4-Methyl-3-nitro-pyridin-2-amine.

In the title compound, C(6)H(7)N(3)O(2), the dihedral angle between the nitro group and the pyridine ring is 15.5 (3)° and an intra-molecular N-H⋯O hydrogen bond occurs. In the crystal, inversion dimers linked by two N-H⋯N hydrogen bonds occur, resulting in R(2) (2)(8) rings. The packing is stabilized by aromatic π-π stacking [centroid-centroid distance = 3.5666 (15) Å] and a short N-O⋯π contact is seen.

Related literature

For a related structure, see: Kvick & Noordik (1977 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H7N3O2

M = 153.15

Monoclinic,

a = 7.3776 (6) Å

b = 12.8673 (11) Å

c = 7.3884 (6) Å

β = 104.364 (4)°

V = 679.45 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 296 K

0.25 × 0.10 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.985, T max = 0.992

7483 measured reflections

1677 independent reflections

759 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.173

S = 1.00

1677 reflections

107 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022582/hb5007sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022582/hb5007Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H7N3O2	F(000) = 320
Mr = 153.15	Dx = 1.497 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1677 reflections
a = 7.3776 (6) Å	θ = 3.2–28.3°
b = 12.8673 (11) Å	µ = 0.12 mm−1
c = 7.3884 (6) Å	T = 296 K
β = 104.364 (4)°	Needle, yellow
V = 679.45 (10) Å3	0.25 × 0.10 × 0.08 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	1677 independent reflections
Radiation source: fine-focus sealed tube	759 reflections with I > 2σ(I)
graphite	Rint = 0.055
Detector resolution: 7.40 pixels mm-1	θmax = 28.3°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→17
Tmin = 0.985, Tmax = 0.992	l = −9→9
7483 measured reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0745P)2 + 0.0769P] where P = (Fo2 + 2Fc2)/3
1677 reflections	(Δ/σ)max < 0.001
107 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.9915 (3)	−0.20091 (18)	0.2978 (3)	0.0860 (10)
O2	1.2249 (3)	−0.11801 (19)	0.4483 (4)	0.0904 (10)
N1	0.7197 (3)	0.06783 (18)	0.0831 (3)	0.0426 (8)
N2	0.6845 (4)	−0.1039 (2)	0.1310 (3)	0.0529 (9)
N3	1.0759 (3)	−0.11908 (19)	0.3358 (3)	0.0475 (9)
C1	0.8004 (4)	−0.0221 (2)	0.1552 (3)	0.0386 (8)
C2	0.9935 (3)	−0.0238 (2)	0.2507 (3)	0.0378 (9)
C3	1.1041 (3)	0.0656 (2)	0.2608 (3)	0.0405 (9)
C4	1.0135 (4)	0.1542 (2)	0.1803 (4)	0.0480 (10)
C5	0.8246 (4)	0.1511 (2)	0.0979 (4)	0.0472 (10)
C6	1.3108 (4)	0.0719 (3)	0.3480 (4)	0.0555 (10)
H2A	0.570 (5)	−0.089 (2)	0.066 (4)	0.0635*
H2B	0.730 (4)	−0.164 (2)	0.156 (4)	0.0635*
H4	1.07986	0.21582	0.18170	0.0576*
H5	0.76702	0.21275	0.04899	0.0566*
H6A	1.35738	0.13785	0.31888	0.0666*
H6B	1.37365	0.01708	0.29973	0.0666*
H6C	1.33334	0.06475	0.48107	0.0666*

