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

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ISSN: 2056-9890

2-Amino-6-chloro-N-methyl­benzamide

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.

Related literature

For background information on substituted anthranilamides, see: Bharate et al. (2013[Bharate, S. B., Yadav, R. R., Khan, S. I., Tekwani, B. L., Jacob, M. R., Khan, I. A. & Vishwakarma, R. A. (2013). Med. Chem. Commun. 4, 1042-1048.]); Gnamm et al. (2012[Gnamm, C., Jeanguenat, A., Dutton, A. C., Grimm, C., Kloer, D. P. & Crossthwaite, A. J. (2012). Bioorg. Med. Chem. Lett. 22, 3800-3806.]); Lahm et al. (2005[Lahm, G. P., Selby, T. P., Freudenberger, J. H., Stevenson, T. M., Myers, B. J., Seburyamo, G., Smith, B. K., Flexner, L., Clark, C. E. & Cordova, D. (2005). Bioorg. Med. Chem. Lett. 15, 4898-4906.]); Norman et al. (1996[Norman, M. H., Rigdon, G. C., Hall, W. R. & Navas, F. III (1996). J. Med. Chem. 39, 1172-1188.]); Roe et al. (1999[Roe, M., Folkes, A., Ashworth, P., Brumwell, J., Chima, L., Hunjan, S., Pretswell, I., Dangerfield, W., Ryder, H. & Charlton, P. (1999). Bioorg. Med. Chem. Lett. 9, 595-600.]). For the synthesis, see: Witt & Bergman (2000[Witt, A. & Bergman, J. (2000). Tetrahedron, 56, 7245-7253.]); Coppola (1980[Coppola, G. M. (1980). Synthesis, 7, 505-536.]).

[Scheme 1]

Experimental

Crystal data
  • C8H9ClN2O

  • Mr = 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[Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.609, Tmax = 1.000

  • 3865 measured reflections

  • 1528 independent reflections

  • 1351 reflections with I > 2σ(I)

  • Rint = 0.042

Refinement
  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.139

  • S = 1.17

  • 1528 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

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 Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(C) for methyl H atoms.

