2,2-Dichloro-1-(4-methyl­phen­yl)ethanone

Wang, P.-A.; Gao, J.-P.; Liu, P.

doi:10.1107/S1600536811000134

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o337

doi:10.1107/S1600536811000134

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2,2-Dichloro-1-(4-methylphenyl)ethanone

Ping-An Wang,^a ^* Jun-Ping Gao ^a and Peng Liu ^a

^aDepartment of Chemistry, School of Pharmacy, Fourth Military Medical University, Changle West Road 17, 710032 Xi-An, People's Republic of China
^*Correspondence e-mail: ping_an1718@yahoo.com.cn

(Received 23 December 2010; accepted 4 January 2011; online 12 January 2011)

The molecule of the title compound, C₉H₈Cl₂O, is almost planar: the dihedral angle between the benzene ring and the plane defined by the carbonyl O and ethane C atoms is 15.5 (2)°. The crystal packing is stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For the preparation, see: Aston et al. (1943 ); Terent'ev et al. (2004 ). For synthetic use of the title compound and mandelic acid derivatives, see: Schiffers & Bolm (2008 ); Blay et al. (2006 ).

Experimental

Crystal data

C₉H₈Cl₂O
M_r = 203.05
Monoclinic, P 2₁ /c
a = 6.650 (5) Å
b = 9.959 (7) Å
c = 14.475 (11) Å
β = 92.921 (9)°
V = 957.4 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 296 K
0.32 × 0.26 × 0.14 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.826, T_max = 0.920
4496 measured reflections
1694 independent reflections
874 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.155
S = 1.03
1694 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	0.93	2.58	3.42	150
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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: Mercury (Macrae et al., 2006 ) and ORTEP-3 (Farrugia, 1997 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000134/bt5447sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000134/bt5447Isup2.hkl

checkCIF report

Comment top

The title compound, 2,2-Dichloro-1-(4-methylphenyl)ethanone, was obtained by chloration of 1-(4-methylphenyl)ethanone with concentrated hydrochloride and aqueous hydroperoxide in hot ethanol (Terent'ev et al., 2004) and it was used for the preparation of substituted mandelic acid and derivatives.

In the title compound, C₉H₈Cl₂O, the lengthes of two C—Cl bonds are different, the distance of C1—Cl1 is 1.757 Å, otherwise, the distance of C1—Cl2 is 1.762 Å. The molecule is nearly planar, the dihedral angle between the phenyl ring and the plane defined by O1, C2 and C1 is 15.5°. The packing of molecules in the crystal structure is stabilized by intermolecular C—H···O hydrogen bonds.

Related literature top

For the preparation, see: Aston et al. (1943); Terent'ev et al. (2004). For synthetic use of the title compound and mandelic acid derivatives, see: Schiffers & Bolm (2008); Blay et al. (2006).

Experimental top

To a stirred hot mixed aqueous concentrated hydrochloride and ethanol solution (300 cm³) of commercially available 1-p-tolylethanone (13.42 g, 0.10 mol) added dropwise aqueous hydropeoxide (35% wt in water, 0.272 mol), and the mixture was stirred for 30 min at 90–100°C. The solution was cooled to room temperature and diluted by addtion of water (300 cm³), it was extracted by ether (2× 400 cm³), the combined organic layer was washed with 1 M NaOH (100 cm³), water (100 cm³), brine (2× 110 cm³), and dried over Na₂SO₄. Evaporation of the solvent afforded the title compound as a light yellow oli (19.8 g, 97%), which was solidfied as a pale block after24 h at room temperature. The melting point and the spectroscopic data of the title compound were consisted with the reported literature (Terent'ev et al., 2004).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: Mercury (Macrae et al., 2006) and ORTEP-3 (Farrugia, 1997).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

