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

Wu, T.-Q.; Xia, L.; Hu, A.-X.; Ye, J.

doi:10.1107/S1600536809004358

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o653

doi:10.1107/S1600536809004358

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

Tian-Quan Wu,^a Lin Xia,^a Ai-Xi Hu ^a ^* and Jiao Ye ^a

^aCollege of Chemistry and Chemical Engineering, Hunan University 410082, Changsha, People's Republic of China
^*Correspondence e-mail: axhu0731@yahoo.com.cn

(Received 8 January 2009; accepted 6 February 2009; online 28 February 2009)

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 ). For related structures, see: 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 ).

Experimental

Crystal data

C₁₃H₁₅ClO
M_r = 222.70
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.094
S = 1.07
2251 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

The title compound is an important intermediate in the pesticide industry, see: Wang et al. (2006). For related structures, see: 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).

Experimental top

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.

Computing details top

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

Figures top

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

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

Crystal data top

C₁₃H₁₅ClO	Z = 2
M_r = 222.70	F(000) = 236
Triclinic, P1	D_x = 1.266 Mg m⁻³
Hall symbol: -P 1	Melting point: 360 K
a = 5.6831 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9156 (6) Å	Cell parameters from 3394 reflections
c = 11.3731 (7) Å	θ = 2.2–27.0°
α = 103.487 (1)°	µ = 0.30 mm⁻¹
β = 101.160 (1)°	T = 173 K
γ = 103.697 (1)°	Block, colorless
V = 584.12 (7) Å³	0.46 × 0.31 × 0.21 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	2251 independent reflections
Radiation source: fine-focus sealed tube	1989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −6→7
T_min = 0.875, T_max = 0.940	k = −12→11
4545 measured reflections	l = −13→13

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0518P)² + 0.1538P] where P = (F_o² + 2F_c²)/3
2251 reflections	(Δ/σ)_max = 0.001
139 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₃H₁₅ClO	γ = 103.697 (1)°
M_r = 222.70	V = 584.12 (7) Å³
Triclinic, P1	Z = 2
a = 5.6831 (4) Å	Mo Kα radiation
b = 9.9156 (6) Å	µ = 0.30 mm⁻¹
c = 11.3731 (7) Å	T = 173 K
α = 103.487 (1)°	0.46 × 0.31 × 0.21 mm
β = 101.160 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2251 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1989 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.940	R_int = 0.016
4545 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	Δρ_max = 0.26 e Å⁻³
2251 reflections	Δρ_min = −0.24 e Å⁻³
139 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	1.79614 (7)	1.22580 (4)	1.45960 (3)	0.03998 (15)
C1	0.8701 (3)	0.81783 (15)	1.07764 (13)	0.0281 (3)
H1	0.7164	0.8160	1.0994	0.034*
C2	0.8553 (3)	0.73017 (15)	0.96684 (13)	0.0292 (3)
H2	1.0047	0.7274	0.9420	0.035*
C3	0.6090 (3)	0.63638 (15)	0.88112 (13)	0.0274 (3)
C4	0.6118 (3)	0.51705 (15)	0.76919 (13)	0.0275 (3)
C5	0.3442 (3)	0.43184 (18)	0.69238 (15)	0.0415 (4)
H5A	0.2516	0.3883	0.7452	0.062*
H5B	0.3480	0.3550	0.6213	0.062*
H5C	0.2609	0.4974	0.6612	0.062*
C6	0.7443 (3)	0.41555 (16)	0.81908 (14)	0.0347 (3)
H6A	0.6574	0.3762	0.8757	0.052*
H6B	0.9188	0.4701	0.8647	0.052*
H6C	0.7412	0.3357	0.7487	0.052*
C7	0.7574 (3)	0.58705 (17)	0.68748 (14)	0.0361 (3)
H7A	0.7492	0.5121	0.6122	0.054*
H7B	0.9330	0.6345	0.7350	0.054*
H7C	0.6827	0.6593	0.6631	0.054*
C8	1.0991 (3)	0.91697 (14)	1.16967 (13)	0.0273 (3)
C9	1.3206 (3)	0.96763 (15)	1.13599 (13)	0.0310 (3)
H9	1.3244	0.9365	1.0510	0.037*
C10	1.5339 (3)	1.06235 (16)	1.22452 (14)	0.0316 (3)
H10	1.6825	1.0972	1.2005	0.038*
C11	1.5282 (3)	1.10569 (14)	1.34851 (13)	0.0291 (3)
C12	1.3137 (3)	1.05773 (16)	1.38509 (14)	0.0328 (3)
H12	1.3126	1.0879	1.4706	0.039*
C13	1.0999 (3)	0.96487 (15)	1.29538 (14)	0.0312 (3)
H13	0.9506	0.9331	1.3199	0.037*
O1	0.41421 (19)	0.65539 (12)	0.90060 (10)	0.0373 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0345 (2)	0.0357 (2)	0.0361 (2)	0.00107 (16)	0.00176 (15)	0.00061 (16)
C1	0.0257 (7)	0.0273 (7)	0.0319 (7)	0.0092 (5)	0.0075 (6)	0.0087 (6)
C2	0.0238 (7)	0.0309 (7)	0.0321 (7)	0.0091 (6)	0.0080 (5)	0.0063 (6)
C3	0.0254 (7)	0.0293 (7)	0.0287 (7)	0.0088 (6)	0.0075 (5)	0.0093 (6)
C4	0.0246 (7)	0.0287 (7)	0.0271 (7)	0.0079 (5)	0.0056 (5)	0.0053 (6)
C5	0.0286 (8)	0.0434 (9)	0.0394 (8)	0.0077 (7)	0.0024 (6)	−0.0039 (7)
C6	0.0376 (8)	0.0324 (8)	0.0378 (8)	0.0137 (6)	0.0122 (6)	0.0121 (6)
C7	0.0434 (9)	0.0384 (8)	0.0333 (8)	0.0166 (7)	0.0163 (7)	0.0134 (6)
C8	0.0289 (7)	0.0237 (7)	0.0299 (7)	0.0106 (6)	0.0065 (5)	0.0071 (5)
C9	0.0318 (8)	0.0323 (7)	0.0277 (7)	0.0087 (6)	0.0085 (6)	0.0068 (6)
C10	0.0272 (7)	0.0324 (7)	0.0342 (8)	0.0067 (6)	0.0087 (6)	0.0097 (6)
C11	0.0283 (7)	0.0219 (6)	0.0320 (7)	0.0065 (5)	0.0024 (6)	0.0039 (5)
C12	0.0360 (8)	0.0310 (7)	0.0284 (7)	0.0095 (6)	0.0081 (6)	0.0039 (6)
C13	0.0286 (7)	0.0312 (7)	0.0333 (7)	0.0081 (6)	0.0112 (6)	0.0067 (6)
O1	0.0247 (5)	0.0442 (6)	0.0382 (6)	0.0109 (5)	0.0093 (4)	0.0016 (5)

