2-Chloro-N-chloro­methyl-N-(2-ethyl-6-methyl­phen­yl)acetamide

Song, Z.-W.

doi:10.1107/S1600536808011902

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o991

doi:10.1107/S1600536808011902

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2-Chloro-N-chloromethyl-N-(2-ethyl-6-methylphenyl)acetamide

Zu-Wei Song ^a ^*

^aCollege of Science, Qingdao Agricultural University, Qingdao 266109, People's Republic of China
^*Correspondence e-mail: songzuwei2008@yahoo.cn

(Received 16 April 2008; accepted 24 April 2008; online 3 May 2008)

The title compound, C₁₂H₁₅Cl₂NO, was synthesized as an intermediate for the synthesis of the herbicide Acetochlor. The crystal structure exhibits weak intermolecular C—H⋯O hydrogen bonds, which link the molecules into zigzag chains along the b axis.

Related literature

For details of the biological activities of Acetochlor, see: Breaux (1986 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₅Cl₂NO
M_r = 260.15
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.3012 (17) Å
b = 9.3787 (19) Å
c = 16.575 (3) Å
V = 1290.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 296 (2) K
0.33 × 0.27 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.857, T_max = 0.922
20457 measured reflections
2403 independent reflections
1506 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.075
S = 0.77
2403 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ), 691 Friedel pairs
Flack parameter: 0.00 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O1ⁱ	0.97	2.43	3.375 (4)	164
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 I, global. DOI: 10.1107/S1600536808011902/cv2400sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011902/cv2400Isup2.hkl

checkCIF report

Comment top

Acetochlor is an herbicide developed by Monsanto and Zeneca. It is a member of the class of herbicides known as chloroacetanilides. Its mode of action is elongase inhibition, and inhibition of geranylgeranyl pyrophosphate (GGPP) cyclization enzymes, part of the gibberellin pathway (Breaux, 1986). It is used to control weeds in corn, and is particularly useful as a replacement for atrazine in the case of some important weeds. The title compound, (I), was synthesized as an intermediate for the synthesis of Acetochlor. We report here the crystal structure of (I).

In (I) (Fig. 1), all bond lengths and angles are normal (Allen et al., 1987). The mean plane N1/O1/C6/C10/C11 (with largest deviation of 0.036 (2) Å) and benzene ring C1-C6 form a dihedral angle of 78.0 (3)°. The crystal packing exhibits weak intermolecular C–H···O hydrogen bonds (Table 1), which link the molecules into zigzag chains along b axis.

Related literature top

For details of the biological activities of Acetochlor, see: Breaux (1986). For bond-length data, see: Allen et al. (1987).

Experimental top

The xylene solution containing N-methylene-2'-methyl-6'-ethyl-aniline was introduced into a mixture of 1.2 g (0.01 mol) of chloroacetyl chloride and 2 g xylene at 293 K to 313 K under continuous stirring. After about 15 minutes of stirring, 2.5 g of dry ethanol were introduced into mixture at 293 K to 313 K. The reaction mixture was stirred for 5 h, whereupon accoholysis proceeded. At the end of the reaction, 6 g of water were introduced into the mixture, and the phases were separated. The upper organic phase was washed acid-free with about 10 g of water,and the xylene solution, containing about 2.5 g of the desired end product, was separated. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol and dichloromethane at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

2-Chloro-N-chloromethyl-N-(2-ethyl-6-methylphenyl)acetamide top

Crystal data top

C₁₂H₁₅Cl₂NO	F(000) = 544
M_r = 260.15	D_x = 1.339 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 987 reflections
a = 8.3012 (17) Å	θ = 2.2–27.5°
b = 9.3787 (19) Å	µ = 0.48 mm⁻¹
c = 16.575 (3) Å	T = 296 K
V = 1290.4 (5) Å³	Plate, colorless
Z = 4	0.33 × 0.27 × 0.17 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2403 independent reflections
Radiation source: rotating anode	1506 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans at fixed χ = 45°	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.857, T_max = 0.923	k = −11→11
20457 measured reflections	l = −19→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0172P)²] where P = (F_o² + 2F_c²)/3
S = 0.77	(Δ/σ)_max = 0.001
2403 reflections	Δρ_max = 0.21 e Å⁻³
145 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 691 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (9)

Crystal data top

C₁₂H₁₅Cl₂NO	V = 1290.4 (5) Å³
M_r = 260.15	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.3012 (17) Å	µ = 0.48 mm⁻¹
b = 9.3787 (19) Å	T = 296 K
c = 16.575 (3) Å	0.33 × 0.27 × 0.17 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2403 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1506 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.923	R_int = 0.051
20457 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.075	Δρ_max = 0.21 e Å⁻³
S = 0.77	Δρ_min = −0.14 e Å⁻³
2403 reflections	Absolute structure: Flack (1983), 691 Friedel pairs
145 parameters	Absolute structure parameter: 0.00 (9)
0 restraints

