organic compounds
1-(4-Bromophenyl)-2-(2-chlorophenoxy)ethanone
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, C14H10BrClO2, a twofold halogenated derivative of phenylated phenyloxyethanone, the least-squares planes defined by the C atoms of the aromatic rings subtend an angle of 71.31 (17)°. In the crystal, C—H⋯O contacts connect the molecules into chains along the b-axis direction.
Related literature
For the biological properties of phenoxyacetic acid derivatives, see: Ali & Shaharyar (2007); Kunsch et al. (2005); Iqbal et al. (2007); Sato et al. (2002); Kitagawa et al. (1991); Bicking et al. (1976); Osborne et al. (1955). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002).
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 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
10.1107/S160053681204785X/rz5023sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: 10.1107/S160053681204785X/rz5023Isup2.cdx
Structure factors: contains datablock I. DOI: 10.1107/S160053681204785X/rz5023Isup3.hkl
Supporting information file. DOI: 10.1107/S160053681204785X/rz5023Isup4.cml
A mixture of 2-bromo-1-(4-bromophenyl)ethanone (200 mg, 0.00072 mol), potassium carbonate (44.3 mg, 0.00079 mol) and 4-chlorophenol (92.56 mg, 0.00072 mol) in DMF (10 ml) was stirred at room temperature for 2 h. On cooling, colourless needle-shaped crystals of the title compound begin to separate. These were collected by filtration and recrystallized from ethanol, yield: 213.6 mg (91.2%).
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 Uiso(H) set to 1.2Ueq(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 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C14H10BrClO2 | F(000) = 648 |
Mr = 325.58 | Dx = 1.690 Mg m−3 |
Monoclinic, P21/c | Melting point = 388–387 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 15.2653 (8) Å | Cell parameters from 8161 reflections |
b = 4.5541 (2) Å | θ = 2.7–28.2° |
c = 23.7336 (9) Å | µ = 3.41 mm−1 |
β = 129.135 (2)° | T = 200 K |
V = 1279.80 (10) Å3 | Needle, colourless |
Z = 4 | 0.36 × 0.07 × 0.06 mm |
Bruker APEXII CCD diffractometer | 3040 independent reflections |
Radiation source: fine-focus sealed tube | 1953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ and ω scans | θmax = 28.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −20→17 |
Tmin = 0.377, Tmax = 0.811 | k = −5→6 |
15447 measured reflections | l = −28→31 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0791P)2 + 0.0906P] where P = (Fo2 + 2Fc2)/3 |
3040 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −1.04 e Å−3 |
C14H10BrClO2 | V = 1279.80 (10) Å3 |
Mr = 325.58 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.2653 (8) Å | µ = 3.41 mm−1 |
b = 4.5541 (2) Å | T = 200 K |
c = 23.7336 (9) Å | 0.36 × 0.07 × 0.06 mm |
β = 129.135 (2)° |
Bruker APEXII CCD diffractometer | 3040 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1953 reflections with I > 2σ(I) |
Tmin = 0.377, Tmax = 0.811 | Rint = 0.076 |
15447 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.65 e Å−3 |