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
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.
2-Amino-6-chloro-N-methylbenzamide top
Crystal data top
C8H9ClN2OF(000) = 768
Mr = 184.62Dx = 1.401 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3698 reflections
a = 9.2709 (19) Åθ = 1.3–27.5°
b = 11.812 (2) ŵ = 0.39 mm1
c = 15.982 (3) ÅT = 173 K
V = 1750.2 (6) Å3Block, colourless
Z = 80.43 × 0.25 × 0.18 mm
Data collection top
Rigaku MM007-HF CCD (Saturn 724+)
diffractometer
1528 independent reflections
Radiation source: fine-focus sealed tube1351 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 28.5714 pixels mm-1θmax = 25.0°, θmin = 2.6°
ω scans at fixed χ = 45°h = 117
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2007)
k = 149
Tmin = 0.609, Tmax = 1.000l = 1019
3865 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-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 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C8H9ClN2OV = 1750.2 (6) Å3
Mr = 184.62Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.2709 (19) ŵ = 0.39 mm1
b = 11.812 (2) ÅT = 173 K
c = 15.982 (3) Å0.43 × 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)
Tmin = 0.609, Tmax = 1.000Rint = 0.042
3865 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.139H-atom parameters constrained
S = 1.17Δρmax = 0.26 e Å3
1528 reflectionsΔρmin = 0.26 e Å3
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
xyzUiso*/Ueq
Cl10.16414 (9)0.67224 (7)0.15558 (6)0.0435 (3)
O10.2070 (2)0.70451 (18)0.04718 (16)0.0403 (6)
C20.0247 (3)0.8296 (2)0.0969 (2)0.0298 (8)
N10.1950 (3)0.9652 (2)0.0421 (2)0.0435 (8)
H1A0.21290.92550.00170.052*
H1B0.22271.03470.04020.052*
C40.0826 (3)0.7415 (2)0.0382 (2)0.0302 (7)
N20.0030 (3)0.7101 (2)0.02413 (17)0.0352 (7)
H20.08700.74050.02800.042*
C60.0854 (3)0.8068 (3)0.1541 (2)0.0332 (8)
C70.0872 (3)0.9385 (3)0.0972 (2)0.0353 (8)
C80.0390 (4)1.0177 (3)0.1558 (2)0.0398 (9)
H80.08091.09110.15680.048*
C90.1338 (4)0.8853 (3)0.2115 (2)0.0413 (9)
H90.20950.86750.24930.050*
C100.0685 (4)0.9910 (3)0.2123 (2)0.0443 (9)
H100.09821.04580.25220.053*
C110.0395 (4)0.6261 (3)0.0866 (3)0.0498 (10)
H11C0.01030.65220.14230.075*
H11B0.14430.61600.08510.075*
H11A0.00790.55380.07420.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0438 (5)0.0390 (5)0.0476 (6)0.0069 (4)0.0035 (4)0.0071 (4)
O10.0297 (12)0.0267 (12)0.0646 (18)0.0043 (10)0.0029 (11)0.0057 (12)
C20.0266 (15)0.0251 (15)0.038 (2)0.0052 (13)0.0062 (14)0.0020 (14)
N10.0440 (16)0.0248 (14)0.062 (2)0.0047 (13)0.0059 (15)0.0056 (14)
C40.0281 (15)0.0200 (14)0.042 (2)0.0012 (13)0.0025 (15)0.0036 (14)
N20.0309 (13)0.0341 (14)0.0405 (17)0.0032 (12)0.0040 (13)0.0069 (13)
C60.0306 (16)0.0300 (17)0.039 (2)0.0008 (14)0.0073 (15)0.0012 (15)
C70.0326 (16)0.0270 (16)0.046 (2)0.0029 (14)0.0076 (16)0.0019 (15)
C80.048 (2)0.0262 (17)0.046 (2)0.0076 (16)0.0130 (18)0.0030 (16)
C90.0365 (18)0.051 (2)0.036 (2)0.0082 (18)0.0047 (16)0.0041 (18)
C100.0447 (19)0.045 (2)0.043 (2)0.0132 (18)0.0148 (18)0.0141 (18)
C110.042 (2)0.052 (2)0.056 (3)0.0000 (18)0.0020 (19)0.021 (2)
Geometric parameters (Å, º) top
Cl1—C61.749 (3)C6—C91.379 (5)
O1—C41.242 (3)C7—C81.397 (5)
C2—C61.395 (4)C8—C101.381 (5)
C2—C71.411 (4)C8—H80.9500
C2—C41.501 (4)C9—C101.388 (5)
N1—C71.369 (4)C9—H90.9500
N1—H1A0.8601C10—H100.9500
N1—H1B0.8600C11—H11C0.9800
C4—N21.326 (4)C11—H11B0.9800
N2—C111.461 (4)C11—H11A0.9800
N2—H20.8600
C6—C2—C7118.4 (3)C8—C7—C2118.7 (3)
C6—C2—C4122.5 (3)C10—C8—C7121.1 (3)
C7—C2—C4119.1 (3)C10—C8—H8119.4
C7—N1—H1A122.6C7—C8—H8119.4
C7—N1—H1B117.4C6—C9—C10118.0 (3)
H1A—N1—H1B115.8C6—C9—H9121.0
O1—C4—N2123.0 (3)C10—C9—H9121.0
O1—C4—C2120.2 (3)C8—C10—C9120.9 (3)
N2—C4—C2116.7 (3)C8—C10—H10119.5
C4—N2—C11122.8 (3)C9—C10—H10119.5
C4—N2—H2118.6N2—C11—H11C109.5
C11—N2—H2118.6N2—C11—H11B109.5
C9—C6—C2122.9 (3)H11C—C11—H11B109.5
C9—C6—Cl1117.7 (3)N2—C11—H11A109.5
C2—C6—Cl1119.3 (2)H11C—C11—H11A109.5
N1—C7—C8120.7 (3)H11B—C11—H11A109.5
N1—C7—C2120.6 (3)
C6—C2—C4—O1111.3 (4)C6—C2—C7—N1179.7 (3)
C7—C2—C4—O166.0 (4)C4—C2—C7—N12.8 (5)
C6—C2—C4—N271.3 (4)C6—C2—C7—C81.6 (5)
C7—C2—C4—N2111.3 (3)C4—C2—C7—C8175.9 (3)
O1—C4—N2—C112.1 (5)N1—C7—C8—C10179.2 (3)
C2—C4—N2—C11179.4 (3)C2—C7—C8—C100.5 (5)
C7—C2—C6—C91.1 (5)C2—C6—C9—C100.5 (5)
C4—C2—C6—C9176.3 (3)Cl1—C6—C9—C10178.0 (3)
C7—C2—C6—Cl1179.6 (2)C7—C8—C10—C91.2 (5)
C4—C2—C6—Cl12.2 (4)C6—C9—C10—C81.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O1i0.862.112.970 (3)175
N2—H2···O1ii0.862.042.895 (4)172
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O1i0.862.112.970 (3)175
N2—H2···O1ii0.862.042.895 (4)172
Symmetry codes: (i) x1/2, 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.

References

First citationBharate, S. B., Yadav, R. R., Khan, S. I., Tekwani, B. L., Jacob, M. R., Khan, I. A. & Vishwakarma, R. A. (2013). Med. Chem. Commun. 4, 1042–1048.  Web of Science CrossRef CAS
First citationCoppola, G. M. (1980). Synthesis, 7, 505–536.  CrossRef
First citationGnamm, C., Jeanguenat, A., Dutton, A. C., Grimm, C., Kloer, D. P. & Crossthwaite, A. J. (2012). Bioorg. Med. Chem. Lett. 22, 3800–3806.  Web of Science CSD CrossRef CAS PubMed
First citationLahm, G. P., Selby, T. P., Freudenberger, J. H., Stevenson, T. M., Myers, B. J., Seburyamo, G., Smith, B. K., Flexner, L., Clark, C. E. & Cordova, D. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906.  Web of Science CrossRef PubMed CAS
First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CrossRef CAS IUCr Journals
First citationNorman, M. H., Rigdon, G. C., Hall, W. R. & Navas, F. III (1996). J. Med. Chem. 39, 1172–1188.  CrossRef CAS PubMed Web of Science
First citationRigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan.
First citationRoe, M., Folkes, A., Ashworth, P., Brumwell, J., Chima, L., Hunjan, S., Pretswell, I., Dangerfield, W., Ryder, H. & Charlton, P. (1999). Bioorg. Med. Chem. Lett. 9, 595–600.  Web of Science CrossRef PubMed CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWitt, A. & Bergman, J. (2000). Tetrahedron, 56, 7245–7253.  Web of Science CrossRef CAS

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