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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2864.
Published online 2010 October 20. doi:  10.1107/S1600536810040869
PMCID: PMC3008978

(E)-2-(3-Chloro­benzyl­idene)-5,6-dimeth­oxy-2,3-dihydro-1H-inden-1-one

Abstract

In the title compound, C18H15ClO3, the dihydro­indenone group makes a dihedral angle of 8.56 (6)° with the bezene ring. In the crystal, the mol­ecules are inter­connected into a three-dimensional network via inter­molecular C—H(...)O hydrogen bonds. Weak C—H(...)π and π(...)π [centroid–centroid distances 3.6598 (9)–3.6913 (9) Å] inter­actions are also observed.

Related literature

For general background to and the biological activity of chalcone derivatives, see: Marzinzik & Felder (1998 [triangle]); Srikanth & Castle (2005 [triangle]); Furusawa et al. (2005 [triangle]) Heidenreich et al. (2008 [triangle]); Syed et al. (2008 [triangle]). For related structures, see: Ali et al. (2010a [triangle],b [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

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Object name is e-66-o2864-scheme1.jpg

Experimental

Crystal data

  • C18H15ClO3
  • M r = 314.75
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-66-o2864-efi1.jpg
  • a = 20.5004 (16) Å
  • c = 7.0241 (7) Å
  • V = 2952.0 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 100 K
  • 0.74 × 0.13 × 0.11 mm

Data collection

  • Bruker APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.826, T max = 0.971
  • 62722 measured reflections
  • 4499 independent reflections
  • 4251 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.084
  • S = 1.06
  • 4499 reflections
  • 259 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.19 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1966 Friedel pairs
  • Flack parameter: −0.01 (5)

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040869/sj5044sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040869/sj5044Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors wish to express their thanks to Universiti of Sains Malysia (USM) for providing research facilities. HKF and CSY also thank USM for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

α,β-unsaturated ketones are useful key intermediates (Marzinzik & Felder, 1998, Srikanth & Castle, 2005) bearing the well known chalcone pharmacophore. Chalcones can be isolated from several plants and are precursors of flavones and anthocyan compounds. Some of them also exhibit antioxidant and anticancer properties. In fact, the pharmacological properties of chalcones are due to the presence of both α,β-unsaturation (Furusawa et al., 2005) and an aromatic ring. Many antitumor drugs have been developed for prostate cancer patients, but their intolerable systemic toxicity often limits their clinical use. Chemoprevention is one of the most promising approaches in prostate cancer research, in which natural or synthetic agents are used to prevent this malignant disease (Heidenreich et al., 2008, Syed et al., 2008).

The molecular structure of the title compound is essentially planar (Fig. 1). The torsion angles of the two methoxy groups are [C18–O3–C13–C14] 4.38 (18) and [C17–O2–C12–C11] -2.01 (17)°. The maximum deviation of the dihydroindenone group is 0.024 (1) Å and it makes dihedral angle of 8.56 (6)° with the benzene ring [C1–C6]. The geometric parameters are comparable to those observed in closely related structures (Ali et al., 2010a,b).

In the crystal structure, the molecules are linked together into a three dimensional network by the intermolecular C7—H7···O1, C11—H11···O1 and C18—H18C···O3 hydrogen bonds (Fig. 2, Table 1). Weak C—H···π and π···π interactions are also observed [Cg1···Cg2v of 3.6913 (9) Å and Cg2···Cg3vi of 3.6598 (9) Å; (v) x, y, 1 + z; (vi) x, y, -1 + z. Cg1, Cg2 and Cg3 are centroids of C8–C10/C15–C16, C1–C6 and C10–C15 rings, respectively].

Experimental

A mixture of 5,6-dimethoxy-2,3-dihydro-1H-indene-1-one (0.001 mmol) and 3-chlorobenzaldehyde (0.001 mmol) were dissolved in methanol (10 ml) and 30% sodium hydroxide solution (5 ml) was added and the mixture stirred for 5 h. After the completion of the reaction as evident from TLC, the mixture was poured into crushed ice then neutralized with concentrated HCl. The precipitated solid was filtered, washed with water and recrystallized from ethanol to reveal the title compound as light yellow crystals.

Refinement

All hydrogen atoms were located from difference Fourier map and refined freely. A total of 1966 Friedel pairs were use to determine the absolute structure.

