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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o653.
Published online 2009 February 28. doi:  10.1107/S1600536809004358
PMCID: PMC2968549

1-(4-Chloro­phen­yl)-4,4-dimethyl­pent-1-en-3-one

Abstract

In the title compound, C13H15ClO, the carbonyl and ethenyl groups are not coplanar with benzene ring system, forming dihedral angles of 35.37 (5) and 36.27 (11)°, respectively. The mol­ecules are packed in an offset face-to-face arrangement showing π–π stacking inter­actions involving the benzene rings [centroid–centroid distance = 3.586 (4) Å].

Related literature

The title compound is an important inter­mediate in the pesticide industry, see: Wang et al. (2006 [triangle]). For related structures, see: Anuradha et al. (2008 [triangle]); Butcher et al. (2007 [triangle]); Gong et al. (2008 [triangle]); Harrison et al. (2007 [triangle]); Patil et al. (2007 [triangle]); Sarojini et al. (2007 [triangle]); Thiruvalluvar et al. (2007 [triangle]); Thiruvalluvar et al. (2008 [triangle]); Xia & Hu (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o653-scheme1.jpg

Experimental

Crystal data

  • C13H15ClO
  • M r = 222.70
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o653-efi1.jpg
  • a = 5.6831 (4) Å
  • b = 9.9156 (6) Å
  • c = 11.3731 (7) Å
  • α = 103.487 (1)°
  • β = 101.160 (1)°
  • γ = 103.697 (1)°
  • V = 584.12 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 173 (2) K
  • 0.46 × 0.31 × 0.21 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.875, T max = 0.940
  • 4545 measured reflections
  • 2251 independent reflections
  • 1989 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.094
  • S = 1.07
  • 2251 reflections
  • 139 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004358/pv2132sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004358/pv2132Isup2.hkl

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

Acknowledgments

The authors express their thanks to the National Key Technology R&D Program (No. 2006BAE01A01–4) for support.

supplementary crystallographic information

Comment

The title compound, 1-(4-chlorophenyl)-4,4-dimethylpentan-3-one, is a very important intermediate in the pesticides industry (Wang et al., 2006). Continuing our work (Xia & Hu 2008) we have now synthsized the title compound, (I). In this article we report the synthesis and crystal structure of (I). Several crystal structures containing phenylprop-2-en-1-one moiety have been recently published, e.g., Anuradha et al. (2008); Butcher et al. (2007); Gong et al. (2008); Harrison et al. (2007); Patil et al. (2007); Sarojini et al. (2007); Thiruvalluvar et al. (2007); Thiruvalluvar et al. (2008); Xia & Hu (2008).

In the title compound (Fig. 1), the carbonyl and ethenyl groups are not coplanar with the benzene ring; the mean planes of the carbonyl group (atoms O1/C2/C3/C4) and ethenyl group (atoms C2, C3, C4 and C8) are inclined at 35.37 (5) and 36.27 (11) °, respectively, with the mean-plane of the phenyl ring (C8-C13). The bond lengths and bond angles in (I) are in excellent agreement with the corresponding bond lengths and angles reported in the related compounds given above. The molecules are packed in an offset face-to-face arrangement showing π–π stacking interaction involving the benzene rings with centroid-to-centroid distance = 3.586 (4) Å. The structure is devoid of any classical hydrogen bonds (Fig. 2).

Experimental

Added 3,3-dimethylbutan-2-one (0.0105 mol) to a solution of 4-dichlorobenzaldehyde (0.01 mol) and 60 ml ethanol drop-wise. Then added 0.1 g 50% NaOH solution as catalyst and stirred at 333 K for 4 h (monitored by TLC). A part of solvent was evaporated, then cooled the mixture to 277 K and the precipitate formed were filtered and dried, giving the desired product (yield: 92.1%). Crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

The methyl H atom were positioned geometrically (C—H=0.98 Å) and torsion angles refine to fit the electron density [Uĩso~(H) = 1.5U~eq~(C)]. Other H atoms were placed in calculated position (methylene C—H=0.95Å and aromatic C—H=0.95 Å) and refine as riding [Uĩso~(H) = 1.2U~eq~(C)].

Figures

Fig. 1.
Molecular structure of the title compound showing 30% probability displacement ellipsoids.
Fig. 2.
Packing diagram of the title compound.

