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Acta Cryst. (2008). E64, o991    [ doi:10.1107/S1600536808011902 ]

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

Z.-W. Song

Abstract top

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.

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.

Refinement top

H atoms were positioned geometrically (C—H = 0.93–0.97 Å), and refined using a riding model, with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

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
[Figure 1] 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
C12H15Cl2NOF000 = 544
Mr = 260.15Dx = 1.339 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 987 reflections
a = 8.3012 (17) Åθ = 2.2–27.5º
b = 9.3787 (19) ŵ = 0.48 mm−1
c = 16.575 (3) ÅT = 296 (2) K
V = 1290.4 (5) Å3Plate, colorless
Z = 40.33 × 0.27 × 0.17 mm
Data collection top
Rigaku R-AXIS RAPID IP area-detector
diffractometer		2403 independent reflections
Radiation source: rotating anode1506 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.051
T = 296(2) Kθmax = 25.5º
ω scans at fixed χ = 45°θmin = 2.5º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→10
Tmin = 0.857, Tmax = 0.923k = −11→11
20457 measured reflectionsl = −19→20
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0172P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075(Δ/σ)max = 0.001
S = 0.77Δρmax = 0.21 e Å−3
2403 reflectionsΔρmin = −0.14 e Å−3
145 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 691 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (9)
Crystal data top
C12H15Cl2NOV = 1290.4 (5) Å3
Mr = 260.15Z = 4
Orthorhombic, P212121Mo Kα
a = 8.3012 (17) ŵ = 0.48 mm−1
b = 9.3787 (19) ÅT = 296 (2) K
c = 16.575 (3) Å0.33 × 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)
Tmin = 0.857, Tmax = 0.923Rint = 0.051
20457 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.075Δρmax = 0.21 e Å−3
S = 0.77Δρmin = −0.14 e Å−3
2403 reflectionsAbsolute structure: Flack (1983), 691 Friedel pairs
145 parametersFlack parameter: 0.00 (9)
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
xyzUiso*/Ueq
Cl10.86248 (17)1.10317 (8)0.59963 (5)0.0986 (4)
Cl20.61827 (15)0.78116 (9)0.88510 (5)0.0859 (3)
O10.6020 (3)0.9889 (2)0.75349 (11)0.0616 (6)
N10.7273 (3)0.8602 (2)0.65690 (13)0.0444 (6)
C10.7314 (4)0.6328 (3)0.58464 (17)0.0495 (7)
C20.8149 (4)0.5122 (3)0.56042 (17)0.0605 (9)
H2A0.76340.44370.52910.073*
C30.9741 (5)0.4929 (3)0.58248 (18)0.0611 (9)
H3A1.02870.41160.56560.073*
C41.0523 (4)0.5913 (3)0.62872 (17)0.0558 (8)
H4A1.15920.57610.64320.067*
C50.9737 (4)0.7147 (3)0.65459 (16)0.0468 (7)
C60.8129 (3)0.7325 (3)0.63222 (14)0.0417 (7)
C70.5558 (4)0.6500 (4)0.56248 (19)0.0717 (10)
H7A0.51650.73900.58320.108*
H7B0.49470.57300.58530.108*
H7C0.54470.64880.50480.108*
C81.0590 (4)0.8198 (4)0.7098 (2)0.0742 (11)
H8A0.99810.90800.71000.089*
H8B1.05630.78190.76430.089*
C100.7080 (4)0.9714 (3)0.59945 (18)0.0631 (9)
H10A0.60571.01810.60940.076*
H10B0.70290.92920.54610.076*
C110.6641 (3)0.8780 (3)0.73246 (16)0.0456 (7)
C120.6724 (4)0.7457 (3)0.78494 (15)0.0586 (8)
H12A0.78120.70800.78370.070*
H12B0.60090.67360.76310.070*
C91.2274 (5)0.8537 (5)0.6897 (3)0.145 (2)
H9A1.26840.92220.72750.217*
H9B1.23250.89260.63620.217*
H9C1.29110.76840.69230.217*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1649 (10)0.0562 (5)0.0746 (6)−0.0264 (7)0.0055 (7)0.0077 (4)
