4-Nitro-N^2^-(pyridin-4-ylmethylidene)benzene-1,2-diamine

Liu, G.-L.; Sun, J.; Zhang, J.-C.; Mei, J.; Guo, C.

doi:10.1107/S1600536813015481

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1073

https://doi.org/10.1107/S1600536813015481

Open

access

4-Nitro-N^2^-(pyridin-4-ylmethylidene)benzene-1,2-diamine

Guang-Lin Liu,^a Jun Sun,^a Jing-Chao Zhang,^a Jie Mei ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No.5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 20 May 2013; accepted 4 June 2013; online 12 June 2013)

In the title compound, C₁₂H₁₀N₄O₂, the dihedral angle between the aromatic rings is 43.18 (16)°. The nitro group is rotated from its attached ring by 7.8 (2)° and a short intramolecular N—H⋯N contact occurs. In the crystal, the molecules are linked by N—H⋯N and C—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For the synthesis, see: Luo et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₀N₄O₂
M_r = 242.24
Monoclinic, C 2/c
a = 21.324 (4) Å
b = 9.1480 (18) Å
c = 12.950 (3) Å
β = 116.36 (3)°
V = 2263.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.970, T_max = 0.990
2128 measured reflections
2070 independent reflections
1247 reflections with I > 2σ(I)
R_int = 0.038
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.175
S = 1.01
2070 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.19 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
N2—H2A⋯N4ⁱ	0.86	2.42	3.091 (3)	135
N2—H2B⋯N3	0.86	2.42	2.751 (3)	103
C10—H10A⋯O1ⁱⁱ	0.93	2.49	3.156 (5)	128
Symmetry codes: (i) $[-x+1, y+1, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks D, I. DOI: https://doi.org/10.1107/S1600536813015481/hb7085sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015481/hb7085Isup2.hkl

checkCIF report

Related literature top

For the synthesis, see: Luo et al. (2009).

Experimental top

The title compound, (I), which may have applications as a metal fluoresence probe, was prepared by the literature method (Luo et al., 2009). Yellow blocks were obtained by dissolving (I) (0.18 g, 1.0mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature.

Structure description top

For the synthesis, see: Luo et al. (2009).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title molecule.

4-Nitro-N²-(pyridin-4-ylmethylidene)benzene-1,2-diamine top

Crystal data top

C₁₂H₁₀N₄O₂	D_x = 1.422 Mg m⁻³
M_r = 242.24	Melting point: 449.65 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.324 (4) Å	Cell parameters from 25 reflections
b = 9.1480 (18) Å	θ = 10–13°
c = 12.950 (3) Å	µ = 0.10 mm⁻¹
β = 116.36 (3)°	T = 293 K
V = 2263.5 (8) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.10 mm
F(000) = 1008

Data collection top

Enraf–Nonius CAD-4 diffractometer	1247 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.4°, θ_min = 2.1°
ω/2θ scans	h = 0→25
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.970, T_max = 0.990	l = −15→14
2128 measured reflections	3 standard reflections every 200 reflections
2070 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.090P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2070 reflections	Δρ_max = 0.19 e Å⁻³
164 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (12)

