1-(2,4-Dichloro­phen­yl)-4,4-dimethyl­pent-1-en-3-one

Xia, L.; Hu, A.-X.

doi:10.1107/S1600536808029838

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1983

doi:10.1107/S1600536808029838

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1-(2,4-Dichlorophenyl)-4,4-dimethylpent-1-en-3-one

Lin Xia ^a and Ai-Xi Hu ^a ^*

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

(Received 28 August 2008; accepted 17 September 2008; online 20 September 2008)

In the title compound, C₁₃H₁₄Cl₂O, the carbonyl and ethenyl groups are coplanar with the aromatic ring. There are four molecules in the asymmetric unit and all atoms in the molecule lie on mirror planes. The molecules are packed in an offset face-to-face arrangement showing π–π stacking interactions involving the benzene rings [centroid–centroid distance = 3.564 (2) Å].

Related literature

For related compounds, see: Wang et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₄Cl₂O
M_r = 257.14
Orthorhombic, P n m a
a = 11.2553 (7) Å
b = 7.0458 (4) Å
c = 15.4969 (9) Å
V = 1228.94 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 173 (2) K
0.47 × 0.39 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.798, T_max = 0.928
6162 measured reflections
1444 independent reflections
1227 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.07
1444 reflections
95 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808029838/sg2260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029838/sg2260Isup2.hkl

checkCIF report

Comment top

Phenyl-4,4-dimethylpentan-3-one derivatives are important intermediates in medicinal industry (Wang et al., 2006). Herein we report the synthesis and crystal structure of 1-(2,4-dichlorophen-yl)-4,4-dimethylpentan-3-one.

Related literature top

A series of related compounds was designed and synthesized by Wang et al. (2006).

Experimental top

3,3-dimethylbutan-2-one(0.0105 mol) was added dropwise into a solution of 2,4-dichlorobenzaldehyde (0.01 mol) and 60 ml ethanol. Then 0.1 g 50% NaOH solution as catalyst was added and the reaction was stirred at 333 K for 5 h . The solvent was evaporated to about half volume, then cooled to 277 K and the precipitate formed.This was filtered and dried to give the desired product (yield: 94.7%). 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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure showing 30% probability displacement ellipsoids.H atoms are omitted for clarity.
	Fig. 2. Packing diagram showing π–π stacking interactions.

1-(2,4-Dichlorophenyl)-4,4-dimethylpent-1-en-3-one top

Crystal data top

C₁₃H₁₄Cl₂O	D_x = 1.390 Mg m⁻³
M_r = 257.14	Melting point: 385 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3552 reflections
a = 11.2553 (7) Å	θ = 2.2–27.0°
b = 7.0458 (4) Å	µ = 0.50 mm⁻¹
c = 15.4969 (9) Å	T = 173 K
V = 1228.94 (13) Å³	Block, colorless
Z = 4	0.47 × 0.39 × 0.15 mm
F(000) = 536

Data collection top

Bruker SMART 1000 CCD diffractometer	1444 independent reflections
Radiation source: fine-focus sealed tube	1227 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −12→14
T_min = 0.798, T_max = 0.928	k = −8→9
6162 measured reflections	l = −19→14

