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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704247X/ci2453sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680704247X/ci2453Isup2.hkl
Contains datablock I

CCDC reference: 663701

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

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of C7 = ... R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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 top

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

Experimental top

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%.

Refinement top

Methyl H atoms were placed in idealized positions (C—H = 0.96 Å), and refined in riding mode with Uiso(H) = 1.5Ueq(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].

Structure description top

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).

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

Computing details top

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 top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 35% probability displacement ellipsoids (arbitrary spheres for the H atoms).
[Figure 2] 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 top
Crystal data top
C13H13N3O3F(000) = 544
Mr = 259.26Dx = 1.349 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1247 reflections
a = 10.661 (2) Åθ = 2.8–24.3°
b = 14.153 (3) ŵ = 0.10 mm1
c = 9.0410 (18) ÅT = 293 K
β = 110.70 (3)°Block, yellow
V = 1276.1 (5) Å30.32 × 0.26 × 0.22 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2500 independent reflections
Radiation source: fine-focus sealed tube1642 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1312
Tmin = 0.969, Tmax = 0.979k = 170
2666 measured reflectionsl = 011
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)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0583P)2 + 0.2385P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2500 reflectionsΔρmax = 0.21 e Å3
214 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.035 (4)
Crystal data top
C13H13N3O3V = 1276.1 (5) Å3
Mr = 259.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.661 (2) ŵ = 0.10 mm1
b = 14.153 (3) ÅT = 293 K
c = 9.0410 (18) Å0.32 × 0.26 × 0.22 mm
β = 110.70 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2500 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1642 reflections with I > 2σ(I)
Tmin = 0.969, Tmax = 0.979Rint = 0.026
2666 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.21 e Å3
2500 reflectionsΔρmin = 0.19 e Å3
214 parameters
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
C10.3678 (2)0.36268 (17)0.0210 (3)0.0376 (6)
C20.3718 (3)0.2834 (2)0.1096 (3)0.0531 (7)
C30.2638 (2)0.2654 (2)0.1565 (3)0.0508 (7)
C40.1559 (2)0.32650 (16)0.1176 (2)0.0342 (5)
