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The title mol­ecule, C15H15BrO3, has an s-cis conformation for the ketone system. The two phenyl rings form a dihedral angle of 11.0 (4)°, and the methacryl­oyl­oxy group is inclined to the attached phenyl ring by 61.5 (4)°. The structure is stabilized by C—H...π interactions and van der Waals interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000126/wn6130sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000126/wn6130Isup2.hkl
Contains datablock I

CCDC reference: 204681

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.011 Å
  • R factor = 0.069
  • wR factor = 0.169
  • Data-to-parameter ratio = 16.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.129 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.26 From the CIF: _reflns_number_total 3381 Count of symmetry unique reflns 2057 Completeness (_total/calc) 164.37% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1324 Fraction of Friedel pairs measured 0.644 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Chalcones, which are α,β-unsaturated ketones, possess multi-protecting biochemical activities, including antibacterial, antifungal, sedative, germicidal, cardiovascular, antifertility etc. It has been proven that halogen substitution at the benzene nucleus enhances greatly the activity of 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 compound, C15H15BrO3, have been polymerized in solution using free radical initiators (Balaji & Nanjundan, 2001; Subramanian et al., 2001). These polymers 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 and photocurable coatings (Nagamatzu & Inui, 1977). The structure determination of the title compound was undertaken as part of our study of chalcones.

In the title molecule, the spatial arrangement of the keto group and the olefenic double bond about the linking single bond is s-cis, as seen from the C7—C8—C9—O1 torsion angle of −7.7 (13)° (Fig. 1). A similar conformation has been reported previously for related structures (Raj et al., 1996, 1997; Jeyabharathi et al., 2002). The unsaturated ketone system is not strictly planar. The two phenyl rings and the unsaturated ketone system together form a curved structure, with a dihedral angle of 11.0 (4)° between the two phenyl rings. This deviation from planarity affects the π-electron conjugation. The mean plane through the methacryloyloxy group forms a dihedral angle of 61.5 (4)°, with the attached phenyl ring. The widening of the C5—C6—C7 angle to 124.1 (7)° and the C6—C7—C8 angle to 128.7 (7)° can be ascribed to the short interatomic contact between atoms H5 and H8 [2.35 Å]. Also, the strain induced by the short H8···H11 [2.17 Å] contact has resulted in a slight opening of the C9—C10—C11 angle to 123.2 (6)°. In the methacryloyloxy group, the two double bonds are in the s-cis conformation, whereas in two closely related structures, they adopt an s-trans conformation (Jeyabharathi et al., 2002). Steric interactions cause the bond angles around atoms C16 and C17 to deviate significantly from 120°. Weak intramolecular C—H···O interactions involving the ketone O atom, O1, are observed. The molecular packing in the solid state is stabilized by weak C—H···π interactions involving H1, H4, H12 and H15 and the phenyl rings of symmetry-related molecules (Table 2). A view of the C—H···π bonded molecular chain is shown in Fig. 2. In Table 2, CgA and CgB denote the centroids of the phenyl rings C1—C6 and C10—C15, respectively.

Experimental top

The synthesis of the title compound consisted of three steps. Methacryloyl chloride was prepared according to the method of Stampel et al. (1950). 3-Bromostyryl-4'-hydroxyphenyl ketone was prepared by the Claissen-Schmidt condensation of 3-bromobenzaldehyde in aqueous alcohol in the presence of sodium hydroxide. The title compound was prepared by reacting 3-bromostyryl-4'-hydroxyphenyl ketone with methacryloyl chloride in methyl ethyl ketone in the presence of triethylamine. Single crystals suitable for X-ray diffraction were grown from a 1:1 methanol–chloroform mixture.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 or 0.96 Å and Uiso(H) = 1.5 Ueq(C) for methyl H and 1.2 Ueq(C) for all others. Rotating group refinement was used for the methyl group. The reflections (0 1 9) and (1 2 31) were removed during refinement, as the observed and calculated structure factors showed large disagreement. The high Rint value (0.129) and low precision of the geometric parameters may be a result of the poor diffraction quality of the crystal. The deepest residual electron density hole occurs at 0.96 Å from Br1.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. A view of the title molecule, with the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. A view of the C—H···π interactions in the title compound.