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) = 0.085	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0391P)² + 0.6612P] where P = (F_o² + 2F_c²)/3
1444 reflections	(Δ/σ)_max < 0.001
95 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₃H₁₄Cl₂O	V = 1228.94 (13) Å³
M_r = 257.14	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.2553 (7) Å	µ = 0.50 mm⁻¹
b = 7.0458 (4) Å	T = 173 K
c = 15.4969 (9) Å	0.47 × 0.39 × 0.15 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1444 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1227 reflections with I > 2σ(I)
T_min = 0.798, T_max = 0.928	R_int = 0.021
6162 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.07	Δρ_max = 0.28 e Å⁻³
1444 reflections	Δρ_min = −0.36 e Å⁻³
95 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.73794 (5)	0.2500	0.45333 (4)	0.03276 (17)
Cl2	0.34147 (5)	0.2500	0.26347 (3)	0.03138 (17)
C1	0.57275 (19)	0.2500	0.61286 (13)	0.0239 (4)
H1	0.6571	0.2500	0.6149	0.029*
C2	0.51505 (19)	0.2500	0.68766 (13)	0.0265 (5)
H2	0.4307	0.2500	0.6869	0.032*
C3	0.57686 (18)	0.2500	0.77240 (13)	0.0225 (4)
C4	0.49783 (18)	0.2500	0.85260 (12)	0.0227 (4)
C5	0.5740 (2)	0.2500	0.93380 (14)	0.0314 (5)
H5A	0.6163	0.1518	0.9347	0.047*	0.50
H5B	0.5225	0.2500	0.9848	0.047*
H5C	0.6252	0.3625	0.9340	0.047*	0.50
C6	0.41949 (13)	0.0709 (2)	0.85096 (10)	0.0285 (3)
H6A	0.3670	0.0751	0.8005	0.043*
H6B	0.3714	0.0656	0.9036	0.043*
H6C	0.4701	−0.0421	0.8477	0.043*
C7	0.51674 (18)	0.2500	0.52726 (13)	0.0224 (4)
C8	0.58317 (17)	0.2500	0.45064 (13)	0.0217 (4)
C9	0.53111 (19)	0.2500	0.36945 (13)	0.0244 (4)
H9	0.5785	0.2500	0.3187	0.029*
C10	0.40892 (19)	0.2500	0.36426 (13)	0.0241 (4)
C11	0.33861 (18)	0.2500	0.43745 (15)	0.0267 (5)
H11	0.2544	0.2500	0.4329	0.032*
C12	0.39335 (19)	0.2500	0.51767 (14)	0.0265 (5)
H12	0.3451	0.2500	0.5680	0.032*
O1	0.68512 (13)	0.2500	0.77742 (10)	0.0323 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0204 (3)	0.0528 (4)	0.0251 (3)	0.000	0.00297 (19)	0.000
Cl2	0.0291 (3)	0.0413 (3)	0.0237 (3)	0.000	−0.0039 (2)	0.000
C1	0.0243 (10)	0.0245 (10)	0.0228 (10)	0.000	0.0018 (8)	0.000
C2	0.0232 (10)	0.0337 (12)	0.0225 (10)	0.000	−0.0004 (8)	0.000
C3	0.0221 (10)	0.0236 (10)	0.0218 (10)	0.000	0.0009 (8)	0.000
C4	0.0202 (9)	0.0284 (11)	0.0195 (9)	0.000	0.0007 (8)	0.000
C5	0.0256 (11)	0.0463 (14)	0.0223 (10)	0.000	−0.0029 (9)	0.000
C6	0.0269 (7)	0.0303 (8)	0.0285 (8)	−0.0032 (6)	0.0043 (6)	0.0008 (6)
C7	0.0238 (10)	0.0204 (10)	0.0229 (10)	0.000	0.0011 (8)	0.000
C8	0.0190 (9)	0.0209 (10)	0.0252 (10)	0.000	0.0019 (8)	0.000
C9	0.0276 (11)	0.0240 (10)	0.0217 (10)	0.000	0.0039 (8)	0.000
C10	0.0286 (11)	0.0220 (10)	0.0217 (10)	0.000	−0.0019 (8)	0.000
C11	0.0205 (10)	0.0311 (12)	0.0285 (11)	0.000	0.0005 (8)	0.000
C12	0.0256 (11)	0.0310 (11)	0.0228 (10)	0.000	0.0055 (8)	0.000
O1	0.0200 (7)	0.0468 (10)	0.0301 (8)	0.000	0.0026 (6)	0.000

