organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(E)-4-(4-Meth­­oxy­phen­yl)but-3-en-2-one

aPost-Graduate Department of Chemistry, University of Jammu, Jammu Tawi 180 006, India, and bPost-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India
*Correspondence e-mail: vivek_gupta2k2@hotmail.com

(Received 14 March 2012; accepted 21 March 2012; online 24 March 2012)

In the title compound, C11H12O2, the dihedral angle between the benzene ring and the but-3-en-2-one group is 4.04 (5)°. The crystal packing features chains, parallel to [-101], composed of dimers connected by weak C—H⋯O inter­actions..

Related literature

For related structures, see: Jasinski et al. (2010[Jasinski, J. P., Pek, A. E., Narayana, B., Kamath, P. K. & Yathirajan, H. S. (2010). Acta Cryst. E66, o1995.]); Fun et al. (2011[Fun, H.-K., Arshad, S., Sarojini, B. K., Khaleel, V. M. & Narayana, B. (2011). Acta Cryst. E67, o1248-o1249.]); Dutkiewicz et al. (2011[Dutkiewicz, G., Siddaraju, B. P., Yathirajan, H. S., Narayana, B. & Kubicki, M. (2011). Acta Cryst. E67, o1024.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Prpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C11H12O2

  • Mr = 176.21

  • Monoclinic, P 21 /c

  • a = 10.1623 (19) Å

  • b = 13.292 (3) Å

  • c = 6.6488 (13) Å

  • β = 98.486 (3)°

  • V = 888.3 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 100 K

  • 0.30 × 0.30 × 0.10 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.920, Tmax = 0.980

  • 4492 measured reflections

  • 1556 independent reflections

  • 1332 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.150

  • S = 1.10

  • 1556 reflections

  • 121 parameters

  • H-atom parameters constrained

  • Δρmax = 0.36 e Å−3

  • Δρmin = −0.60 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C6′—H6′⋯O2i 0.93 2.52 3.296 (2) 141
C6—H6B⋯O2ii 0.96 2.57 3.533 (2) 176
Symmetry codes: (i) -x, -y, -z; (ii) x-1, y, z+1.

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

The title compound belongs to the class of unsaturated α,β- acyclic ketones. α,β- unsaturated ketones have been found useful in the preparation of a wide variety of nitrogen heterocycles both in solution phase and solid state. Many of these synthesis have proceeded through interesting mechanisms. These compounds have been used as substrates for the preparation of anti-cancer, cell-specific triarylpyridines via immobilized bismuth nitrate catalyzed cascade reactions. These compounds have been extensively used in the preparation of cardiovascular Hantzsch products, many of which are prescribed drugs. α,β- unsaturated ketones are easily elaborated to anti-anxiety diazepines which also regulate our central nervous system. When treated with hydrazine, α,β- unsaturated compounds yield substituted pyrazoles which have a wide spectrum of bioactivity. The molecular structure of the title compound is shown in Fig.1. The bond distances are within normal ranges (Allen et al., 1987) and comparable to those in related structures (Jasinski et al., 2010; Fun et al., 2011; Dutkiewicz et al., 2011). The six bond lengths in the benzene ring lie in the range 1.355 (2)–1.391 (2) Å with an average value of 1.372 (2) Å. The average bond angle of the phenyl ring is 120.0 (1)°. In the title compound the benzene ring is perfectly planar with a maximum deviation of 0.006 (2) Å for C2'. The dihedral angle between the benzene ring and the acyclic chain is 4.04 (5)°. In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules into chains (Fig.2).

