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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

(Received 16 November 2012; accepted 22 November 2012; online 28 November 2012)

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[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: Staiger & Wagner (1953[Staiger, R. P. & Wagner, E. C. (1953). J. Org. Chem. 18, 1427-1439.]); Coppola (1980[Coppola, G. M. (1980). Synthesis, 7, 505-536.]); Witt & Bergman (2000[Witt, A. & Bergman, J. (2000). Tetrahedron, 56, 7245-7253.]).

[Scheme 1]

Experimental

Crystal data
  • C9H12N2O

  • Mr = 164.21

  • Monoclinic, P 21

  • a = 9.833 (6) Å

  • b = 5.011 (3) Å

  • c = 9.841 (6) Å

  • β = 118.27 (1)°

  • V = 427.1 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 173 K

  • 0.36 × 0.13 × 0.10 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 = 0.970, Tmax = 0.992

  • 3828 measured reflections

  • 1939 independent reflections

  • 1884 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.111

  • S = 1.05

  • 1939 reflections

  • 112 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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-{\script{1\over 2}}, -z+1]; (ii) x, y+1, 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: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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.

Related literature top

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 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

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.

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: OLEX2 (Dolomanov et al., 2009); 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 and atom-numbering scheme.
2-Amino-N,3-dimethylbenzamide top
Crystal data top
C9H12N2OF(000) = 176
Mr = 164.21Dx = 1.277 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2240 reflections
a = 9.833 (6) Åθ = 2.4–32.7°
b = 5.011 (3) ŵ = 0.09 mm1
c = 9.841 (6) ÅT = 173 K
β = 118.27 (1)°Rod, colourless
V = 427.1 (4) Å30.36 × 0.13 × 0.10 mm
Z = 2
Data collection top
Rigaku MM007-HF CCD (Saturn 724+)
diffractometer
1939 independent reflections
Radiation source: rotating anode1884 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.036
ω scans at fixed χ = 45°θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2007)
h = 1212
Tmin = 0.970, Tmax = 0.992k = 66
3828 measured reflectionsl = 1212
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-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 parametersΔρmax = 0.30 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C9H12N2OV = 427.1 (4) Å3
Mr = 164.21Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.833 (6) ŵ = 0.09 mm1
b = 5.011 (3) ÅT = 173 K
c = 9.841 (6) Å0.36 × 0.13 × 0.10 mm
β = 118.27 (1)°
Data collection top
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 = 0.992Rint = 0.036
3828 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0421 restraint
wR(F2) = 0.111H-atom parameters constrained
S = 1.05Δρmax = 0.30 e Å3
1939 reflectionsΔρmin = 0.22 e Å3
112 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
O10.18145 (16)0.6816 (2)0.25039 (14)0.0310 (3)
N10.08945 (16)0.5876 (3)0.47375 (16)0.0267 (3)
H1A0.04800.58860.37250.032*
H1B0.05040.48530.51930.032*
N20.22924 (17)1.1192 (3)0.24907 (16)0.0276 (3)
H20.25981.26820.30250.033*
C10.21634 (17)0.7472 (3)0.56154 (18)0.0215 (3)
C20.27443 (18)0.7589 (3)0.72312 (19)0.0245 (3)
C30.3954 (2)0.9304 (4)0.80932 (19)0.0300 (4)
H30.43530.93650.91810.036*
C40.4600 (2)1.0941 (4)0.7407 (2)0.0325 (4)
H40.54311.21020.80190.039*
C50.40169 (18)1.0856 (4)0.58261 (19)0.0266 (3)
H50.44431.19900.53510.032*
C60.28106 (17)0.9128 (3)0.49133 (17)0.0211 (3)
C70.2030 (2)0.5880 (4)0.7989 (2)0.0330 (4)
H7B0.09470.63940.76030.050*
H7C0.25930.61390.91090.050*
H7A0.20850.39990.77480.050*
C80.22609 (17)0.8953 (3)0.32129 (18)0.0214 (3)
C90.1841 (2)1.1254 (4)0.08586 (19)0.0343 (4)