Cl20.1260 (8)0.0752 (5)0.0565 (5)−0.0120 (6)0.0273 (6)−0.0026 (4)
O10.0704 (15)0.0524 (12)0.0621 (12)0.0181 (13)0.0044 (12)−0.0097 (10)
N10.0505 (15)0.0416 (13)0.0412 (13)0.0070 (12)−0.0038 (11)−0.0019 (11)
C10.060 (2)0.0421 (16)0.0461 (16)−0.0048 (16)0.0026 (15)−0.0013 (14)
C20.086 (3)0.0459 (18)0.0501 (17)−0.0116 (19)0.0115 (18)−0.0087 (14)
C30.078 (3)0.0427 (17)0.063 (2)0.0139 (19)0.019 (2)0.0035 (16)
C40.051 (2)0.0562 (18)0.0601 (19)0.0094 (17)0.0075 (16)0.0121 (16)
C50.052 (2)0.0452 (16)0.0431 (15)−0.0001 (15)0.0030 (14)0.0026 (14)
C60.0493 (19)0.0379 (15)0.0380 (14)0.0062 (14)0.0014 (13)0.0006 (13)
C70.065 (2)0.078 (2)0.072 (2)−0.0091 (19)−0.0055 (19)−0.0107 (18)
C80.063 (3)0.077 (2)0.083 (3)0.0028 (19)−0.023 (2)−0.002 (2)
C100.084 (2)0.0505 (17)0.0543 (18)0.0211 (17)−0.0101 (18)−0.0019 (15)
C110.0418 (18)0.0460 (17)0.0491 (16)−0.0023 (15)−0.0055 (14)−0.0043 (14)
C120.069 (2)0.0537 (17)0.0531 (17)−0.0057 (17)0.0113 (16)−0.0039 (15)
C90.058 (3)0.104 (3)0.272 (7)−0.018 (3)0.017 (4)−0.060 (4)
Geometric parameters (Å, °) top
Cl1—C101.781 (3)C5—C81.521 (4)
Cl2—C121.752 (3)C7—H7A0.9600
O1—C111.212 (3)C7—H7B0.9600
N1—C111.368 (3)C7—H7C0.9600
N1—C101.421 (3)C8—C91.472 (5)
N1—C61.451 (3)C8—H8A0.9700
C1—C21.387 (4)C8—H8B0.9700
C1—C61.398 (4)C10—H10A0.9700
C1—C71.511 (4)C10—H10B0.9700
C2—C31.384 (4)C11—C121.517 (4)
C2—H2A0.9300C12—H12A0.9700
C3—C41.364 (4)C12—H12B0.9700
C3—H3A0.9300C9—H9A0.9600
C4—C51.396 (4)C9—H9B0.9600
C4—H4A0.9300C9—H9C0.9600
C5—C61.395 (4)
C11—N1—C10118.7 (2)C9—C8—C5116.5 (3)
C11—N1—C6123.1 (2)C9—C8—H8A108.2
C10—N1—C6118.2 (2)C5—C8—H8A108.2
C2—C1—C6117.8 (3)C9—C8—H8B108.2
C2—C1—C7119.9 (3)C5—C8—H8B108.2
C6—C1—C7122.2 (3)H8A—C8—H8B107.3
C3—C2—C1120.5 (3)N1—C10—Cl1115.3 (2)
C3—C2—H2A119.7N1—C10—H10A108.5
C1—C2—H2A119.7Cl1—C10—H10A108.5
C4—C3—C2121.0 (3)N1—C10—H10B108.5
C4—C3—H3A119.5Cl1—C10—H10B108.5
C2—C3—H3A119.5H10A—C10—H10B107.5
C3—C4—C5120.7 (3)O1—C11—N1122.1 (2)
C3—C4—H4A119.6O1—C11—C12123.8 (3)
C5—C4—H4A119.6N1—C11—C12114.1 (2)
C6—C5—C4117.7 (3)C11—C12—Cl2112.13 (19)
C6—C5—C8121.9 (3)C11—C12—H12A109.2
C4—C5—C8120.3 (3)Cl2—C12—H12A109.2
C5—C6—C1122.2 (3)C11—C12—H12B109.2
C5—C6—N1119.5 (3)Cl2—C12—H12B109.2
C1—C6—N1118.3 (2)H12A—C12—H12B107.9
C1—C7—H7A109.5C8—C9—H9A109.5
C1—C7—H7B109.5C8—C9—H9B109.5
H7A—C7—H7B109.5H9A—C9—H9B109.5
C1—C7—H7C109.5C8—C9—H9C109.5
H7A—C7—H7C109.5H9A—C9—H9C109.5
H7B—C7—H7C109.5H9B—C9—H9C109.5
C6—C1—C2—C3−0.5 (4)C11—N1—C6—C5−79.7 (3)
C7—C1—C2—C3−177.9 (3)C10—N1—C6—C5100.6 (3)
C1—C2—C3—C40.3 (5)C11—N1—C6—C1102.0 (3)
C2—C3—C4—C5−0.4 (4)C10—N1—C6—C1−77.7 (3)
C3—C4—C5—C60.6 (4)C6—C5—C8—C9−140.5 (4)
C3—C4—C5—C8176.7 (3)C4—C5—C8—C943.6 (5)
C4—C5—C6—C1−0.9 (4)C11—N1—C10—Cl188.9 (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—N14.9 (4)C6—N1—C11—O1175.2 (3)
C2—C1—C6—C50.8 (4)C10—N1—C11—C12172.3 (3)
C7—C1—C6—C5178.1 (3)C6—N1—C11—C12−7.4 (4)
C2—C1—C6—N1179.1 (2)O1—C11—C12—Cl2−11.6 (4)
C7—C1—C6—N1−3.6 (4)N1—C11—C12—Cl2171.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···O1i0.972.433.375 (4)164
Symmetry codes: (i) −x+1, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···O1i0.972.433.375 (4)164
Symmetry codes: (i) −x+1, y−1/2, −z+3/2.
references
References top

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.

Breaux, E. J. (1986). J. Agric. Food Chem. 34, 884–888.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Takyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.