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Chalcones (α,β-unsaturated ketones) are effective antitumour agents. It has been proved that having halogen or methoxy groups substituted in various positions of the phenyl ring enhances the activity of chalcones many times. The title compounds, C21H20O5 and C19H15BrO3, respectively, were chosen for crystallographic study in order to determine their structures and conformations. In both compounds, the keto group is in the s-cis conformation and is almost planar. There are weak intramolecular interactions in both structures.
Supporting information
CCDC references: 180160; 180161
The syntheses of compounds (I) and (II) consist of two steps.
3,4-Dimethoxystyryl 4'-hydroxyphenyl ketone and 1-bromostyryl 4'-hydroxyphenyl
ketone were prepared by the Claissen-Schmidt condensation of
3,4,dimethoxybenzaldehyde or 1-bromobenzaldehyde with 4-hydroxyacetophenone in
aqueous alcholol. Compounds (I) and (II) were then prepared by reacting
3,4-dimethoxystyryl 4'-hydroxyphenyl ketone or 1-bromostyryl 4'-hydroxyphenyl
ketone in methyl ethyl ketone with methacryloyl chloride in the presence of
triethylamine.
After checking their presence in the difference map, all H atoms were fixed
geometrically and allowed to ride on their attached atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (I); SMART (Siemens, 1996) for (II). Cell refinement: CAD-4 Software for (I); SAINT (Siemens, 1996) for (II). Data reduction: SDP (Frenz, 1978) for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997). Molecular graphics: ZORTEP (Zsolnai,1997) for (I); SHELXTL for (II). Software used to prepare material for publication: PARST (Nardelli, 1995) and PLATON (Spek, 1990) for (I); SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990) for (II).
(I) 4-[3-(3,4-Dimethoxyphenyl)prop-2-enoyl]phenyl methacrylate
top
Crystal data top
C21H20O5 | F(000) = 1488 |
Mr = 352.37 | Dx = 1.286 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54180 Å |
a = 13.381 (2) Å | Cell parameters from 25 reflections |
b = 20.813 (2) Å | θ = 4.1–25.0° |
c = 13.881 (2) Å | µ = 0.75 mm−1 |
β = 109.68 (1)° | T = 293 K |
V = 3640.0 (8) Å3 | Needle, colourless |
Z = 8 | 0.3 × 0.2 × 0.2 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.050 |
Radiation source: fine-focus sealed tube | θmax = 72.0°, θmin = 4.1° |
Graphite monochromator | h = −2→16 |
ω/2θ scans | k = 0→25 |
3812 measured reflections | l = −17→16 |
3549 independent reflections | 3 standard reflections every 200 reflections |
2444 reflections with I > 2σ(I) | intensity decay: <0.1% |
Refinement top
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0922P)2 + 0.6924P] where P = (Fo2 + 2Fc2)/3 |
3549 reflections | (Δ/σ)max < 0.001 |
238 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C21H20O5 | V = 3640.0 (8) Å3 |
Mr = 352.37 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 13.381 (2) Å | µ = 0.75 mm−1 |
b = 20.813 (2) Å | T = 293 K |
c = 13.881 (2) Å | 0.3 × 0.2 × 0.2 mm |
β = 109.68 (1)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.050 |
3812 measured reflections | 3 standard reflections every 200 reflections |
3549 independent reflections | intensity decay: <0.1% |
2444 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.27 e Å−3 |
3549 reflections | Δρmin = −0.22 e Å−3 |
238 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.48118 (16) | 0.16042 (10) | 0.11251 (15) | 0.0637 (5) | |
C10 | −0.07604 (15) | 0.06351 (10) | 0.11849 (14) | 0.0613 (5) | |
O5 | 0.49370 (12) | 0.04848 (7) | 0.11396 (13) | 0.0766 (4) | |