3040 reflections | Δρmin = −1.04 e Å−3 |
163 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.47277 (3) | 0.61050 (9) | 0.417783 (13) | 0.05712 (18) | |
Cl1 | −0.03928 (6) | −0.09989 (17) | −0.16076 (3) | 0.0401 (2) | |
O1 | 0.07748 (15) | 0.1858 (5) | −0.02338 (8) | 0.0382 (5) | |
O2 | 0.27246 (18) | −0.0310 (6) | 0.09698 (10) | 0.0438 (5) | |
C1 | 0.1230 (2) | 0.3184 (8) | 0.04422 (12) | 0.0369 (7) | |
H1A | 0.0676 | 0.3028 | 0.0528 | 0.044* | |
H1B | 0.1366 | 0.5294 | 0.0424 | 0.044* | |
C2 | 0.2335 (2) | 0.1727 (7) | 0.10682 (12) | 0.0306 (6) | |
C11 | 0.1262 (2) | 0.2570 (7) | −0.05457 (12) | 0.0324 (7) | |
C12 | 0.0776 (2) | 0.1275 (7) | −0.12175 (12) | 0.0316 (6) | |
C13 | 0.1196 (3) | 0.1825 (8) | −0.15782 (14) | 0.0428 (8) | |
H13 | 0.0856 | 0.0939 | −0.2036 | 0.051* | |
C14 | 0.2109 (3) | 0.3659 (8) | −0.12732 (16) | 0.0483 (9) | |
H14 | 0.2412 | 0.4013 | −0.1515 | 0.058* | |
C15 | 0.2582 (3) | 0.4979 (9) | −0.06159 (15) | 0.0453 (8) | |
H15 | 0.3198 | 0.6292 | −0.0413 | 0.054* | |
C16 | 0.2173 (2) | 0.4421 (8) | −0.02466 (14) | 0.0403 (7) | |
H16 | 0.2520 | 0.5310 | 0.0212 | 0.048* | |
C21 | 0.2890 (2) | 0.2917 (7) | 0.18133 (11) | 0.0290 (6) | |
C22 | 0.3935 (2) | 0.1744 (8) | 0.23899 (13) | 0.0373 (7) | |
H22 | 0.4271 | 0.0270 | 0.2298 | 0.045* | |
C23 | 0.4487 (2) | 0.2704 (8) | 0.30945 (13) | 0.0398 (7) | |
H23 | 0.5207 | 0.1938 | 0.3485 | 0.048* | |
C24 | 0.3973 (2) | 0.4787 (8) | 0.32182 (12) | 0.0361 (7) | |
C25 | 0.2928 (2) | 0.5983 (7) | 0.26559 (13) | 0.0379 (7) | |
H25 | 0.2582 | 0.7413 | 0.2751 | 0.046* | |
C26 | 0.2403 (2) | 0.5033 (8) | 0.19527 (12) | 0.0332 (6) | |
H26 | 0.1696 | 0.5854 | 0.1561 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0536 (2) | 0.0768 (4) | 0.02415 (17) | −0.00832 (17) | 0.01652 (15) | −0.01059 (11) |
Cl1 | 0.0349 (3) | 0.0493 (6) | 0.0267 (3) | −0.0069 (3) | 0.0150 (3) | −0.0092 (2) |
O1 | 0.0282 (8) | 0.0587 (16) | 0.0232 (8) | −0.0105 (9) | 0.0142 (7) | −0.0105 (8) |
O2 | 0.0493 (12) | 0.0416 (16) | 0.0369 (10) | 0.0035 (11) | 0.0255 (9) | −0.0058 (9) |
C1 | 0.0286 (12) | 0.054 (2) | 0.0227 (10) | 0.0008 (13) | 0.0136 (9) | −0.0059 (11) |
C2 | 0.0279 (11) | 0.036 (2) | 0.0276 (11) | −0.0055 (12) | 0.0171 (9) | −0.0044 (10) |
C11 | 0.0263 (11) | 0.043 (2) | 0.0243 (10) | 0.0033 (12) | 0.0143 (9) | 0.0022 (10) |
C12 | 0.0290 (12) | 0.035 (2) | 0.0242 (10) | 0.0031 (11) | 0.0134 (9) | 0.0024 (9) |
C13 | 0.0496 (16) | 0.049 (2) | 0.0318 (12) | 0.0052 (15) | 0.0265 (12) | 0.0039 (12) |
C14 | 0.0552 (19) | 0.054 (3) | 0.0468 (16) | 0.0000 (16) | 0.0372 (15) | 0.0092 (13) |
C15 | 0.0404 (15) | 0.046 (2) | 0.0441 (15) | −0.0032 (15) | 0.0242 (13) | 0.0077 (14) |
C16 | 0.0327 (13) | 0.047 (2) | 0.0289 (12) | −0.0016 (13) | 0.0134 (11) | −0.0006 (11) |
C21 | 0.0240 (11) | 0.0334 (19) | 0.0255 (10) | −0.0054 (11) | 0.0137 (9) | −0.0034 (10) |
C22 | 0.0246 (11) | 0.050 (2) | 0.0313 (12) | 0.0016 (12) | 0.0148 (10) | 0.0000 (11) |
C23 | 0.0249 (11) | 0.055 (2) | 0.0288 (11) | 0.0004 (13) | 0.0121 (9) | 0.0036 (12) |