Crystal data

C13H15ClOZ = 2
Mr = 222.70F(000) = 236
Triclinic, P1Dx = 1.266 Mg m3
Hall symbol: -P 1Melting point: 360 K
a = 5.6831 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.9156 (6) ÅCell parameters from 3394 reflections
c = 11.3731 (7) Åθ = 2.2–27.0°
α = 103.487 (1)°µ = 0.30 mm1
β = 101.160 (1)°T = 173 K
γ = 103.697 (1)°Block, colorless
V = 584.12 (7) Å30.46 × 0.31 × 0.21 mm

Data collection

Bruker SMART 1000 CCD diffractometer2251 independent reflections
Radiation source: fine-focus sealed tube1989 reflections with I > 2σ(I)
graphiteRint = 0.016
ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −6→7
Tmin = 0.875, Tmax = 0.940k = −12→11
4545 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0518P)2 + 0.1538P] where P = (Fo2 + 2Fc2)/3
2251 reflections(Δ/σ)max = 0.001
139 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

Experimental. 1H NMR(400MHz, CDCl3),delta:1.23(s, 9H, 3×CH3),7.09(d, J= 1.52Hz, 1H, 2-CH), 7.36(d, J=8.4Hz, 2H, benzene 3,5-H), 7.5(d, J= 8.4Hz, 2H, benzene 2,6-H), 7.60(d,J=15.6Hz, 1H, 1-CH).
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
Cl11.79614 (7)1.22580 (4)1.45960 (3)0.03998 (15)
C10.8701 (3)0.81783 (15)1.07764 (13)0.0281 (3)
H10.71640.81601.09940.034*
C20.8553 (3)0.73017 (15)0.96684 (13)0.0292 (3)
H21.00470.72740.94200.035*
C30.6090 (3)0.63638 (15)0.88112 (13)0.0274 (3)
C40.6118 (3)0.51705 (15)0.76919 (13)0.0275 (3)
C50.3442 (3)0.43184 (18)0.69238 (15)0.0415 (4)
H5A0.25160.38830.74520.062*
H5B0.34800.35500.62130.062*
H5C0.26090.49740.66120.062*
C60.7443 (3)0.41555 (16)0.81908 (14)0.0347 (3)
H6A0.65740.37620.87570.052*
H6B0.91880.47010.86470.052*
H6C0.74120.33570.74870.052*
C70.7574 (3)0.58705 (17)0.68748 (14)0.0361 (3)
H7A0.74920.51210.61220.054*
H7B0.93300.63450.73500.054*
H7C0.68270.65930.66310.054*
C81.0991 (3)0.91697 (14)1.16967 (13)0.0273 (3)
C91.3206 (3)0.96763 (15)1.13599 (13)0.0310 (3)
H91.32440.93651.05100.037*
C101.5339 (3)1.06235 (16)1.22452 (14)0.0316 (3)
H101.68251.09721.20050.038*
C111.5282 (3)1.10569 (14)1.34851 (13)0.0291 (3)
C121.3137 (3)1.05773 (16)1.38509 (14)0.0328 (3)
H121.31261.08791.47060.039*
C131.0999 (3)0.96487 (15)1.29538 (14)0.0312 (3)
H130.95060.93311.31990.037*
O10.41421 (19)0.65539 (12)0.90060 (10)0.0373 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0345 (2)0.0357 (2)0.0361 (2)0.00107 (16)0.00176 (15)0.00061 (16)
C10.0257 (7)0.0273 (7)0.0319 (7)0.0092 (5)0.0075 (6)0.0087 (6)
C20.0238 (7)0.0309 (7)0.0321 (7)0.0091 (6)0.0080 (5)0.0063 (6)
C30.0254 (7)0.0293 (7)0.0287 (7)0.0088 (6)0.0075 (5)0.0093 (6)
C40.0246 (7)0.0287 (7)0.0271 (7)0.0079 (5)0.0056 (5)0.0053 (6)
C50.0286 (8)0.0434 (9)0.0394 (8)0.0077 (7)0.0024 (6)−0.0039 (7)
C60.0376 (8)0.0324 (8)0.0378 (8)0.0137 (6)0.0122 (6)0.0121 (6)
C70.0434 (9)0.0384 (8)0.0333 (8)0.0166 (7)0.0163 (7)0.0134 (6)
C80.0289 (7)0.0237 (7)0.0299 (7)0.0106 (6)0.0065 (5)0.0071 (5)
C90.0318 (8)0.0323 (7)0.0277 (7)0.0087 (6)0.0085 (6)0.0068 (6)
C100.0272 (7)0.0324 (7)0.0342 (8)0.0067 (6)0.0087 (6)0.0097 (6)
C110.0283 (7)0.0219 (6)0.0320 (7)0.0065 (5)0.0024 (6)0.0039 (5)
C120.0360 (8)0.0310 (7)0.0284 (7)0.0095 (6)0.0081 (6)0.0039 (6)
C130.0286 (7)0.0312 (7)0.0333 (7)0.0081 (6)0.0112 (6)0.0067 (6)
O10.0247 (5)0.0442 (6)0.0382 (6)0.0109 (5)0.0093 (4)0.0016 (5)

Geometric parameters (Å, °)