1-(4-Methacryloyloxyphenyl)-3-(3-bromophenyl)prop-2-en-1-one top
Crystal data top
C19H15BrO3F(000) = 752
Mr = 371.22Dx = 1.511 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 3329 reflections
a = 7.8096 (2) Åθ = 3.3–28.3°
b = 5.6168 (2) ŵ = 2.53 mm1
c = 37.212 (1) ÅT = 203 K
V = 1632.30 (8) Å3Slab, colorless
Z = 40.40 × 0.28 × 0.04 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3381 independent reflections
Radiation source: fine-focus sealed tube1860 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.129
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 3.3°
ω scansh = 910
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 67
Tmin = 0.431, Tmax = 0.906l = 4943
9099 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.069 w = 1/[σ2(Fo2) + (0.0757P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.169(Δ/σ)max < 0.001
S = 0.93Δρmax = 0.68 e Å3
3381 reflectionsΔρmin = 1.04 e Å3
210 parametersExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0196 (19)
Primary atom site location: structure-invariant direct methodsAbsolute structure: (Flack, 1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (2)
Crystal data top
C19H15BrO3V = 1632.30 (8) Å3
Mr = 371.22Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 7.8096 (2) ŵ = 2.53 mm1
b = 5.6168 (2) ÅT = 203 K
c = 37.212 (1) Å0.40 × 0.28 × 0.04 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3381 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1860 reflections with I > 2σ(I)
Tmin = 0.431, Tmax = 0.906Rint = 0.129
9099 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.069H-atom parameters constrained
wR(F2) = 0.169Δρmax = 0.68 e Å3
S = 0.93Δρmin = 1.04 e Å3
3381 reflectionsAbsolute structure: (Flack, 1983)
210 parametersAbsolute structure parameter: 0.02 (2)
1 restraint
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
xyzUiso*/Ueq
Br10.60774 (10)0.14355 (15)0.26916 (3)0.0420 (3)
O10.6432 (8)0.6434 (11)0.45790 (16)0.0367 (16)
O20.2936 (6)0.5582 (9)0.61016 (12)0.0219 (12)
O30.4186 (10)0.2211 (14)0.63066 (17)0.057 (2)
C10.5657 (9)0.1984 (14)0.34480 (19)0.0200 (17)
H10.62520.34000.34130.024*
C20.5305 (9)0.0506 (15)0.3154 (2)0.0230 (18)
C30.4436 (10)0.1614 (14)0.3204 (2)0.0283 (19)
H30.41910.25850.30090.034*
C40.3929 (10)0.2295 (15)0.3547 (2)0.0271 (18)
H40.33480.37230.35810.033*
C50.4290 (9)0.0845 (15)0.3839 (2)0.0237 (18)
H50.39750.13350.40680.028*
C60.5122 (9)0.1353 (13)0.37940 (19)0.0191 (16)
C70.5464 (10)0.3037 (13)0.4088 (2)0.0209 (17)
H70.61020.43730.40260.025*
C80.4984 (10)0.2905 (14)0.4429 (2)0.0249 (18)
H80.43580.16050.45110.030*
C90.5455 (10)0.4855 (16)0.4680 (2)0.0221 (18)
C100.4756 (9)0.4913 (13)0.50563 (18)0.0150 (15)
C110.3703 (9)0.3112 (13)0.5199 (2)0.0193 (17)
H110.33830.18260.50560.023*
C120.3144 (10)0.3257 (13)0.5553 (2)0.0206 (17)
H120.24870.20430.56520.025*
C130.3575 (9)0.5214 (13)0.5753 (2)0.0153 (16)
C140.4597 (10)0.7053 (15)0.5618 (2)0.0225 (18)
H140.48730.83620.57590.027*
C150.5186 (10)0.6881 (13)0.5269 (2)0.0203 (17)
H150.58730.80790.51740.024*
