organic compounds
3-(3,4-Dichlorobenzylidene)chroman-4-one
aSchool of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X54001, Durban 4000, South Africa, bChemistry Department, University of Cape Town, Rondebosch, 7701, South Africa, and cSchool of Chemical Engineering, University of KwaZulu-Natal, Durban 4041, South Africa
*Correspondence e-mail: Koorbanally@ukzn.ac.za
The distinctive feature of the structure of the title compound, C16H10Cl2O2, is the formation of a zigzag chain along [100] via Cl⋯Cl interactions [3.591 (1) and 3.631 (1) Å]. The chromanone moiety is fused with the benzene ring and adopts a half-chair conformation. The dihedral angle between the benzene ring of the chromanone moiety and the dichlorobenzene plane is 56.14 (8)°.
Related literature
For background to homoisoflavonoids, see: Kirkiacharian et al. (1984). For a related structure, see: Gopaul et al. (2012).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); 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); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812040561/hg5252sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812040561/hg5252Isup2.hkl
A mixture of chroman-4-one (1 g, 6.749 mmol), 3,4-dichlorobenzaldehyde (1.417 g, 8.099 mmol) and 10–15 drops of piperidine was heated at 80°C for 18 hrs. The reaction mixture was monitored for completion by thin layer
Upon completion, the reaction mixture was cooled, diluted with water and neutralized using 10% HCl. The reaction mixture was extracted with ethyl acetate (3 × 30 ml). The ethyl acetate layers were combined, washed with brine (20 ml), water (2 × 10 ml) and dried over anhydrous magnesium sulfate. The solvent was reduced and the compound purified by using silica gel (Merck 9385, 40–63 µm particle size) with a mobile phase of 2% ethyl acetate in hexane to yield the title compound with a m.p. of 165–167 °C.1H NMR: δ (p.p.m.): 5.27 (2H, d, J = 1.88 Hz, H-2), 6.96 (1H, d, J = 8.28 Hz, H-8), 7.07 (1H, td, J = 7.52, 0.68 Hz, H-6), 7.12 (1H, dd, J = 8.28, 1.96 Hz, H-6'), 7.38 (1H, d, J = 1.92 Hz, H-2'), 7.49 (1H, ddd, J = 8.72, 7.48, 1.72 Hz, H-7), 7.50 (1H, d, J = 8.40 Hz, H-5'), 7.72 (1H, s, H-9), 8.00 (1H, dd, J = 7.88, 1.64 Hz, H-5)
13C NMR: δ (p.p.m.): 67.27 (C-2), 118.00 (C-8), 121.79 (C-4a), 122.16 (C-6), 128.00 (C-5), 128.94 (C-6'), 130.79 (C-5'), 131.41 (C-2'), 132.44 (C-3), 133.15 (C-1'), 133.69 (C-3'), 134.28 (C-4'), 134.55 (C-9), 136.19 (C-7), 161.13 (C-8a), 181.71(C-4)
All hydrogen atoms were placed in geometrically idealized positions and constrainted to ride on their parent atoms, with aromatic C—H = 0.95 Å and methylene C—H = 0.99 Å; Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C16H10Cl2O2 | F(000) = 624 |
Mr = 305.14 | Dx = 1.551 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 15291 reflections |
a = 3.9224 (3) Å | θ = 1.9–28.3° |
b = 11.5175 (10) Å | µ = 0.49 mm−1 |
c = 28.957 (3) Å | T = 173 K |
β = 92.270 (2)° | Block, colourless |
V = 1307.12 (19) Å3 | 0.16 × 0.12 × 0.11 mm |
Z = 4 |
Bruker Kappa Duo APEXII Diffractometer | 3258 independent reflections |
Radiation source: fine-focus sealed tube | 2611 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
0.5° ϕ scans and ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −5→5 |
