2-Amino-6-chloro-N-methyl­benzamide

Liang, Y.-H.; Mei, X.-D.; Li, Y.-F.; Pan, W.-L.; Ning, J.

doi:10.1107/S1600536813027827

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1642

doi:10.1107/S1600536813027827

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2-Amino-6-chloro-N-methylbenzamide

Yan-Hui Liang,^a Xiang-Dong Mei,^a ^* Yao-Fa Li,^b Wen-Liang Pan ^b and Jun Ning ^a

^aState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, People's Republic of China, and ^bPlant Protection Institute, Hebei Academy of Agricultural and Forestry Sciences, IPM Center of Hebei Province, Key Laboratory of Integrated Pest Management on Crops in Northern Region of North China, Ministry of Agriculture, Baoding 071000, People's Republic of China
^*Correspondence e-mail: xdmei@ippcaas.cn

(Received 28 September 2013; accepted 10 October 2013; online 16 October 2013)

In the title compound, C₈H₉ClN₂O, the dihedral angle between the benzene ring and the methylamide substituent is 68.39 (11)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming layers parallel to the ab plane.

CCDC reference: 965731

Related literature

For background information on substituted anthranilamides, see: Bharate et al. (2013 ); Gnamm et al. (2012 ); Lahm et al. (2005 ); Norman et al. (1996 ); Roe et al. (1999 ). For the synthesis, see: Witt & Bergman (2000 ); Coppola (1980 ).

Experimental

Crystal data

C₈H₉ClN₂O
M_r = 184.62
Orthorhombic, P b c a
a = 9.2709 (19) Å
b = 11.812 (2) Å
c = 15.982 (3) Å
V = 1750.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 173 K
0.43 × 0.25 × 0.18 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.609, T_max = 1.000
3865 measured reflections
1528 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.139
S = 1.17
1528 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.86	2.11	2.970 (3)	175
N2—H2⋯O1ⁱⁱ	0.86	2.04	2.895 (4)	172
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 965731

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027827/rz5085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027827/rz5085Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813027827/rz5085Isup3.cml

checkCIF report

Comment top

Anthranilamide-based derivatives exhibit interesting biological activities such as antibacterial, antifungal, antiviral, antimalarial and insecticidal activities (Bharate et al., 2013; Gnamm et al., 2012; Lahm et al., 2005; Norman et al., 1996; Roe et al., 1999). We report here the crystal structure of the title compound, 2-amino-6-chloro-N-methylbenzamide, an important organic intermediate in the synthesis of medicines, agricultural chemicals and animal drugs.

In the title compound (Fig. 1) the dihedral angle formed by the benzene ring and the methylamide substituent (r.m.s. deviation 0.0065 Å) is 68.39 (11)°. In the crystal structure, molecules are connected via N—H···O hydrogen bonds (Table 1) into layers running parallel to the ab plane.

Related literature top

For background information on substituted anthranilamides, see: Bharate et al. (2013); Gnamm et al. (2012); Lahm et al. (2005); Norman et al. (1996); Roe et al. (1999). For the synthesis, see: Witt & Bergman (2000); Coppola (1980).

Experimental top

The title compound was prepared according to the literature method (Witt & Bergman, 2000) by stirring isatoic anhydride with aqueous methylamine. Isatoic anhydride was prepared by reaction of anthranilic acid with triphosgene in good yield (Coppola, 1980). The title compound (0.2 g) was dissolved in ethanol (50 ml) at room temperature. Colourless blocks were obtained through slow evaporation after two weeks.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.