C50.1559 (2)0.40548 (17)0.0287 (3)0.0435 (6)
C60.2621 (3)0.42391 (18)0.0214 (3)0.0433 (6)
C70.0357 (2)0.30320 (17)0.1656 (3)0.0362 (5)
C80.0389 (3)0.4362 (2)0.3262 (3)0.0673 (9)
H8A0.05000.39670.41630.101*
H8B0.01030.49190.33250.101*
H8C0.12540.45400.32480.101*
C90.1545 (2)0.19259 (15)0.0689 (2)0.0324 (5)
C100.2478 (3)0.14749 (18)0.0610 (3)0.0447 (6)
C110.3474 (3)0.0958 (2)0.0389 (3)0.0564 (7)
C120.3525 (3)0.0876 (2)0.1113 (3)0.0541 (7)
C130.2556 (3)0.13170 (18)0.2326 (3)0.0451 (6)
N10.4801 (2)0.38099 (16)0.0347 (2)0.0476 (5)
N20.05330 (18)0.24491 (14)0.0468 (2)0.0369 (5)
N30.15594 (18)0.18427 (13)0.2155 (2)0.0356 (5)
O10.58639 (19)0.34165 (17)0.0330 (3)0.0787 (7)
O20.46018 (19)0.43389 (14)0.1466 (2)0.0627 (6)
O30.03278 (16)0.38568 (12)0.1852 (2)0.0482 (5)
H70.068 (2)0.2671 (15)0.266 (3)0.034 (6)*
H100.243 (2)0.1564 (16)0.163 (3)0.044 (7)*
H2B0.070 (2)0.2629 (16)0.050 (3)0.039 (6)*
H30.264 (3)0.2062 (19)0.215 (3)0.064 (8)*
H60.264 (2)0.4794 (18)0.076 (3)0.048 (7)*
H130.252 (2)0.1257 (17)0.340 (3)0.052 (7)*
H50.083 (3)0.4520 (19)0.002 (3)0.059 (7)*
H2A0.445 (3)0.241 (2)0.134 (3)0.065 (8)*
H120.414 (3)0.0485 (18)0.136 (3)0.058 (8)*
H110.416 (3)0.068 (2)0.128 (3)0.065 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0312 (12)0.0492 (14)0.0359 (12)0.0057 (11)0.0162 (10)0.0033 (11)
C20.0367 (14)0.0679 (18)0.0582 (17)0.0125 (13)0.0209 (13)0.0209 (14)
C30.0428 (14)0.0571 (17)0.0552 (16)0.0074 (13)0.0208 (12)0.0252 (14)
C40.0319 (12)0.0423 (13)0.0304 (11)0.0046 (10)0.0136 (9)0.0001 (10)
C50.0421 (14)0.0415 (14)0.0549 (15)0.0058 (12)0.0269 (12)0.0051 (12)
C60.0481 (15)0.0390 (14)0.0527 (15)0.0023 (12)0.0300 (12)0.0075 (12)
C70.0344 (12)0.0442 (13)0.0325 (12)0.0034 (10)0.0151 (10)0.0004 (11)
C80.093 (2)0.0586 (18)0.0662 (18)0.0221 (17)0.0483 (17)0.0214 (15)
C90.0317 (11)0.0351 (12)0.0354 (12)0.0009 (10)0.0179 (10)0.0010 (10)
C100.0496 (15)0.0520 (16)0.0355 (13)0.0111 (12)0.0187 (11)0.0040 (12)
C110.0526 (16)0.0654 (18)0.0520 (16)0.0245 (15)0.0195 (14)0.0117 (14)
C120.0523 (16)0.0569 (17)0.0637 (18)0.0216 (14)0.0335 (14)0.0058 (14)
C130.0521 (15)0.0475 (15)0.0482 (15)0.0039 (12)0.0331 (13)0.0000 (12)
N10.0423 (12)0.0576 (13)0.0507 (13)0.0080 (11)0.0261 (11)0.0066 (11)
N20.0385 (11)0.0483 (12)0.0281 (10)0.0092 (9)0.0168 (8)0.0003 (9)
N30.0375 (10)0.0406 (11)0.0343 (10)0.0017 (9)0.0196 (8)0.0007 (8)
O10.0417 (11)0.1060 (17)0.0993 (17)0.0114 (12)0.0382 (11)0.0213 (14)
O20.0643 (13)0.0778 (13)0.0610 (12)0.0083 (10)0.0406 (10)0.0097 (11)
O30.0494 (10)0.0494 (10)0.0541 (10)0.0037 (8)0.0285 (9)0.0097 (8)
Geometric parameters (Å, º) top
C1—C61.365 (3)C8—H8B0.96
C1—C21.371 (3)C8—H8C0.96
C1—N11.476 (3)C9—N31.337 (3)
C2—C31.384 (4)C9—N21.380 (3)
C2—H2A0.94 (3)C9—C101.396 (3)
C3—C41.381 (3)C10—C111.361 (3)
C3—H30.99 (3)C10—H100.95 (2)
