N-(4-Methyl-phen-yl)-3-nitro-pyridin-2-amine.

Two independent mol-ecules comprise the asymmetric unit of the title compound, C(12)H(11)N(3)O(2). These differ in terms of the relative orientations of the benzene rings as seen in the respective dihedral angles formed between the pyridine and benzene rings [17.42 (16) and 34.64 (16)°]. Both mol-ecules are twisted about the amine-tolyl N-C bonds [respective torsion angles = 22.3 (5) and 35.9 (5)°] but only about the amine-pyridine N-C bond in the first independent mol-ecule [respective torsion angles = -11.7 (5) and 0.8 (5)°]. Intra-molecular N-H⋯O hydrogen bonds preclude the amine H atoms from forming significant inter-molecular inter-actions. The crystal packing features inter-molecular C-H⋯O and C-H⋯π and π-π [centroid-centroid distance: pyridine-benzene = 3.6442 (19) Å and pyridine-pyridine = 3.722 (2) Å] contacts.

Related literature

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001 ▶); Abdullah (2005 ▶). For the structures of related pyrimidine amine derivatives, see: Badaruddin et al., (2009 ▶); Fairuz et al. (2010 ▶).

Experimental

Crystal data

C12H11N3O2

M = 229.24

Monoclinic,

a = 10.6557 (12) Å

b = 7.1415 (8) Å

c = 27.958 (3) Å

β = 91.310 (2)°

V = 2127.0 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.35 × 0.35 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer

13178 measured reflections

4804 independent reflections

3344 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.146

S = 1.04

4804 reflections

317 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 ▶), DIAMOND (Brandenburg, 2006 ▶) and Qmol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810033040/hg2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033040/hg2703Isup2.hkl

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

C12H11N3O2	F(000) = 960
Mr = 229.24	Dx = 1.432 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2221 reflections
a = 10.6557 (12) Å	θ = 3.0–27.8°
b = 7.1415 (8) Å	µ = 0.10 mm−1
c = 27.958 (3) Å	T = 100 K
β = 91.310 (2)°	Plate, red
V = 2127.0 (4) Å3	0.35 × 0.35 × 0.05 mm
Z = 8

Bruker SMART APEX diffractometer	3344 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
graphite	θmax = 27.5°, θmin = 1.5°
ω scans	h = −13→11
13178 measured reflections	k = −8→9
4804 independent reflections	l = −36→36