	U11	U22	U33	U12	U13	U23
O1	0.0667 (16)	0.0497 (16)	0.127 (2)	−0.0025 (12)	−0.0035 (14)	0.0240 (14)
O2	0.0609 (15)	0.0759 (19)	0.110 (2)	0.0105 (13)	−0.0247 (14)	0.0200 (14)
N1	0.0373 (12)	0.0424 (14)	0.0475 (13)	0.0041 (11)	0.0096 (10)	−0.0006 (11)
N2	0.0399 (13)	0.0506 (17)	0.0639 (16)	−0.0020 (13)	0.0048 (12)	0.0097 (14)
N3	0.0416 (14)	0.0502 (17)	0.0506 (14)	0.0091 (12)	0.0110 (12)	0.0076 (12)
C1	0.0355 (14)	0.0427 (16)	0.0394 (14)	0.0019 (13)	0.0126 (11)	−0.0016 (12)
C2	0.0356 (15)	0.0404 (16)	0.0378 (14)	0.0070 (12)	0.0101 (11)	0.0004 (12)
C3	0.0361 (14)	0.0500 (18)	0.0354 (14)	0.0038 (13)	0.0090 (11)	−0.0046 (12)
C4	0.0493 (18)	0.0399 (17)	0.0547 (17)	−0.0042 (14)	0.0126 (14)	−0.0032 (14)
C5	0.0495 (18)	0.0421 (17)	0.0492 (16)	0.0105 (14)	0.0110 (13)	−0.0001 (13)
C6	0.0391 (16)	0.066 (2)	0.0589 (18)	−0.0051 (14)	0.0077 (13)	−0.0058 (16)

O1—N3	1.220 (3)	C2—C3	1.402 (4)
O2—N3	1.203 (3)	C3—C4	1.380 (4)
N1—C1	1.349 (3)	C3—C6	1.503 (4)
N1—C5	1.310 (4)	C4—C5	1.376 (4)
N2—C1	1.340 (4)	C4—H4	0.9300
N3—C2	1.442 (3)	C5—H5	0.9300
N2—H2B	0.85 (3)	C6—H6A	0.9600
N2—H2A	0.88 (3)	C6—H6B	0.9600
C1—C2	1.425 (4)	C6—H6C	0.9600
C1—N1—C5	118.4 (2)	C2—C3—C4	116.2 (2)
O1—N3—O2	119.7 (2)	C4—C3—C6	118.2 (3)
O1—N3—C2	119.9 (2)	C3—C4—C5	119.7 (2)
O2—N3—C2	120.4 (2)	N1—C5—C4	125.0 (3)
H2A—N2—H2B	126 (3)	C3—C4—H4	120.00
C1—N2—H2A	113.3 (18)	C5—C4—H4	120.00
C1—N2—H2B	119 (2)	N1—C5—H5	118.00
N1—C1—N2	114.6 (3)	C4—C5—H5	118.00
N1—C1—C2	119.9 (2)	C3—C6—H6A	109.00
N2—C1—C2	125.5 (2)	C3—C6—H6B	109.00
N3—C2—C1	119.4 (2)	C3—C6—H6C	109.00
N3—C2—C3	119.9 (2)	H6A—C6—H6B	109.00
C1—C2—C3	120.8 (2)	H6A—C6—H6C	109.00
C2—C3—C6	125.6 (2)	H6B—C6—H6C	109.00
C5—N1—C1—N2	−178.7 (2)	N2—C1—C2—N3	−2.1 (4)
C5—N1—C1—C2	2.3 (4)	N2—C1—C2—C3	177.2 (2)
C1—N1—C5—C4	0.8 (4)	N3—C2—C3—C4	−178.3 (2)
O1—N3—C2—C1	13.3 (3)	N3—C2—C3—C6	2.8 (4)
O1—N3—C2—C3	−166.0 (2)	C1—C2—C3—C4	2.4 (3)
O2—N3—C2—C1	−164.5 (2)	C1—C2—C3—C6	−176.4 (2)
O2—N3—C2—C3	16.2 (4)	C2—C3—C4—C5	0.5 (4)
N1—C1—C2—N3	176.7 (2)	C6—C3—C4—C5	179.5 (3)
N1—C1—C2—C3	−4.0 (3)	C3—C4—C5—N1	−2.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.88 (3)	2.17 (4)	3.045 (4)	174 (3)
N2—H2B···O1	0.85 (3)	2.01 (3)	2.612 (4)	127 (2)
N3—O2···Cg1ii	1.203 (3)	3.2743 (3)	3.681 (12)	100.16 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.88 (3)	2.17 (4)	3.045 (4)	174 (3)
N2—H2B⋯O1	0.85 (3)	2.01 (3)	2.612 (4)	127 (2)
N3—O2⋯Cg1ii	1.20 (1)	3.27 (1)	3.681 (12)	100 (1)

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the pyridine ring.