organic compounds
2-Amino-N,3-dimethylbenzamide
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
*Correspondence e-mail: kbli@ippcaas.cn
In the title compound, C9H12N2O, the mean plane through the amide group and the benzene ring form a dihedral angle of 33.93 (7)°. An intramolecular N—H⋯O hydrogen bond is present. In the crystal, molecules are linked by N—H⋯N and N—H⋯O hydrogen bonds, forming double-stranded chains parallel to the b axis.
Related literature
For background to substituted anthranilamides, see: Gnamm et al. (2012); Lahm et al. (2005); Norman et al. (1996); Roe et al. (1999). For the synthesis, see: Staiger & Wagner (1953); Coppola (1980); Witt & Bergman (2000).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812048027/rz5025sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812048027/rz5025Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812048027/rz5025Isup3.cml
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.
The H atoms were placed at calculated positions, with C—H = 0.93–0.98 Å, and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). 841 Friedel pairs were not merged.
Data collection: CrystalClear (Rigaku, 2007); cell
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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids and atom-numbering scheme. |
C9H12N2O | F(000) = 176 |
Mr = 164.21 | Dx = 1.277 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2240 reflections |
a = 9.833 (6) Å | θ = 2.4–32.7° |
b = 5.011 (3) Å | µ = 0.09 mm−1 |
c = 9.841 (6) Å | T = 173 K |
β = 118.27 (1)° | Rod, colourless |
V = 427.1 (4) Å3 | 0.36 × 0.13 × 0.10 mm |
Z = 2 |
Rigaku MM007-HF CCD (Saturn 724+) diffractometer | 1939 independent reflections |
Radiation source: rotating anode | 1884 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.036 |
ω scans at fixed χ = 45° | θmax = 27.5°, θmin = 2.4° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | h = −12→12 |
Tmin = 0.970, Tmax = 0.992 | k = −6→6 |
3828 measured reflections | l = −12→12 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0574P)2 + 0.1149P] where P = (Fo2 + 2Fc2)/3 |
1939 reflections | (Δ/σ)max < 0.001 |
112 parameters | Δρmax = 0.30 e Å−3 |
1 restraint | Δρmin = −0.22 e Å−3 |
C9H12N2O | V = 427.1 (4) Å3 |
Mr = 164.21 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.833 (6) Å | µ = 0.09 mm−1 |
b = 5.011 (3) Å | T = 173 K |
c = 9.841 (6) Å | 0.36 × 0.13 × 0.10 mm |
β = 118.27 (1)° |
Rigaku MM007-HF CCD (Saturn 724+) diffractometer | 1939 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | 1884 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.992 | Rint = 0.036 |
3828 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.30 e Å−3 |
1939 reflections | Δρmin = −0.22 e Å−3 |
112 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 | ||
O1 | 0.18145 (16) | 0.6816 (2) | 0.25039 (14) | 0.0310 (3) | |
N1 | 0.08945 (16) | 0.5876 (3) | 0.47375 (16) | 0.0267 (3) | |
H1A | 0.0480 | 0.5886 | 0.3725 | 0.032* | |
H1B | 0.0504 | 0.4853 | 0.5193 | 0.032* | |
N2 | 0.22924 (17) | 1.1192 (3) | 0.24907 (16) | 0.0276 (3) | |
H2 | 0.2598 | 1.2682 | 0.3025 | 0.033* | |
C1 | 0.21634 (17) | 0.7472 (3) | 0.56154 (18) | 0.0215 (3) | |