2,2-Dichloro-1-(4-methylphenyl)ethanone top

Crystal data top

C₉H₈Cl₂O	F(000) = 416
M_r = 203.05	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.650 (5) Å	θ = 2.5–25.1°
b = 9.959 (7) Å	µ = 0.63 mm⁻¹
c = 14.475 (11) Å	T = 296 K
β = 92.921 (9)°	Block, colorless
V = 957.4 (12) Å³	0.32 × 0.26 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1694 independent reflections
Radiation source: fine-focus sealed tube	874 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.826, T_max = 0.920	k = −11→9
4496 measured reflections	l = −17→15

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0679P)²] where P = (F_o² + 2F_c²)/3
1694 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₈Cl₂O	V = 957.4 (12) Å³
M_r = 203.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.650 (5) Å	µ = 0.63 mm⁻¹
b = 9.959 (7) Å	T = 296 K
c = 14.475 (11) Å	0.32 × 0.26 × 0.14 mm
β = 92.921 (9)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1694 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	874 reflections with I > 2σ(I)
T_min = 0.826, T_max = 0.920	R_int = 0.061
4496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
1694 reflections	Δρ_min = −0.27 e Å⁻³
110 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
Cl1	1.21054 (15)	0.84106 (11)	0.13668 (8)	0.0912 (5)
Cl2	0.79412 (19)	0.87565 (15)	0.07241 (8)	0.1147 (6)
O1	0.9705 (4)	0.6849 (3)	0.2551 (2)	0.0966 (10)
C1	0.9678 (5)	0.8856 (4)	0.1682 (2)	0.0670 (10)
H1	0.9707	0.9780	0.1915	0.080*
C2	0.8918 (5)	0.7929 (4)	0.2428 (2)	0.0627 (9)
C3	0.7161 (5)	0.8368 (3)	0.2934 (2)	0.0562 (9)
C4	0.6500 (5)	0.9690 (4)	0.2946 (2)	0.0662 (10)
H4	0.7173	1.0350	0.2629	0.079*
C5	0.4837 (5)	1.0019 (4)	0.3433 (3)	0.0711 (10)
H5	0.4403	1.0907	0.3436	0.085*
C6	0.3800 (5)	0.9072 (4)	0.3915 (2)	0.0662 (10)
C7	0.4492 (6)	0.7764 (4)	0.3911 (3)	0.0747 (11)
H7	0.3823	0.7111	0.4238	0.090*
C8	0.6142 (6)	0.7406 (4)	0.3439 (3)	0.0691 (10)
H8	0.6588	0.6521	0.3453	0.083*
C9	0.1955 (5)	0.9460 (5)	0.4417 (3)	0.0876 (13)
H9A	0.2314	1.0114	0.4884	0.131*
H9B	0.1410	0.8679	0.4701	0.131*
H9C	0.0965	0.9834	0.3985	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0822 (7)	0.0892 (9)	0.1049 (9)	0.0029 (6)	0.0303 (6)	−0.0065 (6)
Cl2	0.1093 (9)	0.1452 (13)	0.0881 (9)	0.0030 (8)	−0.0091 (7)	0.0200 (7)
O1	0.0959 (19)	0.0598 (18)	0.137 (3)	0.0230 (16)	0.0350 (18)	0.0209 (17)
C1	0.072 (2)	0.050 (2)	0.080 (3)	−0.0003 (18)	0.019 (2)	−0.0037 (18)
C2	0.065 (2)	0.049 (2)	0.075 (2)	0.002 (2)	0.0035 (19)	−0.0052 (19)
C3	0.0566 (19)	0.046 (2)	0.065 (2)	−0.0002 (17)	0.0016 (17)	0.0010 (17)
C4	0.062 (2)	0.049 (2)	0.088 (3)	−0.0012 (19)	0.0076 (19)	0.0019 (18)
C5	0.067 (2)	0.058 (3)	0.088 (3)	0.012 (2)	0.007 (2)	0.000 (2)
C6	0.063 (2)	0.073 (3)	0.063 (2)	0.000 (2)	0.0003 (18)	0.001 (2)
C7	0.081 (3)	0.068 (3)	0.076 (3)	−0.007 (2)	0.016 (2)	0.007 (2)
C8	0.080 (2)	0.051 (2)	0.076 (3)	0.000 (2)	0.003 (2)	0.0040 (19)
C9	0.070 (2)	0.113 (4)	0.081 (3)	0.009 (2)	0.014 (2)	0.002 (2)

