6-Methyl­pyridin-3-amine

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

doi:10.1107/S1600536808040531

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o124

doi:10.1107/S1600536808040531

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6-Methylpyridin-3-amine

Kai Zhu,^a Ning Xun,^a Ping Wei ^a and Ping-Fang Han ^a ^*

^aCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: hpf@njut.edu.cn

(Received 21 November 2008; accepted 2 December 2008; online 13 December 2008)

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.

Related literature

For a related structure, see: Sawanishi et al. (1987 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₈N₂
M_r = 108.14
Monoclinic, P 2₁ /n
a = 8.4240 (17) Å
b = 7.0560 (14) Å
c = 10.658 (2) Å
β = 105.23 (3)°
V = 611.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.978, T_max = 0.993
1183 measured reflections
1106 independent reflections
746 reflections with I > 2σ(I)
R_int = 0.059
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.154
S = 1.02
1106 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1ⁱ	0.86	2.29	3.131 (3)	165
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040531/hk2583sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040531/hk2583Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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

C₆H₈N₂	F(000) = 232
M_r = 108.14	D_x = 1.175 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.4240 (17) Å	θ = 10–12°
b = 7.0560 (14) Å	µ = 0.07 mm⁻¹
c = 10.658 (2) Å	T = 294 K
β = 105.23 (3)°	Block, colorless
V = 611.3 (2) Å³	0.30 × 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 tube	R_int = 0.059
Graphite monochromator	θ_max = 25.3°, θ_min = 2.8°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.978, T_max = 0.993	l = −12→12
1183 measured reflections	3 standard reflections every 120 min
1106 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.05P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1106 reflections	Δρ_max = 0.19 e Å⁻³
73 parameters	Δρ_min = −0.19 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₆H₈N₂	V = 611.3 (2) Å³
M_r = 108.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4240 (17) Å	µ = 0.07 mm⁻¹
b = 7.0560 (14) Å	T = 294 K
c = 10.658 (2) Å	0.30 × 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)	R_int = 0.059
T_min = 0.978, T_max = 0.993	3 standard reflections every 120 min
1183 measured reflections	intensity decay: 1%
1106 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	73 parameters
wR(F²) = 0.154	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
1106 reflections	Δρ_min = −0.19 e Å⁻³

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
N1	0.8161 (3)	0.0759 (3)	0.11504 (18)	0.0480 (6)
N2	1.0351 (3)	0.4188 (3)	0.3558 (2)	0.0595 (7)
H2A	0.9692	0.5137	0.3361	0.071*
H2B	1.1237	0.4285	0.4177	0.071*
C1	0.8752 (4)	−0.2454 (4)	0.0569 (3)	0.0616 (8)
H1B	0.7734	−0.2235	−0.0076	0.092*
H1C	0.8626	−0.3507	0.1105	0.092*
H1D	0.9602	−0.2730	0.0148	0.092*
C2	0.9206 (4)	−0.0734 (4)	0.1390 (2)	0.0483 (7)
C3	0.8578 (3)	0.2310 (4)	0.1886 (2)	0.0474 (7)
H3A	0.7857	0.3333	0.1709	0.057*
C4	0.9987 (3)	0.2519 (4)	0.2884 (2)	0.0478 (7)
C5	1.1033 (3)	0.0962 (4)	0.3130 (2)	0.0503 (7)
H5A	1.2009	0.1007	0.3788	0.060*
C6	1.0608 (4)	−0.0656 (4)	0.2385 (2)	0.0544 (7)
H6A	1.1290	−0.1713	0.2566	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0679 (13)	0.0494 (13)	0.0253 (10)	−0.0054 (11)	0.0098 (9)	0.0006 (10)
N2	0.0703 (15)	0.0579 (15)	0.0413 (13)	0.0013 (12)	−0.0013 (11)	−0.0182 (11)
C1	0.096 (2)	0.0527 (17)	0.0366 (14)	−0.0081 (15)	0.0191 (14)	−0.0067 (13)
C2	0.0835 (18)	0.0426 (14)	0.0242 (12)	−0.0001 (13)	0.0234 (12)	0.0044 (11)
C3	0.0707 (16)	0.0446 (14)	0.0302 (13)	0.0036 (12)	0.0190 (12)	0.0017 (11)
C4	0.0772 (17)	0.0489 (15)	0.0206 (11)	−0.0019 (13)	0.0187 (11)	−0.0033 (11)
C5	0.0622 (15)	0.0554 (16)	0.0301 (12)	0.0096 (13)	0.0062 (11)	0.0047 (12)
C6	0.0844 (19)	0.0481 (15)	0.0326 (13)	0.0087 (14)	0.0190 (13)	0.0038 (12)

Geometric parameters (Å, º) top

N1—C3	1.338 (3)	C1—H1D	0.9600
N1—C2	1.353 (3)	C2—C6	1.365 (4)
N2—C4	1.371 (3)	C3—C4	1.378 (4)
N2—H2A	0.8600	C3—H3A	0.9300
N2—H2B	0.8600	C4—C5	1.390 (4)
C1—C2	1.487 (3)	C5—C6	1.383 (4)
C1—H1B	0.9600	C5—H5A	0.9300
C1—H1C	0.9600	C6—H6A	0.9300

C3—N1—C2	117.9 (2)	N1—C3—C4	125.4 (2)
C4—N2—H2A	120.0	N1—C3—H3A	117.3
C4—N2—H2B	120.0	C4—C3—H3A	117.3
H2A—N2—H2B	120.0	N2—C4—C3	121.6 (2)
C2—C1—H1B	109.5	N2—C4—C5	122.5 (2)
C2—C1—H1C	109.5	C3—C4—C5	115.9 (2)
H1B—C1—H1C	109.5	C6—C5—C4	119.2 (2)
C2—C1—H1D	109.5	C6—C5—H5A	120.4
H1B—C1—H1D	109.5	C4—C5—H5A	120.4
H1C—C1—H1D	109.5	C2—C6—C5	121.3 (3)
N1—C2—C6	120.2 (2)	C2—C6—H6A	119.3
N1—C2—C1	118.1 (2)	C5—C6—H6A	119.3
C6—C2—C1	121.7 (3)

C3—N1—C2—C6	2.2 (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—N2	177.4 (2)	C1—C2—C6—C5	178.9 (2)
N1—C3—C4—C5	−0.4 (4)	C4—C5—C6—C2	1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.86	2.29	3.131 (3)	165

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₈N₂
M_r	108.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	8.4240 (17), 7.0560 (14), 10.658 (2)
β (°)	105.23 (3)
V (Å³)	611.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.978, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	1183, 1106, 746
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.154, 1.02
No. of reflections	1106
No. of parameters	73
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.86	2.29	3.131 (3)	165

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

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

References

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