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	0.86248 (17)	1.10317 (8)	0.59963 (5)	0.0986 (4)
Cl2	0.61827 (15)	0.78116 (9)	0.88510 (5)	0.0859 (3)
O1	0.6020 (3)	0.9889 (2)	0.75349 (11)	0.0616 (6)
N1	0.7273 (3)	0.8602 (2)	0.65690 (13)	0.0444 (6)
C1	0.7314 (4)	0.6328 (3)	0.58464 (17)	0.0495 (7)
C2	0.8149 (4)	0.5122 (3)	0.56042 (17)	0.0605 (9)
H2A	0.7634	0.4437	0.5291	0.073*
C3	0.9741 (5)	0.4929 (3)	0.58248 (18)	0.0611 (9)
H3A	1.0287	0.4116	0.5656	0.073*
C4	1.0523 (4)	0.5913 (3)	0.62872 (17)	0.0558 (8)
H4A	1.1592	0.5761	0.6432	0.067*
C5	0.9737 (4)	0.7147 (3)	0.65459 (16)	0.0468 (7)
C6	0.8129 (3)	0.7325 (3)	0.63222 (14)	0.0417 (7)
C7	0.5558 (4)	0.6500 (4)	0.56248 (19)	0.0717 (10)
H7A	0.5165	0.7390	0.5832	0.108*
H7B	0.4947	0.5730	0.5853	0.108*
H7C	0.5447	0.6488	0.5048	0.108*
C8	1.0590 (4)	0.8198 (4)	0.7098 (2)	0.0742 (11)
H8A	0.9981	0.9080	0.7100	0.089*
H8B	1.0563	0.7819	0.7643	0.089*
C10	0.7080 (4)	0.9714 (3)	0.59945 (18)	0.0631 (9)
H10A	0.6057	1.0181	0.6094	0.076*
H10B	0.7029	0.9292	0.5461	0.076*
C11	0.6641 (3)	0.8780 (3)	0.73246 (16)	0.0456 (7)
C12	0.6724 (4)	0.7457 (3)	0.78494 (15)	0.0586 (8)
H12A	0.7812	0.7080	0.7837	0.070*
H12B	0.6009	0.6736	0.7631	0.070*
C9	1.2274 (5)	0.8537 (5)	0.6897 (3)	0.145 (2)
H9A	1.2684	0.9222	0.7275	0.217*
H9B	1.2325	0.8926	0.6362	0.217*
H9C	1.2911	0.7684	0.6923	0.217*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1649 (10)	0.0562 (5)	0.0746 (6)	−0.0264 (7)	0.0055 (7)	0.0077 (4)
Cl2	0.1260 (8)	0.0752 (5)	0.0565 (5)	−0.0120 (6)	0.0273 (6)	−0.0026 (4)
O1	0.0704 (15)	0.0524 (12)	0.0621 (12)	0.0181 (13)	0.0044 (12)	−0.0097 (10)
N1	0.0505 (15)	0.0416 (13)	0.0412 (13)	0.0070 (12)	−0.0038 (11)	−0.0019 (11)
C1	0.060 (2)	0.0421 (16)	0.0461 (16)	−0.0048 (16)	0.0026 (15)	−0.0013 (14)
C2	0.086 (3)	0.0459 (18)	0.0501 (17)	−0.0116 (19)	0.0115 (18)	−0.0087 (14)
C3	0.078 (3)	0.0427 (17)	0.063 (2)	0.0139 (19)	0.019 (2)	0.0035 (16)
C4	0.051 (2)	0.0562 (18)	0.0601 (19)	0.0094 (17)	0.0075 (16)	0.0121 (16)
C5	0.052 (2)	0.0452 (16)	0.0431 (15)	−0.0001 (15)	0.0030 (14)	0.0026 (14)
C6	0.0493 (19)	0.0379 (15)	0.0380 (14)	0.0062 (14)	0.0014 (13)	0.0006 (13)
C7	0.065 (2)	0.078 (2)	0.072 (2)	−0.0091 (19)	−0.0055 (19)	−0.0107 (18)
C8	0.063 (3)	0.077 (2)	0.083 (3)	0.0028 (19)	−0.023 (2)	−0.002 (2)
C10	0.084 (2)	0.0505 (17)	0.0543 (18)	0.0211 (17)	−0.0101 (18)	−0.0019 (15)
C11	0.0418 (18)	0.0460 (17)	0.0491 (16)	−0.0023 (15)	−0.0055 (14)	−0.0043 (14)
C12	0.069 (2)	0.0537 (17)	0.0531 (17)	−0.0057 (17)	0.0113 (16)	−0.0039 (15)
C9	0.058 (3)	0.104 (3)	0.272 (7)	−0.018 (3)	0.017 (4)	−0.060 (4)

