organic compounds
Methyl (E)-2-cyano-3-(6-nitro-1,3-benzodioxol-5-yl)acrylate
aDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India, bDepartment of Chemistry, Pondicherry University, Puducherry 605 014, India, cDepartment of Physics, C. Abdul Hakeem College of Engineering & Technology, Melvisharam, Vellore 632 509, India, and dDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India
*Correspondence e-mail: smurugavel27@gmail.com
In the title compound, C12H8N2O6, the 1,3-benzodioxole ring system is essentially planar [maximum deviation = 0.036 (2) Å] and the nitro group is oriented at a dihedral angle of 15.4 (1)° with respect to its mean plane. In the crystal, moleucles are linked into C(8) [101] chains by C—H⋯O hydrogen bonds, and weak aromatic π–π stacking [centroid–centroid distance = 3.887 (1) Å] also occurs.
Related literature
For a related structure and background references, see: Karthikeyan et al. (2011); Loghmani-Khouzani et al. (2009).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia (1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812043164/hb6968sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043164/hb6968Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043164/hb6968Isup3.cml
To a solution of methyl 2-cyanoacetate (0.1 g, 1 mmol) in dichloromethane (5 ml), pyrrolidine (0.073 g, 1 mmol) was added and stirred well for 10 minutes. To this solution 6–nitrobenzo [d][1,3]dioxole–5–carbaldehyde (0.2 g, 1 mmol) was added and allowed to stir well 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 20 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 10% ethyl acetate in hexanes successfully provided the desired title compound in 92% yield (0.25 g).
All the H atoms were positioned geometrically with C–H = 0.93–0.97 Å and constrained to ride on their parent atom, with Uiso(H) =1.5Ueq for methyl H atoms and 1.2Ueq(C) for other H atoms.
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia (1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C12H8N2O6 | F(000) = 568 |
Mr = 276.20 | Dx = 1.503 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3589 reflections |
a = 10.8191 (9) Å | θ = 2.3–30.1° |
b = 7.3220 (6) Å | µ = 0.12 mm−1 |
c = 15.4133 (13) Å | T = 293 K |
β = 91.691 (2)° | Block, colourless |
V = 1220.47 (18) Å3 | 0.23 × 0.22 × 0.17 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3567 independent reflections |
Radiation source: fine-focus sealed tube | 2286 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 10.0 pixels mm-1 | θmax = 30.1°, θmin = 2.3° |
ω scans | h = −15→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −6→10 |
Tmin = 0.972, Tmax = 0.979 | l = −21→19 |
14190 measured reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0569P)2 + 0.1956P] where P = (Fo2 + 2Fc2)/3 |
3567 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C12H8N2O6 | V = 1220.47 (18) Å3 |
Mr = 276.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8191 (9) Å | µ = 0.12 mm−1 |
b = 7.3220 (6) Å | T = 293 K |