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0685P)2 + 0.8145P] where P = (Fo2 + 2Fc2)/3
4804 reflections	(Δ/σ)max = 0.001
317 parameters	Δρmax = 0.30 e Å−3
2 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.5737 (2)	0.6059 (3)	0.07334 (8)	0.0224 (6)
O2	0.3802 (2)	0.6139 (4)	0.04820 (8)	0.0265 (6)
O3	0.1554 (2)	0.1650 (4)	−0.07299 (8)	0.0286 (6)
O4	−0.0348 (2)	0.2379 (4)	−0.09457 (8)	0.0286 (6)
N1	0.4595 (3)	0.5848 (4)	0.08003 (9)	0.0186 (6)
N2	0.4564 (3)	0.4326 (4)	0.20794 (9)	0.0193 (6)
N3	0.6278 (2)	0.5089 (4)	0.16220 (9)	0.0163 (6)
N4	0.0469 (3)	0.2118 (4)	−0.06319 (9)	0.0207 (6)
N5	0.0665 (3)	0.2476 (4)	0.06993 (9)	0.0200 (6)
N6	0.2219 (3)	0.1555 (4)	0.01848 (9)	0.0191 (6)
C1	0.4176 (3)	0.5224 (4)	0.12647 (10)	0.0171 (7)
C2	0.2897 (3)	0.4973 (5)	0.13170 (11)	0.0195 (7)
H2	0.2331	0.5196	0.1056	0.023*
C3	0.2457 (3)	0.4396 (5)	0.17510 (11)	0.0206 (7)
H3A	0.1586	0.4213	0.1798	0.025*
C4	0.3327 (3)	0.4092 (5)	0.21164 (11)	0.0211 (7)
H4	0.3022	0.3687	0.2416	0.025*
C5	0.5016 (3)	0.4879 (4)	0.16576 (11)	0.0161 (7)
C6	0.7235 (3)	0.5118 (4)	0.19792 (11)	0.0154 (7)
C7	0.8350 (3)	0.5993 (4)	0.18500 (11)	0.0169 (7)
H7	0.8427	0.6476	0.1535	0.020*
C8	0.9339 (3)	0.6166 (5)	0.21729 (11)	0.0185 (7)
H8	1.0089	0.6759	0.2076	0.022*
C9	0.9263 (3)	0.5489 (5)	0.26396 (11)	0.0179 (7)
C10	0.8168 (3)	0.4554 (5)	0.27559 (11)	0.0184 (7)
H10	0.8106	0.4034	0.3067	0.022*
C11	0.7155 (3)	0.4345 (5)	0.24348 (11)	0.0184 (7)
H11	0.6424	0.3686	0.2526	0.022*
C12	1.0323 (3)	0.5790 (5)	0.29973 (11)	0.0224 (7)
H12A	1.0097	0.5253	0.3306	0.034*
H12B	1.0478	0.7135	0.3035	0.034*
H12C	1.1083	0.5178	0.2883	0.034*
C13	0.0149 (3)	0.2401 (5)	−0.01373 (11)	0.0183 (7)
C14	−0.1058 (3)	0.3001 (5)	−0.00485 (12)	0.0212 (7)
H14	−0.1649	0.3152	−0.0305	0.025*
C15	−0.1398 (3)	0.3376 (5)	0.04115 (12)	0.0220 (7)
H15	−0.2214	0.3817	0.0482	0.026*
C16	−0.0491 (3)	0.3079 (5)	0.07704 (12)	0.0222 (7)
H16	−0.0720	0.3328	0.1091	0.027*
C17	0.1032 (3)	0.2129 (4)	0.02481 (11)	0.0172 (7)
C18	0.3186 (3)	0.1221 (5)	0.05334 (11)	0.0173 (7)
C19	0.4414 (3)	0.1571 (5)	0.03961 (11)	0.0189 (7)
H19	0.4568	0.2063	0.0087	0.023*
C20	0.5413 (3)	0.1203 (5)	0.07102 (11)	0.0188 (7)
H20	0.6246	0.1423	0.0610	0.023*
C21	0.5218 (3)	0.0519 (5)	0.11668 (11)	0.0179 (7)
C22	0.3992 (3)	0.0150 (5)	0.12938 (11)	0.0188 (7)
H22	0.3840	−0.0340	0.1603	0.023*
C23	0.2979 (3)	0.0474 (5)	0.09839 (11)	0.0201 (7)
H23	0.2151	0.0187	0.1079	0.024*
C24	0.6290 (3)	0.0200 (5)	0.15168 (12)	0.0242 (8)
H24A	0.7084	0.0220	0.1347	0.036*
H24B	0.6189	−0.1019	0.1672	0.036*
H24C	0.6296	0.1190	0.1759	0.036*
H3	0.652 (3)	0.552 (5)	0.1350 (8)	0.022 (10)*
H6	0.242 (3)	0.153 (6)	−0.0118 (14)	0.031 (11)*