Crystal data top

C₁₂H₁₀N₄O₂	V = 2263.5 (8) Å³
M_r = 242.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.324 (4) Å	µ = 0.10 mm⁻¹
b = 9.1480 (18) Å	T = 293 K
c = 12.950 (3) Å	0.30 × 0.20 × 0.10 mm
β = 116.36 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1247 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.038
T_min = 0.970, T_max = 0.990	3 standard reflections every 200 reflections
2128 measured reflections	intensity decay: 1%
2070 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.01	Δρ_max = 0.19 e Å⁻³
2070 reflections	Δρ_min = −0.18 e Å⁻³
164 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
C1	0.32477 (14)	0.2795 (3)	−0.0542 (3)	0.0521 (8)
H1A	0.3229	0.2145	−0.1108	0.062*
N1	0.23039 (15)	0.4169 (4)	−0.2041 (3)	0.0792 (10)
O1	0.18599 (16)	0.5126 (4)	−0.2272 (3)	0.1194 (12)
N2	0.42131 (15)	0.3378 (3)	0.2557 (2)	0.0666 (8)
H2A	0.4219	0.3980	0.3072	0.080*
H2B	0.4499	0.2652	0.2754	0.080*
C2	0.27963 (16)	0.3970 (4)	−0.0840 (3)	0.0596 (9)
O2	0.23537 (15)	0.3379 (4)	−0.2766 (3)	0.0991 (10)
N3	0.42154 (12)	0.1420 (2)	0.09465 (19)	0.0461 (6)
C3	0.28139 (17)	0.4952 (4)	−0.0015 (4)	0.0714 (11)
H3B	0.2506	0.5740	−0.0223	0.086*
C4	0.32854 (17)	0.4753 (3)	0.1102 (4)	0.0664 (10)
H4A	0.3297	0.5414	0.1656	0.080*
N4	0.53086 (14)	−0.3605 (2)	0.1282 (2)	0.0546 (7)
C5	0.37562 (15)	0.3574 (3)	0.1443 (3)	0.0526 (8)
C6	0.37257 (14)	0.2579 (3)	0.0586 (2)	0.0455 (7)
C7	0.40423 (15)	0.0216 (3)	0.0405 (2)	0.0472 (7)
H7A	0.3597	0.0141	−0.0205	0.057*
C8	0.45009 (14)	−0.1054 (3)	0.0682 (2)	0.0440 (7)
C9	0.52046 (15)	−0.1025 (3)	0.1456 (2)	0.0475 (8)
H9A	0.5420	−0.0148	0.1789	0.057*
C10	0.55786 (15)	−0.2301 (3)	0.1725 (2)	0.0501 (7)
H10A	0.6050	−0.2258	0.2247	0.060*
C11	0.46362 (17)	−0.3624 (3)	0.0523 (3)	0.0578 (9)
H11A	0.4435	−0.4513	0.0194	0.069*
C12	0.42246 (16)	−0.2395 (3)	0.0201 (3)	0.0541 (8)
H12A	0.3759	−0.2464	−0.0341	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0439 (16)	0.0497 (17)	0.0602 (19)	0.0008 (14)	0.0209 (15)	0.0038 (15)
N1	0.0479 (17)	0.081 (2)	0.093 (3)	0.0097 (17)	0.0174 (18)	0.035 (2)
O1	0.0750 (18)	0.108 (2)	0.143 (3)	0.0420 (18)	0.0195 (18)	0.053 (2)
N2	0.0734 (19)	0.0603 (17)	0.0600 (18)	−0.0034 (15)	0.0241 (15)	−0.0172 (14)
C2	0.0397 (16)	0.056 (2)	0.075 (2)	0.0068 (15)	0.0181 (16)	0.0182 (17)
O2	0.0711 (19)	0.129 (3)	0.072 (2)	0.0121 (17)	0.0095 (15)	0.0210 (18)
N3	0.0456 (14)	0.0417 (14)	0.0456 (14)	0.0029 (11)	0.0154 (11)	0.0011 (11)
C3	0.0437 (18)	0.047 (2)	0.118 (3)	0.0074 (15)	0.031 (2)	0.014 (2)
C4	0.057 (2)	0.0462 (19)	0.102 (3)	−0.0031 (16)	0.041 (2)	−0.0124 (19)
N4	0.0548 (16)	0.0442 (15)	0.0627 (17)	0.0053 (12)	0.0242 (14)	0.0004 (12)
C5	0.0489 (17)	0.0417 (17)	0.070 (2)	−0.0083 (14)	0.0285 (17)	−0.0072 (15)
C6	0.0416 (15)	0.0404 (15)	0.0510 (17)	−0.0003 (13)	0.0174 (14)	0.0020 (13)
C7	0.0415 (15)	0.0455 (17)	0.0451 (16)	−0.0009 (13)	0.0106 (13)	0.0002 (13)
C8	0.0461 (16)	0.0438 (17)	0.0389 (15)	0.0014 (13)	0.0160 (13)	0.0006 (12)
C9	0.0471 (17)	0.0437 (17)	0.0465 (17)	−0.0015 (13)	0.0159 (14)	−0.0017 (13)
C10	0.0442 (16)	0.0512 (18)	0.0503 (17)	0.0023 (14)	0.0170 (13)	0.0015 (14)
C11	0.064 (2)	0.0414 (18)	0.063 (2)	−0.0051 (16)	0.0235 (17)	−0.0064 (15)
C12	0.0486 (17)	0.0504 (19)	0.0527 (17)	−0.0013 (15)	0.0129 (14)	−0.0052 (15)

Geometric parameters (Å, º) top

C1—C6	1.375 (4)	C4—H4A	0.9300
C1—C2	1.379 (4)	N4—C11	1.331 (4)
C1—H1A	0.9300	N4—C10	1.338 (3)
N1—O1	1.225 (4)	C5—C6	1.414 (4)
N1—O2	1.226 (4)	C7—C8	1.457 (4)
N1—C2	1.450 (5)	C7—H7A	0.9300
N2—C5	1.347 (4)	C8—C12	1.383 (4)
N2—H2A	0.8600	C8—C9	1.386 (4)
N2—H2B	0.8600	C9—C10	1.368 (4)
C2—C3	1.384 (5)	C9—H9A	0.9300
N3—C7	1.269 (3)	C10—H10A	0.9300
N3—C6	1.414 (3)	C11—C12	1.372 (4)
C3—C4	1.359 (5)	C11—H11A	0.9300
C3—H3B	0.9300	C12—H12A	0.9300
C4—C5	1.405 (4)

