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Acta Cryst. (2009). E65, o124    [ doi:10.1107/S1600536808040531 ]

6-Methylpyridin-3-amine

K. Zhu, N. Xun, P. Wei and P.-F. Han

Abstract top

In the molecule of the title compound, C6H8N2, the methyl C and amine N atoms are 0.021 (2) and 0.058 (2) Å from the pyridine ring plane. In the crystal structure, intermolecular N-H...N hydrogen bonds link the molecules.

Comment top

Some derivatives of 3-pyridinecarboxylic acid are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. Atoms C1 and N2 are 0.021 (2) Å and 0.058 (2) Å away from the pyridine ring plane.

In the crystal structure, intermolecular N-H···N hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Related literature top

For a related structure, see: Sawanishi et al. (1987). For bond-length data, see: Allen et al. (1987). Figure 2 and scheme are corrupted: please provide new versions.

Experimental top

For the preparation of the title compound, bromine (17.3 g) was added slowly to sodium hydroxide solution (303 ml, 5%), and then 3-pyridinecarboxamide (13 g) was added in about 20 min at 273-278 K. The mixture was heated in an oil bath at 343-353 K for 4 h. The product was extracted with CH2Cl2, washed with water and dried (yield; 8 g, 77.6%) (Sawanishi et al., 1987). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH2) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
6-Methylpyridin-3-amine top
Crystal data top
C6H8N2F(000) = 232
Mr = 108.14Dx = 1.175 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 8.4240 (17) Åθ = 10–12°
b = 7.0560 (14) ŵ = 0.07 mm−1
c = 10.658 (2) ÅT = 294 K
β = 105.23 (3)°Block, colorless
V = 611.3 (2) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		746 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.059
graphiteθmax = 25.3°, θmin = 2.8°
ω/2θ scansh = 0→9
Absorption correction: ψ scan
(North et al., 1968)		k = 0→8
Tmin = 0.978, Tmax = 0.993l = −12→12
1183 measured reflections3 standard reflections every 120 min
1106 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.154 w = 1/[σ2(Fo2) + (0.05P)2 + 0.5P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1106 reflectionsΔρmax = 0.19 e Å−3
73 parametersΔρmin = −0.19 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
C6H8N2V = 611.3 (2) Å3
Mr = 108.14Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4240 (17) ŵ = 0.07 mm−1
b = 7.0560 (14) ÅT = 294 K
c = 10.658 (2) Å0.30 × 0.20 × 0.10 mm
β = 105.23 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		746 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.059
Tmin = 0.978, Tmax = 0.993θmax = 25.3°
1183 measured reflections3 standard reflections every 120 min
1106 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.154Δρmax = 0.19 e Å−3
S = 1.02Δρmin = −0.19 e Å−3
1106 reflectionsAbsolute structure: ?
73 parametersFlack parameter: ?
? restraintsRogers parameter: ?
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
N10.8161 (3)0.0759 (3)0.11504 (18)0.0480 (6)
N21.0351 (3)0.4188 (3)0.3558 (2)0.0595 (7)
H2A0.96920.51370.33610.071*
H2B1.12370.42850.41770.071*
C10.8752 (4)−0.2454 (4)0.0569 (3)0.0616 (8)
H1B0.7734−0.2235−0.00760.092*
H1C0.8626−0.35070.11050.092*
H1D0.9602−0.27300.01480.092*
C20.9206 (4)−0.0734 (4)0.1390 (2)0.0483 (7)
C30.8578 (3)0.2310 (4)0.1886 (2)0.0474 (7)
H3A0.78570.33330.17090.057*
C40.9987 (3)0.2519 (4)0.2884 (2)0.0478 (7)
C51.1033 (3)0.0962 (4)0.3130 (2)0.0503 (7)
H5A1.20090.10070.37880.060*
C61.0608 (4)−0.0656 (4)0.2385 (2)0.0544 (7)
H6A1.1290−0.17130.25660.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0679 (13)0.0494 (13)0.0253 (10)−0.0054 (11)0.0098 (9)0.0006 (10)
N20.0703 (15)0.0579 (15)0.0413 (13)0.0013 (12)−0.0013 (11)−0.0182 (11)
C10.096 (2)0.0527 (17)0.0366 (14)−0.0081 (15)0.0191 (14)−0.0067 (13)
C20.0835 (18)0.0426 (14)0.0242 (12)−0.0001 (13)0.0234 (12)0.0044 (11)
C30.0707 (16)0.0446 (14)0.0302 (13)0.0036 (12)0.0190 (12)0.0017 (11)
C40.0772 (17)0.0489 (15)0.0206 (11)−0.0019 (13)0.0187 (11)−0.0033 (11)
C50.0622 (15)0.0554 (16)0.0301 (12)0.0096 (13)0.0062 (11)0.0047 (12)
C60.0844 (19)0.0481 (15)0.0326 (13)0.0087 (14)0.0190 (13)0.0038 (12)
Geometric parameters (Å, °) top
N1—C31.338 (3)C1—H1D0.9600
N1—C21.353 (3)C2—C61.365 (4)
N2—C41.371 (3)C3—C41.378 (4)
N2—H2A0.8600C3—H3A0.9300
N2—H2B0.8600C4—C51.390 (4)
C1—C21.487 (3)C5—C61.383 (4)
C1—H1B0.9600C5—H5A0.9300
C1—H1C0.9600C6—H6A0.9300
C3—N1—C2117.9 (2)N1—C3—C4125.4 (2)
C4—N2—H2A120.0N1—C3—H3A117.3
C4—N2—H2B120.0C4—C3—H3A117.3
H2A—N2—H2B120.0N2—C4—C3121.6 (2)
C2—C1—H1B109.5N2—C4—C5122.5 (2)
C2—C1—H1C109.5C3—C4—C5115.9 (2)
H1B—C1—H1C109.5C6—C5—C4119.2 (2)
C2—C1—H1D109.5C6—C5—H5A120.4
H1B—C1—H1D109.5C4—C5—H5A120.4
H1C—C1—H1D109.5C2—C6—C5121.3 (3)
N1—C2—C6120.2 (2)C2—C6—H6A119.3
N1—C2—C1118.1 (2)C5—C6—H6A119.3
C6—C2—C1121.7 (3)
C3—N1—C2—C62.2 (3)N2—C4—C5—C6−178.1 (2)
C3—N1—C2—C1−179.6 (2)C3—C4—C5—C6−0.3 (4)
C2—N1—C3—C4−0.5 (4)N1—C2—C6—C5−2.9 (4)
N1—C3—C4—N2177.4 (2)C1—C2—C6—C5178.9 (2)
N1—C3—C4—C5−0.4 (4)C4—C5—C6—C21.9 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.862.293.131 (3)165
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.862.293.131 (3)165
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

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Sawanishi, H., Tajima, K. & Tsuchiya, T. (1987). Chem. Pharm. Bull. 35, 4101–4109.

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