organic compounds
2-Chloro-N-methyl-N-[2-(methylamino)phenyl]acetamide
aCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
*Correspondence e-mail: jinminggao@nwsuaf.edu.cn
The title compound, C10H13ClN2O, was obtained as a by-product in the reaction of 2-chloromethyl-1H-benzimidazole, dimethyl sulfate and toluene to synthesise 2-chloromethyl-1-methylbenzimidazole. The dihedral angle between the benzene ring and the acetamide group is 89.72 (6)° while that between the aromatic ring and the chloracetyl group is 84.40 (4)°. In the crystal, adjacent molecules are linked by pairs of N—H⋯O hydrogen bonds into inversion dimers.
Related literature
For the synthesis of similar compounds, see: Turner & Wood (1965); Bai et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); 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: SHELXTL.
Supporting information
10.1107/S1600536813000494/nc2302sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813000494/nc2302Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813000494/nc2302Isup4.cdx
Supporting information file. DOI: 10.1107/S1600536813000494/nc2302Isup4.cml
2-chloromethyl-1H-benzimidazole (1.01 g, 6.07 mmol), toluene (10 ml),dimethyl sulfate (0.63 ml, 6.67 mmol) were refluxed for 3 h and the reaction was followed by TLC monitoring). After cooling 10 mL of water and an excess of ammonia were added. After filtration, the solution was extracted with chloroform (3 x 20 ml). The organic layer was dried over anhydrous sodium sulfate, concentrated and purified by columnchromatography on silica gel eluting with 4:1–3:1 petroleum ether-acetone. Crystals of the title compound were grown by slow evaporation of the solvent.
All H atoms were positioned with idealized geometry and refined isotropic with Uiso(H) = 1.2 Ueq(C,N) using a riding model.
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with labeling and isplacement ellipsoids drawn at the 30% probability level. |
C10H13ClN2O | F(000) = 448 |
Mr = 212.67 | Dx = 1.305 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2483 (18) Å | Cell parameters from 2090 reflections |
b = 6.6630 (13) Å | θ = 2.6–25.0° |
c = 17.622 (3) Å | µ = 0.32 mm−1 |
β = 94.377 (2)° | T = 296 K |
V = 1082.8 (4) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.35 × 0.21 mm |
Bruker APEXII CCD area-detector diffractometer | 2011 independent reflections |
Radiation source: fine-focus sealed tube | 1487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
phi and ω scans | θmax = 25.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.855, Tmax = 0.935 | k = −8→8 |
7714 measured reflections | l = −21→21 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0697P)2 + 0.4335P] where P = (Fo2 + 2Fc2)/3 |
2011 reflections | (Δ/σ)max < 0.001 |
129 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C10H13ClN2O | V = 1082.8 (4) Å3 |
Mr = 212.67 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2483 (18) Å | µ = 0.32 mm−1 |
b = 6.6630 (13) Å | T = 296 K |
c = 17.622 (3) Å | 0.50 × 0.35 × 0.21 mm |
β = 94.377 (2)° |
Bruker APEXII CCD area-detector diffractometer | 2011 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1487 reflections with I > 2σ(I) |
Tmin = 0.855, Tmax = 0.935 | Rint = 0.023 |