C3 | 0.32772 (16) | 0.09852 (9) | 0.10879 (15) | 0.0608 (5) | |
H3 | 0.2951 | 0.0590 | 0.1082 | 0.073* | |
C2 | 0.43169 (16) | 0.10073 (9) | 0.11195 (15) | 0.0613 (5) | |
O4 | 0.58327 (12) | 0.15740 (7) | 0.11380 (14) | 0.0803 (5) | |
C4 | 0.27059 (16) | 0.15542 (9) | 0.10639 (15) | 0.0636 (5) | |
C9 | −0.01194 (16) | 0.11840 (10) | 0.10340 (16) | 0.0682 (5) | |
O2 | −0.26290 (13) | −0.08349 (9) | 0.17100 (11) | 0.0855 (5) | |
C13 | −0.19997 (17) | −0.03308 (12) | 0.15513 (15) | 0.0694 (5) | |
C17 | −0.32525 (15) | −0.14995 (9) | 0.27588 (17) | 0.0662 (5) | |
C8 | 0.09742 (16) | 0.10715 (10) | 0.10483 (15) | 0.0651 (5) | |
H8 | 0.1227 | 0.0653 | 0.1078 | 0.078* | |
C16 | −0.25796 (16) | −0.09516 (10) | 0.26773 (16) | 0.0665 (5) | |
C15 | −0.16951 (17) | 0.07756 (12) | 0.13748 (17) | 0.0737 (6) | |
H15 | −0.1904 | 0.1202 | 0.1377 | 0.088* | |
O1 | −0.04908 (14) | 0.17312 (8) | 0.09273 (17) | 0.1000 (6) | |
C7 | 0.16029 (17) | 0.15598 (10) | 0.10187 (16) | 0.0672 (5) | |
H7 | 0.1293 | 0.1964 | 0.0961 | 0.081* | |
C11 | −0.04766 (16) | −0.00037 (10) | 0.11653 (15) | 0.0656 (5) | |
H11 | 0.0141 | −0.0107 | 0.1033 | 0.079* | |
O3 | −0.20585 (16) | −0.06307 (9) | 0.33833 (13) | 0.0983 (6) | |
C20 | 0.44644 (19) | −0.01285 (10) | 0.1069 (2) | 0.0784 (6) | |
H20A | 0.4981 | −0.0453 | 0.1092 | 0.118* | |
H20B | 0.3883 | −0.0161 | 0.0436 | 0.118* | |
H20C | 0.4208 | −0.0188 | 0.1631 | 0.118* | |
C5 | 0.32143 (18) | 0.21358 (10) | 0.10825 (18) | 0.0714 (5) | |
H5 | 0.2848 | 0.2516 | 0.1077 | 0.086* | |
C19 | −0.3193 (2) | −0.16732 (11) | 0.3809 (2) | 0.0808 (6) | |
H19A | −0.3531 | −0.2081 | 0.3799 | 0.121* | |
H19B | −0.3546 | −0.1351 | 0.4071 | 0.121* | |
H19C | −0.2462 | −0.1700 | 0.4239 | 0.121* | |
C6 | 0.42588 (18) | 0.21615 (10) | 0.11093 (17) | 0.0719 (6) | |
H6 | 0.4585 | 0.2557 | 0.1117 | 0.086* | |
C14 | −0.23157 (17) | 0.02958 (13) | 0.15588 (17) | 0.0776 (6) | |
H14 | −0.2938 | 0.0395 | 0.1686 | 0.093* | |
C18 | −0.38625 (19) | −0.18055 (12) | 0.1917 (2) | 0.0881 (7) | |
H18A | −0.4282 | −0.2150 | 0.1974 | 0.106* | |
H18B | −0.3866 | −0.1674 | 0.1276 | 0.106* | |
C21 | 0.6354 (2) | 0.21722 (12) | 0.1145 (2) | 0.0877 (7) | |
H21A | 0.7059 | 0.2095 | 0.1138 | 0.132* | |
H21B | 0.6392 | 0.2408 | 0.1751 | 0.132* | |
H21C | 0.5963 | 0.2417 | 0.0552 | 0.132* | |
C12 | −0.10995 (18) | −0.04891 (11) | 0.13405 (16) | 0.0705 (5) | |
H12 | −0.0911 | −0.0917 | 0.1316 | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0659 (11) | 0.0603 (11) | 0.0645 (12) | −0.0067 (9) | 0.0217 (9) | 0.0041 (9) |
C10 | 0.0554 (10) | 0.0722 (12) | 0.0520 (10) | 0.0076 (9) | 0.0124 (8) | 0.0071 (8) |
O5 | 0.0688 (9) | 0.0556 (8) | 0.1095 (12) | −0.0026 (6) | 0.0353 (8) | −0.0002 (7) |
C3 | 0.0652 (11) | 0.0557 (10) | 0.0615 (11) | −0.0059 (8) | 0.0214 (9) | 0.0025 (8) |
C2 | 0.0665 (11) | 0.0555 (10) | 0.0619 (11) | −0.0016 (8) | 0.0216 (9) | 0.0018 (8) |
O4 | 0.0705 (9) | 0.0656 (9) | 0.1086 (12) | −0.0092 (7) | 0.0351 (8) | 0.0071 (8) |
C4 | 0.0681 (12) | 0.0617 (11) | 0.0599 (11) | −0.0002 (9) | 0.0200 (9) | 0.0040 (9) |
C9 | 0.0654 (11) | 0.0675 (12) | 0.0693 (12) | 0.0137 (10) | 0.0195 (9) | 0.0131 (10) |
O2 | 0.0815 (10) | 0.1059 (12) | 0.0691 (9) | −0.0348 (9) | 0.0254 (8) | −0.0158 (8) |
C13 | 0.0623 (11) | 0.0908 (15) | 0.0520 (11) | −0.0138 (10) | 0.0152 (9) | −0.0061 (10) |
C17 | 0.0547 (10) | 0.0593 (11) | 0.0897 (15) | 0.0040 (8) | 0.0310 (10) | −0.0089 (10) |
C8 | 0.0643 (11) | 0.0659 (12) | 0.0646 (12) | 0.0069 (9) | 0.0209 (9) | 0.0086 (9) |
C16 | 0.0594 (11) | 0.0746 (13) | 0.0665 (12) | −0.0033 (9) | 0.0226 (9) | −0.0085 (10) |
C15 | 0.0591 (11) | 0.0815 (14) | 0.0784 (14) | 0.0144 (10) | 0.0202 (10) | 0.0080 (11) |
O1 | 0.0795 (10) | 0.0739 (11) | 0.1498 (18) | 0.0194 (8) | 0.0429 (11) | 0.0263 (10) |
C7 | 0.0686 (12) | 0.0651 (12) | 0.0671 (12) | 0.0078 (9) | 0.0219 (10) | 0.0074 (9) |
C11 | 0.0607 (11) | 0.0759 (13) | 0.0620 (11) | 0.0039 (9) | 0.0230 (9) | 0.0017 (9) |
O3 | 0.1109 (13) | 0.1109 (13) | 0.0701 (10) | −0.0475 (11) | 0.0266 (9) | −0.0144 (9) |
C20 | 0.0723 (13) | 0.0567 (12) | 0.1021 (17) | −0.0018 (10) | 0.0238 (12) | 0.0013 (11) |
C5 | 0.0789 (14) | 0.0558 (11) | 0.0797 (14) | 0.0039 (10) | 0.0271 (11) | 0.0043 (10) |
C19 | 0.0787 (14) | 0.0681 (13) | 0.1035 (18) | 0.0066 (11) | 0.0411 (13) | 0.0042 (12) |
C6 | 0.0788 (14) | 0.0579 (11) | 0.0785 (14) | −0.0111 (10) | 0.0259 (11) | 0.0021 (10) |
C14 | 0.0559 (11) | 0.1020 (18) | 0.0739 (14) | 0.0020 (11) | 0.0204 (10) | −0.0010 (12) |
C18 | 0.0767 (14) | 0.0794 (15) | 0.113 (2) | −0.0158 (12) | 0.0383 (14) | −0.0282 (14) |
C21 | 0.0797 (15) | 0.0717 (14) | 0.116 (2) | −0.0169 (11) | 0.0388 (14) | 0.0087 (13) |
C12 | 0.0728 (13) | 0.0740 (13) | 0.0655 (12) | −0.0033 (10) | 0.0243 (10) | −0.0035 (10) |
Geometric parameters (Å, º) top
C1—O4 | 1.362 (3) | C8—H8 | 0.9300 |
C1—C6 | 1.372 (3) | C16—O3 | 1.197 (2) |
C1—C2 | 1.407 (3) | C15—C14 | 1.377 (3) |
C10—C11 | 1.386 (3) | C15—H15 | 0.9300 |
C10—C15 | 1.393 (3) | C7—H7 | 0.9300 |
C10—C9 | 1.485 (3) | C11—C12 | 1.382 (3) |
O5—C2 | 1.363 (2) | C11—H11 | 0.9300 |
O5—C20 | 1.413 (2) | C20—H20A | 0.9600 |
C3—C2 | 1.378 (3) | C20—H20B | 0.9600 |
C3—C4 | 1.404 (3) | C20—H20C | 0.9600 |
C3—H3 | 0.9300 | C5—C6 | 1.387 (3) |
O4—C21 | 1.426 (3) | C5—H5 | 0.9300 |
C4—C5 | 1.385 (3) | C19—H19A | 0.9600 |
C4—C7 | 1.456 (3) | C19—H19B | 0.9600 |
C9—O1 | 1.231 (2) | C19—H19C | 0.9600 |
C9—C8 | 1.475 (3) | C6—H6 | 0.9300 |
O2—C16 | 1.344 (3) | C14—H14 | 0.9300 |
O2—C13 | 1.408 (3) | C18—H18A | 0.9300 |
C13—C14 | 1.372 (3) | C18—H18B | 0.9300 |
C13—C12 | 1.372 (3) | C21—H21A | 0.9600 |
C17—C18 | 1.340 (3) | C21—H21B | 0.9600 |
C17—C19 | 1.477 (3) | C21—H21C | 0.9600 |
C17—C16 | 1.481 (3) | C12—H12 | 0.9300 |
C8—C7 | 1.329 (3) | | |
| | | |
O4—C1—C6 | 124.93 (18) | C4—C7—H7 | 115.3 |
O4—C1—C2 | 115.32 (18) | C12—C11—C10 | 120.82 (19) |
C6—C1—C2 | 119.75 (19) | C12—C11—H11 | 119.6 |
C11—C10—C15 | 118.3 (2) | C10—C11—H11 | 119.6 |
C11—C10—C9 | 124.07 (18) | O5—C20—H20A | 109.5 |
C15—C10—C9 | 117.59 (19) | O5—C20—H20B | 109.5 |
C2—O5—C20 | 117.66 (16) | H20A—C20—H20B | 109.5 |
C2—C3—C4 | 120.57 (17) | O5—C20—H20C | 109.5 |
C2—C3—H3 | 119.7 | H20A—C20—H20C | 109.5 |
C4—C3—H3 | 119.7 | H20B—C20—H20C | 109.5 |
O5—C2—C3 | 125.13 (17) | C4—C5—C6 | 121.25 (19) |
O5—C2—C1 | 114.99 (17) | C4—C5—H5 | 119.4 |
C3—C2—C1 | 119.87 (18) | C6—C5—H5 | 119.4 |
C1—O4—C21 | 116.50 (17) | C17—C19—H19A | 109.5 |
C5—C4—C3 | 118.48 (19) | C17—C19—H19B | 109.5 |
C5—C4—C7 | 118.57 (19) | H19A—C19—H19B | 109.5 |
C3—C4—C7 | 122.95 (18) | C17—C19—H19C | 109.5 |
O1—C9—C8 | 120.4 (2) | H19A—C19—H19C | 109.5 |
O1—C9—C10 | 119.96 (19) | H19B—C19—H19C | 109.5 |
C8—C9—C10 | 119.56 (18) | C1—C6—C5 | 120.07 (19) |
C16—O2—C13 | 117.39 (16) | C1—C6—H6 | 120.0 |
C14—C13—C12 | 121.7 (2) | C5—C6—H6 | 120.0 |
C14—C13—O2 | 120.3 (2) | C13—C14—C15 | 118.8 (2) |
C12—C13—O2 | 117.9 (2) | C13—C14—H14 | 120.6 |
C18—C17—C19 | 124.0 (2) | C15—C14—H14 | 120.6 |
C18—C17—C16 | 120.5 (2) | C17—C18—H18A | 120.0 |
C19—C17—C16 | 115.56 (19) | C17—C18—H18B | 120.0 |
C7—C8—C9 | 120.91 (19) | H18A—C18—H18B | 120.0 |
C7—C8—H8 | 119.5 | O4—C21—H21A | 109.5 |
C9—C8—H8 | 119.5 | O4—C21—H21B | 109.5 |
O3—C16—O2 | 122.4 (2) | H21A—C21—H21B | 109.5 |
