N-[Meth­oxy(4-nitro­phen­yl)meth­yl]pyridin-2-amine

In the title compound, C₁₃H₁₃N₃O₃, the nitro group is twisted away from the attached benzene ring by 19.5 (3)°. The dihedral angle between the benzene and pyridine rings is 78.2 (1)°. In the crystal structure, mol­ecules are connected into chains along the [001] direction by N—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.050
• wR factor = 0.131
• Data-to-parameter ratio = 11.7

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PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
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S1. Comment

There has been much research interest in the chemistry and biology of Schiff base compounds due to their facile synthesis and wide applications (Che et al., 2007; Habibi et al., 2007; Hodnett et al., 1970; Panneerselvam et al., 2005). To our knowledge, however, the addition products of Schiff bases are relatively less reported. In this paper, we report the synthesis and crystal structure of N-(methoxy(4-nitrophenyl)methyl)pyridin-2-amine (Boedeker et al., 1980), which is a addition product of methyl 4-nitro-N-(pyridin-2-yl)benzimidate with methanol.

In the title molecule (Fig.1), the bond distances and angles are normal. The N3—C9—N2—C7, O3—C7—N2—C9 and N2—C7—O3—C8 torsion angles are -11.0 (3), -73.4 (3) and 165.83 (19)°, respectively. The dihedral angle between the nitryl plane and benzene ring is 19.5 (3)°, and that between the benzene and pyridine rings is 78.2 (1)°.

Intermolecular N2—H2B···N3 hydrogen bonds connect the molecules into chains along the c axis (Fig. 2).

Related literature

For related literature, see: Boedeker & Courault (1980); Che & Wang (2007); Habibi et al. (2007); Hodnett & Dunn (1970); Panneerselvam et al. (2005).

S2. Experimental

Equimolar quantities (0.5 mmol) of 4-nitrobenzaldehyde, 2-pyridinamine and NiCl₂ were dissolved in methanol (10 ml) and stirred at room temperature for several hours. The resulting precipitate was separated by filtration and recrystallized from methanol. Single crystals suitable for X-ray diffraction studies were obtained after 5 d by slow evaporation of an ethanol solution. Analysis found: C 60.21, H 5.08, N 16.19%; calculated for C₁₃H₁₃N₃O₃: C 60.20, H 5.05, N 16.21%.

S3. Refinement

Methyl H atoms were placed in idealized positions (C—H = 0.96 Å), and refined in riding mode with U_iso(H) = 1.5U_eq(C). The remaining H atoms were located in a difference map and refined isotropically [N—H = 0.87 (2) Å and C—H = 0.93 (3)–0.99 (2) Å].

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of the title compound, showing 35% probability displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. A view of an N—H···N hydrogen-bonded (dashed lines) chain in the title compound.