7714 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.29 e Å−3 |
2011 reflections | Δρmin = −0.24 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0326 (2) | 0.5640 (3) | 0.20070 (11) | 0.0443 (5) | |
C2 | 0.9122 (2) | 0.6930 (3) | 0.19791 (11) | 0.0443 (5) | |
C3 | 0.8956 (3) | 0.8109 (3) | 0.26283 (13) | 0.0526 (6) | |
H3 | 0.8181 | 0.8998 | 0.2633 | 0.063* | |
C4 | 0.9928 (3) | 0.7961 (4) | 0.32578 (13) | 0.0594 (7) | |
H4 | 0.9793 | 0.8755 | 0.3681 | 0.071* | |
C5 | 1.1092 (3) | 0.6675 (4) | 0.32793 (13) | 0.0594 (7) | |
H5 | 1.1733 | 0.6584 | 0.3711 | 0.071* | |
C6 | 1.1285 (2) | 0.5519 (4) | 0.26424 (12) | 0.0526 (6) | |
H6 | 1.2072 | 0.4650 | 0.2644 | 0.063* | |
C7 | 0.6897 (3) | 0.8227 (4) | 0.12831 (16) | 0.0648 (7) | |
H7A | 0.6262 | 0.7888 | 0.1670 | 0.097* | |
H7B | 0.6398 | 0.8034 | 0.0791 | 0.097* | |
H7C | 0.7188 | 0.9605 | 0.1340 | 0.097* | |
C8 | 0.9806 (3) | 0.2351 (4) | 0.14078 (16) | 0.0655 (7) | |
H8A | 0.9882 | 0.1661 | 0.0934 | 0.098* | |
H8B | 0.8802 | 0.2518 | 0.1497 | 0.098* | |
H8C | 1.0281 | 0.1580 | 0.1814 | 0.098* | |
C9 | 1.1273 (2) | 0.4748 (4) | 0.07858 (11) | 0.0487 (5) | |
C10 | 1.1969 (3) | 0.6811 (4) | 0.08199 (16) | 0.0740 (8) | |
H10A | 1.2469 | 0.7003 | 0.1319 | 0.089* | |
H10B | 1.1217 | 0.7823 | 0.0753 | 0.089* | |
Cl1 | 1.31970 (9) | 0.71410 (17) | 0.01279 (4) | 0.0981 (4) | |
N1 | 0.8153 (2) | 0.6964 (3) | 0.13566 (11) | 0.0612 (6) | |
H1 | 0.8305 | 0.6177 | 0.0984 | 0.073* | |
N2 | 1.04930 (19) | 0.4308 (3) | 0.13748 (9) | 0.0453 (4) | |
O1 | 1.14232 (19) | 0.3589 (3) | 0.02587 (9) | 0.0643 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0489 (11) | 0.0492 (12) | 0.0357 (10) | −0.0029 (10) | 0.0084 (9) | −0.0016 (9) |
C2 | 0.0519 (12) | 0.0455 (12) | 0.0369 (11) | 0.0002 (9) | 0.0128 (9) | −0.0001 (9) |
C3 | 0.0641 (14) | 0.0470 (13) | 0.0496 (13) | −0.0030 (10) | 0.0228 (11) | −0.0044 (10) |
C4 | 0.0806 (17) | 0.0599 (15) | 0.0400 (12) | −0.0238 (13) | 0.0205 (12) | −0.0133 (11) |
C5 | 0.0654 (15) | 0.0733 (17) | 0.0390 (12) | −0.0196 (13) | 0.0006 (10) | −0.0026 (11) |
C6 | 0.0528 (13) | 0.0604 (14) | 0.0444 (12) | −0.0039 (11) | 0.0028 (10) | 0.0001 (11) |
C7 | 0.0593 (15) | 0.0652 (16) | 0.0700 (16) | 0.0143 (12) | 0.0053 (12) | −0.0009 (13) |
C8 | 0.0724 (17) | 0.0552 (15) | 0.0696 (17) | −0.0062 (12) | 0.0108 (13) | −0.0129 (12) |
C9 | 0.0470 (12) | 0.0606 (14) | 0.0380 (11) | 0.0130 (10) | 0.0011 (9) | −0.0007 (10) |
C10 | 0.0861 (19) | 0.0806 (19) | 0.0593 (16) | −0.0093 (15) | 0.0314 (14) | −0.0046 (13) |
Cl1 | 0.0836 (6) | 0.1459 (9) | 0.0684 (5) | −0.0247 (5) | 0.0304 (4) | 0.0038 (5) |
N1 | 0.0624 (12) | 0.0763 (14) | 0.0449 (11) | 0.0249 (10) | 0.0041 (9) | −0.0101 (10) |
N2 | 0.0484 (10) | 0.0480 (10) | 0.0398 (9) | 0.0030 (8) | 0.0054 (7) | −0.0055 (8) |
O1 | 0.0742 (11) | 0.0775 (12) | 0.0417 (9) | 0.0169 (9) | 0.0064 (8) | −0.0138 (8) |
C1—C6 | 1.377 (3) | C7—H7B | 0.9600 |
C1—C2 | 1.405 (3) | C7—H7C | 0.9600 |
C1—N2 | 1.442 (3) | C8—N2 | 1.454 (3) |
C2—N1 | 1.363 (3) | C8—H8A | 0.9600 |
C2—C3 | 1.406 (3) | C8—H8B | 0.9600 |
C3—C4 | 1.377 (4) | C8—H8C | 0.9600 |
C3—H3 | 0.9300 | C9—O1 | 1.224 (3) |
C4—C5 | 1.374 (4) | C9—N2 | 1.341 (3) |
C4—H4 | 0.9300 | C9—C10 | 1.517 (4) |