C2 | 0.27443 (18) | 0.7589 (3) | 0.72312 (19) | 0.0245 (3) | |
C3 | 0.3954 (2) | 0.9304 (4) | 0.80932 (19) | 0.0300 (4) | |
H3 | 0.4353 | 0.9365 | 0.9181 | 0.036* | |
C4 | 0.4600 (2) | 1.0941 (4) | 0.7407 (2) | 0.0325 (4) | |
H4 | 0.5431 | 1.2102 | 0.8019 | 0.039* | |
C5 | 0.40169 (18) | 1.0856 (4) | 0.58261 (19) | 0.0266 (3) | |
H5 | 0.4443 | 1.1990 | 0.5351 | 0.032* | |
C6 | 0.28106 (17) | 0.9128 (3) | 0.49133 (17) | 0.0211 (3) | |
C7 | 0.2030 (2) | 0.5880 (4) | 0.7989 (2) | 0.0330 (4) | |
H7B | 0.0947 | 0.6394 | 0.7603 | 0.050* | |
H7C | 0.2593 | 0.6139 | 0.9109 | 0.050* | |
H7A | 0.2085 | 0.3999 | 0.7748 | 0.050* | |
C8 | 0.22609 (17) | 0.8953 (3) | 0.32129 (18) | 0.0214 (3) | |
C9 | 0.1841 (2) | 1.1254 (4) | 0.08586 (19) | 0.0343 (4) | |
H9A | 0.0791 | 1.0551 | 0.0268 | 0.051* | |
H9B | 0.2555 | 1.0156 | 0.0663 | 0.051* | |
H9C | 0.1873 | 1.3098 | 0.0542 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0437 (7) | 0.0195 (6) | 0.0277 (6) | −0.0021 (5) | 0.0152 (5) | −0.0023 (4) |
N1 | 0.0268 (7) | 0.0240 (6) | 0.0291 (7) | −0.0067 (6) | 0.0130 (5) | −0.0007 (6) |
N2 | 0.0377 (8) | 0.0188 (7) | 0.0282 (7) | −0.0033 (6) | 0.0173 (6) | −0.0010 (6) |
C1 | 0.0194 (7) | 0.0172 (7) | 0.0290 (8) | 0.0029 (6) | 0.0124 (6) | 0.0013 (6) |
C2 | 0.0247 (8) | 0.0230 (8) | 0.0278 (8) | 0.0043 (7) | 0.0140 (7) | 0.0030 (6) |
C3 | 0.0287 (8) | 0.0356 (9) | 0.0235 (7) | −0.0004 (7) | 0.0106 (7) | −0.0026 (7) |
C4 | 0.0271 (8) | 0.0344 (9) | 0.0328 (8) | −0.0085 (8) | 0.0115 (7) | −0.0077 (8) |
C5 | 0.0260 (7) | 0.0256 (7) | 0.0314 (8) | −0.0056 (7) | 0.0162 (7) | −0.0032 (7) |
C6 | 0.0208 (7) | 0.0185 (7) | 0.0255 (7) | 0.0018 (6) | 0.0123 (6) | −0.0004 (6) |
C7 | 0.0387 (9) | 0.0323 (9) | 0.0313 (8) | −0.0008 (8) | 0.0192 (7) | 0.0052 (8) |
C8 | 0.0207 (7) | 0.0181 (7) | 0.0272 (7) | 0.0016 (6) | 0.0127 (6) | 0.0007 (6) |
C9 | 0.0431 (10) | 0.0314 (10) | 0.0286 (8) | −0.0010 (8) | 0.0171 (8) | 0.0043 (7) |
O1—C8 | 1.239 (2) | C3—H3 | 0.9500 |
N1—C1 | 1.386 (2) | C4—C5 | 1.381 (2) |
N1—H1A | 0.8800 | C4—H4 | 0.9500 |
N1—H1B | 0.8800 | C5—C6 | 1.398 (2) |
N2—C8 | 1.337 (2) | C5—H5 | 0.9500 |
N2—C9 | 1.450 (2) | C6—C8 | 1.498 (2) |
N2—H2 | 0.8800 | C7—H7B | 0.9800 |
C1—C6 | 1.410 (2) | C7—H7C | 0.9800 |
C1—C2 | 1.413 (2) | C7—H7A | 0.9800 |
C2—C3 | 1.384 (2) | C9—H9A | 0.9800 |
C2—C7 | 1.510 (2) | C9—H9B | 0.9800 |
C3—C4 | 1.392 (3) | C9—H9C | 0.9800 |
C1—N1—H1A | 120.0 | C6—C5—H5 | 119.5 |
C1—N1—H1B | 120.0 | C5—C6—C1 | 119.49 (14) |
H1A—N1—H1B | 120.0 | C5—C6—C8 | 120.10 (14) |
C8—N2—C9 | 122.35 (15) | C1—C6—C8 | 120.36 (14) |
C8—N2—H2 | 118.8 | C2—C7—H7B | 109.5 |
C9—N2—H2 | 118.8 | C2—C7—H7C | 109.5 |
N1—C1—C6 | 121.07 (15) | H7B—C7—H7C | 109.5 |
N1—C1—C2 | 119.33 (14) | C2—C7—H7A | 109.5 |
C6—C1—C2 | 119.43 (14) | H7B—C7—H7A | 109.5 |
C3—C2—C1 | 119.16 (14) | H7C—C7—H7A | 109.5 |
C3—C2—C7 | 121.00 (16) | O1—C8—N2 | 121.14 (14) |
C1—C2—C7 | 119.84 (15) | O1—C8—C6 | 121.59 (14) |
C2—C3—C4 | 121.71 (15) | N2—C8—C6 | 117.26 (14) |
C2—C3—H3 | 119.1 | N2—C9—H9A | 109.5 |
C4—C3—H3 | 119.1 | N2—C9—H9B | 109.5 |
C5—C4—C3 | 119.12 (16) | H9A—C9—H9B | 109.5 |
C5—C4—H4 | 120.4 | N2—C9—H9C | 109.5 |
C3—C4—H4 | 120.4 | H9A—C9—H9C | 109.5 |
C4—C5—C6 | 121.09 (15) | H9B—C9—H9C | 109.5 |
