 (6) | 0.0250 (6) | 0.0003 (4) | 0.0036 (4) | −0.0007 (4) |
C22 | 0.0224 (5) | 0.0291 (6) | 0.0290 (6) | 0.0003 (4) | 0.0044 (4) | −0.0006 (5) |
C23 | 0.0274 (6) | 0.0362 (7) | 0.0346 (7) | 0.0064 (5) | 0.0053 (5) | −0.0045 (5) |
C24 | 0.0238 (6) | 0.0517 (8) | 0.0318 (6) | 0.0049 (5) | 0.0068 (5) | −0.0059 (6) |
C25 | 0.0245 (6) | 0.0493 (8) | 0.0328 (7) | −0.0062 (5) | 0.0089 (5) | −0.0022 (6) |
C26 | 0.0271 (6) | 0.0330 (6) | 0.0293 (6) | −0.0041 (5) | 0.0063 (5) | −0.0003 (5) |
Cl1—C12 | 1.7403 (12) | C13—C14 | 1.3849 (17) |
Cl2—C14 | 1.7374 (12) | C13—H13 | 0.9500 |
O1—C2 | 1.3337 (13) | C14—C15 | 1.3804 (17) |
O1—C1 | 1.4383 (13) | C15—C16 | 1.3869 (17) |
O2—C2 | 1.2057 (15) | C15—H15 | 0.9500 |
O3—C22 | 1.3592 (14) | C16—H16 | 0.9500 |
O3—C3 | 1.4267 (15) | C21—C26 | 1.3929 (16) |
C1—C11 | 1.5033 (15) | C21—C22 | 1.4093 (16) |
C1—H1A | 0.9900 | C22—C23 | 1.3973 (16) |
C1—H1B | 0.9900 | C23—C24 | 1.3826 (19) |
C2—C21 | 1.4902 (16) | C23—H23 | 0.9500 |
C3—H3A | 0.9800 | C24—C25 | 1.382 (2) |
C3—H3B | 0.9800 | C24—H24 | 0.9500 |
C3—H3C | 0.9800 | C25—C26 | 1.3811 (17) |
C11—C12 | 1.3929 (16) | C25—H25 | 0.9500 |
C11—C16 | 1.3933 (16) | C26—H26 | 0.9500 |
C12—C13 | 1.3823 (17) | ||
C2—O1—C1 | 116.68 (9) | C15—C14—Cl2 | 119.76 (10) |
C22—O3—C3 | 117.96 (10) | C13—C14—Cl2 | 118.81 (9) |
O1—C1—C11 | 106.55 (9) | C14—C15—C16 | 118.79 (11) |
O1—C1—H1A | 110.4 | C14—C15—H15 | 120.6 |
C11—C1—H1A | 110.4 | C16—C15—H15 | 120.6 |
O1—C1—H1B | 110.4 | C15—C16—C11 | 121.85 (11) |
C11—C1—H1B | 110.4 | C15—C16—H16 | 119.1 |
H1A—C1—H1B | 108.6 | C11—C16—H16 | 119.1 |
O2—C2—O1 | 122.41 (11) | C26—C21—C22 | 118.51 (11) |
O2—C2—C21 | 123.93 (11) | C26—C21—C2 | 115.44 (10) |
O1—C2—C21 | 113.66 (10) | C22—C21—C2 | 126.02 (10) |
O3—C3—H3A | 109.5 | O3—C22—C23 | 122.36 (11) |
O3—C3—H3B | 109.5 | O3—C22—C21 | 118.37 (10) |
H3A—C3—H3B | 109.5 | C23—C22—C21 | 119.27 (11) |
O3—C3—H3C | 109.5 | C24—C23—C22 | 120.50 (12) |
H3A—C3—H3C | 109.5 | C24—C23—H23 | 119.8 |
H3B—C3—H3C | 109.5 | C22—C23—H23 | 119.8 |
C12—C11—C16 | 117.15 (11) | C25—C24—C23 | 120.74 (12) |
C12—C11—C1 | 121.04 (10) | C25—C24—H24 | 119.6 |
C16—C11—C1 | 121.81 (10) | C23—C24—H24 | 119.6 |
C13—C12—C11 | 122.41 (11) | C26—C25—C24 | 118.96 (12) |
C13—C12—Cl1 | 117.53 (9) | C26—C25—H25 | 120.5 |
C11—C12—Cl1 | 120.05 (9) | C24—C25—H25 | 120.5 |
C12—C13—C14 | 118.35 (11) | C25—C26—C21 | 121.99 (12) |
C12—C13—H13 | 120.8 | C25—C26—H26 | 119.0 |
C14—C13—H13 | 120.8 | C21—C26—H26 | 119.0 |
C15—C14—C13 | 121.43 (11) | ||
C2—O1—C1—C11 | 179.67 (10) | O2—C2—C21—C26 | 6.06 (18) |
C1—O1—C2—O2 | 2.90 (17) | O1—C2—C21—C26 | −173.90 (10) |
C1—O1—C2—C21 | −177.14 (10) | O2—C2—C21—C22 | −171.70 (12) |
O1—C1—C11—C12 | 167.09 (10) | O1—C2—C21—C22 | 8.34 (16) |
O1—C1—C11—C16 | −13.58 (15) | C3—O3—C22—C23 | −7.76 (18) |
C16—C11—C12—C13 | 1.25 (18) | C3—O3—C22—C21 | 171.63 (12) |
C1—C11—C12—C13 | −179.38 (11) | C26—C21—C22—O3 | −177.87 (11) |
C16—C11—C12—Cl1 | −178.92 (9) | C2—C21—C22—O3 | −0.17 (18) |
C1—C11—C12—Cl1 | 0.44 (16) | C26—C21—C22—C23 | 1.53 (17) |
C11—C12—C13—C14 | −0.22 (18) | C2—C21—C22—C23 | 179.23 (11) |
Cl1—C12—C13—C14 | 179.96 (9) | O3—C22—C23—C24 | 178.65 (12) |
C12—C13—C14—C15 | −1.10 (19) | C21—C22—C23—C24 | −0.73 (18) |
C12—C13—C14—Cl2 | 178.88 (9) | C22—C23—C24—C25 | −0.9 (2) |
C13—C14—C15—C16 | 1.3 (2) | C23—C24—C25—C26 | 1.7 (2) |