Geometric parameters (Å, º) top

Cl1—C10	1.781 (3)	C5—C8	1.521 (4)
Cl2—C12	1.752 (3)	C7—H7A	0.9600
O1—C11	1.212 (3)	C7—H7B	0.9600
N1—C11	1.368 (3)	C7—H7C	0.9600
N1—C10	1.421 (3)	C8—C9	1.472 (5)
N1—C6	1.451 (3)	C8—H8A	0.9700
C1—C2	1.387 (4)	C8—H8B	0.9700
C1—C6	1.398 (4)	C10—H10A	0.9700
C1—C7	1.511 (4)	C10—H10B	0.9700
C2—C3	1.384 (4)	C11—C12	1.517 (4)
C2—H2A	0.9300	C12—H12A	0.9700
C3—C4	1.364 (4)	C12—H12B	0.9700
C3—H3A	0.9300	C9—H9A	0.9600
C4—C5	1.396 (4)	C9—H9B	0.9600
C4—H4A	0.9300	C9—H9C	0.9600
C5—C6	1.395 (4)

C11—N1—C10	118.7 (2)	C9—C8—C5	116.5 (3)
C11—N1—C6	123.1 (2)	C9—C8—H8A	108.2
C10—N1—C6	118.2 (2)	C5—C8—H8A	108.2
C2—C1—C6	117.8 (3)	C9—C8—H8B	108.2
C2—C1—C7	119.9 (3)	C5—C8—H8B	108.2
C6—C1—C7	122.2 (3)	H8A—C8—H8B	107.3
C3—C2—C1	120.5 (3)	N1—C10—Cl1	115.3 (2)
C3—C2—H2A	119.7	N1—C10—H10A	108.5
C1—C2—H2A	119.7	Cl1—C10—H10A	108.5
C4—C3—C2	121.0 (3)	N1—C10—H10B	108.5
C4—C3—H3A	119.5	Cl1—C10—H10B	108.5
C2—C3—H3A	119.5	H10A—C10—H10B	107.5
C3—C4—C5	120.7 (3)	O1—C11—N1	122.1 (2)
C3—C4—H4A	119.6	O1—C11—C12	123.8 (3)
C5—C4—H4A	119.6	N1—C11—C12	114.1 (2)
C6—C5—C4	117.7 (3)	C11—C12—Cl2	112.13 (19)
C6—C5—C8	121.9 (3)	C11—C12—H12A	109.2
C4—C5—C8	120.3 (3)	Cl2—C12—H12A	109.2
C5—C6—C1	122.2 (3)	C11—C12—H12B	109.2
C5—C6—N1	119.5 (3)	Cl2—C12—H12B	109.2
C1—C6—N1	118.3 (2)	H12A—C12—H12B	107.9
C1—C7—H7A	109.5	C8—C9—H9A	109.5
C1—C7—H7B	109.5	C8—C9—H9B	109.5
H7A—C7—H7B	109.5	H9A—C9—H9B	109.5
C1—C7—H7C	109.5	C8—C9—H9C	109.5
H7A—C7—H7C	109.5	H9A—C9—H9C	109.5
H7B—C7—H7C	109.5	H9B—C9—H9C	109.5

C6—C1—C2—C3	−0.5 (4)	C11—N1—C6—C5	−79.7 (3)
C7—C1—C2—C3	−177.9 (3)	C10—N1—C6—C5	100.6 (3)
C1—C2—C3—C4	0.3 (5)	C11—N1—C6—C1	102.0 (3)
C2—C3—C4—C5	−0.4 (4)	C10—N1—C6—C1	−77.7 (3)
C3—C4—C5—C6	0.6 (4)	C6—C5—C8—C9	−140.5 (4)
C3—C4—C5—C8	176.7 (3)	C4—C5—C8—C9	43.6 (5)
C4—C5—C6—C1	−0.9 (4)	C11—N1—C10—Cl1	88.9 (3)
C8—C5—C6—C1	−176.9 (3)	C6—N1—C10—Cl1	−91.4 (3)
C4—C5—C6—N1	−179.1 (2)	C10—N1—C11—O1	−5.1 (4)
C8—C5—C6—N1	4.9 (4)	C6—N1—C11—O1	175.2 (3)
C2—C1—C6—C5	0.8 (4)	C10—N1—C11—C12	172.3 (3)
C7—C1—C6—C5	178.1 (3)	C6—N1—C11—C12	−7.4 (4)
C2—C1—C6—N1	179.1 (2)	O1—C11—C12—Cl2	−11.6 (4)
C7—C1—C6—N1	−3.6 (4)	N1—C11—C12—Cl2	171.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O1ⁱ	0.97	2.43	3.375 (4)	164

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅Cl₂NO
M_r	260.15
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	8.3012 (17), 9.3787 (19), 16.575 (3)
V (Å³)	1290.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.33 × 0.27 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.857, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	20457, 2403, 1506
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.075, 0.77
No. of reflections	2403
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.14
Absolute structure	Flack (1983), 691 Friedel pairs
Absolute structure parameter	0.00 (9)

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O1ⁱ	0.97	2.43	3.375 (4)	164.4

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Breaux, E. J. (1986). J. Agric. Food Chem. 34, 884–888. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Takyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o991

doi:10.1107/S1600536808011902

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