C4—C5—H5 | 119.5 | ||
N1—C1—C2—C3 | −176.23 (16) | N1—C1—C6—C5 | 175.30 (15) |
C6—C1—C2—C3 | −0.9 (2) | C2—C1—C6—C5 | 0.1 (2) |
N1—C1—C2—C7 | 3.0 (2) | N1—C1—C6—C8 | −7.4 (2) |
C6—C1—C2—C7 | 178.30 (16) | C2—C1—C6—C8 | 177.33 (13) |
C1—C2—C3—C4 | 0.8 (3) | C9—N2—C8—O1 | −1.2 (3) |
C7—C2—C3—C4 | −178.38 (18) | C9—N2—C8—C6 | 177.79 (15) |
C2—C3—C4—C5 | 0.1 (3) | C5—C6—C8—O1 | 144.60 (17) |
C3—C4—C5—C6 | −1.0 (3) | C1—C6—C8—O1 | −32.7 (2) |
C4—C5—C6—C1 | 0.9 (3) | C5—C6—C8—N2 | −34.4 (2) |
C4—C5—C6—C8 | −176.35 (16) | C1—C6—C8—N2 | 148.33 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.88 | 2.21 | 2.785 (2) | 123 |
N1—H1B···N1i | 0.88 | 2.44 | 3.240 (2) | 151 |
N2—H2···O1ii | 0.88 | 2.18 | 2.858 (2) | 133 |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C9H12N2O |
Mr | 164.21 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 9.833 (6), 5.011 (3), 9.841 (6) |
β (°) | 118.27 (1) |
V (Å3) | 427.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.36 × 0.13 × 0.10 |
Data collection | |
Diffractometer | Rigaku MM007-HF CCD (Saturn 724+) diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2007) |
Tmin, Tmax | 0.970, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3828, 1939, 1884 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.111, 1.05 |
No. of reflections | 1939 |
No. of parameters | 112 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Absolute structure parameter | 0.0 (19) |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.88 | 2.21 | 2.785 (2) | 122.8 |
N1—H1B···N1i | 0.88 | 2.44 | 3.240 (2) | 151.4 |
N2—H2···O1ii | 0.88 | 2.18 | 2.858 (2) | 133.0 |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x, y+1, z. |
Acknowledgements
This work was supported by the Natural Science Foundation of China (No. 31101448) and the Special Fund for Agro-Scientific Research in the Public Interest (No. 201003025) of the Chinese government.
References
Coppola, G. M. (1980). Synthesis, 7, 505–536. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gnamm, 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 Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar
Norman, M. H., Rigdon, G. C., Hall, W. R. & Navas, F. III (1996). J. Med. Chem. 39, 1172–1188. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Staiger, R. P. & Wagner, E. C. (1953). J. Org. Chem. 18, 1427–1439. CrossRef CAS Web of Science Google Scholar
Witt, A. & Bergman, J. (2000). Tetrahedron, 56, 7245–7253. Web of Science CrossRef CAS Google Scholar
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Anthranilamide-based derivatives exhibit interesting biological activities such as antibacterial, antifungal, antiviral and insecticidal effects (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-N,3-dimethylbenzamide, an important organic intermediate in the synthesis of medicines, agricultural chemicals, and animal drugs.
In the title compound (Fig. 1), the least-square mean plane through the amide group (C8/C9/O1/N2) form a dihedral angle of 33.93 (7)° with the benzene ring. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). In the crystal structure, intermolecular N—H···N and N—H···O hydrogen interactions link molecules into double chains running parallel to the b axis.