Figures

Fig. 1.
The molecular structure of the title compound with atom labels and 50% probability ellipsoids for non-H atoms.
Fig. 2.
The crystal packing of title compound, showing a three-dimensional network. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C18H15ClO3Dx = 1.416 Mg m3
Mr = 314.75Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421cCell parameters from 9872 reflections
Hall symbol: P -4 2nθ = 2.8–30.4°
a = 20.5004 (16) ŵ = 0.27 mm1
c = 7.0241 (7) ÅT = 100 K
V = 2952.0 (4) Å3Needle, yellow
Z = 80.74 × 0.13 × 0.11 mm
F(000) = 1312

Data collection

Bruker APEXII DUO CCD area-detector diffractometer4499 independent reflections
Radiation source: fine-focus sealed tube4251 reflections with I > 2σ(I)
graphiteRint = 0.045
[var phi] and ω scansθmax = 30.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −29→29
Tmin = 0.826, Tmax = 0.971k = −28→29
62722 measured reflectionsl = −10→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084w = 1/[σ2(Fo2) + (0.0483P)2 + 0.5709P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
4499 reflectionsΔρmax = 0.37 e Å3
259 parametersΔρmin = −0.19 e Å3
0 restraintsAbsolute structure: Flack (1983), 1966 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (5)

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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)

xyzUiso*/Ueq
Cl10.658402 (17)0.24083 (2)0.07331 (5)0.03382 (9)
O10.35460 (5)0.18458 (5)0.76502 (14)0.0273 (2)
O20.38949 (4)0.34023 (5)1.38581 (13)0.02125 (18)
O30.49925 (5)0.39341 (5)1.30773 (13)0.02196 (19)
C10.55261 (6)0.20587 (6)0.27855 (18)0.0204 (2)
C20.59058 (6)0.19228 (7)0.11923 (18)0.0235 (3)
C30.57575 (8)0.14194 (8)−0.0056 (2)0.0300 (3)
C40.52078 (9)0.10399 (8)0.0310 (2)0.0326 (3)
C50.48177 (8)0.11719 (7)0.1883 (2)0.0275 (3)
C60.49729 (7)0.16787 (6)0.31451 (17)0.0206 (2)
C70.45338 (6)0.17840 (6)0.47637 (17)0.0207 (2)
C80.45819 (6)0.21831 (6)0.62791 (17)0.0183 (2)
C90.40455 (6)0.21715 (6)0.77302 (17)0.0190 (2)
C100.42366 (6)0.26270 (6)0.92367 (16)0.0166 (2)
C110.38957 (6)0.27681 (6)1.09221 (17)0.0173 (2)
C120.41636 (6)0.32139 (6)1.21623 (17)0.0169 (2)
C130.47750 (6)0.35135 (6)1.17248 (16)0.0168 (2)
C140.51055 (6)0.33681 (6)1.00419 (17)0.0168 (2)
C150.48283 (6)0.29164 (6)0.87923 (16)0.0156 (2)