	U11	U22	U33	U12	U13	U23
O1	0.0175 (13)	0.0287 (14)	0.0210 (11)	−0.0020 (10)	−0.0014 (9)	0.0037 (10)
O2	0.0236 (13)	0.0349 (15)	0.0206 (11)	0.0030 (11)	−0.0063 (10)	0.0061 (10)
O3	0.0235 (14)	0.0429 (16)	0.0195 (12)	0.0097 (12)	−0.0008 (10)	−0.0016 (11)
O4	0.0288 (14)	0.0353 (15)	0.0212 (12)	−0.0007 (12)	−0.0093 (10)	0.0011 (10)
N1	0.0209 (15)	0.0172 (15)	0.0178 (13)	0.0010 (12)	−0.0025 (11)	0.0008 (10)
N2	0.0189 (15)	0.0212 (15)	0.0179 (13)	−0.0001 (12)	0.0012 (11)	−0.0003 (11)
N3	0.0131 (14)	0.0217 (15)	0.0140 (12)	−0.0016 (11)	−0.0009 (10)	0.0025 (10)
N4	0.0220 (16)	0.0199 (15)	0.0200 (13)	−0.0018 (12)	−0.0040 (11)	0.0017 (11)
N5	0.0177 (15)	0.0224 (15)	0.0198 (13)	0.0022 (12)	0.0000 (11)	0.0008 (11)
N6	0.0172 (15)	0.0254 (16)	0.0147 (13)	0.0025 (12)	−0.0024 (11)	0.0008 (11)
C1	0.0215 (18)	0.0143 (16)	0.0156 (14)	0.0000 (13)	0.0000 (12)	−0.0003 (12)
C2	0.0172 (17)	0.0174 (17)	0.0236 (16)	0.0017 (13)	−0.0046 (13)	−0.0006 (13)
C3	0.0127 (17)	0.0218 (18)	0.0274 (17)	−0.0001 (14)	0.0007 (13)	−0.0011 (14)
C4	0.0199 (18)	0.0232 (18)	0.0203 (15)	−0.0021 (14)	0.0024 (13)	−0.0003 (13)
C5	0.0170 (17)	0.0141 (16)	0.0173 (14)	−0.0002 (13)	−0.0004 (12)	−0.0032 (11)
C6	0.0116 (16)	0.0171 (16)	0.0173 (14)	0.0012 (13)	−0.0018 (12)	−0.0027 (12)
C7	0.0172 (17)	0.0164 (16)	0.0171 (14)	0.0009 (13)	0.0009 (12)	−0.0004 (12)
C8	0.0167 (17)	0.0159 (17)	0.0229 (16)	0.0000 (13)	0.0002 (13)	0.0001 (12)
C9	0.0185 (17)	0.0151 (16)	0.0198 (15)	0.0028 (13)	−0.0025 (12)	−0.0041 (12)
C10	0.0198 (18)	0.0206 (17)	0.0149 (14)	0.0042 (14)	0.0019 (12)	0.0002 (12)
C11	0.0171 (17)	0.0192 (17)	0.0189 (15)	0.0007 (14)	0.0014 (12)	0.0001 (13)
C12	0.0232 (19)	0.0211 (18)	0.0227 (16)	−0.0005 (15)	−0.0064 (14)	−0.0014 (13)
C13	0.0208 (18)	0.0162 (16)	0.0180 (15)	−0.0029 (14)	−0.0017 (12)	0.0009 (12)
C14	0.0195 (18)	0.0172 (17)	0.0265 (17)	−0.0050 (14)	−0.0046 (13)	0.0044 (13)
C15	0.0148 (17)	0.0204 (18)	0.0309 (18)	−0.0001 (14)	0.0025 (14)	0.0040 (14)
C16	0.0219 (18)	0.0226 (18)	0.0222 (16)	0.0002 (15)	0.0038 (13)	0.0028 (13)
C17	0.0181 (17)	0.0144 (16)	0.0190 (15)	−0.0022 (13)	−0.0026 (12)	0.0020 (12)
C18	0.0205 (18)	0.0145 (16)	0.0168 (14)	0.0019 (13)	−0.0017 (12)	−0.0019 (12)
C19	0.0236 (18)	0.0169 (17)	0.0162 (14)	0.0005 (14)	0.0032 (12)	0.0010 (12)
C20	0.0124 (16)	0.0218 (18)	0.0223 (16)	0.0000 (13)	0.0024 (12)	−0.0021 (13)
C21	0.0172 (17)	0.0150 (16)	0.0214 (15)	0.0029 (13)	−0.0036 (13)	−0.0040 (12)
C22	0.0186 (17)	0.0214 (18)	0.0165 (14)	0.0020 (14)	0.0011 (12)	0.0030 (12)
C23	0.0167 (17)	0.0219 (18)	0.0217 (15)	−0.0006 (14)	0.0023 (13)	0.0030 (13)
C24	0.0235 (19)	0.0256 (19)	0.0232 (16)	0.0044 (15)	−0.0049 (14)	−0.0019 (14)