Tmin = 0.925, Tmax = 0.948 | k = −15→15 |
15291 measured reflections | l = −38→38 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0416P)2 + 0.370P] where P = (Fo2 + 2Fc2)/3 |
3258 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C16H10Cl2O2 | V = 1307.12 (19) Å3 |
Mr = 305.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.9224 (3) Å | µ = 0.49 mm−1 |
b = 11.5175 (10) Å | T = 173 K |
c = 28.957 (3) Å | 0.16 × 0.12 × 0.11 mm |
β = 92.270 (2)° |
Bruker Kappa Duo APEXII Diffractometer | 3258 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 2611 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 0.948 | Rint = 0.037 |
15291 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.30 e Å−3 |
3258 reflections | Δρmin = −0.21 e Å−3 |
181 parameters |
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 | 0.42734 (11) | 0.87066 (4) | 0.446666 (14) | 0.03559 (12) | |
Cl2 | 0.24634 (12) | 0.61056 (4) | 0.471571 (14) | 0.04001 (13) | |
O1 | 0.1216 (3) | 0.60873 (9) | 0.19421 (4) | 0.0295 (3) | |
O2 | −0.4016 (3) | 0.91508 (10) | 0.20528 (4) | 0.0370 (3) | |
C1 | 0.0018 (4) | 0.66516 (13) | 0.15546 (5) | 0.0257 (3) | |
C2 | −0.0674 (4) | 0.62604 (13) | 0.23556 (5) | 0.0264 (3) | |
H2A | 0.0689 | 0.5962 | 0.2625 | 0.032* | |
H2B | −0.2815 | 0.5806 | 0.2330 | 0.032* | |
C3 | −0.1530 (4) | 0.75127 (12) | 0.24381 (5) | 0.0246 (3) | |
C4 | −0.2625 (4) | 0.82037 (13) | 0.20229 (6) | 0.0263 (3) | |
C5 | −0.1875 (4) | 0.76778 (13) | 0.15740 (5) | 0.0253 (3) | |
C6 | −0.2890 (4) | 0.82258 (14) | 0.11584 (6) | 0.0316 (4) | |
H6 | −0.4186 | 0.8922 | 0.1166 | 0.038* | |
C7 | −0.2037 (5) | 0.77697 (16) | 0.07401 (6) | 0.0374 (4) | |
H7 | −0.2737 | 0.8148 | 0.0461 | 0.045* | |
C8 | −0.0143 (5) | 0.67520 (16) | 0.07285 (6) | 0.0365 (4) | |
H8 | 0.0453 | 0.6437 | 0.0439 | 0.044* | |
C9 | 0.0882 (4) | 0.61927 (14) | 0.11313 (6) | 0.0315 (3) | |
H9 | 0.2174 | 0.5496 | 0.1120 | 0.038* | |
C10 | −0.1366 (4) | 0.80455 (13) | 0.28501 (5) | 0.0269 (3) | |
H10 | −0.1923 | 0.8848 | 0.2848 | 0.032* | |
C11 | −0.0434 (4) | 0.75431 (13) | 0.33026 (5) | 0.0253 (3) | |
C12 | 0.1296 (4) | 0.82387 (13) | 0.36316 (5) | 0.0258 (3) | |
H12 | 0.1865 | 0.9015 | 0.3555 | 0.031* | |
C13 | 0.2187 (4) | 0.78142 (13) | 0.40650 (5) | 0.0256 (3) | |
C14 | 0.1346 (4) | 0.66795 (14) | 0.41804 (5) | 0.0263 (3) | |
C15 | −0.0449 (4) | 0.59937 (13) | 0.38621 (6) | 0.0275 (3) | |
H15 | −0.1075 | 0.5226 | 0.3944 | 0.033* | |
C16 | −0.1336 (4) | 0.64150 (13) | 0.34272 (5) | 0.0261 (3) | |
H16 | −0.2565 | 0.5936 | 0.3212 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0386 (2) | 0.0369 (2) | 0.0310 (2) | −0.00723 (17) | −0.00110 (17) | −0.00681 (16) |
Cl2 | 0.0470 (3) | 0.0436 (3) | 0.0291 (2) | −0.00285 (19) | −0.00218 (18) | 0.00968 (17) |
O1 | 0.0354 (6) | 0.0268 (6) | 0.0265 (6) | 0.0085 (4) | 0.0024 (5) | 0.0026 (4) |
O2 | 0.0447 (7) | 0.0258 (6) | 0.0400 (7) | 0.0113 (5) | −0.0050 (6) | 0.0018 (5) |
C1 | 0.0265 (7) | 0.0234 (7) | 0.0269 (8) | −0.0051 (6) | −0.0014 (6) | 0.0021 (6) |
C2 | 0.0314 (8) | 0.0232 (7) | 0.0245 (7) | 0.0025 (6) | 0.0013 (6) | 0.0011 (6) |
C3 | 0.0226 (7) | 0.0227 (7) | 0.0283 (8) | 0.0016 (5) | −0.0007 (6) | 0.0020 (6) |
C4 | 0.0247 (7) | 0.0217 (7) | 0.0321 (8) | 0.0006 (6) | −0.0032 (6) | 0.0020 (6) |