C160.50915 (6)0.26751 (6)0.68977 (16)0.0178 (2)
C170.32745 (6)0.31173 (7)1.4304 (2)0.0237 (2)
C180.55815 (7)0.42822 (7)1.2670 (2)0.0266 (3)
H10.5664 (9)0.2390 (9)0.359 (3)0.029 (5)*
H30.6019 (10)0.1348 (10)−0.102 (3)0.044 (6)*
H40.5118 (11)0.0700 (10)−0.069 (4)0.051 (6)*
H50.4430 (11)0.0892 (10)0.215 (3)0.051 (6)*
H70.4154 (8)0.1528 (8)0.465 (3)0.025 (4)*
H110.3500 (9)0.2539 (8)1.115 (3)0.026 (4)*
H140.5503 (8)0.3565 (9)0.974 (3)0.024 (4)*
H18A0.5551 (10)0.4571 (9)1.158 (3)0.031 (5)*
H18B0.5953 (9)0.3989 (9)1.237 (3)0.031 (5)*
H18C0.5683 (11)0.4553 (10)1.375 (3)0.047 (6)*
H16A0.5126 (8)0.3044 (8)0.600 (3)0.020 (4)*
H16B0.5517 (8)0.2491 (8)0.703 (2)0.020 (4)*
H17A0.3144 (9)0.3303 (9)1.556 (3)0.031 (5)*
H17B0.2950 (8)0.3251 (8)1.341 (2)0.020 (4)*
H17C0.3292 (8)0.2645 (8)1.439 (3)0.022 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02695 (16)0.0484 (2)0.02614 (16)0.00242 (14)0.00952 (13)0.00399 (15)
O10.0264 (5)0.0360 (5)0.0195 (4)−0.0121 (4)0.0032 (4)−0.0053 (4)
O20.0214 (4)0.0246 (4)0.0178 (4)−0.0037 (3)0.0070 (3)−0.0051 (3)
O30.0234 (4)0.0250 (4)0.0175 (4)−0.0077 (4)0.0032 (3)−0.0038 (3)
C10.0232 (6)0.0233 (6)0.0147 (5)0.0064 (4)0.0015 (4)0.0019 (4)
C20.0227 (6)0.0293 (6)0.0184 (5)0.0103 (5)0.0031 (4)0.0062 (5)
C30.0372 (8)0.0338 (7)0.0189 (5)0.0146 (6)0.0066 (6)−0.0015 (5)
C40.0449 (8)0.0292 (7)0.0238 (6)0.0079 (6)0.0037 (6)−0.0084 (5)
C50.0341 (7)0.0271 (6)0.0213 (6)0.0015 (5)0.0031 (5)−0.0048 (5)
C60.0241 (6)0.0228 (6)0.0150 (5)0.0053 (4)0.0005 (4)0.0008 (4)
C70.0234 (6)0.0235 (6)0.0154 (5)0.0006 (5)0.0024 (4)−0.0003 (4)
C80.0197 (5)0.0213 (5)0.0139 (5)−0.0001 (4)0.0024 (4)0.0001 (4)
C90.0205 (5)0.0222 (5)0.0144 (5)−0.0021 (4)0.0022 (4)−0.0004 (4)
C100.0176 (5)0.0191 (5)0.0130 (4)0.0002 (4)0.0010 (4)0.0005 (4)
C110.0173 (5)0.0195 (5)0.0152 (5)−0.0011 (4)0.0027 (4)−0.0001 (4)
C120.0179 (5)0.0182 (5)0.0148 (5)0.0008 (4)0.0027 (4)0.0006 (4)
C130.0184 (5)0.0172 (5)0.0150 (5)0.0000 (4)−0.0003 (4)0.0011 (4)
C140.0155 (5)0.0186 (5)0.0163 (4)0.0004 (4)0.0003 (4)0.0013 (4)
C150.0166 (5)0.0180 (5)0.0122 (4)0.0018 (4)0.0012 (4)0.0015 (4)
C160.0183 (5)0.0216 (5)0.0136 (5)0.0005 (4)0.0037 (4)0.0004 (4)
C170.0206 (6)0.0310 (6)0.0195 (5)−0.0026 (5)0.0064 (5)−0.0010 (5)
C180.0240 (6)0.0327 (7)0.0232 (6)−0.0098 (5)0.0013 (5)−0.0047 (5)