C24 | 0.0320 (12) | 0.050 (2) | 0.0208 (10) | −0.0104 (13) | 0.0141 (10) | −0.0063 (10) |
C25 | 0.0343 (13) | 0.047 (2) | 0.0276 (12) | −0.0023 (13) | 0.0171 (10) | −0.0071 (10) |
C26 | 0.0265 (12) | 0.041 (2) | 0.0256 (11) | −0.0014 (12) | 0.0133 (9) | −0.0028 (10) |
Br1—C24 | 1.887 (2) | C14—H14 | 0.9500 |
Cl1—C12 | 1.740 (3) | C15—C16 | 1.383 (4) |
O1—C11 | 1.379 (3) | C15—H15 | 0.9500 |
O1—C1 | 1.419 (3) | C16—H16 | 0.9500 |
O2—C2 | 1.202 (4) | C21—C26 | 1.378 (4) |
C1—C2 | 1.526 (4) | C21—C22 | 1.396 (4) |
C1—H1A | 0.9900 | C22—C23 | 1.385 (4) |
C1—H1B | 0.9900 | C22—H22 | 0.9500 |
C2—C21 | 1.499 (3) | C23—C24 | 1.376 (5) |
C11—C16 | 1.380 (4) | C23—H23 | 0.9500 |
C11—C12 | 1.395 (3) | C24—C25 | 1.391 (4) |
C12—C13 | 1.379 (4) | C25—C26 | 1.388 (3) |
C13—C14 | 1.375 (5) | C25—H25 | 0.9500 |
C13—H13 | 0.9500 | C26—H26 | 0.9500 |
C14—C15 | 1.376 (5) | ||
C11—O1—C1 | 117.5 (2) | C14—C15—H15 | 119.5 |
O1—C1—C2 | 111.6 (2) | C16—C15—H15 | 119.5 |
O1—C1—H1A | 109.3 | C11—C16—C15 | 119.9 (3) |
C2—C1—H1A | 109.3 | C11—C16—H16 | 120.1 |
O1—C1—H1B | 109.3 | C15—C16—H16 | 120.1 |
C2—C1—H1B | 109.3 | C26—C21—C22 | 119.2 (2) |
H1A—C1—H1B | 108.0 | C26—C21—C2 | 123.2 (2) |
O2—C2—C21 | 121.9 (2) | C22—C21—C2 | 117.6 (3) |
O2—C2—C1 | 121.7 (2) | C23—C22—C21 | 120.7 (3) |
C21—C2—C1 | 116.5 (2) | C23—C22—H22 | 119.6 |
O1—C11—C16 | 125.3 (2) | C21—C22—H22 | 119.6 |
O1—C11—C12 | 115.8 (2) | C24—C23—C22 | 118.7 (2) |
C16—C11—C12 | 118.9 (2) | C24—C23—H23 | 120.6 |
C13—C12—C11 | 120.8 (3) | C22—C23—H23 | 120.6 |
C13—C12—Cl1 | 120.0 (2) | C23—C24—C25 | 121.9 (2) |
C11—C12—Cl1 | 119.2 (2) | C23—C24—Br1 | 118.72 (19) |
C14—C13—C12 | 119.9 (3) | C25—C24—Br1 | 119.4 (2) |
C14—C13—H13 | 120.1 | C26—C25—C24 | 118.3 (3) |
C12—C13—H13 | 120.1 | C26—C25—H25 | 120.9 |
C13—C14—C15 | 119.6 (3) | C24—C25—H25 | 120.9 |
C13—C14—H14 | 120.2 | C21—C26—C25 | 121.1 (2) |
C15—C14—H14 | 120.2 | C21—C26—H26 | 119.4 |
C14—C15—C16 | 121.0 (3) | C25—C26—H26 | 119.4 |
C11—O1—C1—C2 | −77.1 (3) | C14—C15—C16—C11 | −1.5 (6) |
O1—C1—C2—O2 | −0.8 (4) | O2—C2—C21—C26 | −172.8 (3) |
O1—C1—C2—C21 | −179.2 (2) | C1—C2—C21—C26 | 5.6 (4) |
C1—O1—C11—C16 | 1.5 (4) | O2—C2—C21—C22 | 5.4 (4) |
C1—O1—C11—C12 | −178.6 (3) | C1—C2—C21—C22 | −176.2 (3) |
O1—C11—C12—C13 | −179.8 (3) | C26—C21—C22—C23 | −0.6 (4) |
C16—C11—C12—C13 | 0.1 (4) | C2—C21—C22—C23 | −178.9 (3) |
O1—C11—C12—Cl1 | 1.5 (4) | C21—C22—C23—C24 | 1.6 (5) |
C16—C11—C12—Cl1 | −178.6 (2) | C22—C23—C24—C25 | −1.1 (5) |
C11—C12—C13—C14 | 0.3 (5) | C22—C23—C24—Br1 | −179.8 (2) |
Cl1—C12—C13—C14 | 179.0 (3) | C23—C24—C25—C26 | −0.3 (5) |
C12—C13—C14—C15 | −1.3 (5) | Br1—C24—C25—C26 | 178.4 (2) |
C13—C14—C15—C16 | 1.9 (6) | C22—C21—C26—C25 | −0.8 (4) |
O1—C11—C16—C15 | −179.6 (3) | C2—C21—C26—C25 | 177.3 (3) |
C12—C11—C16—C15 | 0.5 (5) | C24—C25—C26—C21 | 1.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O2i | 0.99 | 2.57 | 3.457 (4) | 149 |
C16—H16···O2i | 0.95 | 2.57 | 3.425 (4) | 150 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H10BrClO2 |