c = 15.4133 (13) Å | 0.23 × 0.22 × 0.17 mm |
β = 91.691 (2)° |
Bruker APEXII CCD diffractometer | 3567 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2286 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.979 | Rint = 0.027 |
14190 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.20 e Å−3 |
3567 reflections | Δρmin = −0.18 e Å−3 |
182 parameters |
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 | 0.34825 (14) | 0.0705 (2) | 0.14286 (9) | 0.0415 (3) | |
H1 | 0.3194 | 0.0163 | 0.1929 | 0.050* | |
C2 | 0.44834 (14) | 0.1836 (2) | 0.14611 (9) | 0.0408 (3) | |
C3 | 0.60882 (16) | 0.3581 (3) | 0.18676 (11) | 0.0560 (4) | |
H3A | 0.5974 | 0.4774 | 0.2126 | 0.067* | |
H3B | 0.6912 | 0.3149 | 0.2026 | 0.067* | |
C4 | 0.49334 (13) | 0.26561 (19) | 0.07304 (10) | 0.0395 (3) | |
C5 | 0.43953 (14) | 0.2399 (2) | −0.00694 (9) | 0.0406 (3) | |
H5 | 0.4697 | 0.2955 | −0.0563 | 0.049* | |
C6 | 0.33678 (13) | 0.12542 (19) | −0.01065 (8) | 0.0372 (3) | |
C7 | 0.28993 (13) | 0.03817 (19) | 0.06181 (9) | 0.0375 (3) | |
C8 | 0.18022 (14) | −0.0796 (2) | 0.05853 (9) | 0.0428 (3) | |
H8 | 0.1115 | −0.0384 | 0.0266 | 0.051* | |
C9 | 0.17142 (13) | −0.2415 (2) | 0.09786 (9) | 0.0414 (3) | |
C10 | 0.05270 (16) | −0.3443 (2) | 0.09545 (10) | 0.0481 (4) | |
C11 | −0.0446 (2) | −0.6111 (3) | 0.14488 (14) | 0.0865 (8) | |
H11A | −0.0937 | −0.5637 | 0.1906 | 0.130* | |
H11B | −0.0215 | −0.7349 | 0.1579 | 0.130* | |
H11C | −0.0917 | −0.6077 | 0.0911 | 0.130* | |
C12 | 0.27569 (16) | −0.3259 (2) | 0.14154 (11) | 0.0484 (4) | |
N1 | 0.35768 (15) | −0.3935 (2) | 0.17628 (12) | 0.0710 (5) | |
N2 | 0.28260 (12) | 0.09294 (19) | −0.09677 (8) | 0.0472 (3) | |
O1 | 0.51784 (12) | 0.23313 (16) | 0.21683 (7) | 0.0566 (3) | |
O2 | 0.59385 (11) | 0.36932 (17) | 0.09442 (7) | 0.0549 (3) | |
O3 | 0.21209 (14) | −0.03492 (18) | −0.10801 (8) | 0.0666 (4) | |
O4 | 0.31029 (14) | 0.1961 (2) | −0.15503 (8) | 0.0796 (5) | |
O5 | −0.03967 (12) | −0.2902 (2) | 0.06023 (9) | 0.0704 (4) | |
O6 | 0.06541 (12) | −0.50122 (16) | 0.13725 (8) | 0.0589 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0503 (9) | 0.0418 (8) | 0.0322 (6) | −0.0033 (7) | 0.0004 (6) | 0.0053 (6) |
C2 | 0.0479 (8) | 0.0384 (8) | 0.0357 (7) | 0.0000 (6) | −0.0082 (6) | 0.0024 (6) |
C3 | 0.0527 (10) | 0.0612 (10) | 0.0530 (9) | −0.0109 (8) | −0.0154 (8) | 0.0049 (8) |
C4 | 0.0381 (7) | 0.0362 (7) | 0.0440 (7) | −0.0009 (6) | −0.0040 (6) | 0.0060 (6) |
C5 | 0.0440 (8) | 0.0405 (7) | 0.0374 (7) | 0.0013 (6) | 0.0008 (6) | 0.0083 (6) |
C6 | 0.0411 (7) | 0.0374 (7) | 0.0327 (6) | 0.0029 (6) | −0.0050 (6) | 0.0023 (6) |
C7 | 0.0390 (7) | 0.0346 (7) | 0.0389 (7) | 0.0005 (6) | −0.0001 (6) | 0.0027 (6) |
C8 | 0.0398 (8) | 0.0483 (8) | 0.0403 (7) | −0.0002 (7) | −0.0014 (6) | −0.0014 (6) |
C9 | 0.0381 (7) | 0.0464 (8) | 0.0400 (7) | −0.0044 (6) | 0.0054 (6) | −0.0008 (6) |
C10 | 0.0468 (9) | 0.0586 (10) | 0.0395 (7) | −0.0135 (8) | 0.0091 (7) | −0.0080 (7) |
C11 | 0.0961 (16) | 0.0936 (16) | 0.0707 (13) | −0.0623 (14) | 0.0181 (11) | −0.0093 (12) |
