2-(4-Nitro­benzyl­idene)malononitrile

Chang, M.-J.; Fang, T.-C.; Tsai, H.-Y.; Luo, M.-H.; Chen, K.-Y.

doi:10.1107/S1600536812008896

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o957

doi:10.1107/S1600536812008896

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2-(4-Nitrobenzylidene)malononitrile

Ming-Jen Chang,^a Tzu-Chien Fang,^a Hsing-Yang Tsai,^a Ming-Hui Luo ^a and Kew-Yu Chen ^a ^*

^aDepartment of Chemical Engineering, Feng Chia University, 40724 Taichung, Taiwan
^*Correspondence e-mail: kyuchen@fcu.edu.tw

(Received 13 January 2012; accepted 28 February 2012; online 3 March 2012)

In the title compound, C₁₀H₅N₃O₂, the benzylidenemalononitrile unit is nearly planar, with a maximum deviation of 0.129 (2) Å for a terminal N atom; the nitro group is approximately coplanar with the benzene ring [dihedral angle = 8.8 (3)°]. An intramolecular C—H⋯N hydrogen bond stabilizes the molecular conformation.

Related literature

For the preparation of the title compound, see: Baheti et al. (2011 ). For the spectroscopy and applications of benzylidenemalononitrile derivatives, see: Cao et al. (2010 ); Ding & Zhao (2010 ); Elinson et al. (2010 ); Herbivo et al. (2010 ); Shigemitsu et al. (2011 ); Ye et al. (2010 ). For related structures, see: El Brahmi et al. (2011 ); Karthikeyan et al. (2011 ); Mehdi et al. (2010 ); Ouzidan et al. (2011 ); Raza et al. (2010 ).

Experimental

Crystal data

C₁₀H₅N₃O₂
M_r = 199.17
Orthorhombic, P n a 2₁
a = 19.5557 (9) Å
b = 3.8732 (2) Å
c = 11.9823 (5) Å
V = 907.58 (7) Å³
Z = 4
Cu Kα radiation
μ = 0.89 mm⁻¹
T = 297 K
0.76 × 0.60 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.674, T_max = 1.000
3111 measured reflections
1517 independent reflections
1420 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.091
S = 1.06
1517 reflections
136 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 582 Friedel pairs
Flack parameter: −0.2 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N3	0.93	2.58	3.431 (3)	152

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008896/xu5449sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008896/xu5449Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008896/xu5449Isup3.cml

checkCIF report

Comment top

Organic compounds bearing benzylidenemalononitrile moieties have attracted considerable attention due to their potential applications in the design of molecular devices (Cao et al., 2010; Herbivo et al., 2010; Shigemitsu et al., 2011). In addition, the title compound and its derivatives have been used as potential precursors to prepare 5,7-diazaspiro[2,5]octane (Elinson et al., 2010), 2-amino-4H-chromene-3-carbonitrile (Ding et al., 2010) and 4H-pyran derivatives (Ye et al., 2010).

The molecular structure of the title compound is shown in Figure 1. The nitro group is close to being coplanar with the benzene ring (dihedral angle = 8.8 (3)°), which is consistent with previous studies (El Brahmi et al., 2011; Mehdi et al., 2010; Ouzidan et al., 2011; Raza et al., 2010). In addition, the benzylidenemalononitrile moiety is nearly planar with a maximum deviation of 0.129 (2))Å for atom N2 (Karthikeyan et al., 2011). An intramolecular C—H···N hydrogen bond stabilizes the molecular conformation.

Related literature top

For the preparation of the title compound, see: Baheti et al. (2011). For the spectroscopy and applications of benzylidenemalononitrile derivatives, see: Cao et al. (2010); Ding & Zhao (2010); Elinson et al. (2010); Herbivo et al. (2010); Shigemitsu et al. (2011); Ye et al. (2010). For related structures, see: El Brahmi et al. (2011); Karthikeyan et al. (2011); Mehdi et al. (2010); Ouzidan et al. (2011); Raza et al. (2010).

Experimental top

The title compound was synthesized by the Knoevenagel condensation of malononitrile with 4-nitrobenzaldehyde (Baheti et al., 2011). Colorless crystals suitable for the crystallographic studies reported here were isolated over a period of four weeks by slow evaporation from a chloroform solution.