Cl1—C111.7401 (15)C6—H6B0.9800
C1—C21.328 (2)C6—H6C0.9800
C1—C81.464 (2)C7—H7A0.9800
C1—H10.9500C7—H7B0.9800
C2—C31.4855 (19)C7—H7C0.9800
C2—H20.9500C8—C131.396 (2)
C3—O11.2185 (17)C8—C91.400 (2)
C3—C41.5281 (19)C9—C101.383 (2)
C4—C51.5242 (19)C9—H90.9500
C4—C71.535 (2)C10—C111.384 (2)
C4—C61.5368 (19)C10—H100.9500
C5—H5A0.9800C11—C121.378 (2)
C5—H5B0.9800C12—C131.385 (2)
C5—H5C0.9800C12—H120.9500
C6—H6A0.9800C13—H130.9500
C2—C1—C8126.64 (13)H6B—C6—H6C109.5
C2—C1—H1116.7C4—C7—H7A109.5
C8—C1—H1116.7C4—C7—H7B109.5
C1—C2—C3121.13 (13)H7A—C7—H7B109.5
C1—C2—H2119.4C4—C7—H7C109.5
C3—C2—H2119.4H7A—C7—H7C109.5
O1—C3—C2120.51 (13)H7B—C7—H7C109.5
O1—C3—C4122.12 (13)C13—C8—C9118.03 (13)
C2—C3—C4117.37 (12)C13—C8—C1119.85 (13)
C5—C4—C3110.10 (12)C9—C8—C1122.13 (13)
C5—C4—C7109.81 (12)C10—C9—C8121.03 (13)
C3—C4—C7108.91 (11)C10—C9—H9119.5
C5—C4—C6110.00 (12)C8—C9—H9119.5
C3—C4—C6108.29 (11)C9—C10—C11119.20 (13)
C7—C4—C6109.71 (12)C9—C10—H10120.4
C4—C5—H5A109.5C11—C10—H10120.4
C4—C5—H5B109.5C12—C11—C10121.34 (13)
H5A—C5—H5B109.5C12—C11—Cl1119.52 (11)
C4—C5—H5C109.5C10—C11—Cl1119.13 (11)
H5A—C5—H5C109.5C11—C12—C13119.01 (13)
H5B—C5—H5C109.5C11—C12—H12120.5
C4—C6—H6A109.5C13—C12—H12120.5
C4—C6—H6B109.5C12—C13—C8121.37 (13)
H6A—C6—H6B109.5C12—C13—H13119.3
C4—C6—H6C109.5C8—C13—H13119.3
H6A—C6—H6C109.5
C8—C1—C2—C3−178.96 (13)C13—C8—C9—C100.0 (2)
C1—C2—C3—O112.6 (2)C1—C8—C9—C10179.39 (13)
C1—C2—C3—C4−167.46 (13)C8—C9—C10—C110.9 (2)
O1—C3—C4—C5−0.29 (19)C9—C10—C11—C12−0.8 (2)
C2—C3—C4—C5179.76 (12)C9—C10—C11—Cl1−179.58 (11)
O1—C3—C4—C7120.17 (15)C10—C11—C12—C13−0.3 (2)
C2—C3—C4—C7−59.79 (16)Cl1—C11—C12—C13178.49 (11)
O1—C3—C4—C6−120.59 (15)C11—C12—C13—C81.3 (2)
C2—C3—C4—C659.46 (16)C9—C8—C13—C12−1.1 (2)
C2—C1—C8—C13−158.39 (14)C1—C8—C13—C12179.47 (13)
C2—C1—C8—C922.2 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2132).

References

  • Anuradha, N., Thiruvalluvar, A., Mahalinga, M. & Butcher, R. J. (2008). Acta Cryst. E64, o2118–o2119. [PMC free article] [PubMed]
  • Bruker (2001). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Butcher, R. J., Yathirajan, H. S., Narayana, B., Mithun, A. & Sarojini, B. K. (2007). Acta Cryst. E63, o30–o32.
  • Gong, Z.-Q., Liu, G.-S. & Xia, H.-Y. (2008). Acta Cryst. E64, o151. [PMC free article] [PubMed]
  • Harrison, W. T. A., Ravindra, H. J., Kumar, M. R. S. & Dharmaprakash, S. M. (2007). Acta Cryst. E63, o4675.
  • Patil, P. S., Chantrapromma, S., Fun, H.-K. & Dharmaprakash, S. M. (2007). Acta Cryst. E63, o1738–o1740.
  • Sarojini, B. K., Yathirajan, H. S., Mustafa, K., Sarfraz, H. & Bolte, M. (2007). Acta Cryst. E63, o4448.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Thiruvalluvar, A., Subramanyam, M., Butcher, R. J., Adhikari, A. V. & Karabasanagouda, T. (2007). Acta Cryst. E63, o4716.
  • Thiruvalluvar, A., Subramanyam, M., Butcher, R. J., Karabasanagouda, T. & Adhikari, A. V. (2008). Acta Cryst. E64, o1263. [PMC free article] [PubMed]
  • Wang, Y., Hu, A.-X., Chen, P., Chen, M. & Liu, Zh.-L. (2006). Chin. Agrochem.45, 397–398.
  • Xia, L. & Hu, A.-X. (2008). Acta Cryst. E64, o1983. [PMC free article] [PubMed]

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