Mr | 325.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 200 |
a, b, c (Å) | 15.2653 (8), 4.5541 (2), 23.7336 (9) |
β (°) | 129.135 (2) |
V (Å3) | 1279.80 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.41 |
Crystal size (mm) | 0.36 × 0.07 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.377, 0.811 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15447, 3040, 1953 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.125, 1.02 |
No. of reflections | 3040 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −1.04 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (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 |
C1—H1B···O2i | 0.99 | 2.57 | 3.457 (4) | 149.3 |
C16—H16···O2i | 0.95 | 2.57 | 3.425 (4) | 150.1 |
Symmetry code: (i) x, y+1, z. |
Acknowledgements
AMI thanks the Board for Research in Nuclear Sciences, Department of Atomic Energy, Government of India, for a 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.
Derivatives of phenoxyacetic acid are among the most potent fungicides. They demonstrate a variety of biological properties such as antimycobacterial (Ali & Shaharyar, 2007), anti-inflammatory and antioxidant (Kunsch et al., 2005), antibacterial (Iqbal et al., 2007), analgesic (Sato et al., 2002), diuretic (Kitagawa et al., 1991; Bicking et al., 1976) and growth regulatory (Osborne et al., 1955) activity. In continuation of our ongoing interest in bioactive compounds, the title compound was synthesized and its crystal structure was determined.
The O–C–C–O dihedral angle is found at -0.8 (4) °. A statistics of values for dihedral angles of comparable compounds whose molecular and crystal structure has been deposited with the CSD (Allen, 2002) shows that this eclipsed conformation is considerably smaller than the average angle found for the majority of these compounds. The least-squares planes defined by the carbon atoms of the two aromatic moieties enclose an angle of 71.31 (17) ° (Fig. 1 and Fig. 2).
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 of the atoms participating are apparent. These are supported by one of the hydrogen atoms of the methylene group as well as the hydrogen atom in ortho position to the oxygen atom on the chlorophenyl moiety as donors and have the ketonic oxygen atom as acceptor. These connect the molecules to chains along the crystallographic b axis. Information about metrical parameters as well as the symmetry of these contacts is summarized in Table 1. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is C11(4)C11(7) on the unary level. In addition, a dispersive Br···Br contact (3.583 (5) Å) was detected. The shortest intercentroid distance between two aromatic systems was measured at 4.554 (2) Å and is present between the chlorinated phenyl moiety and its symmetry-generated equivalent as well as between the brominated phenyl moiety and its symmetry-generated equivalent (Fig. 3). This value is in agreement with the length of cell axis b.
The packing of the title compound in the crystal structure is shown in Figure 4.