Structure description top

For the preparation of the title compound, see: Baheti et al. (2011). For the spectroscopy and applications of benzylidenemalononitrile derivatives, see: Cao et al. (2010); Ding & Zhao (2010); Elinson et al. (2010); Herbivo et al. (2010); Shigemitsu et al. (2011); Ye et al. (2010). For related structures, see: El Brahmi et al. (2011); Karthikeyan et al. (2011); Mehdi et al. (2010); Ouzidan et al. (2011); Raza et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

2-(4-Nitrobenzylidene)propanedinitrile top

Crystal data top

C₁₀H₅N₃O₂	F(000) = 408
M_r = 199.17	D_x = 1.458 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 2320 reflections
a = 19.5557 (9) Å	θ = 3.7–71.5°
b = 3.8732 (2) Å	µ = 0.89 mm⁻¹
c = 11.9823 (5) Å	T = 297 K
V = 907.58 (7) Å³	Parallelepiped, colorless
Z = 4	0.76 × 0.60 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1517 independent reflections
Radiation source: fine-focus sealed tube	1420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 71.7°, θ_min = 4.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −24→15
T_min = 0.674, T_max = 1.000	k = −4→3
3111 measured reflections	l = −14→14

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0621P)² + 0.0168P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1517 reflections	Δρ_max = 0.13 e Å⁻³
136 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 582 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.2 (2)

Crystal data top

C₁₀H₅N₃O₂	V = 907.58 (7) Å³
M_r = 199.17	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 19.5557 (9) Å	µ = 0.89 mm⁻¹
b = 3.8732 (2) Å	T = 297 K
c = 11.9823 (5) Å	0.76 × 0.60 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1517 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1420 reflections with I > 2σ(I)
T_min = 0.674, T_max = 1.000	R_int = 0.016
3111 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.091	Δρ_max = 0.13 e Å⁻³
S = 1.06	Δρ_min = −0.16 e Å⁻³
1517 reflections	Absolute structure: Flack (1983), 582 Friedel pairs
136 parameters	Absolute structure parameter: −0.2 (2)
1 restraint

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.

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 > σ(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
O1	0.19540 (9)	1.1888 (6)	−0.10487 (14)	0.0798 (6)
O2	0.17348 (9)	1.4626 (5)	0.04698 (17)	0.0790 (6)
N1	0.21000 (8)	1.2840 (4)	−0.01057 (15)	0.0530 (4)
N2	0.61988 (11)	0.5187 (6)	0.25478 (17)	0.0672 (5)
N3	0.53572 (10)	0.5513 (7)	−0.07973 (17)	0.0743 (6)
C1	0.38494 (10)	0.9176 (5)	0.00650 (14)	0.0445 (4)
H1A	0.4165	0.8120	−0.0404	0.053*
C2	0.32231 (10)	1.0153 (5)	−0.03437 (15)	0.0449 (4)
H2A	0.3110	0.9738	−0.1086	0.054*
C3	0.27635 (9)	1.1752 (5)	0.03563 (14)	0.0405 (4)
C4	0.29078 (10)	1.2411 (5)	0.14638 (16)	0.0471 (5)
H4A	0.2591	1.3505	0.1922	0.056*
C5	0.35351 (10)	1.1396 (5)	0.18681 (15)	0.0447 (4)
H5A	0.3641	1.1811	0.2613	0.054*
C6	0.40158 (9)	0.9766 (4)	0.11918 (14)	0.0387 (4)
C7	0.46578 (10)	0.8685 (5)	0.17120 (14)	0.0415 (4)
H7A	0.4690	0.9154	0.2471	0.050*
C8	0.52069 (10)	0.7129 (4)	0.12720 (15)	0.0408 (4)
C9	0.57642 (11)	0.6105 (5)	0.19838 (16)	0.0478 (5)
C10	0.52915 (9)	0.6242 (6)	0.01095 (17)	0.0489 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0629 (11)	0.1147 (15)	0.0617 (10)	0.0171 (10)	−0.0179 (8)	−0.0051 (10)
O2	0.0585 (9)	0.0933 (14)	0.0852 (13)	0.0283 (9)	0.0017 (9)	−0.0088 (10)
N1	0.0435 (9)	0.0578 (10)	0.0577 (12)	0.0029 (7)	0.0036 (8)	0.0085 (9)
N2	0.0659 (12)	0.0835 (14)	0.0521 (10)	0.0141 (11)	−0.0141 (10)	0.0016 (9)
N3	0.0567 (11)	0.1197 (18)	0.0464 (10)	0.0190 (11)	−0.0019 (9)	−0.0203 (11)
C1	0.0467 (9)	0.0544 (11)	0.0324 (8)	0.0064 (8)	0.0011 (7)	−0.0025 (8)
C2	0.0470 (9)	0.0543 (11)	0.0334 (8)	0.0003 (8)	−0.0011 (8)	−0.0006 (8)
C3	0.0391 (8)	0.0424 (9)	0.0399 (10)	−0.0019 (7)	0.0009 (7)	0.0045 (7)
C4	0.0480 (10)	0.0506 (11)	0.0426 (10)	0.0023 (9)	0.0106 (8)	−0.0029 (9)
C5	0.0501 (10)	0.0529 (11)	0.0312 (8)	−0.0032 (8)	0.0027 (8)	−0.0009 (8)
C6	0.0447 (9)	0.0394 (9)	0.0321 (8)	−0.0029 (7)	0.0016 (7)	0.0030 (7)
C7	0.0515 (10)	0.0439 (11)	0.0290 (7)	−0.0038 (8)	−0.0023 (7)	0.0013 (7)
C8	0.0447 (9)	0.0407 (9)	0.0370 (9)	−0.0041 (8)	−0.0039 (7)	0.0024 (8)
C9	0.0502 (10)	0.0520 (11)	0.0413 (10)	0.0009 (9)	−0.0029 (9)	0.0011 (9)
C10	0.0401 (9)	0.0618 (12)	0.0449 (10)	0.0041 (8)	−0.0009 (8)	−0.0037 (9)