C4—C51.377 (3)C11—C121.383 (4)
C4—C71.528 (3)C11—H110.96 (3)
C5—C61.385 (3)C12—C131.363 (4)
C5—H50.98 (3)C12—H120.94 (3)
C6—H60.93 (3)C13—N31.350 (3)
C7—N21.419 (3)C13—H130.96 (3)
C7—O31.421 (3)N1—O21.215 (3)
C7—H70.99 (2)N1—O11.216 (3)
C8—O31.426 (3)N2—H2B0.87 (2)
C8—H8A0.96
C6—C1—C2122.4 (2)O3—C8—H8C109.5
C6—C1—N1118.8 (2)H8A—C8—H8C109.5
C2—C1—N1118.8 (2)H8B—C8—H8C109.5
C1—C2—C3118.2 (2)N3—C9—N2118.30 (19)
C1—C2—H2A120.3 (17)N3—C9—C10122.6 (2)
C3—C2—H2A121.5 (17)N2—C9—C10119.01 (19)
C4—C3—C2121.0 (2)C11—C10—C9118.9 (2)
C4—C3—H3120.7 (15)C11—C10—H10121.9 (15)
C2—C3—H3118.3 (15)C9—C10—H10119.1 (14)
C5—C4—C3119.0 (2)C10—C11—C12119.5 (3)
C5—C4—C7120.9 (2)C10—C11—H11120.0 (16)
C3—C4—C7120.0 (2)C12—C11—H11120.4 (16)
C4—C5—C6120.8 (2)C13—C12—C11118.0 (2)
C4—C5—H5121.6 (15)C13—C12—H12118.2 (16)
C6—C5—H5117.6 (15)C11—C12—H12123.5 (16)
C1—C6—C5118.5 (2)N3—C13—C12124.3 (2)
C1—C6—H6120.8 (15)N3—C13—H13114.4 (15)
C5—C6—H6120.5 (15)C12—C13—H13121.3 (15)
N2—C7—O3109.65 (18)O2—N1—O1124.0 (2)
N2—C7—C4108.29 (17)O2—N1—C1117.9 (2)
O3—C7—C4112.19 (18)O1—N1—C1118.2 (2)
N2—C7—H7108.5 (12)C9—N2—C7123.40 (18)
O3—C7—H7109.9 (12)C9—N2—H2B114.1 (15)
C4—C7—H7108.2 (12)C7—N2—H2B116.0 (15)
O3—C8—H8A109.5C9—N3—C13116.6 (2)
O3—C8—H8B109.5C7—O3—C8112.76 (19)
H8A—C8—H8B109.5
C6—C1—C2—C30.3 (4)C9—C10—C11—C121.2 (4)
N1—C1—C2—C3177.8 (2)C10—C11—C12—C130.6 (4)
C1—C2—C3—C41.1 (4)C11—C12—C13—N31.2 (4)
C2—C3—C4—C51.0 (4)C6—C1—N1—O218.6 (3)
C2—C3—C4—C7177.8 (2)C2—C1—N1—O2159.5 (2)
C3—C4—C5—C60.0 (4)C6—C1—N1—O1162.1 (2)
C7—C4—C5—C6176.7 (2)C2—C1—N1—O119.8 (3)
C2—C1—C6—C50.7 (4)N3—C9—N2—C711.0 (3)
N1—C1—C6—C5178.8 (2)C10—C9—N2—C7171.5 (2)
C4—C5—C6—C10.9 (4)O3—C7—N2—C973.4 (3)
C5—C4—C7—N290.5 (3)C4—C7—N2—C9163.9 (2)
C3—C4—C7—N286.2 (3)N2—C9—N3—C13179.29 (19)
C5—C4—C7—O330.7 (3)C10—C9—N3—C131.9 (3)
C3—C4—C7—O3152.6 (2)C12—C13—N3—C90.0 (4)
N3—C9—C10—C112.5 (4)N2—C7—O3—C8165.83 (19)
N2—C9—C10—C11179.9 (2)C4—C7—O3—C873.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N3i0.87 (2)2.13 (2)2.976 (3)167 (2)
Symmetry code: (i) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC13H13N3O3
Mr259.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)10.661 (2), 14.153 (3), 9.0410 (18)
β (°) 110.70 (3)
V3)1276.1 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.32 × 0.26 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.969, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
2666, 2500, 1642
Rint0.026
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.131, 1.01
No. of reflections2500
No. of parameters214
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.19

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N3i0.87 (2)2.13 (2)2.976 (3)167 (2)
Symmetry code: (i) x, y+1/2, z1/2.
 

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