O3—C16—C17 | 124.7 (2) | O4—C21—H21C | 109.5 |
O2—C16—C17 | 112.88 (18) | H21A—C21—H21C | 109.5 |
C14—C15—C10 | 121.3 (2) | H21B—C21—H21C | 109.5 |
C14—C15—H15 | 119.4 | C13—C12—C11 | 119.1 (2) |
C10—C15—H15 | 119.4 | C13—C12—H12 | 120.4 |
C8—C7—C4 | 129.5 (2) | C11—C12—H12 | 120.4 |
C8—C7—H7 | 115.3 | | |
| | | |
C20—O5—C2—C3 | 3.5 (3) | C18—C17—C16—O3 | 175.7 (2) |
C20—O5—C2—C1 | −176.04 (19) | C19—C17—C16—O3 | −4.5 (3) |
C4—C3—C2—O5 | −179.67 (18) | C18—C17—C16—O2 | −2.8 (3) |
C4—C3—C2—C1 | −0.2 (3) | C19—C17—C16—O2 | 177.09 (18) |
O4—C1—C2—O5 | 0.7 (3) | C11—C10—C15—C14 | 1.2 (3) |
C6—C1—C2—O5 | −179.81 (18) | C9—C10—C15—C14 | −177.7 (2) |
O4—C1—C2—C3 | −178.84 (18) | C9—C8—C7—C4 | 177.5 (2) |
C6—C1—C2—C3 | 0.6 (3) | C5—C4—C7—C8 | −176.0 (2) |
C6—C1—O4—C21 | 0.6 (3) | C3—C4—C7—C8 | 4.1 (4) |
C2—C1—O4—C21 | −179.93 (19) | C15—C10—C11—C12 | −0.7 (3) |
C2—C3—C4—C5 | −0.6 (3) | C9—C10—C11—C12 | 178.19 (19) |
C2—C3—C4—C7 | 179.30 (19) | C3—C4—C5—C6 | 0.9 (3) |
C11—C10—C9—O1 | 170.4 (2) | C7—C4—C5—C6 | −179.0 (2) |
C15—C10—C9—O1 | −10.8 (3) | O4—C1—C6—C5 | 179.1 (2) |
C11—C10—C9—C8 | −11.7 (3) | C2—C1—C6—C5 | −0.3 (3) |
C15—C10—C9—C8 | 167.17 (19) | C4—C5—C6—C1 | −0.5 (3) |
C16—O2—C13—C14 | −78.2 (3) | C12—C13—C14—C15 | −1.7 (3) |
C16—O2—C13—C12 | 105.0 (2) | O2—C13—C14—C15 | −178.35 (18) |
O1—C9—C8—C7 | 4.7 (3) | C10—C15—C14—C13 | −0.1 (3) |
C10—C9—C8—C7 | −173.18 (19) | C14—C13—C12—C11 | 2.2 (3) |
C13—O2—C16—O3 | 2.8 (3) | O2—C13—C12—C11 | 178.98 (18) |
C13—O2—C16—C17 | −178.71 (18) | C10—C11—C12—C13 | −1.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1 | 0.93 | 2.42 | 2.784 (3) | 103 |
C18—H18B···O2 | 0.93 | 2.34 | 2.685 (3) | 101 |
(II) 4-[3-(2-bromophenyl)prop-2-enoyl]phenyl methacrylate
top
Crystal data top
C19H15BrO3 | Z = 2 |
Mr = 371.22 | F(000) = 376 |
Triclinic, P1 | Dx = 1.502 Mg m−3 |
a = 7.5272 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.1940 (4) Å | Cell parameters from 4174 reflections |
c = 11.5780 (4) Å | θ = 1.8–29.5° |
α = 96.227 (1)° | µ = 2.52 mm−1 |
β = 98.428 (1)° | T = 293 K |
γ = 108.763 (1)° | Block, light yellow |
V = 820.54 (5) Å3 | 0.44 × 0.32 × 0.12 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2840 independent reflections |
Radiation source: fine-focus sealed tube | 2355 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −8→8 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −12→8 |
Tmin = 0.404, Tmax = 0.752 | l = −13→13 |
4721 measured reflections | |
Refinement top
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0895P)2] where P = (Fo2 + 2Fc2)/3 |
2840 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.58 e Å−3 |
2 restraints | Δρmin = −1.08 e Å−3 |
Crystal data top
C19H15BrO3 | γ = 108.763 (1)° |
Mr = 371.22 | V = 820.54 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5272 (3) Å | Mo Kα radiation |
b = 10.1940 (4) Å | µ = 2.52 mm−1 |
c = 11.5780 (4) Å | T = 293 K |
α = 96.227 (1)° | 0.44 × 0.32 × 0.12 mm |
β = 98.428 (1)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2840 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2355 reflections with I > 2σ(I) |
Tmin = 0.404, Tmax = 0.752 | Rint = 0.052 |
4721 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 2 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.58 e Å−3 |
2840 reflections | Δρmin = −1.08 e Å−3 |
209 parameters | |
Special details top
Experimental. The data collection covered over a hemisphere of reciprocal space by a
combination of three sets of exposures; each set had a different ϕ angle (0,
88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω.