Related literature top

For related structures, see: Jasinski et al. (2010); Fun et al. (2011); Dutkiewicz et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

Normally, α,β-unsaturated compounds are prepared by the reaction of an aldehyde and an active methylene compounds by Claisen-Schmidt reaction, using a strong base or an acid as catalyst. Under these reaction conditions, aromatic aldehydes and acetone react hard to form diarylidene ketone by double Claisen condensation. Monocondensation processes are known but yields are poor. To improve yield of monocondensation products, a search for catalyst was undertaken and sodium tungstate in ethanol was found as the catalyst of choice. The title compound was prepared in 96% yield by stirring the mixture of anisaldehyde (1 X 10-2 mol) and acetone (1 X 10-2 mol) in the presence of sodium tungstate (30 mol %) using ethanol as solvent at room temperature (25°C) for 24h. The reaction was monitored by thin layer chromatography. On completion of the reaction, the reaction mixture was diluted with water (25ml) and extracted with ethyl acetate (50 ml). The organic layer was washed with water, brine and water, dried over anhydrous sodium sulphate and concentrated. The title compound was purified by column chromatography on silica gel, using CH2Cl2-EtOAC (9:1v/v) as solvent. The compound was crystallized from chloroform-methanol, m.p. 445K. Single crystals for XRD study were obtained by slow evaporation of chloroform solution.

Refinement top

All H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C), except for the methyl groups where Uiso(H) = 1.5Ueq(C),.

Structure description top

The title compound belongs to the class of unsaturated α,β- acyclic ketones. α,β- unsaturated ketones have been found useful in the preparation of a wide variety of nitrogen heterocycles both in solution phase and solid state. Many of these synthesis have proceeded through interesting mechanisms. These compounds have been used as substrates for the preparation of anti-cancer, cell-specific triarylpyridines via immobilized bismuth nitrate catalyzed cascade reactions. These compounds have been extensively used in the preparation of cardiovascular Hantzsch products, many of which are prescribed drugs. α,β- unsaturated ketones are easily elaborated to anti-anxiety diazepines which also regulate our central nervous system. When treated with hydrazine, α,β- unsaturated compounds yield substituted pyrazoles which have a wide spectrum of bioactivity. The molecular structure of the title compound is shown in Fig.1. The bond distances are within normal ranges (Allen et al., 1987) and comparable to those in related structures (Jasinski et al., 2010; Fun et al., 2011; Dutkiewicz et al., 2011). The six bond lengths in the benzene ring lie in the range 1.355 (2)–1.391 (2) Å with an average value of 1.372 (2) Å. The average bond angle of the phenyl ring is 120.0 (1)°. In the title compound the benzene ring is perfectly planar with a maximum deviation of 0.006 (2) Å for C2'. The dihedral angle between the benzene ring and the acyclic chain is 4.04 (5)°. In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules into chains (Fig.2).