2-Amino-6-chloro-N-methylbenzamide top

Crystal data top

C₈H₉ClN₂O	F(000) = 768
M_r = 184.62	D_x = 1.401 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3698 reflections
a = 9.2709 (19) Å	θ = 1.3–27.5°
b = 11.812 (2) Å	µ = 0.39 mm⁻¹
c = 15.982 (3) Å	T = 173 K
V = 1750.2 (6) Å³	Block, colourless
Z = 8	0.43 × 0.25 × 0.18 mm

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1528 independent reflections
Radiation source: fine-focus sealed tube	1351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.0°, θ_min = 2.6°
ω scans at fixed χ = 45°	h = −11→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	k = −14→9
T_min = 0.609, T_max = 1.000	l = −10→19
3865 measured reflections

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0417P)² + 1.8852P] where P = (F_o² + 2F_c²)/3
1528 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₈H₉ClN₂O	V = 1750.2 (6) Å³
M_r = 184.62	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.2709 (19) Å	µ = 0.39 mm⁻¹
b = 11.812 (2) Å	T = 173 K
c = 15.982 (3) Å	0.43 × 0.25 × 0.18 mm

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1528 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	1351 reflections with I > 2σ(I)
T_min = 0.609, T_max = 1.000	R_int = 0.042
3865 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.17	Δρ_max = 0.26 e Å⁻³
1528 reflections	Δρ_min = −0.26 e Å⁻³
110 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
Cl1	0.16414 (9)	0.67224 (7)	0.15558 (6)	0.0435 (3)
O1	−0.2070 (2)	0.70451 (18)	0.04718 (16)	0.0403 (6)
C2	−0.0247 (3)	0.8296 (2)	0.0969 (2)	0.0298 (8)
N1	−0.1950 (3)	0.9652 (2)	0.0421 (2)	0.0435 (8)
H1A	−0.2129	0.9255	−0.0017	0.052*
H1B	−0.2227	1.0347	0.0402	0.052*
C4	−0.0826 (3)	0.7415 (2)	0.0382 (2)	0.0302 (7)
N2	0.0030 (3)	0.7101 (2)	−0.02413 (17)	0.0352 (7)
H2	0.0870	0.7405	−0.0280	0.042*
C6	0.0854 (3)	0.8068 (3)	0.1541 (2)	0.0332 (8)
C7	−0.0872 (3)	0.9385 (3)	0.0972 (2)	0.0353 (8)
C8	−0.0390 (4)	1.0177 (3)	0.1558 (2)	0.0398 (9)
H8	−0.0809	1.0911	0.1568	0.048*
C9	0.1338 (4)	0.8853 (3)	0.2115 (2)	0.0413 (9)
H9	0.2095	0.8675	0.2493	0.050*
C10	0.0685 (4)	0.9910 (3)	0.2123 (2)	0.0443 (9)
H10	0.0982	1.0458	0.2522	0.053*
C11	−0.0395 (4)	0.6261 (3)	−0.0866 (3)	0.0498 (10)
H11C	−0.0103	0.6522	−0.1423	0.075*
H11B	−0.1443	0.6160	−0.0851	0.075*
H11A	0.0079	0.5538	−0.0742	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0438 (5)	0.0390 (5)	0.0476 (6)	0.0069 (4)	−0.0035 (4)	0.0071 (4)
O1	0.0297 (12)	0.0267 (12)	0.0646 (18)	−0.0043 (10)	0.0029 (11)	−0.0057 (12)
C2	0.0266 (15)	0.0251 (15)	0.038 (2)	−0.0052 (13)	0.0062 (14)	0.0020 (14)
N1	0.0440 (16)	0.0248 (14)	0.062 (2)	0.0047 (13)	−0.0059 (15)	−0.0056 (14)
C4	0.0281 (15)	0.0200 (14)	0.042 (2)	0.0012 (13)	−0.0025 (15)	0.0036 (14)
N2	0.0309 (13)	0.0341 (14)	0.0405 (17)	−0.0032 (12)	0.0040 (13)	−0.0069 (13)
C6	0.0306 (16)	0.0300 (17)	0.039 (2)	−0.0008 (14)	0.0073 (15)	0.0012 (15)
C7	0.0326 (16)	0.0270 (16)	0.046 (2)	−0.0029 (14)	0.0076 (16)	−0.0019 (15)
C8	0.048 (2)	0.0262 (17)	0.046 (2)	−0.0076 (16)	0.0130 (18)	−0.0030 (16)
C9	0.0365 (18)	0.051 (2)	0.036 (2)	−0.0082 (18)	0.0047 (16)	−0.0041 (18)
C10	0.0447 (19)	0.045 (2)	0.043 (2)	−0.0132 (18)	0.0148 (18)	−0.0141 (18)
C11	0.042 (2)	0.052 (2)	0.056 (3)	0.0000 (18)	−0.0020 (19)	−0.021 (2)