O1—N1	1.245 (3)	C9—C10	1.389 (5)
O2—N1	1.230 (3)	C9—C12	1.507 (4)
O3—N4	1.240 (4)	C10—C11	1.396 (4)
O4—N4	1.236 (3)	C10—H10	0.9500
N1—C1	1.452 (4)	C11—H11	0.9500
N2—C4	1.335 (4)	C12—H12A	0.9800
N2—C5	1.343 (4)	C12—H12B	0.9800
N3—C5	1.359 (4)	C12—H12C	0.9800
N3—C6	1.412 (4)	C13—C14	1.383 (5)
N3—H3	0.867 (15)	C13—C17	1.428 (4)
N4—C13	1.446 (4)	C14—C15	1.370 (5)
N5—C16	1.324 (4)	C14—H14	0.9500
N5—C17	1.352 (4)	C15—C16	1.393 (5)
N6—C17	1.345 (4)	C15—H15	0.9500
N6—C18	1.422 (4)	C16—H16	0.9500
N6—H6	0.88 (4)	C18—C23	1.390 (4)
C1—C2	1.386 (5)	C18—C19	1.394 (4)
C1—C5	1.422 (4)	C19—C20	1.390 (4)
C2—C3	1.374 (4)	C19—H19	0.9500
C2—H2	0.9500	C20—C21	1.387 (4)
C3—C4	1.380 (4)	C20—H20	0.9500
C3—H3A	0.9500	C21—C22	1.388 (4)
C4—H4	0.9500	C21—C24	1.505 (4)
C6—C11	1.393 (4)	C22—C23	1.388 (4)
C6—C7	1.397 (4)	C22—H22	0.9500
C7—C8	1.377 (4)	C23—H23	0.9500
C7—H7	0.9500	C24—H24A	0.9800
C8—C9	1.396 (4)	C24—H24B	0.9800
C8—H8	0.9500	C24—H24C	0.9800
O2—N1—O1	121.9 (3)	C10—C11—H11	120.5
O2—N1—C1	118.6 (3)	C9—C12—H12A	109.5
O1—N1—C1	119.5 (2)	C9—C12—H12B	109.5
C4—N2—C5	118.6 (3)	H12A—C12—H12B	109.5
C5—N3—C6	130.6 (3)	C9—C12—H12C	109.5
C5—N3—H3	115 (2)	H12A—C12—H12C	109.5
C6—N3—H3	113 (2)	H12B—C12—H12C	109.5
O4—N4—O3	121.9 (3)	C14—C13—C17	120.4 (3)
O4—N4—C13	118.7 (3)	C14—C13—N4	117.1 (3)
O3—N4—C13	119.4 (3)	C17—C13—N4	122.5 (3)
C16—N5—C17	119.3 (3)	C15—C14—C13	119.7 (3)
C17—N6—C18	129.0 (3)	C15—C14—H14	120.2
C17—N6—H6	113 (3)	C13—C14—H14	120.2
C18—N6—H6	118 (3)	C14—C15—C16	116.9 (3)
C2—C1—C5	119.9 (3)	C14—C15—H15	121.5
C2—C1—N1	117.2 (3)	C16—C15—H15	121.5
C5—C1—N1	122.9 (3)	N5—C16—C15	125.0 (3)
C3—C2—C1	119.2 (3)	N5—C16—H16	117.5
C3—C2—H2	120.4	C15—C16—H16	117.5
C1—C2—H2	120.4	N6—C17—N5	118.1 (3)
C2—C3—C4	117.7 (3)	N6—C17—C13	123.2 (3)
C2—C3—H3A	121.2	N5—C17—C13	118.6 (3)
C4—C3—H3A	121.2	C23—C18—C19	119.2 (3)
N2—C4—C3	124.8 (3)	C23—C18—N6	123.9 (3)
N2—C4—H4	117.6	C19—C18—N6	116.8 (3)
C3—C4—H4	117.6	C20—C19—C18	120.2 (3)
N2—C5—N3	118.2 (3)	C20—C19—H19	119.9
N2—C5—C1	119.8 (3)	C18—C19—H19	119.9
N3—C5—C1	122.0 (3)	C21—C20—C19	121.3 (3)
C11—C6—C7	119.0 (3)	C21—C20—H20	119.3
C11—C6—N3	125.7 (3)	C19—C20—H20	119.3
C7—C6—N3	115.4 (3)	C22—C21—C20	117.7 (3)
C8—C7—C6	120.8 (3)	C22—C21—C24	120.7 (3)
C8—C7—H7	119.6	C20—C21—C24	121.6 (3)
C6—C7—H7	119.6	C21—C22—C23	122.1 (3)
C7—C8—C9	121.5 (3)	C21—C22—H22	118.9
C7—C8—H8	119.3	C23—C22—H22	118.9
C9—C8—H8	119.3	C22—C23—C18	119.5 (3)
C10—C9—C8	116.9 (3)	C22—C23—H23	120.2
C10—C9—C12	122.3 (3)	C18—C23—H23	120.2
C8—C9—C12	120.8 (3)	C21—C24—H24A	109.5
C9—C10—C11	122.8 (3)	C21—C24—H24B	109.5
C9—C10—H10	118.6	H24A—C24—H24B	109.5
C11—C10—H10	118.6	C21—C24—H24C	109.5
C6—C11—C10	118.9 (3)	H24A—C24—H24C	109.5
C6—C11—H11	120.5	H24B—C24—H24C	109.5
O2—N1—C1—C2	0.8 (4)	O4—N4—C13—C14	−1.7 (4)
O1—N1—C1—C2	−178.6 (3)	O3—N4—C13—C14	177.3 (3)
O2—N1—C1—C5	−179.0 (3)	O4—N4—C13—C17	179.9 (3)
O1—N1—C1—C5	1.5 (5)	O3—N4—C13—C17	−1.1 (5)
C5—C1—C2—C3	0.3 (5)	C17—C13—C14—C15	1.4 (5)
N1—C1—C2—C3	−179.6 (3)	N4—C13—C14—C15	−177.0 (3)
C1—C2—C3—C4	−0.1 (5)	C13—C14—C15—C16	−1.5 (5)
C5—N2—C4—C3	−0.7 (5)	C17—N5—C16—C15	0.9 (5)
C2—C3—C4—N2	0.3 (5)	C14—C15—C16—N5	0.4 (5)
C4—N2—C5—N3	−179.1 (3)	C18—N6—C17—N5	0.8 (5)
C4—N2—C5—C1	0.8 (5)	C18—N6—C17—C13	−179.7 (3)
C6—N3—C5—N2	−11.7 (5)	C16—N5—C17—N6	178.6 (3)
C6—N3—C5—C1	168.4 (3)	C16—N5—C17—C13	−0.9 (5)
C2—C1—C5—N2	−0.6 (5)	C14—C13—C17—N6	−179.7 (3)
N1—C1—C5—N2	179.2 (3)	N4—C13—C17—N6	−1.4 (5)
C2—C1—C5—N3	179.3 (3)	C14—C13—C17—N5	−0.2 (5)
N1—C1—C5—N3	−0.8 (5)	N4—C13—C17—N5	178.1 (3)
C5—N3—C6—C11	22.3 (5)	C17—N6—C18—C23	35.9 (5)
C5—N3—C6—C7	−158.4 (3)	C17—N6—C18—C19	−148.1 (3)
C11—C6—C7—C8	−2.8 (5)	C23—C18—C19—C20	−1.0 (5)
N3—C6—C7—C8	177.8 (3)	N6—C18—C19—C20	−177.3 (3)
C6—C7—C8—C9	−0.5 (5)	C18—C19—C20—C21	−1.3 (5)
C7—C8—C9—C10	3.1 (5)	C19—C20—C21—C22	2.3 (5)
C7—C8—C9—C12	−176.3 (3)	C19—C20—C21—C24	−177.1 (3)
C8—C9—C10—C11	−2.6 (5)	C20—C21—C22—C23	−1.1 (5)
C12—C9—C10—C11	176.8 (3)	C24—C21—C22—C23	178.3 (3)
C7—C6—C11—C10	3.2 (5)	C21—C22—C23—C18	−1.1 (5)
N3—C6—C11—C10	−177.4 (3)	C19—C18—C23—C22	2.2 (5)
C9—C10—C11—C6	−0.6 (5)	N6—C18—C23—C22	178.1 (3)

