2-[2-(4-Nitro­phenyl)hy­dra­zin­yl­idene]malononitrile

Han, L.-N.; Zhang, M.; Lu, R.-Z.; Wei, W.-B.; Wang, H.-B.

doi:10.1107/S1600536809053136

organic compounds

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Volume 66| Part 1| January 2010| Page o196

doi:10.1107/S1600536809053136

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2-[2-(4-Nitrophenyl)hydrazinylidene]malononitrile

Lu-Na Han,^a,^b Min Zhang,^a,^b Ran-Zhe Lu,^a,^b Wen-Bin Wei ^a,^b and Hai-Bo Wang ^b ^*

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

(Received 1 December 2009; accepted 10 December 2009; online 19 December 2009)

The title compound, C₁₀H₈N₈, is close to planar (r.m.s. deviation from the mean plane = 0.118 Å). In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R₂²(12) loops.

Related literature

For background to the use of the title compound as a dye, see: Tsai (2005 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₈N₄
M_r = 184.20
Monoclinic, P 2₁ /n
a = 11.961 (2) Å
b = 5.8310 (12) Å
c = 14.569 (3) Å
β = 110.98 (3)°
V = 948.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 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 = 0.975, T_max = 0.992
1797 measured reflections
1712 independent reflections
1191 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections every 200 reflections
intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.172
S = 1.01
1712 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N2ⁱ	0.86	2.36	3.174 (3)	157
Symmetry code: (i) -x+1, -y+1, -z+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 global, I. DOI: 10.1107/S1600536809053136/hb5262sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053136/hb5262Isup2.hkl

checkCIF report

Related literature top

For background to the use of the title compound as a dye, see: Tsai (2005). For reference structural data, see: Allen et al. (1987).

Experimental top

A hydrochloric acid solution (6 ml) of p-toluidine (1.07 g, 0.01 mol) and an aqueous solution (3 ml) of sodium nitrite (0.72 g, 0.0105 mol) were mixed and stirred at 273 K for 1h, followed by the addition of an aqueous solution (10 ml) of malononitrile (0.66 g, 0.01 mol) and further stirring at 273 K for 2 h. The resulting product was filtered and washed with water, dried, and recrystallized from ethanol to give the title compound as yellow crystals (yield; 78%, m.p. 409 K). Yellow blocks of (I) were obtained by slow evaporation of an ethyl acetate solution.

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 (I) showing 50% displacement ellipsoids.
	Fig. 2. The packing for (I).

2-[2-(4-Nitrophenyl)hydrazinylidene]malononitrile top

Crystal data top

C₁₀H₈N₄	F(000) = 384
M_r = 184.20	D_x = 1.289 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 409 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.961 (2) Å	Cell parameters from 25 reflections
b = 5.8310 (12) Å	θ = 10–13°
c = 14.569 (3) Å	µ = 0.08 mm⁻¹
β = 110.98 (3)°	T = 293 K
V = 948.7 (3) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1191 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.975, T_max = 0.992	l = −17→16
1797 measured reflections	3 standard reflections every 200 reflections
1712 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.170P] where P = (F_o² + 2F_c²)/3
1712 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₀H₈N₄	V = 948.7 (3) Å³
M_r = 184.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.961 (2) Å	µ = 0.08 mm⁻¹
b = 5.8310 (12) Å	T = 293 K
c = 14.569 (3) Å	0.30 × 0.20 × 0.10 mm
β = 110.98 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1191 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.975, T_max = 0.992	3 standard reflections every 200 reflections
1797 measured reflections	intensity decay: 1%
1712 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
1712 reflections	Δρ_min = −0.25 e Å⁻³
127 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	0.2746 (2)	−0.1077 (5)	0.8662 (2)	0.0513 (6)
N1	0.2481 (2)	−0.2797 (4)	0.8277 (2)	0.0739 (8)
N2	0.5027 (2)	0.3075 (4)	0.92534 (19)	0.0692 (7)
C2	0.4155 (2)	0.2173 (4)	0.91795 (18)	0.0489 (6)
N3	0.24161 (17)	0.1817 (3)	0.96436 (14)	0.0445 (5)
C3	0.3086 (2)	0.1060 (4)	0.91713 (17)	0.0448 (6)
N4	0.26745 (16)	0.3729 (3)	1.01369 (14)	0.0445 (5)
H4A	0.3268	0.4542	1.0123	0.053*
C4	0.19927 (19)	0.4484 (4)	1.06931 (16)	0.0406 (6)
C5	0.1092 (2)	0.3138 (4)	1.08016 (17)	0.0455 (6)
H5A	0.0907	0.1720	1.0492	0.055*
C6	0.0477 (2)	0.3931 (4)	1.13736 (18)	0.0486 (6)
H6A	−0.0128	0.3027	1.1445	0.058*
C7	0.0728 (2)	0.6037 (4)	1.18486 (17)	0.0461 (6)
C8	0.1624 (2)	0.7356 (4)	1.17157 (18)	0.0492 (6)
H8A	0.1806	0.8781	1.2019	0.059*
C9	0.2249 (2)	0.6599 (4)	1.11451 (18)	0.0468 (6)
H9A	0.2845	0.7512	1.1064	0.056*
C10	0.0070 (2)	0.6860 (5)	1.2494 (2)	0.0630 (8)
H10A	−0.0512	0.5734	1.2502	0.094*
H10B	−0.0327	0.8281	1.2241	0.094*
H10C	0.0629	0.7091	1.3150	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0532 (14)	0.0468 (15)	0.0609 (15)	−0.0056 (12)	0.0288 (12)	−0.0017 (13)
N1	0.0860 (18)	0.0582 (16)	0.0907 (19)	−0.0204 (13)	0.0476 (15)	−0.0187 (14)
N2	0.0589 (14)	0.0656 (16)	0.0930 (18)	−0.0156 (13)	0.0393 (13)	−0.0197 (14)
C2	0.0506 (15)	0.0408 (14)	0.0592 (15)	−0.0008 (12)	0.0244 (12)	−0.0060 (12)
N3	0.0498 (11)	0.0389 (12)	0.0464 (11)	−0.0051 (9)	0.0194 (9)	0.0010 (9)
C3	0.0432 (12)	0.0398 (13)	0.0539 (14)	−0.0042 (11)	0.0205 (11)	−0.0008 (11)
N4	0.0467 (11)	0.0377 (11)	0.0545 (12)	−0.0055 (9)	0.0246 (9)	0.0002 (9)
C4	0.0446 (12)	0.0355 (12)	0.0435 (12)	0.0002 (10)	0.0180 (10)	0.0053 (10)
C5	0.0470 (13)	0.0356 (13)	0.0546 (14)	−0.0059 (10)	0.0190 (11)	−0.0001 (11)
C6	0.0451 (13)	0.0475 (15)	0.0563 (14)	−0.0072 (11)	0.0219 (11)	0.0033 (12)
C7	0.0430 (13)	0.0475 (15)	0.0468 (13)	0.0037 (11)	0.0149 (10)	0.0057 (11)
C8	0.0549 (14)	0.0373 (13)	0.0556 (14)	−0.0026 (11)	0.0200 (12)	−0.0017 (11)
C9	0.0495 (13)	0.0367 (13)	0.0578 (14)	−0.0104 (11)	0.0236 (11)	−0.0005 (11)
C10	0.0573 (16)	0.0739 (19)	0.0632 (16)	0.0063 (14)	0.0281 (13)	−0.0021 (14)

