organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Breaux, E. J. (1986). J. Agric. Food Chem. 34, 884-888.]). For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C12H15Cl2NO

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.857, Tmax = 0.922

  • 20457 measured reflections

  • 2403 independent reflections

  • 1506 reflections with I > 2σ(I)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.075

  • S = 0.77

  • 2403 reflections

  • 145 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.14 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 691 Friedel pairs

  • Flack parameter: 0.00 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Takyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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
C12H15Cl2NOF(000) = 544
Mr = 260.15Dx = 1.339 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 987 reflections
a = 8.3012 (17) Åθ = 2.2–27.5°
b = 9.3787 (19) ŵ = 0.48 mm1
c = 16.575 (3) ÅT = 296 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)
Graphite monochromatorRint = 0.051
ω scans at fixed χ = 45°θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1010
Tmin = 0.857, Tmax = 0.923k = 1111
20457 measured reflectionsl = 1920
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.075 w = 1/[σ2(Fo2) + (0.0172P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.77(Δ/σ)max = 0.001
2403 reflectionsΔρmax = 0.21 e Å3
145 parametersΔρmin = 0.14 e Å3
0 restraintsAbsolute structure: Flack (1983), 691 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (9)
Crystal data top
C12H15Cl2NOV = 1290.4 (5) Å3
Mr = 260.15Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.3012 (17) ŵ = 0.48 mm1
b = 9.3787 (19) ÅT = 296 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 Å3
S = 0.77Δρmin = 0.14 e Å3
2403 reflectionsAbsolute structure: Flack (1983), 691 Friedel pairs
145 parametersAbsolute 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
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, º) 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—C30.5 (4)C11—N1—C6—C579.7 (3)
C7—C1—C2—C3177.9 (3)C10—N1—C6—C5100.6 (3)
C1—C2—C3—C40.3 (5)C11—N1—C6—C1102.0 (3)
C2—C3—C4—C50.4 (4)C10—N1—C6—C177.7 (3)
C3—C4—C5—C60.6 (4)C6—C5—C8—C9140.5 (4)
C3—C4—C5—C8176.7 (3)C4—C5—C8—C943.6 (5)
C4—C5—C6—C10.9 (4)C11—N1—C10—Cl188.9 (3)
C8—C5—C6—C1176.9 (3)C6—N1—C10—Cl191.4 (3)
C4—C5—C6—N1179.1 (2)C10—N1—C11—O15.1 (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—C127.4 (4)
C2—C1—C6—N1179.1 (2)O1—C11—C12—Cl211.6 (4)
C7—C1—C6—N13.6 (4)N1—C11—C12—Cl2171.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···O1i0.972.433.375 (4)164
Symmetry code: (i) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC12H15Cl2NO
Mr260.15
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)8.3012 (17), 9.3787 (19), 16.575 (3)
V3)1290.4 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.33 × 0.27 × 0.17
Data collection
DiffractometerRigaku R-AXIS RAPID IP area-detector
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.857, 0.923
No. of measured, independent and
observed [I > 2σ(I)] reflections
20457, 2403, 1506
Rint0.051
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.075, 0.77
No. of reflections2403
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.14
Absolute structureFlack (1983), 691 Friedel pairs
Absolute structure parameter0.00 (9)

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···O1i0.972.433.375 (4)164.4
Symmetry code: (i) x+1, y1/2, z+3/2.
 

References

First citationAllen, 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
First citationBreaux, E. J. (1986). J. Agric. Food Chem. 34, 884–888.  CrossRef CAS Web of Science Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (2004). RAPID-AUTO. Rigaku Corporation, Takyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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