Cg1 is the centroid of the C6–C11 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.87 (3)	1.94 (3)	2.630 (3)	136 (3)
N6—H6···O3	0.88 (4)	1.93 (4)	2.639 (3)	137 (3)
N3—H3···N1	0.87 (3)	2.55 (3)	2.932 (4)	108 (2)
N6—H6···N4	0.88 (4)	2.54 (4)	2.942 (4)	109 (2)
C14—H14···O2i	0.95	2.39	3.199 (4)	143
C4—H4···Cg1ii	0.95	2.90	3.604 (4)	132
C12—H12b···Cg1iii	0.98	2.80	3.654 (4)	146

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C6–C11 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1	0.87 (3)	1.94 (3)	2.630 (3)	136 (3)
N6—H6⋯O3	0.88 (4)	1.93 (4)	2.639 (3)	137 (3)
N3—H3⋯N1	0.87 (3)	2.55 (3)	2.932 (4)	108 (2)
N6—H6⋯N4	0.88 (4)	2.54 (4)	2.942 (4)	109 (2)
C14—H14⋯O2i	0.95	2.39	3.199 (4)	143
C4—H4⋯Cg1ii	0.95	2.90	3.604 (4)	132
C12—H12b⋯Cg1iii	0.98	2.80	3.654 (4)	146

Symmetry codes: (i) ; (ii) ; (iii) .