C5 | 0.0236 (7) | 0.0240 (7) | 0.0279 (8) | −0.0047 (6) | −0.0030 (6) | 0.0034 (6) |
C6 | 0.0283 (8) | 0.0314 (8) | 0.0348 (9) | −0.0041 (6) | −0.0046 (7) | 0.0082 (7) |
C7 | 0.0363 (9) | 0.0467 (10) | 0.0286 (9) | −0.0110 (8) | −0.0049 (7) | 0.0108 (7) |
C8 | 0.0387 (9) | 0.0440 (10) | 0.0271 (8) | −0.0118 (8) | 0.0044 (7) | −0.0016 (7) |
C9 | 0.0332 (8) | 0.0298 (8) | 0.0317 (9) | −0.0066 (7) | 0.0052 (7) | −0.0013 (6) |
C10 | 0.0262 (7) | 0.0224 (7) | 0.0322 (8) | 0.0013 (6) | 0.0014 (6) | 0.0013 (6) |
C11 | 0.0264 (7) | 0.0232 (7) | 0.0265 (8) | 0.0030 (6) | 0.0044 (6) | −0.0008 (6) |
C12 | 0.0282 (8) | 0.0207 (7) | 0.0287 (8) | 0.0000 (6) | 0.0052 (6) | −0.0021 (6) |
C13 | 0.0242 (7) | 0.0266 (7) | 0.0261 (8) | −0.0008 (6) | 0.0030 (6) | −0.0038 (6) |
C14 | 0.0258 (7) | 0.0299 (8) | 0.0233 (7) | 0.0020 (6) | 0.0036 (6) | 0.0039 (6) |
C15 | 0.0274 (8) | 0.0224 (7) | 0.0330 (8) | −0.0016 (6) | 0.0058 (6) | 0.0021 (6) |
C16 | 0.0257 (7) | 0.0239 (7) | 0.0287 (8) | −0.0010 (6) | 0.0020 (6) | −0.0032 (6) |
Cl1—C13 | 1.7330 (15) | C7—C8 | 1.389 (3) |
Cl2—C14 | 1.7256 (15) | C7—H7 | 0.9500 |
O1—C1 | 1.3641 (18) | C8—C9 | 1.378 (2) |
O1—C2 | 1.4470 (19) | C8—H8 | 0.9500 |
O2—C4 | 1.2243 (19) | C9—H9 | 0.9500 |
C1—C9 | 1.389 (2) | C10—C11 | 1.465 (2) |
C1—C5 | 1.398 (2) | C10—H10 | 0.9500 |
C2—C3 | 1.502 (2) | C11—C16 | 1.398 (2) |
C2—H2A | 0.9900 | C11—C12 | 1.400 (2) |
C2—H2B | 0.9900 | C12—C13 | 1.379 (2) |
C3—C10 | 1.341 (2) | C12—H12 | 0.9500 |
C3—C4 | 1.491 (2) | C13—C14 | 1.392 (2) |
C4—C5 | 1.474 (2) | C14—C15 | 1.385 (2) |
C5—C6 | 1.402 (2) | C15—C16 | 1.381 (2) |
C6—C7 | 1.374 (3) | C15—H15 | 0.9500 |
C6—H6 | 0.9500 | C16—H16 | 0.9500 |
C1—O1—C2 | 116.35 (12) | C9—C8—H8 | 119.6 |
O1—C1—C9 | 117.15 (14) | C7—C8—H8 | 119.6 |
O1—C1—C5 | 122.42 (14) | C8—C9—C1 | 119.71 (16) |
C9—C1—C5 | 120.37 (15) | C8—C9—H9 | 120.1 |
O1—C2—C3 | 112.89 (12) | C1—C9—H9 | 120.1 |
O1—C2—H2A | 109.0 | C3—C10—C11 | 128.05 (14) |
C3—C2—H2A | 109.0 | C3—C10—H10 | 116.0 |
O1—C2—H2B | 109.0 | C11—C10—H10 | 116.0 |
C3—C2—H2B | 109.0 | C16—C11—C12 | 118.51 (14) |
H2A—C2—H2B | 107.8 | C16—C11—C10 | 122.76 (14) |
C10—C3—C4 | 118.39 (13) | C12—C11—C10 | 118.66 (13) |
C10—C3—C2 | 125.29 (14) | C13—C12—C11 | 121.01 (14) |
C4—C3—C2 | 116.32 (13) | C13—C12—H12 | 119.5 |
O2—C4—C5 | 122.25 (14) | C11—C12—H12 | 119.5 |
O2—C4—C3 | 122.24 (15) | C12—C13—C14 | 119.84 (14) |
C5—C4—C3 | 115.51 (13) | C12—C13—Cl1 | 119.77 (12) |
C1—C5—C6 | 118.63 (15) | C14—C13—Cl1 | 120.38 (12) |
C1—C5—C4 | 120.50 (13) | C15—C14—C13 | 119.66 (14) |
C6—C5—C4 | 120.79 (14) | C15—C14—Cl2 | 118.93 (12) |
C7—C6—C5 | 120.90 (16) | C13—C14—Cl2 | 121.41 (12) |
C7—C6—H6 | 119.5 | C16—C15—C14 | 120.64 (14) |
C5—C6—H6 | 119.5 | C16—C15—H15 | 119.7 |
C6—C7—C8 | 119.56 (16) | C14—C15—H15 | 119.7 |
C6—C7—H7 | 120.2 | C15—C16—C11 | 120.31 (14) |
C8—C7—H7 | 120.2 | C15—C16—H16 | 119.8 |
C9—C8—C7 | 120.82 (16) | C11—C16—H16 | 119.8 |
C2—O1—C1—C9 | −156.47 (14) | C7—C8—C9—C1 | −0.1 (2) |
C2—O1—C1—C5 | 26.3 (2) | O1—C1—C9—C8 | −177.45 (14) |
C1—O1—C2—C3 | −46.21 (17) | C5—C1—C9—C8 | −0.2 (2) |
O1—C2—C3—C10 | −138.89 (16) | C4—C3—C10—C11 | 178.67 (15) |
O1—C2—C3—C4 | 40.74 (18) | C2—C3—C10—C11 | −1.7 (3) |
C10—C3—C4—O2 | −15.1 (2) | C3—C10—C11—C16 | −36.4 (2) |
