organic compounds
(E)-1-(Benzo[d][1,3]dioxol-5-yl)-3-(2,3-dichlorophenyl)prop-2-en-1-one
aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, bDepartment of Chemistry, GSSS Institute of Engineering and Technology for Women, Mysuru 570 016, India, cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and dInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India
*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, ajaykumar@ycm.uni-mysore.ac.in
In the title compound, C16H10Cl2O3, the olefinic double bond adopts an E conformation [C—C=C—C torsion angle = −172.9 (3)°]. The dihedral angle between the benzodioxole and dichlorobenzene rings is 5.57 (9)°. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯Cl hydrogen bonds, forming chains propagating along the c-axis direction.
Keywords: crystal structure; bis-chalcone; E configuration.
CCDC reference: 1528716
Structure description
et al., 2016). As part of our ongoing work on such molecules (Kumara et al., 2017), we report the synthesis and of the title compound here.
constitute the central cores for the construction of a wide range of bioactive compounds (NaveenThe structure of the molecule is shown in Fig. 1. The molecule is nearly planar, with a dihedral angle of 5.57 (9)° between the benzodioxole and dichloro benzene rings that are bridged by the olefinic double bond. This value is comparable with the value of 6.99 (6)° reported earlier between the aromatic rings in the related chalcone derivative (E)-1-(1,3-benzodioxol-5-yl)-3-(2,4,5-trimethoxy-phenyl)prop-2-en-1-one. (Sunitha et al., 2017). The trans conformation about the C7=C8 double bond in the central enone group is confirmed by the C4—C7=C8—C9 torsion angle, −172.9 (3)°. The carbonyl group at C7 lies almost in the plane of the olefinic double bond and benzodioxole ring as indicated by the C3—C4—C7—O3 and O3—C7—C8—C9 torsion angles 6.2 (3)° and 7.6 (4)° respectively.
In the crystal, the molecules are linked via weak C—H⋯O and C—H⋯Cl hydrogen bonds, forming chains propagating along the c-axis direction (Table 1 and Fig. 2).
Synthesis and crystallization
A mixture of 2,3-dichlorobenzaldehyde (5 mmol), 1-(benzo[d][1,3]dioxol-5-yl)ethanone (5 mmol) and sodium hydroxide (5 mmol) in methanol (25 ml) was stirred at room temperature for 3 h. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was poured into ice-cold water and kept in a refrigerator for 18 h. The solid that formed was filtered, and washed with cold hydrochloric acid (5%). Pure white crystals were obtained by slow evaporation from a methanol solution (yield 88%, m.p. 401–402 K).
Refinement
Crystal data, data collection and structure .
details are summarized in Table. 2Structural data
CCDC reference: 1528716