Geometric parameters (Å, º) top

Cl1—C11	1.7401 (15)	C6—H6B	0.9800
C1—C2	1.328 (2)	C6—H6C	0.9800
C1—C8	1.464 (2)	C7—H7A	0.9800
C1—H1	0.9500	C7—H7B	0.9800
C2—C3	1.4855 (19)	C7—H7C	0.9800
C2—H2	0.9500	C8—C13	1.396 (2)
C3—O1	1.2185 (17)	C8—C9	1.400 (2)
C3—C4	1.5281 (19)	C9—C10	1.383 (2)
C4—C5	1.5242 (19)	C9—H9	0.9500
C4—C7	1.535 (2)	C10—C11	1.384 (2)
C4—C6	1.5368 (19)	C10—H10	0.9500
C5—H5A	0.9800	C11—C12	1.378 (2)
C5—H5B	0.9800	C12—C13	1.385 (2)
C5—H5C	0.9800	C12—H12	0.9500
C6—H6A	0.9800	C13—H13	0.9500

C2—C1—C8	126.64 (13)	H6B—C6—H6C	109.5
C2—C1—H1	116.7	C4—C7—H7A	109.5
C8—C1—H1	116.7	C4—C7—H7B	109.5
C1—C2—C3	121.13 (13)	H7A—C7—H7B	109.5
C1—C2—H2	119.4	C4—C7—H7C	109.5
C3—C2—H2	119.4	H7A—C7—H7C	109.5
O1—C3—C2	120.51 (13)	H7B—C7—H7C	109.5
O1—C3—C4	122.12 (13)	C13—C8—C9	118.03 (13)
C2—C3—C4	117.37 (12)	C13—C8—C1	119.85 (13)
C5—C4—C3	110.10 (12)	C9—C8—C1	122.13 (13)
C5—C4—C7	109.81 (12)	C10—C9—C8	121.03 (13)
C3—C4—C7	108.91 (11)	C10—C9—H9	119.5
C5—C4—C6	110.00 (12)	C8—C9—H9	119.5
C3—C4—C6	108.29 (11)	C9—C10—C11	119.20 (13)
C7—C4—C6	109.71 (12)	C9—C10—H10	120.4
C4—C5—H5A	109.5	C11—C10—H10	120.4
C4—C5—H5B	109.5	C12—C11—C10	121.34 (13)
H5A—C5—H5B	109.5	C12—C11—Cl1	119.52 (11)
C4—C5—H5C	109.5	C10—C11—Cl1	119.13 (11)
H5A—C5—H5C	109.5	C11—C12—C13	119.01 (13)
H5B—C5—H5C	109.5	C11—C12—H12	120.5
C4—C6—H6A	109.5	C13—C12—H12	120.5
C4—C6—H6B	109.5	C12—C13—C8	121.37 (13)
H6A—C6—H6B	109.5	C12—C13—H13	119.3
C4—C6—H6C	109.5	C8—C13—H13	119.3
H6A—C6—H6C	109.5

C8—C1—C2—C3	−178.96 (13)	C13—C8—C9—C10	0.0 (2)
C1—C2—C3—O1	12.6 (2)	C1—C8—C9—C10	179.39 (13)
C1—C2—C3—C4	−167.46 (13)	C8—C9—C10—C11	0.9 (2)
O1—C3—C4—C5	−0.29 (19)	C9—C10—C11—C12	−0.8 (2)
C2—C3—C4—C5	179.76 (12)	C9—C10—C11—Cl1	−179.58 (11)
O1—C3—C4—C7	120.17 (15)	C10—C11—C12—C13	−0.3 (2)
C2—C3—C4—C7	−59.79 (16)	Cl1—C11—C12—C13	178.49 (11)
O1—C3—C4—C6	−120.59 (15)	C11—C12—C13—C8	1.3 (2)
C2—C3—C4—C6	59.46 (16)	C9—C8—C13—C12	−1.1 (2)
C2—C1—C8—C13	−158.39 (14)	C1—C8—C13—C12	179.47 (13)
C2—C1—C8—C9	22.2 (2)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅ClO
M_r	222.70
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	5.6831 (4), 9.9156 (6), 11.3731 (7)
α, β, γ (°)	103.487 (1), 101.160 (1), 103.697 (1)
V (Å³)	584.12 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.46 × 0.31 × 0.21

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.875, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	4545, 2251, 1989
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.094, 1.07
No. of reflections	2251
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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