Geometric parameters (Å, º) top

O1—N1	1.222 (2)	C3—C4	1.381 (3)
O2—N1	1.210 (2)	C4—C5	1.376 (3)
N1—C3	1.472 (2)	C4—H4A	0.9300
N2—C9	1.143 (3)	C5—C6	1.393 (3)
N3—C10	1.130 (3)	C5—H5A	0.9300
C1—C2	1.372 (3)	C6—C7	1.463 (3)
C1—C6	1.407 (2)	C7—C8	1.339 (3)
C1—H1A	0.9300	C7—H7A	0.9300
C2—C3	1.377 (3)	C8—C10	1.444 (3)
C2—H2A	0.9300	C8—C9	1.440 (3)

O2—N1—O1	124.15 (19)	C4—C5—C6	121.76 (17)
O2—N1—C3	118.00 (17)	C4—C5—H5A	119.1
O1—N1—C3	117.85 (17)	C6—C5—H5A	119.1
C2—C1—C6	120.27 (17)	C5—C6—C1	118.41 (17)
C2—C1—H1A	119.9	C5—C6—C7	117.46 (17)
C6—C1—H1A	119.9	C1—C6—C7	124.11 (16)
C3—C2—C1	119.29 (17)	C8—C7—C6	130.47 (17)
C3—C2—H2A	120.4	C8—C7—H7A	114.8
C1—C2—H2A	120.4	C6—C7—H7A	114.8
C2—C3—C4	122.37 (17)	C7—C8—C10	125.34 (17)
C2—C3—N1	118.37 (15)	C7—C8—C9	119.85 (17)
C4—C3—N1	119.25 (16)	C10—C8—C9	114.78 (16)
C5—C4—C3	117.89 (18)	N2—C9—C8	177.8 (2)
C5—C4—H4A	121.1	N3—C10—C8	179.3 (3)
C3—C4—H4A	121.1

C6—C1—C2—C3	0.8 (3)	C3—C4—C5—C6	0.2 (3)
C1—C2—C3—C4	−0.2 (3)	C4—C5—C6—C1	0.4 (3)
C1—C2—C3—N1	178.79 (16)	C4—C5—C6—C7	−177.94 (17)
O2—N1—C3—C2	−170.72 (19)	C2—C1—C6—C5	−0.9 (3)
O1—N1—C3—C2	9.0 (3)	C2—C1—C6—C7	177.29 (17)
O2—N1—C3—C4	8.3 (3)	C5—C6—C7—C8	−179.0 (2)
O1—N1—C3—C4	−172.0 (2)	C1—C6—C7—C8	2.8 (3)
C2—C3—C4—C5	−0.3 (3)	C6—C7—C8—C10	2.3 (3)
N1—C3—C4—C5	−179.30 (17)	C6—C7—C8—C9	−175.70 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N3	0.93	2.58	3.431 (3)	152

Experimental details

Crystal data
Chemical formula	C₁₀H₅N₃O₂
M_r	199.17
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	297
a, b, c (Å)	19.5557 (9), 3.8732 (2), 11.9823 (5)
V (Å³)	907.58 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.76 × 0.60 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.674, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3111, 1517, 1420
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.06
No. of reflections	1517
No. of parameters	136
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16
Absolute structure	Flack (1983), 582 Friedel pairs
Absolute structure parameter	−0.2 (2)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N3	0.93	2.58	3.431 (3)	152

Acknowledgements

This work was supported by the National Science Council (grant No. NSC 99–2113-M-035–001-MY2) and Feng Chia University in Taiwan.

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