C160.3358 (10)0.3949 (16)0.6364 (2)0.028 (2)
C170.2640 (10)0.4738 (16)0.6715 (2)0.0279 (19)
C180.3066 (14)0.3351 (17)0.7002 (2)0.048 (3)
H18A0.26830.37530.72310.057*
H18B0.37400.20030.69700.057*
C190.1600 (11)0.6873 (15)0.6733 (2)0.034 (2)
H19A0.13470.72290.69800.051*
H19B0.05520.66250.66040.051*
H19C0.22140.81800.66280.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0517 (5)0.0607 (6)0.0136 (4)0.0036 (5)0.0052 (6)0.0037 (6)
O10.047 (4)0.041 (4)0.021 (3)0.022 (3)0.010 (3)0.007 (3)
O20.033 (3)0.025 (3)0.008 (3)0.003 (2)0.002 (2)0.003 (2)
O30.089 (5)0.059 (5)0.022 (4)0.040 (4)0.001 (4)0.008 (3)
C10.025 (4)0.021 (5)0.014 (4)0.003 (3)0.000 (3)0.006 (3)
C20.020 (4)0.032 (5)0.017 (4)0.005 (3)0.003 (3)0.008 (3)
C30.029 (4)0.032 (5)0.023 (4)0.008 (4)0.004 (3)0.014 (4)
C40.027 (4)0.020 (4)0.035 (5)0.002 (4)0.001 (4)0.012 (3)
C50.019 (4)0.035 (5)0.017 (4)0.004 (3)0.003 (3)0.002 (3)
C60.017 (4)0.028 (4)0.012 (4)0.002 (3)0.000 (3)0.006 (3)
C70.022 (4)0.023 (5)0.018 (4)0.003 (3)0.004 (3)0.004 (3)
C80.027 (4)0.025 (5)0.023 (4)0.005 (3)0.001 (3)0.007 (3)
C90.019 (4)0.030 (5)0.017 (4)0.007 (4)0.004 (4)0.003 (4)
C100.016 (4)0.011 (4)0.017 (4)0.003 (3)0.001 (3)0.006 (3)
C110.020 (4)0.020 (4)0.018 (4)0.001 (3)0.003 (3)0.003 (3)
C120.021 (4)0.015 (4)0.025 (4)0.006 (3)0.004 (3)0.001 (3)
C130.019 (4)0.013 (4)0.015 (4)0.003 (3)0.001 (3)0.004 (3)
C140.029 (4)0.020 (5)0.018 (4)0.000 (3)0.005 (3)0.004 (3)
C150.022 (4)0.017 (4)0.022 (4)0.007 (3)0.004 (3)0.002 (3)
C160.025 (4)0.044 (6)0.015 (4)0.001 (4)0.004 (3)0.006 (4)
C170.033 (5)0.037 (5)0.014 (4)0.008 (4)0.002 (3)0.007 (4)
C180.084 (7)0.046 (6)0.013 (4)0.007 (5)0.003 (5)0.009 (4)
C190.044 (5)0.040 (5)0.017 (4)0.008 (4)0.010 (4)0.003 (3)
Geometric parameters (Å, º) top
Br1—C21.896 (8)C9—C101.505 (10)
O1—C91.228 (10)C10—C151.400 (10)
O2—C161.379 (9)C10—C111.407 (10)
O2—C131.404 (9)C11—C121.389 (11)
O3—C161.190 (10)C11—H110.93
C1—C61.399 (10)C12—C131.371 (11)
C1—C21.401 (10)C12—H120.93
C1—H10.93C13—C141.399 (12)
C2—C31.383 (11)C14—C151.381 (10)
C3—C41.389 (12)C14—H140.93
C3—H30.93C15—H150.93
C4—C51.386 (11)C16—C171.489 (11)
C4—H40.93C17—C181.365 (12)
C5—C61.405 (10)C17—C191.450 (11)
C5—H50.93C18—H18A0.93
C6—C71.470 (10)C18—H18B0.93
C7—C81.326 (11)C19—H19A0.96
C7—H70.93C19—H19B0.96
C8—C91.485 (11)C19—H19C0.96
C8—H80.93
C16—O2—C13118.0 (6)C12—C11—C10119.9 (7)
C6—C1—C2120.7 (7)C12—C11—H11120.1
C6—C1—H1119.7C10—C11—H11120.1
C2—C1—H1119.7C13—C12—C11119.1 (7)
C3—C2—C1120.0 (7)C13—C12—H12120.5
C3—C2—Br1121.1 (6)C11—C12—H12120.5
C1—C2—Br1118.9 (6)C12—C13—C14122.4 (7)
C2—C3—C4120.1 (7)C12—C13—O2122.2 (7)
C2—C3—H3119.9C14—C13—O2115.3 (6)
C4—C3—H3119.9C15—C14—C13118.5 (7)
C5—C4—C3119.9 (8)C15—C14—H14120.7
C5—C4—H4120.0C13—C14—H14120.7
C3—C4—H4120.0C14—C15—C10120.4 (7)
C4—C5—C6121.1 (8)C14—C15—H15119.8
C4—C5—H5119.4C10—C15—H15119.8
C6—C5—H5119.4O3—C16—O2123.3 (7)
C1—C6—C5118.1 (7)O3—C16—C17127.2 (7)
C1—C6—C7117.8 (7)O2—C16—C17109.4 (7)
C5—C6—C7124.1 (7)C18—C17—C19124.8 (8)
C8—C7—C6128.7 (7)C18—C17—C16115.2 (8)
