Crystal structure of 4-nitro-N-[(pyridin-2-yl)methyl­idene]aniline

Saphu, W.; Chainok, K.

doi:10.1107/S2056989015016928

organic compounds

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Volume 71| Part 10| October 2015| Page o760

doi:10.1107/S2056989015016928

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Crystal structure of 4-nitro-N-[(pyridin-2-yl)methylidene]aniline

Watcharin Saphu ^a and Kittipong Chainok ^b ^*

^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

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 2 September 2015; accepted 10 September 2015; online 17 September 2015)

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

C₁₂H₉N₃O₂
M_r = 227.22
Monoclinic, P 2₁ /n
a = 3.8573 (8) Å
b = 20.334 (4) Å
c = 13.629 (3) Å
β = 90.57 (3)°
V = 1068.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.22 × 0.14 × 0.14 mm

2.2. Data collection

Bruker D8 QUEST CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ) T_min = 0.983, T_max = 0.986
4963 measured reflections
2729 independent reflections
1389 reflections with I > 2σ(I)
R_int = 0.044

2.3. Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.146
S = 0.96
2729 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.65	3.343 (3)	132
C6—H6⋯O2ⁱⁱ	0.93	2.65	3.527 (2)	158
C11—H11⋯N1ⁱⁱⁱ	0.93	2.60	3.465 (2)	155
Symmetry codes: (i) x-1, y, z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2014); cell refinement: 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

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015016928/tk5383sup1.cif

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

checkCIF report

Synthesis and crystallization top

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).

Refinement top

The C–bound hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atom positions with a C—H distances of 0.93 Å, and with U_iso(H) = 1.2U_eq(C).

Related literature top

For related crystal structures, see: Zheng & Lee (2012); Marjani et al. (2011); Tzimopoulos et al. (2010); Heinze & Bueno Toro (2004).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

Figures top

	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.

4-Nitro-N-[(pyridin-2-yl)methylidene]aniline top

Crystal data top

C₁₂H₉N₃O₂	F(000) = 472
M_r = 227.22	D_x = 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

Data collection top

Bruker D8 QUEST CMOS diffractometer	1389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 28.8°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −5→5
T_min = 0.983, T_max = 0.986	k = −27→26
4963 measured reflections	l = −18→18
2729 independent reflections

Refinement top

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(F_o²) + (0.0721P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
2729 reflections	Δρ_max = 0.15 e Å⁻³
154 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints

Crystal data top

C₁₂H₉N₃O₂	V = 1068.9 (4) Å³
M_r = 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)°

Data collection top

Bruker D8 QUEST CMOS diffractometer	2729 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	1389 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.986	R_int = 0.044
4963 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.96	Δρ_max = 0.15 e Å⁻³
2729 reflections	Δρ_min = −0.18 e Å⁻³
154 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···N1^iv	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.

Hydrogen-bond geometry (Å, º) top

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···N1^iv	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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Page o760

doi:10.1107/S2056989015016928

Open

access