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organic compounds
(E)-3-(4-Chlorophenyl)-1-(2,4-dichloro-5-fluorophenyl)prop-2-en-1-one
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, bDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, cDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and dSyngene International Pvt Limited Plot No. 2 & 3 C, Unit-II Bommansandra Industrial Area, Bangalore 99, India
*Correspondence e-mail: hkfun@usm.my
In the title chalcone derivative, C15H8Cl3FO, the dihedral angle between the two benzene rings is 43.35 (8)°. Weak C—H⋯O and C—H⋯Cl intramolecular interactions involving the enone group generate S(5) and S(6) ring motifs, respectively. In the molecules are linked into antiparallel chains along the a axis. These chains are stacked along the b axis and short Cl⋯F contacts of 3.100 (1) Å link adjacent molecules of the antiparallel chains into dimers.
Related literature
For hydrogen bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987
). For related structures, see, for example: Fun et al. (2007
); Patil et al. (2007a
,b). For background to the applications of substituted see, for example: Agrinskaya et al. (1999
); Patil et al. (2006
); Shivarama Holla et al. (2004
). For related literature, see: Gu et al. (2008
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2005); cell APEX2; data reduction: SAINT (Bruker, 2005
); program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003
).
Supporting information
10.1107/S1600536808012178/sj2488sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808012178/sj2488Isup2.hkl
The title compound was synthesized by the condensation of 4-chlorobenzaldehyde (0.01 mol) with 2,4-dichloro-5-fluoroacetophenone (0.01 mol) in methanol (60 ml) in the presence of a catalytic amount of sodium hydroxide solution (10 ml, 10%). After stirring for 8 hr, the contents of the flask were poured into ice-cold water (500 ml) and left to stand for 5 hr. The resulting crude solid was filtered and dried. Colorless block-shaped single crystals of the title compound suitable for x-ray
were recrystallized from acetone.All H atoms were placed in calculated positions with d(C—H) = 0.93 Å, Uiso=1.2Ueq(C) for CH and aromatic atoms. The highest residual electron density peak is located at 0.67 Å from C4 and the deepest hole is located at 0.54 Å from Cl1.
Data collection: APEX2 (Bruker, 2005); cell
APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).C15H8Cl3FO | F(000) = 664 |
Mr = 329.56 | Dx = 1.638 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5852 reflections |
a = 6.8271 (1) Å | θ = 0.8–35.0° |
b = 3.7832 (1) Å | µ = 0.69 mm−1 |
c = 52.0206 (10) Å | T = 100 K |
β = 96.100 (1)° | Block, colorless |
V = 1336.00 (5) Å3 | 0.35 × 0.29 × 0.18 mm |
Z = 4 |
Bruker SMART APEX2 CCD area-detector diffractometer | 5852 independent reflections |
Radiation source: fine-focus sealed tube | 5257 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 8.33 pixels mm-1 | θmax = 35.0°, θmin = 0.8° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −6→6 |
Tmin = 0.794, Tmax = 0.889 | l = −83→72 |
42462 measured 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0246P)2 + 1.777P] where P = (Fo2 + 2Fc2)/3 |