The crystal-to-detector distance was 4 cm and the detector swing angle was
-35°. Crystal decay was monitored by repeating fifty initial frames at the
end of data collection and analysing the intensity of duplicate reflections,
and was found to be negligible. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | −0.40576 (6) | −0.15977 (4) | −0.03665 (4) | 0.0564 (2) | |
O1 | 0.2418 (4) | −0.0783 (4) | 0.1754 (3) | 0.0716 (10) | |
O2 | 0.8047 (4) | −0.1698 (4) | 0.5954 (3) | 0.0610 (8) | |
O3 | 0.8349 (5) | −0.3662 (4) | 0.5073 (3) | 0.0698 (9) | |
C1 | −0.4797 (5) | −0.2994 (4) | 0.0605 (3) | 0.0404 (8) | |
C2 | −0.6723 (6) | −0.3763 (5) | 0.0457 (4) | 0.0533 (10) | |
H2A | −0.7599 | −0.3597 | −0.0112 | 0.064* | |
C3 | −0.7355 (6) | −0.4774 (5) | 0.1147 (4) | 0.0575 (11) | |
H3A | −0.8648 | −0.5300 | 0.1038 | 0.069* | |
C4 | −0.6045 (6) | −0.4998 (5) | 0.2003 (4) | 0.0559 (11) | |
H4A | −0.6457 | −0.5674 | 0.2476 | 0.067* | |
C5 | −0.4135 (6) | −0.4222 (4) | 0.2153 (3) | 0.0458 (9) | |
H5A | −0.3276 | −0.4378 | 0.2740 | 0.055* | |
C6 | −0.3438 (5) | −0.3211 (4) | 0.1458 (3) | 0.0378 (8) | |
C7 | −0.1388 (5) | −0.2422 (4) | 0.1599 (3) | 0.0416 (8) | |
H7A | −0.1024 | −0.1881 | 0.1020 | 0.050* | |
C8 | −0.0002 (5) | −0.2395 (4) | 0.2455 (3) | 0.0459 (9) | |
H8A | −0.0300 | −0.2907 | 0.3061 | 0.055* | |
C9 | 0.2024 (5) | −0.1559 (4) | 0.2467 (4) | 0.0436 (9) | |
C10 | 0.3567 (5) | −0.1671 (4) | 0.3382 (3) | 0.0384 (8) | |
C11 | 0.3250 (6) | −0.2649 (4) | 0.4151 (3) | 0.0472 (9) | |
H11A | 0.2020 | −0.3271 | 0.4112 | 0.057* | |
C12 | 0.4750 (6) | −0.2705 (5) | 0.4973 (4) | 0.0548 (10) | |
H12A | 0.4539 | −0.3372 | 0.5472 | 0.066* | |
C13 | 0.6548 (5) | −0.1763 (4) | 0.5039 (3) | 0.0455 (9) | |
C14 | 0.6911 (6) | −0.0798 (5) | 0.4292 (4) | 0.0526 (10) | |
H14A | 0.8146 | −0.0177 | 0.4345 | 0.063* | |
C15 | 0.5430 (5) | −0.0756 (4) | 0.3463 (4) | 0.0501 (10) | |
H15A | 0.5674 | −0.0107 | 0.2948 | 0.060* | |
C16 | 0.8803 (5) | −0.2743 (4) | 0.5912 (3) | 0.0424 (9) | |
C17 | 1.0245 (5) | −0.2530 (4) | 0.7005 (3) | 0.0445 (9) | |
C18 | 1.0487 (7) | −0.1542 (5) | 0.7963 (4) | 0.0649 (13) | |
H18A | 1.1360 | −0.1466 | 0.8646 | 0.078* | |
H18C | 0.9780 | −0.0943 | 0.7933 | 0.078* | |
C19 | 1.1292 (7) | −0.3521 (5) | 0.6967 (4) | 0.0631 (12) | |
H19A | 1.2521 | −0.3104 | 0.7482 | 0.095* | |
H19B | 1.1461 | −0.3741 | 0.6172 | 0.095* | |
H19C | 1.0581 | −0.4367 | 0.7222 | 0.095* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0533 (3) | 0.0556 (3) | 0.0546 (3) | 0.0156 (2) | −0.0086 (2) | 0.0209 (2) |
O1 | 0.0464 (18) | 0.086 (2) | 0.089 (2) | 0.0188 (17) | 0.0099 (17) | 0.057 (2) |
O2 | 0.0484 (17) | 0.065 (2) | 0.0609 (18) | 0.0271 (15) | −0.0204 (14) | −0.0057 (15) |
O3 | 0.078 (2) | 0.084 (2) | 0.0485 (17) | 0.0455 (19) | −0.0129 (15) | −0.0075 (16) |
C1 | 0.041 (2) | 0.042 (2) | 0.0356 (18) | 0.0154 (16) | −0.0013 (16) | 0.0040 (15) |
C2 | 0.039 (2) | 0.068 (3) | 0.046 (2) | 0.017 (2) | −0.0062 (17) | 0.0045 (19) |
C3 | 0.038 (2) | 0.070 (3) | 0.052 (2) | 0.006 (2) | 0.0011 (19) | 0.007 (2) |
C4 | 0.049 (3) | 0.061 (3) | 0.053 (2) | 0.010 (2) | 0.011 (2) | 0.014 (2) |
C5 | 0.043 (2) | 0.051 (2) | 0.044 (2) | 0.0174 (18) | 0.0034 (17) | 0.0136 (17) |
C6 | 0.0357 (19) | 0.040 (2) | 0.0367 (18) | 0.0158 (16) | 0.0009 (15) | 0.0028 (14) |