C8—C7—H7115.7C19—C17—C16119.9 (7)
C6—C7—H7115.7C17—C18—H18A120.0
C7—C8—C9119.4 (8)C17—C18—H18B120.0
C7—C8—H8120.3H18A—C18—H18B120.0
C9—C8—H8120.3C17—C19—H19A109.5
O1—C9—C8119.7 (8)C17—C19—H19B109.5
O1—C9—C10119.6 (7)H19A—C19—H19B109.5
C8—C9—C10120.7 (7)C17—C19—H19C109.5
C15—C10—C11119.7 (6)H19A—C19—H19C109.5
C15—C10—C9117.1 (6)H19B—C19—H19C109.5
C11—C10—C9123.2 (6)
C6—C1—C2—C30.7 (11)C15—C10—C11—C122.1 (11)
C6—C1—C2—Br1179.5 (5)C9—C10—C11—C12178.2 (7)
C1—C2—C3—C40.8 (12)C10—C11—C12—C132.6 (11)
Br1—C2—C3—C4178.0 (6)C11—C12—C13—C141.6 (12)
C2—C3—C4—C50.2 (12)C11—C12—C13—O2174.4 (7)
C3—C4—C5—C61.9 (11)C16—O2—C13—C1262.9 (10)
C2—C1—C6—C52.6 (11)C16—O2—C13—C14120.8 (7)
C2—C1—C6—C7177.2 (7)C12—C13—C14—C150.1 (12)
C4—C5—C6—C13.2 (10)O2—C13—C14—C15176.2 (7)
C4—C5—C6—C7176.6 (7)C13—C14—C15—C100.4 (11)
C1—C6—C7—C8175.1 (8)C11—C10—C15—C140.5 (11)
C5—C6—C7—C84.8 (13)C9—C10—C15—C14179.7 (7)
C6—C7—C8—C9179.0 (7)C13—O2—C16—O32.6 (12)
C7—C8—C9—O17.7 (13)C13—O2—C16—C17176.8 (6)
C7—C8—C9—C10172.6 (7)O3—C16—C17—C183.5 (14)
O1—C9—C10—C153.7 (11)O2—C16—C17—C18175.8 (7)
C8—C9—C10—C15176.5 (7)O3—C16—C17—C19177.7 (10)
O1—C9—C10—C11176.6 (8)O2—C16—C17—C192.9 (11)
C8—C9—C10—C113.2 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.932.382.748 (10)104
C15—H15···O10.932.442.757 (10)100
C1—H1···CgAi0.932.953.690 (8)138
C4—H4···CgAii0.932.873.541 (8)130
C12—H12···CgBiii0.933.003.670 (8)130
C15—H15···CgBiv0.932.903.582 (8)131
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x1/2, y1/2, z; (iii) x1/2, y+1/2, z; (iv) x+1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC19H15BrO3
Mr371.22
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)203
a, b, c (Å)7.8096 (2), 5.6168 (2), 37.212 (1)
V3)1632.30 (8)
Z4
Radiation typeMo Kα
µ (mm1)2.53
Crystal size (mm)0.40 × 0.28 × 0.04
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.431, 0.906
No. of measured, independent and
observed [I > 2σ(I)] reflections
9099, 3381, 1860
Rint0.129
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.169, 0.93
No. of reflections3381
No. of parameters210
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.68, 1.04
Absolute structure(Flack, 1983)
Absolute structure parameter0.02 (2)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected bond and torsion angles (º) top
C5—C6—C7124.1 (7)C14—C13—O2115.3 (6)
C8—C7—C6128.7 (7)O3—C16—O2123.3 (7)
C15—C10—C9117.1 (6)O3—C16—C17127.2 (7)
C11—C10—C9123.2 (6)O2—C16—C17109.4 (7)
C12—C13—C14122.4 (7)C18—C17—C19124.8 (8)
C12—C13—O2122.2 (7)C18—C17—C16115.2 (8)
C1—C6—C7—C8175.1 (8)C7—C8—C9—C10172.6 (7)
C6—C7—C8—C9179.0 (7)C8—C9—C10—C15176.5 (7)
C7—C8—C9—O17.7 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.932.382.748 (10)104
C15—H15···O10.932.442.757 (10)100
C1—H1···CgAi0.932.953.690 (8)138
C4—H4···CgAii0.932.873.541 (8)130
C12—H12···CgBiii0.933.003.670 (8)130
C15—H15···CgBiv0.932.903.582 (8)131
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x1/2, y1/2, z; (iii) x1/2, y+1/2, z; (iv) x+1/2, y+3/2, z.
 

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