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

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 intra-molecular N-H⋯N contact occurs. In the crystal, the mol-ecules 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 = 242.24

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.175

S = 1.01

2070 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.18 e Å−3

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) ▶.

Crystal structure: contains datablock(s) D, I. DOI: 10.1107/S1600536813015481/hb7085sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015481/hb7085Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H10N4O2	Dx = 1.422 Mg m−3
Mr = 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

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

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(Fo2) + (0.090P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2070 reflections	Δρmax = 0.19 e Å−3
164 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) .