Geometric parameters (Å, º) top

Cl1—C8	1.742 (2)	C5—H5C	0.9800
Cl2—C10	1.737 (2)	C6—H6A	0.9800
C1—C2	1.329 (3)	C6—H6B	0.9800
C1—C7	1.469 (3)	C6—H6C	0.9800
C1—H1	0.9500	C7—C12	1.397 (3)
C2—C3	1.486 (3)	C7—C8	1.403 (3)
C2—H2	0.9500	C8—C9	1.388 (3)
C3—O1	1.221 (2)	C9—C10	1.378 (3)
C3—C4	1.528 (3)	C9—H9	0.9500
C4—C5	1.522 (3)	C10—C11	1.383 (3)
C4—C6	1.5398 (19)	C11—C12	1.387 (3)
C4—C6ⁱ	1.5398 (19)	C11—H11	0.9500
C5—H5A	0.8400	C12—H12	0.9500
C5—H5B	0.9799

C2—C1—C7	125.3 (2)	H6A—C6—H6B	109.5
C2—C1—H1	117.3	C4—C6—H6C	109.5
C7—C1—H1	117.3	H6A—C6—H6C	109.5
C1—C2—C3	122.83 (19)	H6B—C6—H6C	109.5
C1—C2—H2	118.6	C12—C7—C8	116.09 (18)
C3—C2—H2	118.6	C12—C7—C1	121.53 (19)
O1—C3—C2	121.57 (19)	C8—C7—C1	122.39 (18)
O1—C3—C4	121.93 (18)	C9—C8—C7	122.84 (19)
C2—C3—C4	116.50 (17)	C9—C8—Cl1	116.34 (15)
C5—C4—C3	110.15 (17)	C7—C8—Cl1	120.82 (15)
C5—C4—C6	109.64 (11)	C10—C9—C8	118.32 (19)
C3—C4—C6	108.65 (11)	C10—C9—H9	120.8
C5—C4—C6ⁱ	109.64 (11)	C8—C9—H9	120.8
C3—C4—C6ⁱ	108.65 (11)	C9—C10—C11	121.55 (19)
C6—C4—C6ⁱ	110.09 (17)	C9—C10—Cl2	119.27 (16)
C4—C5—H5A	109.5	C11—C10—Cl2	119.17 (16)
C4—C5—H5B	109.5	C10—C11—C12	118.73 (19)
H5A—C5—H5B	108.7	C10—C11—H11	120.6
C4—C5—H5C	109.4	C12—C11—H11	120.6
H5A—C5—H5C	109.5	C11—C12—C7	122.5 (2)
H5B—C5—H5C	110.2	C11—C12—H12	118.8
C4—C6—H6A	109.5	C7—C12—H12	118.8
C4—C6—H6B	109.5

C7—C1—C2—C3	180.0	C1—C7—C8—C9	180.0
C1—C2—C3—O1	0.0	C12—C7—C8—Cl1	180.0
C1—C2—C3—C4	180.0	C1—C7—C8—Cl1	0.0
O1—C3—C4—C5	0.0	C7—C8—C9—C10	0.0
C2—C3—C4—C5	180.0	Cl1—C8—C9—C10	180.0
O1—C3—C4—C6	−120.11 (11)	C8—C9—C10—C11	0.0
C2—C3—C4—C6	59.89 (11)	C8—C9—C10—Cl2	180.0
O1—C3—C4—C6ⁱ	120.11 (11)	C9—C10—C11—C12	0.0
C2—C3—C4—C6ⁱ	−59.89 (11)	Cl2—C10—C11—C12	180.0
C2—C1—C7—C12	0.0	C10—C11—C12—C7	0.0
C2—C1—C7—C8	180.0	C8—C7—C12—C11	0.0
C12—C7—C8—C9	0.0	C1—C7—C12—C11	180.0

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄Cl₂O
M_r	257.14
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	11.2553 (7), 7.0458 (4), 15.4969 (9)
V (Å³)	1228.94 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.47 × 0.39 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.798, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	6162, 1444, 1227
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.07
No. of reflections	1444
No. of parameters	95
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.36

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

Acknowledgements

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

References

Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Wang, Y., Hu, A.-X., Cao, G., Li, G.-X., Zhang, J.-Y., Xia, L., Ou, X.-M. & Xu, J.-B. (2008). Chin. J. Org. Chem. 28, 443–448. CAS Google Scholar