Geometric parameters (Å, º) top

C1—N1	1.137 (3)	C5—H5A	0.9300
C1—C3	1.433 (3)	C6—C7	1.389 (3)
N2—C2	1.138 (3)	C6—H6A	0.9300
C2—C3	1.430 (3)	C7—C8	1.388 (3)
N3—N4	1.302 (3)	C7—C10	1.504 (3)
N3—C3	1.305 (3)	C8—C9	1.375 (3)
N4—C4	1.410 (3)	C8—H8A	0.9300
N4—H4A	0.8600	C9—H9A	0.9300
C4—C9	1.380 (3)	C10—H10A	0.9600
C4—C5	1.387 (3)	C10—H10B	0.9600
C5—C6	1.375 (3)	C10—H10C	0.9600

N1—C1—C3	178.5 (3)	C7—C6—H6A	118.9
N2—C2—C3	175.3 (3)	C8—C7—C6	117.4 (2)
N4—N3—C3	120.74 (19)	C8—C7—C10	120.9 (2)
N3—C3—C2	123.9 (2)	C6—C7—C10	121.7 (2)
N3—C3—C1	117.0 (2)	C9—C8—C7	121.4 (2)
C2—C3—C1	119.1 (2)	C9—C8—H8A	119.3
N3—N4—C4	120.83 (19)	C7—C8—H8A	119.3
N3—N4—H4A	119.6	C8—C9—C4	119.9 (2)
C4—N4—H4A	119.6	C8—C9—H9A	120.0
C9—C4—C5	120.0 (2)	C4—C9—H9A	120.0
C9—C4—N4	118.5 (2)	C7—C10—H10A	109.5
C5—C4—N4	121.4 (2)	C7—C10—H10B	109.5
C6—C5—C4	119.1 (2)	H10A—C10—H10B	109.5
C6—C5—H5A	120.5	C7—C10—H10C	109.5
C4—C5—H5A	120.5	H10A—C10—H10C	109.5
C5—C6—C7	122.1 (2)	H10B—C10—H10C	109.5
C5—C6—H6A	118.9

N4—N3—C3—C2	2.4 (4)	N4—C4—C5—C6	178.3 (2)
N4—N3—C3—C1	179.0 (2)	C4—C5—C6—C7	−0.1 (4)
N2—C2—C3—N3	45 (3)	C5—C6—C7—C8	0.9 (4)
N2—C2—C3—C1	−131 (3)	C5—C6—C7—C10	−178.4 (2)
N1—C1—C3—N3	−65 (10)	C6—C7—C8—C9	−0.7 (4)
N1—C1—C3—C2	112 (10)	C10—C7—C8—C9	178.6 (2)
C3—N3—N4—C4	−176.4 (2)	C7—C8—C9—C4	−0.2 (4)
N3—N4—C4—C9	−175.4 (2)	C5—C4—C9—C8	1.0 (3)
N3—N4—C4—C5	5.4 (3)	N4—C4—C9—C8	−178.1 (2)
C9—C4—C5—C6	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱ	0.86	2.36	3.174 (3)	157

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₄
M_r	184.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.961 (2), 5.8310 (12), 14.569 (3)
β (°)	110.98 (3)
V (Å³)	948.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.975, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	1797, 1712, 1191
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.172, 1.01
No. of reflections	1712
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

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
N4—H4A···N2ⁱ	0.86	2.36	3.174 (3)	157

Symmetry code: (i) −x+1, −y+1, −z+2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. 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
Tsai, P. S. (2005). Dyes Pigments, 11, 259–264. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o196

doi:10.1107/S1600536809053136

Open

access