N-[Methoxy(4-nitrophenyl)methyl]pyridin-2-amine

Crystal data

C13H13N3O3	F(000) = 544
Mr = 259.26	Dx = 1.349 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1247 reflections
a = 10.661 (2) Å	θ = 2.8–24.3°
b = 14.153 (3) Å	µ = 0.10 mm^−1
c = 9.0410 (18) Å	T = 293 K
β = 110.70 (3)°	Block, yellow
V = 1276.1 (5) Å^3	0.32 × 0.26 × 0.22 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	1642 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −13→12
Tmin = 0.969, Tmax = 0.979	k = −17→0
2666 measured reflections	l = 0→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.2385P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2500 reflections	Δρmax = 0.21 e Å^−3
214 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3678 (2)	0.36268 (17)	0.0210 (3)	0.0376 (6)
C2	0.3718 (3)	0.2834 (2)	0.1096 (3)	0.0531 (7)
C3	0.2638 (2)	0.2654 (2)	0.1565 (3)	0.0508 (7)
C4	0.1559 (2)	0.32650 (16)	0.1176 (2)	0.0342 (5)
C5	0.1559 (2)	0.40548 (17)	0.0287 (3)	0.0435 (6)
C6	0.2621 (3)	0.42391 (18)	−0.0214 (3)	0.0433 (6)
C7	0.0357 (2)	0.30320 (17)	0.1656 (3)	0.0362 (5)
C8	0.0389 (3)	0.4362 (2)	0.3262 (3)	0.0673 (9)
H8A	0.0500	0.3967	0.4163	0.101*
H8B	−0.0103	0.4919	0.3325	0.101*
H8C	0.1254	0.4540	0.3248	0.101*
C9	−0.1545 (2)	0.19259 (15)	0.0689 (2)	0.0324 (5)
C10	−0.2478 (3)	0.14749 (18)	−0.0610 (3)	0.0447 (6)
C11	−0.3474 (3)	0.0958 (2)	−0.0389 (3)	0.0564 (7)
C12	−0.3525 (3)	0.0876 (2)	0.1113 (3)	0.0541 (7)
C13	−0.2556 (3)	0.13170 (18)	0.2326 (3)	0.0451 (6)
N1	0.4801 (2)	0.38099 (16)	−0.0347 (2)	0.0476 (5)
N2	−0.05330 (18)	0.24491 (14)	0.0468 (2)	0.0369 (5)
N3	−0.15594 (18)	0.18427 (13)	0.2155 (2)	0.0356 (5)
O1	0.58639 (19)	0.34165 (17)	0.0330 (3)	0.0787 (7)
O2	0.46018 (19)	0.43389 (14)	−0.1466 (2)	0.0627 (6)
O3	−0.03278 (16)	0.38568 (12)	0.1852 (2)	0.0482 (5)
H7	0.068 (2)	0.2671 (15)	0.266 (3)	0.034 (6)*
H10	−0.243 (2)	0.1564 (16)	−0.163 (3)	0.044 (7)*
H2B	−0.070 (2)	0.2629 (16)	−0.050 (3)	0.039 (6)*
H3	0.264 (3)	0.2062 (19)	0.215 (3)	0.064 (8)*
H6	0.264 (2)	0.4794 (18)	−0.076 (3)	0.048 (7)*
H13	−0.252 (2)	0.1257 (17)	0.340 (3)	0.052 (7)*
H5	0.083 (3)	0.4520 (19)	0.002 (3)	0.059 (7)*
H2A	0.445 (3)	0.241 (2)	0.134 (3)	0.065 (8)*
H12	−0.414 (3)	0.0485 (18)	0.136 (3)	0.058 (8)*
H11	−0.416 (3)	0.068 (2)	−0.128 (3)	0.065 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0312 (12)	0.0492 (14)	0.0359 (12)	−0.0057 (11)	0.0162 (10)	−0.0033 (11)
C2	0.0367 (14)	0.0679 (18)	0.0582 (17)	0.0125 (13)	0.0209 (13)	0.0209 (14)
C3	0.0428 (14)	0.0571 (17)	0.0552 (16)	0.0074 (13)	0.0208 (12)	0.0252 (14)
C4	0.0319 (12)	0.0423 (13)	0.0304 (11)	−0.0046 (10)	0.0136 (9)	−0.0001 (10)
C5	0.0421 (14)	0.0415 (14)	0.0549 (15)	0.0058 (12)	0.0269 (12)	0.0051 (12)
C6	0.0481 (15)	0.0390 (14)	0.0527 (15)	−0.0023 (12)	0.0300 (12)	0.0075 (12)
C7	0.0344 (12)	0.0442 (13)	0.0325 (12)	−0.0034 (10)	0.0151 (10)	0.0004 (11)
C8	0.093 (2)	0.0586 (18)	0.0662 (18)	−0.0221 (17)	0.0483 (17)	−0.0214 (15)
C9	0.0317 (11)	0.0351 (12)	0.0354 (12)	0.0009 (10)	0.0179 (10)	−0.0010 (10)
C10	0.0496 (15)	0.0520 (16)	0.0355 (13)	−0.0111 (12)	0.0187 (11)	−0.0040 (12)
C11	0.0526 (16)	0.0654 (18)	0.0520 (16)	−0.0245 (15)	0.0195 (14)	−0.0117 (14)
C12	0.0523 (16)	0.0569 (17)	0.0637 (18)	−0.0216 (14)	0.0335 (14)	−0.0058 (14)
C13	0.0521 (15)	0.0475 (15)	0.0482 (15)	−0.0039 (12)	0.0331 (13)	0.0000 (12)
N1	0.0423 (12)	0.0576 (13)	0.0507 (13)	−0.0080 (11)	0.0261 (11)	−0.0066 (11)
N2	0.0385 (11)	0.0483 (12)	0.0281 (10)	−0.0092 (9)	0.0168 (8)	−0.0003 (9)
N3	0.0375 (10)	0.0406 (11)	0.0343 (10)	−0.0017 (9)	0.0196 (8)	−0.0007 (8)
O1	0.0417 (11)	0.1060 (17)	0.0993 (17)	0.0114 (12)	0.0382 (11)	0.0213 (14)
O2	0.0643 (13)	0.0778 (13)	0.0610 (12)	−0.0083 (10)	0.0406 (10)	0.0097 (11)
O3	0.0494 (10)	0.0494 (10)	0.0541 (10)	−0.0037 (8)	0.0285 (9)	−0.0097 (8)

Geometric parameters (Å, º)