C7 | 0.036 (2) | 0.045 (2) | 0.046 (2) | 0.0169 (17) | 0.0038 (16) | 0.0141 (16) |
C8 | 0.0336 (19) | 0.057 (2) | 0.048 (2) | 0.0141 (17) | 0.0045 (17) | 0.0190 (17) |
C9 | 0.038 (2) | 0.049 (2) | 0.049 (2) | 0.0206 (18) | 0.0060 (17) | 0.0143 (17) |
C10 | 0.0318 (18) | 0.040 (2) | 0.044 (2) | 0.0152 (15) | 0.0027 (16) | 0.0059 (15) |
C11 | 0.0347 (19) | 0.054 (2) | 0.051 (2) | 0.0133 (17) | −0.0001 (17) | 0.0174 (18) |
C12 | 0.047 (2) | 0.064 (3) | 0.053 (2) | 0.020 (2) | −0.0016 (19) | 0.020 (2) |
C13 | 0.039 (2) | 0.051 (2) | 0.043 (2) | 0.0211 (18) | −0.0087 (17) | 0.0000 (17) |
C14 | 0.031 (2) | 0.052 (3) | 0.066 (3) | 0.0085 (18) | −0.0025 (19) | 0.008 (2) |
C15 | 0.038 (2) | 0.050 (2) | 0.060 (2) | 0.0118 (18) | 0.0071 (19) | 0.0163 (18) |
C16 | 0.0311 (18) | 0.049 (2) | 0.046 (2) | 0.0106 (16) | 0.0043 (16) | 0.0163 (17) |
C17 | 0.0332 (19) | 0.052 (2) | 0.042 (2) | 0.0053 (17) | 0.0003 (16) | 0.0166 (17) |
C18 | 0.064 (3) | 0.067 (3) | 0.054 (3) | 0.026 (2) | −0.017 (2) | −0.001 (2) |
C19 | 0.059 (3) | 0.079 (3) | 0.056 (3) | 0.036 (2) | −0.003 (2) | 0.013 (2) |
Geometric parameters (Å, º) top
Br1—C1 | 1.903 (4) | C9—C10 | 1.495 (5) |
O1—C9 | 1.207 (5) | C10—C11 | 1.395 (5) |
O2—C16 | 1.359 (5) | C10—C15 | 1.395 (5) |
O2—C13 | 1.410 (5) | C11—C12 | 1.386 (6) |
O3—C16 | 1.199 (5) | C11—H11A | 0.9300 |
C1—C2 | 1.383 (6) | C12—C13 | 1.370 (6) |
C1—C6 | 1.403 (5) | C12—H12A | 0.9300 |
C2—C3 | 1.379 (7) | C13—C14 | 1.368 (6) |
C2—H2A | 0.9300 | C14—C15 | 1.376 (6) |
C3—C4 | 1.383 (6) | C14—H14A | 0.9300 |
C3—H3A | 0.9300 | C15—H15A | 0.9300 |
C4—C5 | 1.375 (6) | C16—C17 | 1.487 (5) |
C4—H4A | 0.9300 | C17—C18 | 1.363 (4) |
C5—C6 | 1.393 (5) | C17—C19 | 1.469 (4) |
C5—H5A | 0.9300 | C18—H18A | 0.9300 |
C6—C7 | 1.468 (5) | C18—H18C | 0.9300 |
C7—C8 | 1.320 (5) | C19—H19A | 0.9600 |
C7—H7A | 0.9300 | C19—H19B | 0.9600 |
C8—C9 | 1.486 (5) | C19—H19C | 0.9600 |
C8—H8A | 0.9300 | | |
| | | |
C16—O2—C13 | 119.2 (3) | C12—C11—C10 | 120.7 (4) |
C2—C1—C6 | 121.3 (4) | C12—C11—H11A | 119.7 |
C2—C1—Br1 | 117.6 (3) | C10—C11—H11A | 119.7 |
C6—C1—Br1 | 121.0 (3) | C13—C12—C11 | 119.1 (4) |
C3—C2—C1 | 120.5 (4) | C13—C12—H12A | 120.5 |
C3—C2—H2A | 119.8 | C11—C12—H12A | 120.5 |
C1—C2—H2A | 119.8 | C14—C13—C12 | 121.7 (4) |
C2—C3—C4 | 119.3 (4) | C14—C13—O2 | 118.2 (4) |
C2—C3—H3A | 120.3 | C12—C13—O2 | 119.9 (4) |
C4—C3—H3A | 120.3 | C13—C14—C15 | 119.3 (4) |
C5—C4—C3 | 119.9 (4) | C13—C14—H14A | 120.4 |
C5—C4—H4A | 120.0 | C15—C14—H14A | 120.4 |
C3—C4—H4A | 120.0 | C14—C15—C10 | 121.0 (4) |
C4—C5—C6 | 122.4 (4) | C14—C15—H15A | 119.5 |
C4—C5—H5A | 118.8 | C10—C15—H15A | 119.5 |
C6—C5—H5A | 118.8 | O3—C16—O2 | 122.1 (4) |
C5—C6—C1 | 116.6 (3) | O3—C16—C17 | 127.4 (4) |
C5—C6—C7 | 121.9 (3) | O2—C16—C17 | 110.4 (3) |
C1—C6—C7 | 121.5 (3) | C18—C17—C19 | 124.0 (4) |
C8—C7—C6 | 127.3 (4) | C18—C17—C16 | 122.2 (3) |
C8—C7—H7A | 116.3 | C19—C17—C16 | 113.7 (3) |
C6—C7—H7A | 116.3 | C17—C18—H18A | 120.0 |
C7—C8—C9 | 121.1 (4) | C17—C18—H18C | 120.0 |
C7—C8—H8A | 119.4 | H18A—C18—H18C | 120.0 |
C9—C8—H8A | 119.4 | C17—C19—H19A | 109.5 |
O1—C9—C8 | 120.3 (4) | C17—C19—H19B | 109.5 |
O1—C9—C10 | 120.3 (4) | H19A—C19—H19B | 109.5 |
C8—C9—C10 | 119.4 (3) | C17—C19—H19C | 109.5 |
C11—C10—C15 | 118.2 (4) | H19A—C19—H19C | 109.5 |
C11—C10—C9 | 123.6 (3) | H19B—C19—H19C | 109.5 |
C15—C10—C9 | 118.2 (4) | | |
| | | |
C6—C1—C2—C3 | −0.3 (6) | C8—C9—C10—C15 | −172.5 (3) |
Br1—C1—C2—C3 | −178.9 (3) | C15—C10—C11—C12 | 0.1 (6) |
C1—C2—C3—C4 | 1.0 (7) | C9—C10—C11—C12 | 179.5 (4) |
C2—C3—C4—C5 | −0.4 (7) | C10—C11—C12—C13 | 1.5 (6) |
C3—C4—C5—C6 | −0.9 (6) | C11—C12—C13—C14 | −2.0 (6) |
C4—C5—C6—C1 | 1.5 (5) | C11—C12—C13—O2 | 172.8 (3) |
C4—C5—C6—C7 | −177.9 (4) | C16—O2—C13—C14 | −111.7 (4) |
C2—C1—C6—C5 | −0.9 (5) | C16—O2—C13—C12 | 73.3 (5) |
Br1—C1—C6—C5 | 177.7 (3) | C12—C13—C14—C15 | 0.9 (6) |
C2—C1—C6—C7 | 178.5 (4) | O2—C13—C14—C15 | −174.0 (3) |
Br1—C1—C6—C7 | −3.0 (5) | C13—C14—C15—C10 | 0.7 (6) |
C5—C6—C7—C8 | −10.1 (6) | C11—C10—C15—C14 | −1.1 (6) |
C1—C6—C7—C8 | 170.6 (4) | C9—C10—C15—C14 | 179.4 (4) |
C6—C7—C8—C9 | 178.9 (3) | C13—O2—C16—O3 | 6.3 (6) |
C7—C8—C9—O1 | 7.2 (6) | C13—O2—C16—C17 | −175.3 (3) |
C7—C8—C9—C10 | −173.8 (4) | O3—C16—C17—C18 | −172.2 (5) |
O1—C9—C10—C11 | −172.9 (4) | O2—C16—C17—C18 | 9.6 (6) |
C8—C9—C10—C11 | 8.1 (6) | O3—C16—C17—C19 | 5.1 (6) |
O1—C9—C10—C15 | 6.5 (6) | O2—C16—C17—C19 | −173.1 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···Br1 | 0.93 | 2.71 | 3.175 (4) | 112 |
C7—H7A···O1 | 0.93 | 2.44 | 2.781 (5) | 101 |
C18—H18C···O2 | 0.93 | 2.38 | 2.700 (6) | 100 |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C21H20O5 | C19H15BrO3 |
Mr | 352.37 | 371.22 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 13.381 (2), 20.813 (2), 13.881 (2) | 7.5272 (3), 10.1940 (4), 11.5780 (4) |
α, β, γ (°) | 90, 109.68 (1), 90 | 96.227 (1), 98.428 (1), 108.763 (1) |
V (Å3) | 3640.0 (8) | 820.54 (5) |
Z | 8 | 2 |
Radiation type | Cu Kα | Mo Kα |
µ (mm−1) | 0.75 | 2.52 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 | 0.44 × 0.32 × 0.12 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | – | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | – | 0.404, 0.752 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3812, 3549, 2444 | 4721, 2840, 2355 |
Rint | 0.050 | 0.052 |
(sin θ/λ)max (Å−1) | 0.617 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.163, 1.04 | 0.056, 0.146, 0.99 |
No. of reflections | 3549 | 2840 |
No. of parameters | 238 | 209 |
No. of restraints | 0 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 | 0.58, −1.08 |
Selected geometric parameters (Å, º) for (I) topC1—O4 | 1.362 (3) | C9—C8 | 1.475 (3) |
O5—C2 | 1.363 (2) | O2—C16 | 1.344 (3) |
O5—C20 | 1.413 (2) | O2—C13 | 1.408 (3) |
O4—C21 | 1.426 (3) | C16—O3 | 1.197 (2) |
C9—O1 | 1.231 (2) | | |
| | | |
O4—C1—C6 | 124.93 (18) | O5—C2—C3 | 125.13 (17) |
O4—C1—C2 | 115.32 (18) | O5—C2—C1 | 114.99 (17) |
C11—C10—C9 | 124.07 (18) | C8—C7—C4 | 129.5 (2) |
C15—C10—C9 | 117.59 (19) | | |
| | | |
C15—C10—C9—C8 | 167.17 (19) | C9—C8—C7—C4 | 177.5 (2) |
O1—C9—C8—C7 | 4.7 (3) | C5—C4—C7—C8 | −176.0 (2) |
C10—C9—C8—C7 | −173.18 (19) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1 | 0.93 | 2.42 | 2.784 (3) | 103 |
C18—H18B···O2 | 0.93 | 2.34 | 2.685 (3) | 101 |
Selected geometric parameters (Å, º) for (II) topBr1—C1 | 1.903 (4) | O2—C13 | 1.410 (5) |
O1—C9 | 1.207 (5) | O3—C16 | 1.199 (5) |
O2—C16 | 1.359 (5) | C7—C8 | 1.320 (5) |
| | | |
C11—C10—C9 | 123.6 (3) | C15—C10—C9 | 118.2 (4) |
| | | |
C1—C6—C7—C8 | 170.6 (4) | C7—C8—C9—C10 | −173.8 (4) |
C6—C7—C8—C9 | 178.9 (3) | C8—C9—C10—C11 | 8.1 (6) |
