2-Amino-N,3-dimethyl­benzamide

Mei, X.; Liang, Y.; Li, K.-B.

doi:10.1107/S1600536812048027

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3474

doi:10.1107/S1600536812048027

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2-Amino-N,3-dimethylbenzamide

Xiang-dong Mei,^a Yan-hui Liang ^a and Ke-Bin Li ^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
^*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 ); 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

C₉H₁₂N₂O
M_r = 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 ) T_min = 0.970, T_max = 0.992
3828 measured reflections
1939 independent reflections
1884 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y+1, 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: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812048027/rz5025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048027/rz5025Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812048027/rz5025Isup3.cml

checkCIF report

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.

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

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

C₉H₁₂N₂O	F(000) = 176
M_r = 164.21	D_x = 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

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1939 independent reflections
Radiation source: rotating anode	1884 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.036
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −12→12
T_min = 0.970, T_max = 0.992	k = −6→6
3828 measured reflections	l = −12→12

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0574P)² + 0.1149P] where P = (F_o² + 2F_c²)/3
1939 reflections	(Δ/σ)_max < 0.001
112 parameters	Δρ_max = 0.30 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₁₂N₂O	V = 427.1 (4) Å³
M_r = 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)°

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)
T_min = 0.970, T_max = 0.992	R_int = 0.036
3828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.111	H-atom parameters constrained
S = 1.05	Δρ_max = 0.30 e Å⁻³
1939 reflections	Δρ_min = −0.22 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.970, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	3828, 1939, 1884
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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.

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