C12 | 0.0437 (9) | 0.0436 (8) | 0.0584 (9) | −0.0069 (7) | 0.0090 (7) | 0.0084 (7) |
N1 | 0.0541 (9) | 0.0636 (10) | 0.0951 (13) | 0.0040 (8) | 0.0009 (9) | 0.0224 (9) |
N2 | 0.0523 (8) | 0.0526 (8) | 0.0364 (6) | −0.0010 (7) | −0.0047 (6) | 0.0011 (6) |
O1 | 0.0685 (8) | 0.0590 (7) | 0.0412 (6) | −0.0174 (6) | −0.0175 (5) | 0.0084 (5) |
O2 | 0.0505 (7) | 0.0605 (7) | 0.0529 (6) | −0.0165 (6) | −0.0125 (5) | 0.0109 (6) |
O3 | 0.0882 (9) | 0.0585 (8) | 0.0520 (7) | −0.0219 (7) | −0.0152 (6) | −0.0052 (6) |
O4 | 0.0919 (10) | 0.1096 (12) | 0.0367 (6) | −0.0364 (9) | −0.0120 (6) | 0.0199 (7) |
O5 | 0.0437 (7) | 0.0963 (10) | 0.0708 (8) | −0.0157 (7) | −0.0048 (6) | 0.0024 (7) |
O6 | 0.0640 (8) | 0.0560 (7) | 0.0575 (7) | −0.0254 (6) | 0.0143 (6) | −0.0048 (6) |
C1—C2 | 1.363 (2) | C7—C8 | 1.467 (2) |
C1—C7 | 1.403 (2) | C8—C9 | 1.336 (2) |
C1—H1 | 0.9300 | C8—H8 | 0.9300 |
C2—O1 | 1.3553 (17) | C9—C12 | 1.436 (2) |
C2—C4 | 1.378 (2) | C9—C10 | 1.488 (2) |
C3—O2 | 1.430 (2) | C10—O5 | 1.191 (2) |
C3—O1 | 1.431 (2) | C10—O6 | 1.323 (2) |
C3—H3A | 0.9700 | C11—O6 | 1.444 (2) |
C3—H3B | 0.9700 | C11—H11A | 0.9600 |
C4—O2 | 1.3589 (18) | C11—H11B | 0.9600 |
C4—C5 | 1.361 (2) | C11—H11C | 0.9600 |
C5—C6 | 1.392 (2) | C12—N1 | 1.136 (2) |
C5—H5 | 0.9300 | N2—O3 | 1.2169 (17) |
C6—C7 | 1.3949 (19) | N2—O4 | 1.2177 (17) |
C6—N2 | 1.4547 (18) | ||
C2—C1—C7 | 118.11 (13) | C1—C7—C8 | 118.17 (13) |
C2—C1—H1 | 120.9 | C9—C8—C7 | 125.06 (14) |
C7—C1—H1 | 120.9 | C9—C8—H8 | 117.5 |
O1—C2—C1 | 127.85 (13) | C7—C8—H8 | 117.5 |
O1—C2—C4 | 109.86 (13) | C8—C9—C12 | 121.93 (14) |
C1—C2—C4 | 122.29 (13) | C8—C9—C10 | 120.68 (14) |
O2—C3—O1 | 107.47 (12) | C12—C9—C10 | 117.36 (14) |
O2—C3—H3A | 110.2 | O5—C10—O6 | 125.79 (15) |
O1—C3—H3A | 110.2 | O5—C10—C9 | 123.73 (16) |
O2—C3—H3B | 110.2 | O6—C10—C9 | 110.48 (15) |
O1—C3—H3B | 110.2 | O6—C11—H11A | 109.5 |
H3A—C3—H3B | 108.5 | O6—C11—H11B | 109.5 |
O2—C4—C5 | 127.95 (13) | H11A—C11—H11B | 109.5 |
O2—C4—C2 | 110.18 (13) | O6—C11—H11C | 109.5 |
C5—C4—C2 | 121.88 (13) | H11A—C11—H11C | 109.5 |
C4—C5—C6 | 116.13 (13) | H11B—C11—H11C | 109.5 |
C4—C5—H5 | 121.9 | N1—C12—C9 | 179.57 (18) |
C6—C5—H5 | 121.9 | O3—N2—O4 | 122.63 (13) |
C5—C6—C7 | 123.46 (13) | O3—N2—C6 | 119.32 (13) |
C5—C6—N2 | 115.83 (12) | O4—N2—C6 | 118.05 (13) |
C7—C6—N2 | 120.64 (13) | C2—O1—C3 | 106.34 (11) |
C6—C7—C1 | 118.12 (13) | C4—O2—C3 | 105.99 (12) |
C6—C7—C8 | 123.67 (13) | C10—O6—C11 | 116.71 (16) |
C7—C1—C2—O1 | 179.97 (15) | C7—C8—C9—C12 | −6.3 (2) |
C7—C1—C2—C4 | −0.1 (2) | C7—C8—C9—C10 | 175.68 (13) |
O1—C2—C4—O2 | 0.51 (18) | C8—C9—C10—O5 | −0.7 (2) |
C1—C2—C4—O2 | −179.41 (14) | C12—C9—C10—O5 | −178.88 (16) |
O1—C2—C4—C5 | −179.43 (13) | C8—C9—C10—O6 | 179.10 (13) |
C1—C2—C4—C5 | 0.7 (2) | C12—C9—C10—O6 | 0.96 (19) |
O2—C4—C5—C6 | 179.86 (14) | C5—C6—N2—O3 | 163.45 (14) |
C2—C4—C5—C6 | −0.2 (2) | C7—C6—N2—O3 | −13.6 (2) |
C4—C5—C6—C7 | −0.7 (2) | C5—C6—N2—O4 | −16.5 (2) |
C4—C5—C6—N2 | −177.74 (13) | C7—C6—N2—O4 | 166.40 (15) |