Geometric parameters (Å, º) top

Cl1—C6	1.749 (3)	C6—C9	1.379 (5)
O1—C4	1.242 (3)	C7—C8	1.397 (5)
C2—C6	1.395 (4)	C8—C10	1.381 (5)
C2—C7	1.411 (4)	C8—H8	0.9500
C2—C4	1.501 (4)	C9—C10	1.388 (5)
N1—C7	1.369 (4)	C9—H9	0.9500
N1—H1A	0.8601	C10—H10	0.9500
N1—H1B	0.8600	C11—H11C	0.9800
C4—N2	1.326 (4)	C11—H11B	0.9800
N2—C11	1.461 (4)	C11—H11A	0.9800
N2—H2	0.8600

C6—C2—C7	118.4 (3)	C8—C7—C2	118.7 (3)
C6—C2—C4	122.5 (3)	C10—C8—C7	121.1 (3)
C7—C2—C4	119.1 (3)	C10—C8—H8	119.4
C7—N1—H1A	122.6	C7—C8—H8	119.4
C7—N1—H1B	117.4	C6—C9—C10	118.0 (3)
H1A—N1—H1B	115.8	C6—C9—H9	121.0
O1—C4—N2	123.0 (3)	C10—C9—H9	121.0
O1—C4—C2	120.2 (3)	C8—C10—C9	120.9 (3)
N2—C4—C2	116.7 (3)	C8—C10—H10	119.5
C4—N2—C11	122.8 (3)	C9—C10—H10	119.5
C4—N2—H2	118.6	N2—C11—H11C	109.5
C11—N2—H2	118.6	N2—C11—H11B	109.5
C9—C6—C2	122.9 (3)	H11C—C11—H11B	109.5
C9—C6—Cl1	117.7 (3)	N2—C11—H11A	109.5
C2—C6—Cl1	119.3 (2)	H11C—C11—H11A	109.5
N1—C7—C8	120.7 (3)	H11B—C11—H11A	109.5
N1—C7—C2	120.6 (3)

C6—C2—C4—O1	111.3 (4)	C6—C2—C7—N1	179.7 (3)
C7—C2—C4—O1	−66.0 (4)	C4—C2—C7—N1	−2.8 (5)
C6—C2—C4—N2	−71.3 (4)	C6—C2—C7—C8	−1.6 (5)
C7—C2—C4—N2	111.3 (3)	C4—C2—C7—C8	175.9 (3)
O1—C4—N2—C11	−2.1 (5)	N1—C7—C8—C10	179.2 (3)
C2—C4—N2—C11	−179.4 (3)	C2—C7—C8—C10	0.5 (5)
C7—C2—C6—C9	1.1 (5)	C2—C6—C9—C10	0.5 (5)
C4—C2—C6—C9	−176.3 (3)	Cl1—C6—C9—C10	−178.0 (3)
C7—C2—C6—Cl1	179.6 (2)	C7—C8—C10—C9	1.2 (5)
C4—C2—C6—Cl1	2.2 (4)	C6—C9—C10—C8	−1.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86	2.11	2.970 (3)	175
N2—H2···O1ⁱⁱ	0.86	2.04	2.895 (4)	172

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86	2.11	2.970 (3)	175
N2—H2···O1ⁱⁱ	0.86	2.04	2.895 (4)	172

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 31101448 and 31321004), the National Basic Research Program of China (2014CB932201 and 2012CB114104), the Public Service Sector R & D Project (200903033), the Open Fund of SKLBPI (SKL2012IP06), the National Key Technologies R & D Program of China (2011BAE06B03) and the Special Fund for Agro-Scientific Research in the Public Interest (No. 201003025) of the Chinese government.

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