H9A0.07911.05510.02680.051*
H9B0.25551.01560.06630.051*
H9C0.18731.30980.05420.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0437 (7)0.0195 (6)0.0277 (6)0.0021 (5)0.0152 (5)0.0023 (4)
N10.0268 (7)0.0240 (6)0.0291 (7)0.0067 (6)0.0130 (5)0.0007 (6)
N20.0377 (8)0.0188 (7)0.0282 (7)0.0033 (6)0.0173 (6)0.0010 (6)
C10.0194 (7)0.0172 (7)0.0290 (8)0.0029 (6)0.0124 (6)0.0013 (6)
C20.0247 (8)0.0230 (8)0.0278 (8)0.0043 (7)0.0140 (7)0.0030 (6)
C30.0287 (8)0.0356 (9)0.0235 (7)0.0004 (7)0.0106 (7)0.0026 (7)
C40.0271 (8)0.0344 (9)0.0328 (8)0.0085 (8)0.0115 (7)0.0077 (8)
C50.0260 (7)0.0256 (7)0.0314 (8)0.0056 (7)0.0162 (7)0.0032 (7)
C60.0208 (7)0.0185 (7)0.0255 (7)0.0018 (6)0.0123 (6)0.0004 (6)
C70.0387 (9)0.0323 (9)0.0313 (8)0.0008 (8)0.0192 (7)0.0052 (8)
C80.0207 (7)0.0181 (7)0.0272 (7)0.0016 (6)0.0127 (6)0.0007 (6)
C90.0431 (10)0.0314 (10)0.0286 (8)0.0010 (8)0.0171 (8)0.0043 (7)
Geometric parameters (Å, º) top
O1—C81.239 (2)C3—H30.9500
N1—C11.386 (2)C4—C51.381 (2)
N1—H1A0.8800C4—H40.9500
N1—H1B0.8800C5—C61.398 (2)
N2—C81.337 (2)C5—H50.9500
N2—C91.450 (2)C6—C81.498 (2)
N2—H20.8800C7—H7B0.9800
C1—C61.410 (2)C7—H7C0.9800
C1—C21.413 (2)C7—H7A0.9800
C2—C31.384 (2)C9—H9A0.9800
C2—C71.510 (2)C9—H9B0.9800
C3—C41.392 (3)C9—H9C0.9800
C1—N1—H1A120.0C6—C5—H5119.5
C1—N1—H1B120.0C5—C6—C1119.49 (14)
H1A—N1—H1B120.0C5—C6—C8120.10 (14)
C8—N2—C9122.35 (15)C1—C6—C8120.36 (14)
C8—N2—H2118.8C2—C7—H7B109.5
C9—N2—H2118.8C2—C7—H7C109.5
N1—C1—C6121.07 (15)H7B—C7—H7C109.5
N1—C1—C2119.33 (14)C2—C7—H7A109.5
C6—C1—C2119.43 (14)H7B—C7—H7A109.5
C3—C2—C1119.16 (14)H7C—C7—H7A109.5
C3—C2—C7121.00 (16)O1—C8—N2121.14 (14)
C1—C2—C7119.84 (15)O1—C8—C6121.59 (14)
C2—C3—C4121.71 (15)N2—C8—C6117.26 (14)
C2—C3—H3119.1N2—C9—H9A109.5
C4—C3—H3119.1N2—C9—H9B109.5
C5—C4—C3119.12 (16)H9A—C9—H9B109.5
C5—C4—H4120.4N2—C9—H9C109.5
C3—C4—H4120.4H9A—C9—H9C109.5
C4—C5—C6121.09 (15)H9B—C9—H9C109.5
C4—C5—H5119.5
N1—C1—C2—C3176.23 (16)N1—C1—C6—C5175.30 (15)
C6—C1—C2—C30.9 (2)C2—C1—C6—C50.1 (2)
N1—C1—C2—C73.0 (2)N1—C1—C6—C87.4 (2)
C6—C1—C2—C7178.30 (16)C2—C1—C6—C8177.33 (13)
C1—C2—C3—C40.8 (3)C9—N2—C8—O11.2 (3)
C7—C2—C3—C4178.38 (18)C9—N2—C8—C6177.79 (15)
C2—C3—C4—C50.1 (3)C5—C6—C8—O1144.60 (17)
C3—C4—C5—C61.0 (3)C1—C6—C8—O132.7 (2)
C4—C5—C6—C10.9 (3)C5—C6—C8—N234.4 (2)
C4—C5—C6—C8176.35 (16)C1—C6—C8—N2148.33 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.882.212.785 (2)123
N1—H1B···N1i0.882.443.240 (2)151
N2—H2···O1ii0.882.182.858 (2)133
Symmetry codes: (i) x, y1/2, z+1; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC9H12N2O
Mr164.21
Crystal system, space groupMonoclinic, P21
Temperature (K)173
a, b, c (Å)9.833 (6), 5.011 (3), 9.841 (6)
β (°) 118.27 (1)
V3)427.1 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.36 × 0.13 × 0.10
Data collection
DiffractometerRigaku MM007-HF CCD (Saturn 724+)
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2007)
Tmin, Tmax0.970, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
3828, 1939, 1884
Rint0.036
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.111, 1.05
No. of reflections1939
No. of parameters112
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.22
Absolute structure parameter0.0 (19)

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.882.212.785 (2)122.8
N1—H1B···N1i0.882.443.240 (2)151.4
N2—H2···O1ii0.882.182.858 (2)133.0
Symmetry codes: (i) x, y1/2, 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

First citationCoppola, G. M. (1980). Synthesis, 7, 505–536.  CrossRef
First citationDolomanov, 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
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 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 citationStaiger, R. P. & Wagner, E. C. (1953). J. Org. Chem. 18, 1427–1439.  CrossRef CAS Web of Science
First citationWitt, A. & Bergman, J. (2000). Tetrahedron, 56, 7245–7253.  Web of Science CrossRef CAS

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds