Abstract
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,
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[F 2 > 2σ(F 2)] = 0.034
wR(F 2) = 0.091
S = 1.06
1517 reflections
136 parameters
1 restraint
H-atom parameters constrained
Δρmax = 0.13 e Å−3
Δρmin = −0.16 e Å−3
Absolute structure: Flack (1983 ▶), 582 Friedel pairs
Flack parameter: −0.2 (2)
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 ▶).
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008896/xu5449sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008896/xu5449Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812008896/xu5449Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
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 |
Acknowledgments
This work was supported by the National Science Council (grant No. NSC 99–2113-M-035–001-MY2) and Feng Chia University in Taiwan.
supplementary crystallographic information
Comment
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.
Experimental
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.
Refinement
H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Figures
Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
Crystal data
| C10H5N3O2 | F(000) = 408 |
| Mr = 199.17 | Dx = 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
| Bruker SMART CCD area-detector diffractometer | 1517 independent reflections |
| Radiation source: fine-focus sealed tube | 1420 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.016 |
| ω scans | θmax = 71.7°, θmin = 4.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −24→15 |
| Tmin = 0.674, Tmax = 1.000 | k = −4→3 |
| 3111 measured reflections | l = −14→14 |
Refinement
| 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(Fo2) + (0.0621P)2 + 0.0168P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 1517 reflections | Δρmax = 0.13 e Å−3 |
| 136 parameters | Δρmin = −0.16 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 582 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.2 (2) |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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)
| 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)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···N3 | 0.93 | 2.58 | 3.431 (3) | 152 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5449).
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008896/xu5449sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008896/xu5449Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812008896/xu5449Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report