For related structures, see: Jasinski et al. (2010); Fun et al. (2011); Dutkiewicz et al. (2011). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing arrangement of molecules viewed down the a axis. Hydrogen bonds are shown with dashed lines.
(E)-4-(4-Methoxyphenyl)but-3-en-2-one top
Crystal data top
C11H12O2F(000) = 376
Mr = 176.21Dx = 1.318 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2041 reflections
a = 10.1623 (19) Åθ = 2.5–28.1°
b = 13.292 (3) ŵ = 0.09 mm1
c = 6.6488 (13) ÅT = 100 K
β = 98.486 (3)°Hexagonal plate, colourless
V = 888.3 (3) Å30.30 × 0.30 × 0.10 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
1556 independent reflections
Radiation source: fine-focus sealed tube1332 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 0 pixels mm-1θmax = 25.0°, θmin = 2.5°
phi and ω scansh = 1112
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 1514
Tmin = 0.920, Tmax = 0.980l = 77
4492 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.0943P)2 + 0.0951P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
1556 reflectionsΔρmax = 0.36 e Å3
121 parametersΔρmin = 0.60 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.093 (13)
Crystal data top
C11H12O2V = 888.3 (3) Å3
Mr = 176.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.1623 (19) ŵ = 0.09 mm1
b = 13.292 (3) ÅT = 100 K
c = 6.6488 (13) Å0.30 × 0.30 × 0.10 mm
β = 98.486 (3)°
Data collection top
Bruker APEXII CCD
diffractometer
1556 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
1332 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.980Rint = 0.057
4492 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.10Δρmax = 0.36 e Å3
1556 reflectionsΔρmin = 0.60 e Å3
121 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C10.32731 (14)0.16937 (12)0.2922 (2)0.0270 (4)
H1A0.40290.17510.22180.040*
H1B0.35050.12930.41230.040*
H1C0.30050.23520.32980.040*
O20.23069 (10)0.09565 (8)0.01128 (16)0.0272 (4)
C20.21533 (15)0.12060 (11)0.1565 (2)0.0216 (4)
C30.08653 (15)0.10549 (11)0.2238 (2)0.0205 (4)
H30.01840.07780.13180.025*
C40.06085 (14)0.12829 (10)0.4045 (2)0.0197 (4)
H40.13140.15310.49610.024*
O50.42876 (10)0.09838 (8)0.69111 (15)0.0255 (4)
C60.43869 (14)0.12266 (12)0.8912 (2)0.0257 (4)
H6A0.37940.08080.98090.039*
H6B0.52840.11190.91570.039*
H6C0.41520.19200.91550.039*
C1'0.06661 (14)0.11909 (10)0.4784 (2)0.0194 (4)
C2'0.07619 (13)0.15059 (11)0.6694 (2)0.0209 (4)
H2'0.00090.17590.75020.025*
C3'0.19429 (14)0.14616 (11)0.7475 (2)0.0220 (4)
H3'0.19840.16930.87840.026*
C4'0.30685 (14)0.10736 (10)0.6309 (2)0.0199 (4)
C5'0.29933 (14)0.07434 (11)0.4401 (2)0.0221 (4)
H5'0.37430.04790.36050.027*
C6'0.18091 (14)0.07994 (11)0.3644 (2)0.0212 (4)
H6'0.17700.05690.23330.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0235 (8)0.0307 (8)0.0275 (9)0.0024 (6)0.0064 (6)0.0031 (6)
O20.0258 (7)0.0343 (7)0.0224 (7)0.0017 (4)0.0069 (5)0.0039 (4)
C20.0237 (8)0.0181 (7)0.0232 (9)0.0031 (6)0.0047 (6)0.0033 (6)
C30.0185 (8)0.0207 (8)0.0217 (9)0.0005 (5)0.0012 (6)0.0005 (5)
C40.0193 (8)0.0163 (7)0.0229 (9)0.0002 (5)0.0010 (6)0.0018 (6)
O50.0179 (6)0.0374 (7)0.0217 (7)0.0014 (4)0.0039 (4)0.0016 (4)
C60.0222 (8)0.0321 (9)0.0241 (9)0.0019 (6)0.0077 (6)0.0007 (7)
C1'0.0206 (8)0.0153 (7)0.0220 (8)0.0018 (5)0.0021 (6)0.0027 (6)
C2'0.0198 (8)0.0189 (8)0.0227 (9)0.0015 (6)0.0006 (6)0.0003 (6)
C3'0.0250 (8)0.0205 (8)0.0201 (8)0.0009 (6)0.0021 (6)0.0006 (6)
C4'0.0181 (8)0.0207 (8)0.0210 (9)0.0023 (6)0.0035 (6)0.0030 (6)
C5'0.0209 (7)0.0247 (8)0.0194 (8)0.0007 (6)0.0012 (6)0.0006 (6)
C6'0.0229 (8)0.0226 (8)0.0177 (8)0.0016 (6)0.0015 (6)0.0006 (6)
Geometric parameters (Å, º) top
C1—C21.492 (2)C6—H6B0.9600
C1—H1A0.9600C6—H6C0.9600
C1—H1B0.9600C1'—C2'1.355 (2)
C1—H1C0.9600C1'—C6'1.391 (2)
O2—C21.1959 (18)C2'—C3'1.377 (2)
C2—C31.458 (2)C2'—H2'0.9300
C3—C41.302 (2)C3'—C4'1.383 (2)
C3—H30.9300C3'—H3'0.9300
C4—C1'1.4568 (19)C4'—C5'1.355 (2)
C4—H40.9300C5'—C6'1.373 (2)
O5—C4'1.3622 (16)C5'—H5'0.9300
O5—C61.3872 (18)C6'—H6'0.9300
C6—H6A0.9600
C2—C1—H1A109.5H6A—C6—H6C109.5
C2—C1—H1B109.5H6B—C6—H6C109.5
H1A—C1—H1B109.5C2'—C1'—C6'117.18 (13)
C2—C1—H1C109.5C2'—C1'—C4118.74 (13)
H1A—C1—H1C109.5C6'—C1'—C4124.08 (14)
H1B—C1—H1C109.5C1'—C2'—C3'121.82 (13)
O2—C2—C3119.65 (14)C1'—C2'—H2'119.1
O2—C2—C1119.45 (13)C3'—C2'—H2'119.1
C3—C2—C1120.87 (13)C2'—C3'—C4'119.97 (14)
C4—C3—C2124.22 (14)C2'—C3'—H3'120.0
C4—C3—H3117.9C4'—C3'—H3'120.0
C2—C3—H3117.9C5'—C4'—O5115.21 (13)
C3—C4—C1'126.94 (14)C5'—C4'—C3'119.27 (13)
C3—C4—H4116.5O5—C4'—C3'125.52 (13)
C1'—C4—H4116.5C4'—C5'—C6'119.95 (13)
C4'—O5—C6117.34 (11)C4'—C5'—H5'120.0
O5—C6—H6A109.5C6'—C5'—H5'120.0
O5—C6—H6B109.5C5'—C6'—C1'121.81 (14)
H6A—C6—H6B109.5C5'—C6'—H6'119.1
O5—C6—H6C109.5C1'—C6'—H6'119.1
O2—C2—C3—C4178.60 (14)C6—O5—C4'—C3'5.4 (2)
C1—C2—C3—C43.1 (2)C2'—C3'—C4'—C5'0.2 (2)
C2—C3—C4—C1'177.22 (12)C2'—C3'—C4'—O5179.55 (12)
C3—C4—C1'—C2'177.26 (15)O5—C4'—C5'—C6'179.98 (12)
C3—C4—C1'—C6'2.5 (2)C3'—C4'—C5'—C6'0.2 (2)
C6'—C1'—C2'—C3'1.2 (2)C4'—C5'—C6'—C1'0.1 (2)
C4—C1'—C2'—C3'178.55 (12)C2'—C1'—C6'—C5'0.8 (2)
C1'—C2'—C3'—C4'1.0 (2)C4—C1'—C6'—C5'178.96 (12)
C6—O5—C4'—C5'174.34 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.523.296 (2)141
C6—H6B···O2ii0.962.573.533 (2)176
Symmetry codes: (i) x, y, z; (ii) x1, y, z+1.