C5—C6—C7—C1 | 1.2 (2) | C1—C2—O1—C3 | −178.04 (16) |
N2—C6—C7—C1 | 178.11 (13) | C4—C2—O1—C3 | 2.05 (18) |
C5—C6—C7—C8 | 178.73 (13) | O2—C3—O1—C2 | −3.74 (18) |
N2—C6—C7—C8 | −4.4 (2) | C5—C4—O2—C3 | 177.10 (16) |
C2—C1—C7—C6 | −0.8 (2) | C2—C4—O2—C3 | −2.83 (17) |
C2—C1—C7—C8 | −178.41 (13) | O1—C3—O2—C4 | 4.01 (18) |
C6—C7—C8—C9 | 135.22 (16) | O5—C10—O6—C11 | −3.8 (2) |
C1—C7—C8—C9 | −47.3 (2) | C9—C10—O6—C11 | 176.34 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O4i | 0.97 | 2.51 | 3.247 (2) | 132 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H8N2O6 |
Mr | 276.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.8191 (9), 7.3220 (6), 15.4133 (13) |
β (°) | 91.691 (2) |
V (Å3) | 1220.47 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.23 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.972, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14190, 3567, 2286 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.129, 1.03 |
No. of reflections | 3567 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia (1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O4i | 0.97 | 2.51 | 3.247 (2) | 132 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
Footnotes
‡Additional correspondence author, e-mail: bhakthadoss@yahoo.com.
Acknowledgements
The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.
References
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Karthikeyan, S., Sethusankar, K., Devaraj, A. & Bakthadoss, M. (2011). Acta Cryst. E67, o3469. Web of Science CSD CrossRef IUCr Journals Google Scholar
Loghmani-Khouzani, H., Abdul Rahman, N., Robinson, W. T., Yaeghoobi, M. & Kia, R. (2009). Acta Cryst. E65, o2545. Web of Science CSD CrossRef IUCr Journals Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
As part of our ongoing studies of benzodioxoles with possible biological activities (Karthikeyan et al., 2011), the crystal structure of the title compound has been determined and the results are presented here.
Fig. 1. shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The benzodioxole ring system is essentially planar [maximum deviation = 0.036 (2) Å for the C3 atom] and is oriented at a dihedral angle of 15.4 (1)° with respect to the nitro group. The sum of bond angles around N2 (360°) indicates that N2 is in sp2 hybridization. The carbonitrile side chain (C9–C12–N1) is almost linear, with the angle around central carbon atom being 179.6 (2)°. The geometric parameters of the title molecule agrees well with those reported for similar structures (Karthikeyan et al., 2011, Loghmani-Khouzani et al., 2009).
The crystal packing features C—H···O hydrogen bonds. Atom C3 in the molecule at x, y, z) directs its C—H bonds towards atom O4 at 1/2+x,1/2-y,1/2+z, forming a C(8) chain along [101] (Fig. 2). Weak aromatic π—π interactions between the benzene rings of neighbouring molecules, with Cg—Cgv distance of 3.887 (1) Å [Fig. 3; Cg is the centroid of the C1/C2/C4/C5/C6/C7 benzene ring, Symmetry code as in Fig. 3] are also observed.