Cl2—C14—C15—C16 | −178.68 (10) | C24—C25—C26—C21 | −0.90 (19) |
C14—C15—C16—C11 | −0.19 (19) | C22—C21—C26—C25 | −0.73 (18) |
C12—C11—C16—C15 | −1.04 (18) | C2—C21—C26—C25 | −178.67 (11) |
C1—C11—C16—C15 | 179.60 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2i | 0.98 | 2.59 | 3.5433 (18) | 165 |
C15—H15···O2i | 0.95 | 2.51 | 3.3945 (15) | 154 |
C16—H16···O3 | 0.95 | 2.48 | 3.3989 (15) | 163 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H12Cl2O3 |
Mr | 311.15 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 200 |
a, b, c (Å) | 12.1816 (5), 15.2481 (6), 7.4207 (4) |
β (°) | 99.299 (2) |
V (Å3) | 1360.25 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.38 × 0.37 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.847, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12933, 3379, 2868 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.080, 1.03 |
No. of reflections | 3379 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.23 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2i | 0.98 | 2.59 | 3.5433 (18) | 165.0 |
C15—H15···O2i | 0.95 | 2.51 | 3.3945 (15) | 154.4 |
C16—H16···O3 | 0.95 | 2.48 | 3.3989 (15) | 163.1 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Acknowledgements
AMI thanks Professor Swapan Bhattacharya, Director of the National Institute of Technology Karnataka, Surathkal, India, for encouragement and for providing research facilities. He also thanks the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India, for the Young Scientist award.
References
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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.
For decades, phenyl benzoate derivatives have found ample application in the identification of organic acids. 2,4-Dichlorobenzyl derivatives show pharmacological activity such as acting as mild antiseptics and showing the ability to kill bacteria and viruses associated with mouth and throat infections (Oxford et al., 2005; Ostergaard 1994). In continuation of our research focused on the crystal structures of medical compounds, the title compound was synthesized.
The molecule is essentially flat. The atom deviating most from the least-squares plane defined by all non-hydrogen atoms is the chlorine atom in para position to the benzyloxy moiety with a deviation of 0.237 (1) Å. The least-squares planes defined by the respective carbon atoms of the aromatic systems intersect at an angle of 10.78 (4) ° (Fig. 1).
In the crystal, intermolecular C–H···O contacts whose range falls by more than 0.1 Å below the sum of van-der-Waals radii are observed. These are established between one of the hydrogen atoms of the methoxy group as well as one of the two hydrogen atoms in ortho position to the chlorine atom in para position to the benzyloxy group and chelate the ketonic oxygen atom of the ester moiety. In total, the molecules are connected to chains along the crystallographic b axis. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is C11(7)C11(8) on the unary level. Information about metrical parameters as well as the symmetry of those contacts has been summarized in Table 1. The shortest intercentroid distance between two aromatic systems was measured at 3.7416 (8) Å and is apparent between the benzoic acid moiety and its symmetry-generated equivalent (Fig. 2).
The packing of the title compound in the crystal structure is shown in Figure 3.