https://doi.org/10.1107/S2414314617001031/sj4082sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001031/sj4082Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617001031/sj4082Isup3.cml
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).C16H10Cl2O3 | F(000) = 656 |
Mr = 321.14 | Dx = 1.568 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 2086 reflections |
a = 10.1854 (7) Å | θ = 4.4–64.5° |
b = 11.0820 (8) Å | µ = 4.36 mm−1 |
c = 12.2077 (9) Å | T = 296 K |
β = 99.068 (3)° | Rectangle, white |
V = 1360.72 (17) Å3 | 0.28 × 0.26 × 0.24 mm |
Z = 4 |
Bruker X8 Proteum diffractometer | 2232 independent reflections |
Radiation source: Bruker MicroStar microfocus rotating anode | 2086 reflections with I > 2σ(I) |
Helios multilayer optics monochromator | Rint = 0.048 |
Detector resolution: 18.4 pixels mm-1 | θmax = 64.5°, θmin = 4.4° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −10→12 |
Tmin = 0.375, Tmax = 0.421 | l = −14→13 |
8712 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1218P)2 + 0.554P] where P = (Fo2 + 2Fc2)/3 |
2232 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
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 esds 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 > 2sigma(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 | −0.13750 (6) | 0.03536 (6) | 0.24874 (5) | 0.0316 (3) | |
Cl2 | −0.37087 (6) | −0.00563 (6) | 0.38206 (6) | 0.0377 (3) | |
O1 | 0.76711 (18) | 0.39765 (18) | 0.31535 (15) | 0.0353 (6) | |
O2 | 0.80348 (18) | 0.45912 (17) | 0.49834 (15) | 0.0322 (6) | |
O3 | 0.3035 (2) | 0.20086 (19) | 0.24062 (16) | 0.0393 (7) | |
C1 | 0.8544 (3) | 0.4624 (2) | 0.3945 (2) | 0.0304 (8) | |
C2 | 0.6590 (2) | 0.3683 (2) | 0.3649 (2) | 0.0260 (7) | |
C3 | 0.5445 (2) | 0.3131 (2) | 0.3184 (2) | 0.0272 (8) | |
C4 | 0.4480 (2) | 0.2919 (2) | 0.3881 (2) | 0.0261 (7) | |
C5 | 0.4743 (3) | 0.3250 (2) | 0.4999 (2) | 0.0273 (7) | |
C6 | 0.5927 (2) | 0.3814 (2) | 0.5459 (2) | 0.0282 (7) | |
C7 | 0.3208 (3) | 0.2367 (2) | 0.3373 (2) | 0.0292 (8) | |
C8 | 0.2132 (3) | 0.2262 (3) | 0.4053 (2) | 0.0353 (8) | |
C9 | 0.1024 (3) | 0.1677 (2) | 0.3710 (2) | 0.0287 (8) | |
C10 | −0.0084 (2) | 0.1487 (2) | 0.4320 (2) | 0.0252 (7) | |
C11 | −0.1248 (2) | 0.0878 (2) | 0.3834 (2) | 0.0255 (7) | |
C12 | −0.2286 (2) | 0.0698 (2) | 0.4426 (2) | 0.0273 (8) | |
C13 | −0.2211 (3) | 0.1102 (2) | 0.5504 (2) | 0.0311 (8) | |
C14 | −0.1074 (3) | 0.1695 (2) | 0.5994 (2) | 0.0311 (8) | |
C15 | −0.0023 (3) | 0.1880 (2) | 0.5422 (2) | 0.0284 (8) | |
C16 | 0.6823 (2) | 0.4034 (2) | 0.4754 (2) | 0.0256 (7) | |
H1 | 0.86110 | 0.54520 | 0.37040 | 0.0360* | |
H3 | 0.94230 | 0.42640 | 0.40360 | 0.0360* | |
H5 | 0.41090 | 0.30880 | 0.54500 | 0.0330* | |
H6 | 0.61000 | 0.40300 | 0.62040 | 0.0340* | |
H8 | 0.22450 | 0.26250 | 0.47490 | 0.0420* | |