Geometric parameters (Å, °)

Cl1—C21.7401 (15)C8—C161.5160 (17)
O1—C91.2237 (15)C9—C101.4647 (16)
O2—C121.3680 (14)C10—C151.3860 (16)
O2—C171.4343 (15)C10—C111.4048 (16)
O3—C131.3582 (14)C11—C121.3768 (17)
O3—C181.4314 (16)C11—H110.951 (18)
C1—C21.3914 (17)C12—C131.4293 (16)
C1—C61.3988 (19)C13—C141.3948 (16)
C1—H10.926 (19)C14—C151.3968 (16)
C2—C31.388 (2)C14—H140.935 (17)
C3—C41.393 (2)C15—C161.5188 (16)
C3—H30.87 (2)C16—H16A0.989 (17)
C4—C51.390 (2)C16—H16B0.955 (17)
C4—H41.01 (2)C17—H17A0.994 (19)
C5—C61.4025 (18)C17—H17B0.953 (17)
C5—H51.00 (2)C17—H17C0.971 (17)
C6—C71.4661 (17)C18—H18A0.97 (2)
C7—C81.3461 (17)C18—H18B0.994 (19)
C7—H70.943 (17)C18—H18C0.96 (2)
C8—C91.4995 (16)
C12—O2—C17115.60 (10)C12—C11—H11124.0 (11)
C13—O3—C18116.98 (10)C10—C11—H11117.8 (11)
C2—C1—C6119.16 (12)O2—C12—C11125.30 (11)
C2—C1—H1117.7 (12)O2—C12—C13114.76 (10)
C6—C1—H1123.1 (12)C11—C12—C13119.94 (11)
C3—C2—C1122.31 (14)O3—C13—C14124.68 (11)
C3—C2—Cl1118.89 (11)O3—C13—C12114.23 (10)
C1—C2—Cl1118.79 (11)C14—C13—C12121.09 (11)
C2—C3—C4118.40 (13)C13—C14—C15118.47 (11)
C2—C3—H3118.6 (14)C13—C14—H14121.7 (12)
C4—C3—H3123.0 (14)C15—C14—H14119.9 (12)
C5—C4—C3120.22 (14)C10—C15—C14119.89 (11)
C5—C4—H4125.7 (14)C10—C15—C16111.65 (10)
C3—C4—H4113.9 (14)C14—C15—C16128.46 (11)
C4—C5—C6121.06 (14)C8—C16—C15102.88 (9)
C4—C5—H5119.9 (13)C8—C16—H16A112.0 (10)
C6—C5—H5119.0 (13)C15—C16—H16A109.8 (10)
C1—C6—C5118.84 (12)C8—C16—H16B113.2 (10)
C1—C6—C7123.76 (12)C15—C16—H16B111.7 (10)
C5—C6—C7117.39 (12)H16A—C16—H16B107.4 (14)
C8—C7—C6131.13 (12)O2—C17—H17A106.0 (11)
C8—C7—H7117.8 (11)O2—C17—H17B111.0 (10)
C6—C7—H7111.1 (11)H17A—C17—H17B106.4 (14)
C7—C8—C9118.31 (11)O2—C17—H17C112.8 (10)
C7—C8—C16132.96 (11)H17A—C17—H17C109.7 (15)
C9—C8—C16108.73 (10)H17B—C17—H17C110.5 (14)
O1—C9—C10127.22 (11)O3—C18—H18A114.1 (12)
O1—C9—C8126.23 (11)O3—C18—H18B112.8 (11)
C10—C9—C8106.55 (10)H18A—C18—H18B104.5 (15)
C15—C10—C11122.49 (11)O3—C18—H18C108.2 (14)
C15—C10—C9110.14 (10)H18A—C18—H18C106.5 (16)
C11—C10—C9127.37 (11)H18B—C18—H18C110.5 (17)
C12—C11—C10118.13 (11)
C6—C1—C2—C3−0.32 (19)C9—C10—C11—C12179.81 (12)
C6—C1—C2—Cl1178.78 (10)C17—O2—C12—C11−2.01 (17)
C1—C2—C3—C40.0 (2)C17—O2—C12—C13178.74 (11)
Cl1—C2—C3—C4−179.06 (12)C10—C11—C12—O2−179.80 (11)
C2—C3—C4—C50.7 (2)C10—C11—C12—C13−0.59 (17)
C3—C4—C5—C6−1.1 (2)C18—O3—C13—C144.38 (18)
C2—C1—C6—C5−0.09 (19)C18—O3—C13—C12−176.10 (11)
C2—C1—C6—C7−179.15 (12)O2—C12—C13—O30.50 (15)
C4—C5—C6—C10.8 (2)C11—C12—C13—O3−178.79 (11)
C4—C5—C6—C7179.91 (14)O2—C12—C13—C14−179.96 (11)
C1—C6—C7—C8−7.7 (2)C11—C12—C13—C140.74 (18)
C5—C6—C7—C8173.26 (14)O3—C13—C14—C15178.91 (11)
C6—C7—C8—C9−179.20 (12)C12—C13—C14—C15−0.58 (17)
C6—C7—C8—C160.6 (2)C11—C10—C15—C14−0.16 (18)
C7—C8—C9—O1−2.7 (2)C9—C10—C15—C14−179.73 (11)
C16—C8—C9—O1177.46 (13)C11—C10—C15—C16179.72 (10)
C7—C8—C9—C10177.72 (11)C9—C10—C15—C160.15 (14)
C16—C8—C9—C10−2.16 (13)C13—C14—C15—C100.29 (17)
O1—C9—C10—C15−178.36 (13)C13—C14—C15—C16−179.57 (11)
C8—C9—C10—C151.25 (13)C7—C8—C16—C15−177.69 (13)
O1—C9—C10—C112.1 (2)C9—C8—C16—C152.15 (12)
C8—C9—C10—C11−178.30 (11)C10—C15—C16—C8−1.44 (13)
C15—C10—C11—C120.32 (18)C14—C15—C16—C8178.43 (12)

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
C7—H7···O1i0.942 (16)2.489 (18)3.2650 (16)139.6 (15)
C11—H11···O1ii0.951 (18)2.561 (17)3.3229 (16)137.3 (14)
C18—H18C···O3iii0.96 (2)2.53 (2)3.4684 (17)165.2 (17)
C3—H3···Cg2iv0.87 (2)2.86 (2)3.6072 (17)144.4 (17)

Symmetry codes: (i) −y+1/2, −x+1/2, z−1/2; (ii) −y+1/2, −x+1/2, z+1/2; (iii) −y+1, x, −z+3; (iv) y+1/2, x−1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5044).

References

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