C2—C3—C4—O2 | 165.28 (15) | C3—C10—C11—C12 | 146.59 (17) |
C10—C3—C4—C5 | 164.10 (14) | C16—C11—C12—C13 | 1.9 (2) |
C2—C3—C4—C5 | −15.56 (19) | C10—C11—C12—C13 | 179.04 (14) |
O1—C1—C5—C6 | 177.47 (13) | C11—C12—C13—C14 | −0.4 (2) |
C9—C1—C5—C6 | 0.3 (2) | C11—C12—C13—Cl1 | −179.05 (12) |
O1—C1—C5—C4 | 0.7 (2) | C12—C13—C14—C15 | −1.4 (2) |
C9—C1—C5—C4 | −176.41 (14) | Cl1—C13—C14—C15 | 177.26 (12) |
O2—C4—C5—C1 | 173.56 (15) | C12—C13—C14—Cl2 | 179.08 (12) |
C3—C4—C5—C1 | −5.6 (2) | Cl1—C13—C14—Cl2 | −2.23 (19) |
O2—C4—C5—C6 | −3.1 (2) | C13—C14—C15—C16 | 1.6 (2) |
C3—C4—C5—C6 | 177.72 (14) | Cl2—C14—C15—C16 | −178.85 (12) |
C1—C5—C6—C7 | −0.3 (2) | C14—C15—C16—C11 | −0.1 (2) |
C4—C5—C6—C7 | 176.48 (15) | C12—C11—C16—C15 | −1.7 (2) |
C5—C6—C7—C8 | 0.0 (2) | C10—C11—C16—C15 | −178.69 (15) |
C6—C7—C8—C9 | 0.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C16H10Cl2O2 |
Mr | 305.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 3.9224 (3), 11.5175 (10), 28.957 (3) |
β (°) | 92.270 (2) |
V (Å3) | 1307.12 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.16 × 0.12 × 0.11 |
Data collection | |
Diffractometer | Bruker Kappa Duo APEXII Diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.925, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15291, 3258, 2611 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.089, 1.03 |
No. of reflections | 3258 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.21 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).
Acknowledgements
We thank the University of KwaZulu-Natal and the South Africa Research Chairs initiative of the Department of Science and Technology for financial support and the National Research Foundation of South Africa for a bursary for KG.
References
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gopaul, K., Shaikh, M., Ramjugernath, D., Koorbanally, N. A. & Omondi, B. (2012). Acta Cryst. E68, o1006. CSD CrossRef IUCr Journals Google Scholar
Kirkiacharian, B. S., Gomis, M., Tongo, H. G., Mahuteau, J. & Brion, J. D. (1984). Org. Magn. Reson. 22, 106–108. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany. 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 title compound, 3-(3,4-dichlorobenzylidene)chroman-4-one (C16H10Cl2O2), belongs to a class of compounds called homoisoflavonoids, which are C-16, α,β unsaturated carbonyl compounds containing two aromatic rings. They are a group of naturally occurring molecules that are structurally related to isoflavonoids but differ by containing one more carbon atom (Kirkiacharian et al., 1984; Gopaul et al., 2012).
A view of the the title compound is shown in Fig. 1. The chromanone moiety is fused with the benzene ring and adopts a half chair conformation. The dihedral angle between the benzene ring of the chromanone moiety and the dichlorobenzene plane is 56.14 (8)°. The inversion-related molecules are linked into zigzag chains via Cl···Cl interactions between Cl2 at (x, y, z) and Cl2 at (1 - x, 1 - y, 1 - z) and Cl2 at (-x, 1 - y, 1 - z) with distances of 3.591 (1) Å and 3.631 (1) Å respectively. Molecules related by translation along the a axis stack via double π···π interactions of the aromatic rings, with a centroid distance equal to the length of a axis. This feature is illustrated in Fig. 2.