H9 | 0.09340 | 0.13470 | 0.30020 | 0.0340* | |
H10 | 0.53010 | 0.29020 | 0.24420 | 0.0330* | |
H13 | −0.29130 | 0.09770 | 0.58940 | 0.0370* | |
H14 | −0.10160 | 0.19730 | 0.67180 | 0.0370* | |
H15 | 0.07360 | 0.22720 | 0.57720 | 0.0340* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0261 (4) | 0.0429 (5) | 0.0243 (4) | −0.0032 (2) | −0.0007 (3) | −0.0032 (2) |
Cl2 | 0.0241 (4) | 0.0427 (5) | 0.0458 (5) | −0.0060 (3) | 0.0038 (3) | −0.0033 (3) |
O1 | 0.0295 (10) | 0.0491 (11) | 0.0295 (10) | −0.0069 (8) | 0.0113 (8) | −0.0014 (8) |
O2 | 0.0233 (10) | 0.0450 (11) | 0.0277 (10) | −0.0076 (8) | 0.0026 (8) | 0.0003 (8) |
O3 | 0.0365 (11) | 0.0494 (12) | 0.0314 (11) | −0.0144 (9) | 0.0039 (8) | −0.0068 (9) |
C1 | 0.0240 (13) | 0.0345 (14) | 0.0344 (15) | −0.0024 (11) | 0.0103 (11) | 0.0075 (11) |
C2 | 0.0224 (12) | 0.0284 (13) | 0.0274 (12) | 0.0036 (10) | 0.0045 (10) | 0.0040 (10) |
C3 | 0.0279 (13) | 0.0290 (13) | 0.0246 (13) | 0.0002 (10) | 0.0042 (10) | −0.0016 (10) |
C4 | 0.0240 (13) | 0.0234 (12) | 0.0303 (13) | 0.0023 (10) | 0.0027 (10) | 0.0005 (10) |
C5 | 0.0231 (12) | 0.0290 (13) | 0.0307 (13) | 0.0012 (10) | 0.0069 (10) | 0.0051 (10) |
C6 | 0.0273 (13) | 0.0342 (13) | 0.0229 (12) | 0.0005 (11) | 0.0037 (10) | 0.0023 (10) |
C7 | 0.0282 (14) | 0.0260 (12) | 0.0334 (14) | −0.0007 (10) | 0.0048 (11) | 0.0015 (10) |
C8 | 0.0293 (14) | 0.0390 (15) | 0.0387 (15) | −0.0037 (12) | 0.0092 (12) | −0.0097 (12) |
C9 | 0.0308 (14) | 0.0293 (13) | 0.0245 (12) | −0.0035 (11) | −0.0004 (11) | 0.0002 (10) |
C10 | 0.0258 (13) | 0.0201 (12) | 0.0286 (13) | 0.0010 (10) | 0.0013 (10) | 0.0026 (10) |
C11 | 0.0268 (13) | 0.0233 (12) | 0.0245 (12) | 0.0034 (10) | −0.0015 (10) | 0.0008 (10) |
C12 | 0.0218 (13) | 0.0216 (12) | 0.0369 (14) | 0.0021 (10) | −0.0005 (11) | 0.0008 (10) |
C13 | 0.0310 (14) | 0.0275 (13) | 0.0365 (14) | 0.0056 (11) | 0.0103 (11) | 0.0025 (11) |
C14 | 0.0392 (15) | 0.0249 (13) | 0.0302 (13) | −0.0001 (11) | 0.0086 (11) | −0.0031 (10) |
C15 | 0.0320 (14) | 0.0237 (13) | 0.0280 (13) | −0.0030 (10) | −0.0001 (10) | −0.0003 (10) |
C16 | 0.0217 (12) | 0.0251 (12) | 0.0286 (13) | 0.0015 (10) | −0.0002 (10) | 0.0043 (10) |
Cl1—C11 | 1.729 (2) | C10—C11 | 1.411 (3) |
Cl2—C12 | 1.734 (2) | C10—C15 | 1.406 (3) |
O1—C1 | 1.403 (3) | C11—C12 | 1.386 (3) |
O1—C2 | 1.376 (3) | C12—C13 | 1.381 (3) |
O2—C1 | 1.444 (3) | C13—C14 | 1.383 (4) |
O2—C16 | 1.369 (3) | C14—C15 | 1.383 (4) |
O3—C7 | 1.231 (3) | C1—H1 | 0.9700 |
C2—C3 | 1.359 (3) | C1—H3 | 0.9700 |
C2—C16 | 1.388 (3) | C3—H10 | 0.9300 |
C3—C4 | 1.417 (3) | C5—H5 | 0.9300 |
C4—C5 | 1.398 (3) | C6—H6 | 0.9300 |
C4—C7 | 1.478 (4) | C8—H8 | 0.9300 |
C5—C6 | 1.395 (4) | C9—H9 | 0.9300 |
C6—C16 | 1.371 (3) | C13—H13 | 0.9300 |
C7—C8 | 1.480 (4) | C14—H14 | 0.9300 |
C8—C9 | 1.312 (4) | C15—H15 | 0.9300 |
