2-[(6-Nitro-1,3-benzodioxol-5-yl)methyl­idene]malononitrile

S Karthikeyan; K Sethusankar; Anthonisamy Devaraj; Manickam Bakthadoss

doi:10.1107/S1600536811049816

. 2011 Nov 30;67(Pt 12):o3469. doi: 10.1107/S1600536811049816

2-[(6-Nitro-1,3-benzodioxol-5-yl)methylidene]malononitrile

S Karthikeyan ^a, K Sethusankar ^a,^*, Anthonisamy Devaraj ^b, Manickam Bakthadoss ^b

PMCID: PMC3239096 PMID: 22199944

Abstract

In the title compound, C₁₁H₅N₃O₄, the nitro group is rotated by 29.91 (16)° out of the plane of the adjacent aryl ring. The 1,3-benzodioxole ring is nearly planar, with a maximium deviation of 0.0562 (10) Å. The dioxolene ring adopts an envelope conformation on the O—C—O C atom. In the crystal, molecules are linked via C—H⋯O interactions, resulting in R ₂ ²(6) and R ₂ ²(12) graph-set motifs.

Related literature

For applications of malononitrile derivatives, see: Brimblecombe et al. (1972 ▶). For related structure, see: Loghmani–Khouzani et al. (2009 ▶). For comparison of molecular dimensions, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph–set motif notations, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₅N₃O₄
M _r = 243.18
Triclinic,
a = 7.0953 (2) Å
b = 8.8847 (3) Å
c = 9.2212 (3) Å
α = 84.470 (2)°
β = 67.634 (2)°
γ = 78.874 (2)°
V = 527.30 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.30 × 0.28 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
13806 measured reflections
3494 independent reflections
2700 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.03
3494 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 (Farrugia, 1997 ▶) and Mercury (Macrae et al. 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811049816/rk2314sup1.cif

e-67-o3469-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049816/rk2314Isup2.hkl

e-67-o3469-Isup2.hkl^{(167.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049816/rk2314Isup3.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—H1B⋯O1ⁱ	0.97	2.53	3.2692 (16)	133
C8—H8⋯O4ⁱⁱ	0.93	2.52	3.3640 (17)	152

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

SK and KS thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, for providing facilities in the department for carrying out this work.

supplementary crystallographic information

Comment

The malononitrile derivative is used to investigate a variety of possible pharmacological effects when administered by various routes to whole animals and when applied to isolated organs and tissues (Brimblecombe et al., 1972). Also, it is a component of "tear gas" commonly reffered as CS gas, which is used as a riot control agent.

In the title compound C₁₁H₅N₃O₄, the benzodioxole ring is nearly planar with a maximum deviation 0.0562Å for the atom O2. The O═N═O angle is much larger than the ideal tetrahedral or trigonal values, respectively, doubtless as a consequence of the substantial negative charge on the paired O atoms. The bond lengths C9—C10 = 1.4388 (16)Å and C9—C11 = 1.4342 (16)Å is significantly shorter than the expected value for a C—C single bond because of conjugation effects.

In the dioxole ring C1/O2/C2/C7/O1, the deviation of atom C1 is -0.0724 (16)Å. The dioxole ring adopts a envelope conformation on C1 with puckering parameters (Cremer & Pople, 1975): Q₂ = 0.1145 (13)Å and φ₂ = 36.7 (6)°. The malononitrile group (C9—C10≡N2) and (C9—C11≡N3) is almost linear, with the angle around central carbon atoms C10 and C11 being 179.14 (15)° and 179.09 (15)° respectively.

The values of the torsion angles C5–C4–C8–C9 = -154.85 (11)° and C4–C5–N1–O4 = -151.10 (12)° indicates that the conformation of molecule is (-)anti–periplanar. The nitro group is not co–planar to the benzodioxole ring to which it is attached, making a dihedral angle of 29.76 (4)°. The benzodioxole unit is oriented at a dihedral angle of 36.90 (4)° with respect to the malononitrile group. The triple bond distances C10≡N2 and C11≡N3 are in agreement with the literature values (1.138 (7)Å; Allen et al., 1987). The title compound exhibits structural similarities with the already reported related structures (Loghmani–Khouzani et al., 2009).

The crystal packing is stabilized by non–classical intermolecular C—H···O interactions. The molecules are linked into centrosymmetric dimers. Atom C1 acts as a donor to dioxole O1ⁱ, so forming an R²₂(6) graph–set motif and atom C8 acts as a donor to nitro group O4ⁱⁱ at forming an R²₂(12) graph–set motif (Bernstein, et al., 1995). Symmetry codes: (i) -x, 1-y, 2-z; (ii) -1-x, 2-y, 1-z).

Experimental

To a solution of malononitrile (0.082 g, 1.24 mmol) in dichloromethane (5 ml), pyrrolidine (0.073 g, 1.03 mmol) was added and stirred well for 10 minutes. To this solution 6–nitrobenzo[d][1,3]dioxole–5–carbaldehyde (0.2 g, 1.03 mmol) was added and stirring was continued for 12 h. After the completion of the reaction as evidenced by TLC, the reaction mixture was poured into 2 N HCl solution (10 ml) and extracted using 25 ml of dichloromethane. The organic layer thus obtained was concentrated under reduced pressure. Column purification (silica gel, mesh size: 60–120) of the crude mixture using 15% ethyl acetate in hexanes successfully provided the desired 2–((6–nitrobenzo[d][1,3]dioxol–5–yl)methylene)malononitrile in 90% yield (0.23 g).