5852 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C15H8Cl3FO | V = 1336.00 (5) Å3 |
Mr = 329.56 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.8271 (1) Å | µ = 0.69 mm−1 |
b = 3.7832 (1) Å | T = 100 K |
c = 52.0206 (10) Å | 0.35 × 0.29 × 0.18 mm |
β = 96.100 (1)° |
Bruker SMART APEX2 CCD area-detector diffractometer | 5852 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 5257 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.889 | Rint = 0.036 |
42462 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.29 | Δρmax = 0.47 e Å−3 |
5852 reflections | Δρmin = −0.31 e Å−3 |
181 parameters |
Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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 | 0.75834 (7) | 0.29526 (14) | 0.494133 (8) | 0.02272 (10) | |
Cl2 | 0.27758 (6) | −0.21297 (12) | 0.414214 (9) | 0.01926 (9) | |
Cl3 | −0.33602 (6) | 0.43796 (13) | 0.273464 (9) | 0.02136 (9) | |
F1 | 1.03386 (16) | 0.3790 (4) | 0.45548 (2) | 0.0240 (2) | |
O1 | 0.75361 (19) | −0.1864 (4) | 0.37069 (3) | 0.0211 (3) | |
C1 | 0.8267 (2) | 0.1756 (5) | 0.41951 (3) | 0.0159 (3) | |
H1 | 0.9260 | 0.2170 | 0.4090 | 0.019* | |
C2 | 0.8591 (2) | 0.2477 (5) | 0.44562 (3) | 0.0164 (3) | |
C3 | 0.7139 (3) | 0.1882 (5) | 0.46193 (3) | 0.0163 (3) | |
C4 | 0.5343 (2) | 0.0489 (5) | 0.45181 (3) | 0.0169 (3) | |
H4 | 0.4363 | 0.0044 | 0.4625 | 0.020* | |
C5 | 0.5022 (2) | −0.0237 (4) | 0.42545 (3) | 0.0147 (3) | |
C6 | 0.6458 (2) | 0.0408 (4) | 0.40887 (3) | 0.0144 (3) | |
C7 | 0.6216 (2) | −0.0317 (5) | 0.38025 (3) | 0.0153 (3) | |
C8 | 0.4414 (2) | 0.0999 (5) | 0.36537 (3) | 0.0163 (3) | |
H8 | 0.3552 | 0.2390 | 0.3737 | 0.020* | |
C9 | 0.3966 (2) | 0.0265 (5) | 0.34022 (3) | 0.0160 (3) | |
H9 | 0.4878 | −0.1048 | 0.3322 | 0.019* | |
C10 | 0.2173 (2) | 0.1348 (4) | 0.32437 (3) | 0.0142 (3) | |
C11 | 0.1999 (2) | 0.0697 (5) | 0.29770 (3) | 0.0160 (3) | |
H11 | 0.3036 | −0.0370 | 0.2904 | 0.019* | |
C12 | 0.0306 (3) | 0.1616 (5) | 0.28197 (3) | 0.0163 (3) | |
H12 | 0.0205 | 0.1187 | 0.2643 | 0.020* | |
C13 | −0.1239 (2) | 0.3191 (5) | 0.29314 (3) | 0.0161 (3) | |
C14 | −0.1123 (2) | 0.3856 (5) | 0.31941 (3) | 0.0166 (3) | |
H14 | −0.2171 | 0.4903 | 0.3266 | 0.020* | |
C15 | 0.0583 (2) | 0.2938 (5) | 0.33493 (3) | 0.0167 (3) | |
H15 | 0.0672 | 0.3383 | 0.3526 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0267 (2) | 0.0276 (2) | 0.01395 (17) | −0.00233 (17) | 0.00251 (14) | −0.00137 (16) |
Cl2 | 0.01366 (16) | 0.02036 (19) | 0.02387 (19) | −0.00204 (14) | 0.00256 (13) | −0.00089 (15) |
Cl3 | 0.01787 (17) | 0.0229 (2) | 0.0221 (2) | 0.00123 (15) | −0.00347 (14) | 0.00159 (16) |
F1 | 0.0177 (5) | 0.0353 (7) | 0.0186 (5) | −0.0072 (5) | 0.0003 (4) | −0.0023 (5) |
O1 | 0.0187 (6) | 0.0267 (7) | 0.0183 (6) | 0.0044 (5) | 0.0036 (4) | −0.0029 (5) |
C1 | 0.0135 (6) | 0.0179 (7) | 0.0163 (7) | 0.0005 (5) | 0.0023 (5) | 0.0005 (6) |
C2 | 0.0139 (6) | 0.0184 (7) | 0.0167 (7) | −0.0008 (5) | 0.0008 (5) | 0.0006 (6) |
C3 | 0.0187 (7) | 0.0173 (7) | 0.0132 (6) | 0.0012 (6) | 0.0027 (5) | 0.0010 (6) |
C4 | 0.0160 (7) | 0.0190 (7) | 0.0163 (7) | 0.0008 (6) | 0.0046 (5) | 0.0022 (6) |
