organic compounds
N-[(pyridin-2-yl)methylidene]aniline
of 4-nitro-aDepartment of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok 65000, Thailand, and bDepartment of Physics, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani 12120, Thailand
*Correspondence e-mail: kc@tu.ac.th
The title compound, C12H9N3O2, adopts an E conformation at the imine double bond. The pyridyl ring makes a dihedral angle of 47.78 (5)° with the benzene ring, indicating the molecule is twisted. In the crystal, molecules are π–π stacked into columns parallel to [100], with an interplanar separation of 3.8537 (8) Å, corresponding to the length of the a axis. The chains are further linked via weak C—H⋯O and C—H⋯N hydrogen bonds, forming two-dimensional sheets parallel to (010). The sheets interact by van der Waals interactions.
Keywords: crystal structure; hydrogen bonds; Schiff base; π–π stacking.
CCDC reference: 1423407
1. Related literature
For related crystal structures, see: Zheng & Lee (2012); Marjani et al. (2011); Tzimopoulos et al. (2010); Heinze & Bueno Toro (2004).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2014); cell SAINT (Bruker, 2014); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).
Supporting information
CCDC reference: 1423407
10.1107/S2056989015016928/tk5383sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016928/tk5383Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016928/tk5383Isup3.cdx
Supporting information file. DOI: 10.1107/S2056989015016928/tk5383Isup4.cml
At room temperature, 2-pyridinecarboxaldehyde (1.90 ml, 0.02 mol) was added to a benzene solution (100 ml) of 4-nitroaniline (2.76 g, 0.02 mol), with a few drops of acetic acid added as catalyst. The reaction mixture was stirred under reflux at 110 °C. After 6 h of reflux, the yellow solution was neutralized with Na2CO3 (2 mmol), filtered, and concentrated to dryness in vacuo. The residue was recrystallized from a mixture of CH2Cl2 and petroleum ether (2:1, v/v) to give light-yellow crystalline solid of (I).
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).Fig. 1. The molecular structure of (I), showing 35% probability displacement ellipsoids nd atom labels. | |
Fig. 2. A packing view of (I) along (010). Hydrogen bonds are shown as dashed lines. |
C12H9N3O2 | F(000) = 472 |
Mr = 227.22 | Dx = 1.412 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8573 (8) Å | θ = 3.4–25.0° |
b = 20.334 (4) Å | µ = 0.10 mm−1 |
c = 13.629 (3) Å | T = 296 K |
β = 90.57 (3)° | Block, light-yellow |
V = 1068.9 (4) Å3 | 0.22 × 0.14 × 0.14 mm |
Z = 4 |
Bruker D8 QUEST CMOS diffractometer | 1389 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 28.8°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −5→5 |
Tmin = 0.983, Tmax = 0.986 | k = −27→26 |
4963 measured reflections | l = −18→18 |
2729 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.0721P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
2729 reflections | Δρmax = 0.15 e Å−3 |
154 parameters | Δρmin = −0.18 e Å−3 |
0 restraints |
C12H9N3O2 | V = 1068.9 (4) Å3 |
Mr = 227.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 3.8573 (8) Å | µ = 0.10 mm−1 |
b = 20.334 (4) Å | T = 296 K |
c = 13.629 (3) Å | 0.22 × 0.14 × 0.14 mm |
β = 90.57 (3)° |
Bruker D8 QUEST CMOS diffractometer | 2729 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 1389 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.986 | Rint = 0.044 |
4963 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.15 e Å−3 |
2729 reflections | Δρmin = −0.18 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.1083 (5) | 0.13951 (9) | 0.12132 (11) | 0.0956 (6) | |
O2 | 0.8270 (5) | 0.22866 (8) | 0.14401 (10) | 0.0803 (5) | |
N1 | 0.7398 (4) | 0.15745 (8) | 0.80644 (11) | 0.0590 (5) | |
N2 | 0.7157 (4) | 0.09779 (7) | 0.56225 (11) | 0.0514 (4) | |
N3 | 0.9470 (5) | 0.17696 (9) | 0.17367 (11) | 0.0593 (5) | |
C1 | 0.6529 (6) | 0.14026 (10) | 0.89705 (15) | 0.0665 (6) | |
H1 | 0.7013 | 0.1697 | 0.9476 | 0.080* | |
C2 | 0.4961 (6) | 0.08178 (10) | 0.92062 (15) | 0.0649 (6) | |
H2 | 0.4409 | 0.0721 | 0.9853 | 0.078* | |
C3 | 0.4229 (5) | 0.03823 (10) | 0.84726 (14) | 0.0608 (5) | |
H3 | 0.3171 | −0.0018 | 0.8611 | 0.073* | |
C4 | 0.5083 (5) | 0.05437 (9) | 0.75229 (13) | 0.0515 (5) | |
H4 | 0.4605 | 0.0256 | 0.7008 | 0.062* | |
C5 | 0.6660 (5) | 0.11411 (8) | 0.73519 (12) | 0.0460 (4) | |
C6 | 0.7641 (5) | 0.13469 (8) | 0.63552 (13) | 0.0488 (5) | |
H6 | 0.8641 | 0.1758 | 0.6265 | 0.059* | |
C7 | 0.7881 (5) | 0.12104 (8) | 0.46689 (12) | 0.0453 (4) | |
C8 | 0.9466 (5) | 0.07832 (8) | 0.40174 (13) | 0.0508 (5) | |
H8 | 1.0149 | 0.0367 | 0.4228 | 0.061* | |
C9 | 1.0034 (5) | 0.09701 (9) | 0.30649 (13) | 0.0506 (5) | |
H9 | 1.1141 | 0.0688 | 0.2632 | 0.061* | |
C10 | 0.8940 (5) | 0.15815 (8) | 0.27591 (12) | 0.0459 (5) | |
C11 | 0.7340 (5) | 0.20177 (8) | 0.33848 (13) | 0.0489 (5) | |
H11 | 0.6609 | 0.2428 | 0.3163 | 0.059* | |
C12 | 0.6854 (5) | 0.18309 (8) | 0.43442 (13) | 0.0494 (5) | |
H12 | 0.5828 | 0.2122 | 0.4780 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1297 (16) | 0.1088 (13) | 0.0488 (9) | 0.0354 (12) | 0.0238 (9) | −0.0004 (9) |
O2 | 0.1152 (14) | 0.0682 (10) | 0.0575 (9) | 0.0082 (9) | 0.0074 (8) | 0.0176 (8) |
N1 | 0.0777 (12) | 0.0518 (9) | 0.0473 (9) | 0.0002 (8) | −0.0048 (8) | −0.0048 (7) |
N2 | 0.0641 (11) | 0.0471 (8) | 0.0431 (9) | −0.0009 (7) | 0.0031 (7) | −0.0005 (7) |
N3 | 0.0723 (12) | 0.0635 (11) | 0.0421 (9) | −0.0019 (9) | 0.0024 (8) | 0.0009 (8) |
C1 | 0.0924 (17) | 0.0614 (13) | 0.0455 (12) | 0.0092 (12) | −0.0062 (11) | −0.0079 (9) |
C2 | 0.0821 (16) | 0.0690 (14) | 0.0438 (11) | 0.0121 (12) | 0.0072 (10) | 0.0064 (10) |
C3 | 0.0689 (14) | 0.0559 (11) | 0.0576 (13) | −0.0003 (10) | 0.0044 (10) | 0.0096 (10) |
C4 | 0.0591 (12) | 0.0471 (11) | 0.0483 (11) | 0.0026 (9) | −0.0018 (8) | −0.0016 (8) |
C5 | 0.0531 (11) | 0.0421 (9) | 0.0427 (10) | 0.0063 (8) | −0.0015 (8) | −0.0017 (8) |
C6 | 0.0544 (12) | 0.0422 (9) | 0.0497 (11) | −0.0014 (8) | −0.0001 (9) | 0.0002 (8) |
C7 | 0.0542 (11) | 0.0413 (9) | 0.0402 (10) | −0.0055 (8) | −0.0001 (8) | −0.0005 (7) |
C8 | 0.0680 (13) | 0.0385 (9) | 0.0459 (10) | 0.0044 (9) | −0.0015 (9) | −0.0013 (8) |
C9 | 0.0595 (12) | 0.0473 (10) | 0.0449 (10) | 0.0058 (9) | 0.0026 (9) | −0.0085 (8) |
C10 | 0.0529 (12) | 0.0460 (10) | 0.0390 (10) | −0.0046 (8) | 0.0003 (8) | −0.0006 (8) |