C1—C6	1.365 (3)	C8—H8B	0.96
C1—C2	1.371 (3)	C8—H8C	0.96
C1—N1	1.476 (3)	C9—N3	1.337 (3)
C2—C3	1.384 (4)	C9—N2	1.380 (3)
C2—H2A	0.94 (3)	C9—C10	1.396 (3)
C3—C4	1.381 (3)	C10—C11	1.361 (3)
C3—H3	0.99 (3)	C10—H10	0.95 (2)
C4—C5	1.377 (3)	C11—C12	1.383 (4)
C4—C7	1.528 (3)	C11—H11	0.96 (3)
C5—C6	1.385 (3)	C12—C13	1.363 (4)
C5—H5	0.98 (3)	C12—H12	0.94 (3)
C6—H6	0.93 (3)	C13—N3	1.350 (3)
C7—N2	1.419 (3)	C13—H13	0.96 (3)
C7—O3	1.421 (3)	N1—O2	1.215 (3)
C7—H7	0.99 (2)	N1—O1	1.216 (3)
C8—O3	1.426 (3)	N2—H2B	0.87 (2)
C8—H8A	0.96
C6—C1—C2	122.4 (2)	O3—C8—H8C	109.5
C6—C1—N1	118.8 (2)	H8A—C8—H8C	109.5
C2—C1—N1	118.8 (2)	H8B—C8—H8C	109.5
C1—C2—C3	118.2 (2)	N3—C9—N2	118.30 (19)
C1—C2—H2A	120.3 (17)	N3—C9—C10	122.6 (2)
C3—C2—H2A	121.5 (17)	N2—C9—C10	119.01 (19)
C4—C3—C2	121.0 (2)	C11—C10—C9	118.9 (2)
C4—C3—H3	120.7 (15)	C11—C10—H10	121.9 (15)
C2—C3—H3	118.3 (15)	C9—C10—H10	119.1 (14)
C5—C4—C3	119.0 (2)	C10—C11—C12	119.5 (3)
C5—C4—C7	120.9 (2)	C10—C11—H11	120.0 (16)
C3—C4—C7	120.0 (2)	C12—C11—H11	120.4 (16)
C4—C5—C6	120.8 (2)	C13—C12—C11	118.0 (2)
C4—C5—H5	121.6 (15)	C13—C12—H12	118.2 (16)
C6—C5—H5	117.6 (15)	C11—C12—H12	123.5 (16)
C1—C6—C5	118.5 (2)	N3—C13—C12	124.3 (2)
C1—C6—H6	120.8 (15)	N3—C13—H13	114.4 (15)
C5—C6—H6	120.5 (15)	C12—C13—H13	121.3 (15)
N2—C7—O3	109.65 (18)	O2—N1—O1	124.0 (2)
N2—C7—C4	108.29 (17)	O2—N1—C1	117.9 (2)
O3—C7—C4	112.19 (18)	O1—N1—C1	118.2 (2)
N2—C7—H7	108.5 (12)	C9—N2—C7	123.40 (18)
O3—C7—H7	109.9 (12)	C9—N2—H2B	114.1 (15)
C4—C7—H7	108.2 (12)	C7—N2—H2B	116.0 (15)
O3—C8—H8A	109.5	C9—N3—C13	116.6 (2)
O3—C8—H8B	109.5	C7—O3—C8	112.76 (19)
H8A—C8—H8B	109.5
C6—C1—C2—C3	0.3 (4)	C9—C10—C11—C12	−1.2 (4)
N1—C1—C2—C3	−177.8 (2)	C10—C11—C12—C13	−0.6 (4)
C1—C2—C3—C4	−1.1 (4)	C11—C12—C13—N3	1.2 (4)
C2—C3—C4—C5	1.0 (4)	C6—C1—N1—O2	−18.6 (3)
C2—C3—C4—C7	177.8 (2)	C2—C1—N1—O2	159.5 (2)
C3—C4—C5—C6	0.0 (4)	C6—C1—N1—O1	162.1 (2)
C7—C4—C5—C6	−176.7 (2)	C2—C1—N1—O1	−19.8 (3)
C2—C1—C6—C5	0.7 (4)	N3—C9—N2—C7	−11.0 (3)
N1—C1—C6—C5	178.8 (2)	C10—C9—N2—C7	171.5 (2)
C4—C5—C6—C1	−0.9 (4)	O3—C7—N2—C9	−73.4 (3)
C5—C4—C7—N2	90.5 (3)	C4—C7—N2—C9	163.9 (2)
C3—C4—C7—N2	−86.2 (3)	N2—C9—N3—C13	−179.29 (19)
C5—C4—C7—O3	−30.7 (3)	C10—C9—N3—C13	−1.9 (3)
C3—C4—C7—O3	152.6 (2)	C12—C13—N3—C9	0.0 (4)
N3—C9—C10—C11	2.5 (4)	N2—C7—O3—C8	165.83 (19)
N2—C9—C10—C11	179.9 (2)	C4—C7—O3—C8	−73.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N3^i	0.87 (2)	2.13 (2)	2.976 (3)	167 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.