C5 | 0.0123 (6) | 0.0139 (7) | 0.0178 (7) | 0.0008 (5) | 0.0015 (5) | 0.0007 (5) |
C6 | 0.0139 (6) | 0.0142 (7) | 0.0149 (7) | 0.0022 (5) | 0.0013 (5) | 0.0012 (5) |
C7 | 0.0160 (6) | 0.0151 (7) | 0.0148 (7) | 0.0002 (5) | 0.0015 (5) | −0.0004 (5) |
C8 | 0.0160 (7) | 0.0159 (7) | 0.0167 (7) | 0.0022 (6) | 0.0006 (5) | −0.0008 (6) |
C9 | 0.0156 (6) | 0.0156 (7) | 0.0166 (7) | −0.0001 (5) | 0.0014 (5) | 0.0001 (6) |
C10 | 0.0152 (6) | 0.0126 (6) | 0.0148 (6) | −0.0005 (5) | 0.0017 (5) | −0.0001 (5) |
C11 | 0.0177 (7) | 0.0158 (7) | 0.0148 (7) | 0.0004 (6) | 0.0036 (5) | −0.0008 (6) |
C12 | 0.0201 (7) | 0.0145 (7) | 0.0141 (7) | 0.0005 (6) | 0.0010 (5) | 0.0001 (5) |
C13 | 0.0156 (6) | 0.0154 (7) | 0.0166 (7) | −0.0013 (6) | −0.0009 (5) | 0.0016 (6) |
C14 | 0.0157 (6) | 0.0168 (7) | 0.0175 (7) | 0.0017 (6) | 0.0028 (5) | −0.0003 (6) |
C15 | 0.0169 (7) | 0.0190 (7) | 0.0143 (6) | 0.0007 (6) | 0.0023 (5) | −0.0006 (6) |
Cl1—C3 | 1.7190 (17) | C8—C9 | 1.341 (2) |
Cl2—C5 | 1.7366 (17) | C8—H8 | 0.9300 |
Cl3—C13 | 1.7412 (17) | C9—C10 | 1.460 (2) |
F1—C2 | 1.343 (2) | C9—H9 | 0.9300 |
O1—C7 | 1.224 (2) | C10—C11 | 1.402 (2) |
C1—C2 | 1.380 (2) | C10—C15 | 1.403 (2) |
C1—C6 | 1.395 (2) | C11—C12 | 1.388 (2) |
C1—H1 | 0.9300 | C11—H11 | 0.9300 |
C2—C3 | 1.390 (2) | C12—C13 | 1.391 (2) |
C3—C4 | 1.386 (2) | C12—H12 | 0.9300 |
C4—C5 | 1.392 (2) | C13—C14 | 1.383 (2) |
C4—H4 | 0.9300 | C14—C15 | 1.389 (2) |
C5—C6 | 1.394 (2) | C14—H14 | 0.9300 |
C6—C7 | 1.505 (2) | C15—H15 | 0.9300 |
C7—C8 | 1.469 (2) | ||
C2—C1—C6 | 120.37 (15) | C7—C8—H8 | 118.8 |
C2—C1—H1 | 119.8 | C8—C9—C10 | 125.68 (16) |
C6—C1—H1 | 119.8 | C8—C9—H9 | 117.2 |
F1—C2—C1 | 119.49 (15) | C10—C9—H9 | 117.2 |
F1—C2—C3 | 119.28 (15) | C11—C10—C15 | 118.36 (15) |
C1—C2—C3 | 121.23 (16) | C11—C10—C9 | 119.16 (15) |
C4—C3—C2 | 119.29 (15) | C15—C10—C9 | 122.45 (15) |
C4—C3—Cl1 | 121.14 (13) | C12—C11—C10 | 121.15 (16) |
C2—C3—Cl1 | 119.55 (13) | C12—C11—H11 | 119.4 |
C3—C4—C5 | 119.29 (15) | C10—C11—H11 | 119.4 |
C3—C4—H4 | 120.4 | C11—C12—C13 | 118.82 (15) |
C5—C4—H4 | 120.4 | C11—C12—H12 | 120.6 |
C4—C5—C6 | 121.82 (15) | C13—C12—H12 | 120.6 |
C4—C5—Cl2 | 116.97 (13) | C14—C13—C12 | 121.60 (15) |
C6—C5—Cl2 | 121.17 (13) | C14—C13—Cl3 | 119.38 (13) |
C5—C6—C1 | 117.98 (15) | C12—C13—Cl3 | 119.02 (13) |
C5—C6—C7 | 124.71 (15) | C13—C14—C15 | 119.06 (16) |
C1—C6—C7 | 117.29 (15) | C13—C14—H14 | 120.5 |
O1—C7—C8 | 124.03 (16) | C15—C14—H14 | 120.5 |
O1—C7—C6 | 118.75 (15) | C14—C15—C10 | 121.01 (16) |
C8—C7—C6 | 117.19 (14) | C14—C15—H15 | 119.5 |
C9—C8—C7 | 122.36 (16) | C10—C15—H15 | 119.5 |
C9—C8—H8 | 118.8 | ||
C6—C1—C2—F1 | −179.66 (16) | C5—C6—C7—C8 | 49.0 (2) |
C6—C1—C2—C3 | 0.1 (3) | C1—C6—C7—C8 | −132.33 (17) |
F1—C2—C3—C4 | −179.28 (16) | O1—C7—C8—C9 | 7.5 (3) |
C1—C2—C3—C4 | 0.9 (3) | C6—C7—C8—C9 | −174.50 (16) |
F1—C2—C3—Cl1 | 1.8 (2) | C7—C8—C9—C10 | 177.37 (16) |
C1—C2—C3—Cl1 | −177.94 (14) | C8—C9—C10—C11 | 173.51 (18) |
C2—C3—C4—C5 | −0.9 (3) | C8—C9—C10—C15 | −8.3 (3) |
Cl1—C3—C4—C5 | 177.97 (14) | C15—C10—C11—C12 | 0.4 (3) |
C3—C4—C5—C6 | −0.2 (3) | C9—C10—C11—C12 | 178.70 (16) |
C3—C4—C5—Cl2 | 177.69 (14) | C10—C11—C12—C13 | −0.4 (3) |
C4—C5—C6—C1 | 1.2 (3) | C11—C12—C13—C14 | 0.0 (3) |