C6—C1—C2	120.4 (3)	C4—C5—C6	118.1 (3)
C6—C1—H1A	119.8	C1—C6—C5	119.7 (3)
C2—C1—H1A	119.8	C1—C6—N3	123.3 (3)
O1—N1—O2	123.7 (4)	C5—C6—N3	117.0 (2)
O1—N1—C2	117.7 (4)	N3—C7—C8	123.8 (3)
O2—N1—C2	118.6 (3)	N3—C7—H7A	118.1
C5—N2—H2A	120.0	C8—C7—H7A	118.1
C5—N2—H2B	120.0	C12—C8—C9	116.8 (3)
H2A—N2—H2B	120.0	C12—C8—C7	119.4 (2)
C1—C2—C3	120.9 (3)	C9—C8—C7	123.7 (3)
C1—C2—N1	118.7 (4)	C10—C9—C8	119.3 (3)
C3—C2—N1	120.3 (3)	C10—C9—H9A	120.4
C7—N3—C6	118.5 (2)	C8—C9—H9A	120.4
C4—C3—C2	119.3 (3)	N4—C10—C9	124.1 (3)
C4—C3—H3B	120.4	N4—C10—H10A	118.0
C2—C3—H3B	120.4	C9—C10—H10A	118.0
C3—C4—C5	121.7 (3)	N4—C11—C12	123.2 (3)
C3—C4—H4A	119.2	N4—C11—H11A	118.4
C5—C4—H4A	119.2	C12—C11—H11A	118.4
C11—N4—C10	116.5 (2)	C11—C12—C8	120.2 (3)
N2—C5—C4	120.9 (3)	C11—C12—H12A	119.9
N2—C5—C6	121.0 (3)	C8—C12—H12A	119.9

C6—C1—C2—C3	0.0 (5)	N2—C5—C6—N3	−2.8 (4)
C6—C1—C2—N1	179.5 (3)	C4—C5—C6—N3	178.6 (2)
O1—N1—C2—C1	172.5 (3)	C7—N3—C6—C1	−32.3 (4)
O2—N1—C2—C1	−7.6 (5)	C7—N3—C6—C5	149.7 (3)
O1—N1—C2—C3	−8.0 (5)	C6—N3—C7—C8	179.3 (2)
O2—N1—C2—C3	171.9 (3)	N3—C7—C8—C12	167.2 (3)
C1—C2—C3—C4	0.3 (5)	N3—C7—C8—C9	−9.4 (4)
N1—C2—C3—C4	−179.2 (3)	C12—C8—C9—C10	−1.7 (4)
C2—C3—C4—C5	0.0 (5)	C7—C8—C9—C10	175.0 (3)
C3—C4—C5—N2	−178.9 (3)	C11—N4—C10—C9	1.1 (4)
C3—C4—C5—C6	−0.4 (4)	C8—C9—C10—N4	0.2 (4)
C2—C1—C6—C5	−0.4 (4)	C10—N4—C11—C12	−0.7 (5)
C2—C1—C6—N3	−178.3 (3)	N4—C11—C12—C8	−0.9 (5)
N2—C5—C6—C1	179.1 (3)	C9—C8—C12—C11	2.0 (4)
C4—C5—C6—C1	0.6 (4)	C7—C8—C12—C11	−174.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N4ⁱ	0.86	2.42	3.091 (3)	135
N2—H2B···N3	0.86	2.42	2.751 (3)	103
C10—H10A···O1ⁱⁱ	0.93	2.49	3.156 (5)	128

Symmetry codes: (i) −x+1, y+1, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₄O₂
M_r	242.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	21.324 (4), 9.1480 (18), 12.950 (3)
β (°)	116.36 (3)
V (Å³)	2263.5 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.970, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2128, 2070, 1247
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.175, 1.01
No. of reflections	2070
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.18

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N4ⁱ	0.86	2.42	3.091 (3)	135
N2—H2B···N3	0.86	2.42	2.751 (3)	103
C10—H10A···O1ⁱⁱ	0.93	2.49	3.156 (5)	128

Symmetry codes: (i) −x+1, y+1, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The authors thank the Center of Test and Analysis, Nanjing University, for support.

References

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Luo, T. T., Wu, H. C. & Jao, Y. C. (2009). Angew. Chem. 48, 9461–9464. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar