2-Amino-6-chloro-N-methyl­benzamide

Abstract

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.

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,

• a = 9.2709 (19) Å

• b = 11.812 (2) Å

• c = 15.982 (3) Å

• V = 1750.2 (6) ų

• 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[F ² > 2σ(F ²)] = 0.065

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

1. Comment

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.

2. Experimental

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.

3. Refinement

All H atoms were placed at calculated positions, with C—H = 0.93–0.98 Å, N—H = 0.86 Å, and refined as riding with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

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

Crystal data

C8H9ClN2O	F(000) = 768
Mr = 184.62	Dx = 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

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

Refinement

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(Fo2) + (0.0417P)2 + 1.8852P] where P = (Fo2 + 2Fc2)/3
1528 reflections	(Δ/σ)max < 0.001
110 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.