Geometric parameters (Å, º) top

Cl1—C1	1.756 (4)	C5—C6	1.378 (5)
Cl2—C1	1.761 (4)	C5—H5	0.9300
O1—C2	1.206 (4)	C6—C7	1.382 (5)
C1—C2	1.527 (5)	C6—C9	1.508 (5)
C1—H1	0.9800	C7—C8	1.369 (5)
C2—C3	1.476 (5)	C7—H7	0.9300
C3—C4	1.388 (5)	C8—H8	0.9300
C3—C8	1.401 (5)	C9—H9A	0.9600
C4—C5	1.380 (5)	C9—H9B	0.9600
C4—H4	0.9300	C9—H9C	0.9600

C2—C1—Cl1	111.9 (3)	C4—C5—H5	119.0
C2—C1—Cl2	107.2 (2)	C5—C6—C7	117.9 (3)
Cl1—C1—Cl2	110.86 (19)	C5—C6—C9	120.6 (4)
C2—C1—H1	109.0	C7—C6—C9	121.5 (4)
Cl1—C1—H1	109.0	C8—C7—C6	121.5 (4)
Cl2—C1—H1	109.0	C8—C7—H7	119.2
O1—C2—C3	122.6 (3)	C6—C7—H7	119.2
O1—C2—C1	119.2 (3)	C7—C8—C3	120.2 (4)
C3—C2—C1	118.1 (3)	C7—C8—H8	119.9
C4—C3—C8	118.7 (3)	C3—C8—H8	119.9
C4—C3—C2	123.1 (3)	C6—C9—H9A	109.5
C8—C3—C2	118.2 (3)	C6—C9—H9B	109.5
C5—C4—C3	119.6 (3)	H9A—C9—H9B	109.5
C5—C4—H4	120.2	C6—C9—H9C	109.5
C3—C4—H4	120.2	H9A—C9—H9C	109.5
C6—C5—C4	122.0 (4)	H9B—C9—H9C	109.5
C6—C5—H5	119.0

Cl1—C1—C2—O1	−19.0 (4)	C2—C3—C4—C5	179.7 (3)
Cl2—C1—C2—O1	102.8 (3)	C3—C4—C5—C6	0.1 (6)
Cl1—C1—C2—C3	164.5 (2)	C4—C5—C6—C7	1.0 (5)
Cl2—C1—C2—C3	−73.7 (3)	C4—C5—C6—C9	−178.3 (3)
O1—C2—C3—C4	166.2 (4)	C5—C6—C7—C8	−0.7 (5)
C1—C2—C3—C4	−17.4 (5)	C9—C6—C7—C8	178.5 (3)
O1—C2—C3—C8	−12.5 (5)	C6—C7—C8—C3	−0.7 (5)
C1—C2—C3—C8	163.8 (3)	C4—C3—C8—C7	1.9 (5)
C8—C3—C4—C5	−1.6 (5)	C2—C3—C8—C7	−179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.58	3.42	150

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈Cl₂O
M_r	203.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	6.650 (5), 9.959 (7), 14.475 (11)
β (°)	92.921 (9)
V (Å³)	957.4 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.32 × 0.26 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.826, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	4496, 1694, 874
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.155, 1.03
No. of reflections	1694
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006) and ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.58	3.42	150

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Acknowledgements

We thank the Natural Science Foundation of China (grant No. 20802092) for financial support.

References

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