Cl2—C5—C6—C1 | −176.57 (13) | C11—C12—C13—Cl3 | 179.54 (14) |
C4—C5—C6—C7 | 179.86 (16) | C12—C13—C14—C15 | 0.2 (3) |
Cl2—C5—C6—C7 | 2.1 (2) | Cl3—C13—C14—C15 | −179.27 (14) |
C2—C1—C6—C5 | −1.2 (3) | C13—C14—C15—C10 | −0.2 (3) |
C2—C1—C6—C7 | −179.91 (16) | C11—C10—C15—C14 | −0.2 (3) |
C5—C6—C7—O1 | −132.87 (19) | C9—C10—C15—C14 | −178.37 (17) |
C1—C6—C7—O1 | 45.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cl2 | 0.93 | 2.81 | 3.1164 (16) | 101 |
C9—H9···O1 | 0.93 | 2.57 | 2.878 (2) | 100 |
Experimental details
Crystal data | |
Chemical formula | C15H8Cl3FO |
Mr | 329.56 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 6.8271 (1), 3.7832 (1), 52.0206 (10) |
β (°) | 96.100 (1) |
V (Å3) | 1336.00 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.35 × 0.29 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.794, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42462, 5852, 5257 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.807 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.113, 1.29 |
No. of reflections | 5852 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.31 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cl2 | 0.93 | 2.81 | 3.1164 (16) | 101 |
C9—H9···O1 | 0.93 | 2.57 | 2.878 (2) | 100 |
Footnotes
‡Additional correspondence author, e-mail: suchada.c@psu.ac.th.
Acknowledgements
This work is supported by Department of Science and Technology (DST), Government of India, under grant No. SR/S2/LOP-17/2006. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.
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.
In recent years extensive research has been carried out on organic nonlinear optical materials particularly chalcone derivatives due to their high nonlinearity, varied synthesis, and better laser damage resistance as compared to their inorganic counterparts (Agrinskaya et al., 1999; Shivarama Holla et al., 2004; Patil et al., 2006). In view of the importance of these organic materials, the title compound (I) was synthesized and its crystal structure is reported here.
The total molecular structure of the title compound (Fig. 1) is not planar, the dihedral angles between the two benzene rings is 43.35 (8)°. Atoms O1, C6, C7 and C8 lie on a plane and the least-squares plane through this moiety makes dihedral angles of 47.45 (10)° and 4.16 (10)° with the C1–C6 and C10–C15 benzene rings, repectively. The orientation of the prop-2-en-1-one unit can be indicated by the torsion angles C7–C8–C9–C10 = 177.37 (16)° and O1–C7–C8–C9 = 7.5 (3)°. Bond lengths and angles in (I) are in normal ranges (Allen et al., 1987) and comparable to those in related structures (Fun et al., 2007; Patil et al., 2007a; 2007b).
In the structure, weak C9—H9···O1 and C8—H8···Cl2 intramolecular interactions generate S(5) and S(6) ring motifs (Bernstein et al., 1995) (Table 1). In the crystal structure (Fig. 2), the molecules are linked into anti-parallel chains along the a axis. These chains are stacked along the b-axis and short Cl···F contacts of 3.100 (1) Å link adjacent molecules of the anti-parallel chains into dimers. The crystal is also stabilized by weak C—H···O and C—H···Cl intramolecular interactions (Table 1).