C5—C6 | 1.384 (3) | C10—Cl1 | 1.742 (3) |
C5—H5 | 0.9300 | C10—H10A | 0.9700 |
C6—H6 | 0.9300 | C10—H10B | 0.9700 |
C7—N1 | 1.432 (3) | N1—H1 | 0.8600 |
C7—H7A | 0.9600 | ||
C6—C1—C2 | 121.60 (19) | H7B—C7—H7C | 109.5 |
C6—C1—N2 | 119.48 (19) | N2—C8—H8A | 109.5 |
C2—C1—N2 | 118.76 (18) | N2—C8—H8B | 109.5 |
N1—C2—C3 | 122.7 (2) | H8A—C8—H8B | 109.5 |
N1—C2—C1 | 120.60 (19) | N2—C8—H8C | 109.5 |
C3—C2—C1 | 116.7 (2) | H8A—C8—H8C | 109.5 |
C4—C3—C2 | 120.7 (2) | H8B—C8—H8C | 109.5 |
C4—C3—H3 | 119.6 | O1—C9—N2 | 123.3 (2) |
C2—C3—H3 | 119.6 | O1—C9—C10 | 122.0 (2) |
C5—C4—C3 | 121.9 (2) | N2—C9—C10 | 114.78 (19) |
C5—C4—H4 | 119.0 | C9—C10—Cl1 | 112.58 (19) |
C3—C4—H4 | 119.0 | C9—C10—H10A | 109.1 |
C4—C5—C6 | 118.3 (2) | Cl1—C10—H10A | 109.1 |
C4—C5—H5 | 120.8 | C9—C10—H10B | 109.1 |
C6—C5—H5 | 120.8 | Cl1—C10—H10B | 109.1 |
C1—C6—C5 | 120.8 (2) | H10A—C10—H10B | 107.8 |
C1—C6—H6 | 119.6 | C2—N1—C7 | 124.2 (2) |
C5—C6—H6 | 119.6 | C2—N1—H1 | 117.9 |
N1—C7—H7A | 109.5 | C7—N1—H1 | 117.9 |
N1—C7—H7B | 109.5 | C9—N2—C1 | 124.03 (19) |
H7A—C7—H7B | 109.5 | C9—N2—C8 | 119.30 (19) |
N1—C7—H7C | 109.5 | C1—N2—C8 | 116.63 (18) |
H7A—C7—H7C | 109.5 | ||
C6—C1—C2—N1 | −177.2 (2) | N2—C9—C10—Cl1 | 170.27 (17) |
N2—C1—C2—N1 | −1.9 (3) | C3—C2—N1—C7 | 1.9 (4) |
C6—C1—C2—C3 | 0.8 (3) | C1—C2—N1—C7 | 179.8 (2) |
N2—C1—C2—C3 | 176.12 (18) | O1—C9—N2—C1 | 178.84 (19) |
N1—C2—C3—C4 | 177.1 (2) | C10—C9—N2—C1 | −1.0 (3) |
C1—C2—C3—C4 | −0.8 (3) | O1—C9—N2—C8 | 1.3 (3) |
C2—C3—C4—C5 | 0.2 (3) | C10—C9—N2—C8 | −178.6 (2) |
C3—C4—C5—C6 | 0.6 (4) | C6—C1—N2—C9 | −91.2 (3) |
C2—C1—C6—C5 | 0.0 (3) | C2—C1—N2—C9 | 93.3 (3) |
N2—C1—C6—C5 | −175.32 (19) | C6—C1—N2—C8 | 86.4 (3) |
C4—C5—C6—C1 | −0.7 (3) | C2—C1—N2—C8 | −89.1 (2) |
O1—C9—C10—Cl1 | −9.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.23 | 2.926 (2) | 138 |
Symmetry code: (i) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H13ClN2O |
Mr | 212.67 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 9.2483 (18), 6.6630 (13), 17.622 (3) |
β (°) | 94.377 (2) |
V (Å3) | 1082.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.50 × 0.35 × 0.21 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.855, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7714, 2011, 1487 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.140, 1.01 |
No. of reflections | 2011 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.24 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.23 | 2.926 (2) | 138.1 |
Symmetry code: (i) −x+2, −y+1, −z. |
Acknowledgements
This work was supported financially by grants from the National Natural Science Foundation of China (No. 30971882), the Program of Natural Science Basis Research in Shaanxi (No. 2009JM3010) and Shaanxi Province Science and Technology (No. 2011k02–07).
References
Bai, Y., Li, C., Sun, W., Zhao, G. & Shi, Z. (2008). Hua Xue Shiji, 30, 409–411. CAS Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconin, USA. Google Scholar
Sheldrick, G. M. (1996). 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
Turner, A. B. & Wood, H. C. S. (1965). J. Chem. Soc. pp. 5270–5275. CrossRef Web of Science Google Scholar
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