C11 | 0.0615 (12) | 0.0375 (9) | 0.0476 (11) | 0.0013 (8) | 0.0000 (8) | 0.0000 (8) |
C12 | 0.0608 (12) | 0.0423 (10) | 0.0452 (10) | 0.0018 (9) | 0.0053 (8) | −0.0055 (8) |
O1—N3 | 1.219 (2) | C4—C5 | 1.380 (3) |
O2—N3 | 1.216 (2) | C5—C6 | 1.474 (3) |
N1—C1 | 1.330 (3) | C6—H6 | 0.9300 |
N1—C5 | 1.340 (2) | C7—C8 | 1.388 (2) |
N2—C6 | 1.262 (2) | C7—C12 | 1.393 (2) |
N2—C7 | 1.413 (2) | C8—H8 | 0.9300 |
N3—C10 | 1.461 (2) | C8—C9 | 1.372 (3) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C1—C2 | 1.374 (3) | C9—C10 | 1.376 (2) |
C2—H2 | 0.9300 | C10—C11 | 1.380 (2) |
C2—C3 | 1.363 (3) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C11—C12 | 1.376 (3) |
C3—C4 | 1.378 (3) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | ||
C1—N1—C5 | 116.52 (17) | N2—C6—H6 | 119.2 |
C6—N2—C7 | 119.98 (15) | C5—C6—H6 | 119.2 |
O1—N3—C10 | 118.14 (17) | C8—C7—N2 | 118.10 (15) |
O2—N3—O1 | 122.71 (16) | C8—C7—C12 | 119.28 (16) |
O2—N3—C10 | 119.14 (17) | C12—C7—N2 | 122.47 (16) |
N1—C1—H1 | 118.0 | C7—C8—H8 | 119.8 |
N1—C1—C2 | 124.10 (19) | C9—C8—C7 | 120.47 (16) |
C2—C1—H1 | 118.0 | C9—C8—H8 | 119.8 |
C1—C2—H2 | 120.7 | C8—C9—H9 | 120.5 |
C3—C2—C1 | 118.63 (19) | C8—C9—C10 | 119.04 (16) |
C3—C2—H2 | 120.7 | C10—C9—H9 | 120.5 |
C2—C3—H3 | 120.5 | C9—C10—N3 | 118.69 (16) |
C2—C3—C4 | 118.98 (19) | C9—C10—C11 | 122.07 (16) |
C4—C3—H3 | 120.5 | C11—C10—N3 | 119.24 (16) |
C3—C4—H4 | 120.7 | C10—C11—H11 | 120.8 |
C3—C4—C5 | 118.57 (17) | C12—C11—C10 | 118.40 (15) |
C5—C4—H4 | 120.7 | C12—C11—H11 | 120.8 |
N1—C5—C4 | 123.20 (17) | C7—C12—H12 | 119.6 |
N1—C5—C6 | 115.24 (16) | C11—C12—C7 | 120.71 (16) |
C4—C5—C6 | 121.55 (16) | C11—C12—H12 | 119.6 |
N2—C6—C5 | 121.55 (16) | ||
O1—N3—C10—C9 | −5.2 (3) | C3—C4—C5—C6 | −179.92 (17) |
O1—N3—C10—C11 | 175.38 (18) | C4—C5—C6—N2 | −1.8 (3) |
O2—N3—C10—C9 | 174.23 (18) | C5—N1—C1—C2 | 0.1 (3) |
O2—N3—C10—C11 | −5.2 (3) | C6—N2—C7—C8 | 139.41 (19) |
N1—C1—C2—C3 | −0.1 (3) | C6—N2—C7—C12 | −45.1 (3) |
N1—C5—C6—N2 | 178.44 (17) | C7—N2—C6—C5 | 175.13 (15) |
N2—C7—C8—C9 | 175.98 (17) | C7—C8—C9—C10 | −1.4 (3) |
N2—C7—C12—C11 | −174.32 (16) | C8—C7—C12—C11 | 1.1 (3) |
N3—C10—C11—C12 | 179.77 (15) | C8—C9—C10—N3 | −178.34 (16) |
C1—N1—C5—C4 | 0.0 (3) | C8—C9—C10—C11 | 1.1 (3) |
C1—N1—C5—C6 | 179.76 (17) | C9—C10—C11—C12 | 0.3 (3) |
C1—C2—C3—C4 | −0.1 (3) | C10—C11—C12—C7 | −1.5 (3) |
C2—C3—C4—C5 | 0.2 (3) | C12—C7—C8—C9 | 0.3 (3) |
C3—C4—C5—N1 | −0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.93 | 2.89 | 3.510 (3) | 125 |
C2—H2···O1ii | 0.93 | 2.65 | 3.343 (3) | 132 |
C6—H6···O2iii | 0.93 | 2.65 | 3.527 (2) | 158 |
C11—H11···N1iv | 0.93 | 2.60 | 3.465 (2) | 155 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z+1; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.93 | 2.89 | 3.510 (3) | 125 |
C2—H2···O1ii | 0.93 | 2.65 | 3.343 (3) | 132 |
C6—H6···O2iii | 0.93 | 2.65 | 3.527 (2) | 158 |
C11—H11···N1iv | 0.93 | 2.60 | 3.465 (2) | 155 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z+1; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
This research was supported financially by a research career development grant (No. RSA5780056) from the Thailand Research Fund.
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