C7—C8—C9—O1 | 7.2 (6) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···Br1 | 0.93 | 2.7064 | 3.175 (4) | 112 |
C7—H7A···O1 | 0.93 | 2.4434 | 2.781 (5) | 101 |
C18—H18C···O2 | 0.93 | 2.3747 | 2.700 (6) | 100 |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
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Chalcones possess multiprotecting, biochemical, antifungal, antimalarial and antifertility activities. The carbonyl group is a characteristic functional group in chalcones. In recent years, the synthesis of polymers having a photosensitive functional group has been an active field of research in polymer science. Monomers having structures similar to the title compounds, 4-[3-(3,4-dimethoxyphenyl)prop-2-enoyl]phenyl methacrylate, (I), and 4-[3-(2-bromophenyl)prop-2-enoyl]phenyl methacrylate, (II), have been polymerized in solution using free-radical initiators (Balaji et al., 2000; Subramanian et al., 2001). These polymers, containing an α,β-unsaturated carbonyl group, undergo crosslinking upon irradiation with UV light or an electron beam and are being used as photoresistors (Hyder Ali & Srinivasan, 1997; Rehab & Salahuddin, 1999). These photosensitive polymers find application in the fields of integrated circuit technology, printing technology and photocurable coatings (Nagamatzu & Inui, 1977).
The keto group is in an s-cis conformation in compounds (I) and (II), as can be seen from the torsion-angle values [C7—C8—C9—O1 = 4.7 (3)° for (I) and 7.2 (6)° for (II)]. The two phenyl rings make dihedral angles with the keto group of 8.5 (2) and 11.8 (1)° for (I), and 4.8 (2) and 7.6 (2)° for (II). In general, the bond lengths in these conjugated systems are longer than the double bonds and shorter than the single bonds. In both structures, the bond lengths agree with reported values (Carpy et al., 1997). From the torsion angle values C5—C4—C7—C8 = -176.0 (2)°, C4—C7—C8—C9 = 177.5 (2)°, C7—C8—C9—C10 = -173.2 (2)° and C8—C9—C10—C15 = -167.2 (2)° in (I) and C1—C6—C7—C8 = 170.6 (4)°, C6—C7—C8—C9 = 178.9 (3)°, C7—C8—C9—C10 = -173.8 (4)° and C8—C9—C10—C11 = 8.1 (6)° in (II), it is clear that the unsaturated ketone system is not strictly planar. This deviation from planarity affects the π-electron conjugation. The H atoms at C7 and C8 are trans. The opening of the C4—C7—C8 angle to 129.5 (2)° in (I) and the C6—C7—C8 angle to 127.3 (4)° in (II) can be ascribed to the short interatomic non-bonded interaction between atoms H8 and H3 in (I), which are separated by a distance of 2.309 (2) Å, and the interaction between atoms H5 and H8 in (II), which are at a distance of 2.211 (1) Å (Tokuno et al., 1986). This non-bonded interaction also produces an appreciable twist about the C4—C7 bond at the expense of the conjugation energy of the system. The exocyclic angles about C10 reveal deviations from normal trigonal values, with a larger C9—C10—C11 angle [124.1 (2)° for (I) and 123.5 (3)° for (II)] and a smaller C9—C10—C15 angle [117.6 (2)° for (I) and 118.1 (3)° for (II)]. There are two weak C—H···O intramolecular interactions in (I) and (II), and one weak C—H···Br interaction in (II) (Tables 3 and 4).
Displacement-ellipsoid plots of (I) and (II) are shown in Figs. 1 and 2, respectively. Figs. 3 and 4 show the packing of molecules (I) and (II), viewed down the a axis in each case.