2-Chloro-N-methyl-N-[2-(methyl­amino)­phen­yl]acetamide

Bai, Y.-B.; Chen, X.-H.; Ma, Y.-T.; Zhang, A.-L.; Gao, J.-M.

doi:10.1107/S1600536813000494

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o229

doi:10.1107/S1600536813000494

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2-Chloro-N-methyl-N-[2-(methylamino)phenyl]acetamide

Yu-Bin Bai,^a Xia-Hui Chen,^a Ya-Tuan Ma,^a An-Ling Zhang ^a and Jin-Ming Gao ^a ^*

^aCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
^*Correspondence e-mail: jinminggao@nwsuaf.edu.cn

(Received 17 December 2012; accepted 6 January 2013; online 12 January 2013)

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

C₁₀H₁₃ClN₂O
M_r = 212.67
Monoclinic, P 2₁ /n
a = 9.2483 (18) Å
b = 6.6630 (13) Å
c = 17.622 (3) Å
β = 94.377 (2)°
V = 1082.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.50 × 0.35 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.855, T_max = 0.935
7714 measured reflections
2011 independent reflections
1487 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.140
S = 1.01
2011 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813000494/nc2302sup1.cif

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

checkCIF report

Related literature top

For the synthesis of similar compounds, see: Turner & Wood (1965); Bai et al. (2008).

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

Figures top

Fig. 1. The molecular structure of the title compound with labeling and isplacement ellipsoids drawn at the 30% probability level.

2-Chloro-N-methyl-N-[2-(methylamino)phenyl]acetamide top

Crystal data top

C₁₀H₁₃ClN₂O	F(000) = 448
M_r = 212.67	D_x = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	2011 independent reflections
Radiation source: fine-focus sealed tube	1487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
phi and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.855, T_max = 0.935	k = −8→8
7714 measured reflections	l = −21→21

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0697P)² + 0.4335P] where P = (F_o² + 2F_c²)/3
2011 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₀H₁₃ClN₂O	V = 1082.8 (4) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2011 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1487 reflections with I > 2σ(I)
T_min = 0.855, T_max = 0.935	R_int = 0.023
7714 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
2011 reflections	Δρ_min = −0.24 e Å⁻³
129 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.855, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	7714, 2011, 1487
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

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