Experimental details

Crystal data
Chemical formulaC11H12O2
Mr176.21
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)10.1623 (19), 13.292 (3), 6.6488 (13)
β (°) 98.486 (3)
V3)888.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.30 × 0.10
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.920, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
4492, 1556, 1332
Rint0.057
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.150, 1.10
No. of reflections1556
No. of parameters121
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.60

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6'—H6'···O2i0.932.523.296 (2)141
C6—H6B···O2ii0.962.573.533 (2)176
Symmetry codes: (i) x, y, z; (ii) x1, y, z+1.
 

Acknowledgements

The authors are thankful to Professor P. K. Bharadwaj, Department of Chemistry, IIT, Kanpur, India, for the single-crystal X-ray diffraction data. VKG is thankful to the University of Jammu, Jammu, India, for financial support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Prpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDutkiewicz, G., Siddaraju, B. P., Yathirajan, H. S., Narayana, B. & Kubicki, M. (2011). Acta Cryst. E67, o1024.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFun, H.-K., Arshad, S., Sarojini, B. K., Khaleel, V. M. & Narayana, B. (2011). Acta Cryst. E67, o1248–o1249.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationJasinski, J. P., Pek, A. E., Narayana, B., Kamath, P. K. & Yathirajan, H. S. (2010). Acta Cryst. E66, o1995.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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