C9—C10 | 1.462 (4) | ||
C1—O1—C2 | 106.40 (19) | C13—C14—C15 | 121.0 (2) |
C1—O2—C16 | 105.59 (19) | C10—C15—C14 | 121.1 (2) |
O1—C1—O2 | 108.4 (2) | O2—C16—C2 | 109.62 (19) |
O1—C2—C3 | 128.0 (2) | O2—C16—C6 | 128.3 (2) |
O1—C2—C16 | 109.56 (19) | C2—C16—C6 | 122.1 (2) |
C3—C2—C16 | 122.4 (2) | O1—C1—H1 | 110.00 |
C2—C3—C4 | 117.0 (2) | O1—C1—H3 | 110.00 |
C3—C4—C5 | 119.9 (2) | O2—C1—H1 | 110.00 |
C3—C4—C7 | 117.5 (2) | O2—C1—H3 | 110.00 |
C5—C4—C7 | 122.6 (2) | H1—C1—H3 | 108.00 |
C4—C5—C6 | 122.1 (2) | C2—C3—H10 | 122.00 |
C5—C6—C16 | 116.5 (2) | C4—C3—H10 | 121.00 |
O3—C7—C4 | 121.3 (3) | C4—C5—H5 | 119.00 |
O3—C7—C8 | 120.4 (3) | C6—C5—H5 | 119.00 |
C4—C7—C8 | 118.4 (2) | C5—C6—H6 | 122.00 |
C7—C8—C9 | 122.4 (2) | C16—C6—H6 | 122.00 |
C8—C9—C10 | 127.1 (2) | C7—C8—H8 | 119.00 |
C9—C10—C11 | 121.3 (2) | C9—C8—H8 | 119.00 |
C9—C10—C15 | 121.4 (2) | C8—C9—H9 | 116.00 |
C11—C10—C15 | 117.3 (2) | C10—C9—H9 | 116.00 |
Cl1—C11—C10 | 119.50 (17) | C12—C13—H13 | 121.00 |
Cl1—C11—C12 | 119.90 (17) | C14—C13—H13 | 121.00 |
C10—C11—C12 | 120.6 (2) | C13—C14—H14 | 120.00 |
Cl2—C12—C11 | 120.14 (18) | C15—C14—H14 | 120.00 |
Cl2—C12—C13 | 118.65 (19) | C10—C15—H15 | 120.00 |
C11—C12—C13 | 121.2 (2) | C14—C15—H15 | 119.00 |
C12—C13—C14 | 118.9 (2) | ||
C2—O1—C1—O2 | 6.8 (2) | C5—C6—C16—O2 | 178.6 (2) |
C1—O1—C2—C3 | 174.9 (2) | C5—C6—C16—C2 | −2.0 (3) |
C1—O1—C2—C16 | −5.4 (3) | O3—C7—C8—C9 | 7.6 (4) |
C16—O2—C1—O1 | −5.7 (2) | C4—C7—C8—C9 | −172.9 (3) |
C1—O2—C16—C2 | 2.4 (2) | C7—C8—C9—C10 | 178.1 (2) |
C1—O2—C16—C6 | −178.1 (2) | C8—C9—C10—C11 | 177.4 (3) |
O1—C2—C3—C4 | 179.5 (2) | C8—C9—C10—C15 | −4.0 (4) |
C16—C2—C3—C4 | −0.2 (3) | C9—C10—C11—Cl1 | −0.4 (3) |
O1—C2—C16—O2 | 1.8 (3) | C9—C10—C11—C12 | 179.6 (2) |
O1—C2—C16—C6 | −177.7 (2) | C15—C10—C11—Cl1 | −179.11 (17) |
C3—C2—C16—O2 | −178.5 (2) | C15—C10—C11—C12 | 0.9 (3) |
C3—C2—C16—C6 | 2.0 (4) | C9—C10—C15—C14 | −179.9 (2) |
C2—C3—C4—C5 | −1.5 (3) | C11—C10—C15—C14 | −1.2 (3) |
C2—C3—C4—C7 | 177.4 (2) | Cl1—C11—C12—Cl2 | 0.2 (3) |
C3—C4—C5—C6 | 1.4 (3) | Cl1—C11—C12—C13 | 179.73 (18) |
C7—C4—C5—C6 | −177.4 (2) | C10—C11—C12—Cl2 | −179.78 (17) |
C3—C4—C7—O3 | 6.2 (3) | C10—C11—C12—C13 | −0.3 (3) |
C3—C4—C7—C8 | −173.3 (2) | Cl2—C12—C13—C14 | 179.45 (18) |
C5—C4—C7—O3 | −175.0 (2) | C11—C12—C13—C14 | −0.1 (3) |
C5—C4—C7—C8 | 5.5 (3) | C12—C13—C14—C15 | −0.3 (4) |
C4—C5—C6—C16 | 0.3 (3) | C13—C14—C15—C10 | 0.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···Cl1 | 0.93 | 2.58 | 3.033 (3) | 110 |
C9—H9···O3 | 0.93 | 2.48 | 2.809 (4) | 101 |
C14—H14···O1i | 0.93 | 2.59 | 3.194 (3) | 123 |
Symmetry code: (i) x−1, −y+1/2, z+1/2. |
Acknowledgements
The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility.
References
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