Methyl (E)-2-cyano-3-(6-nitro-1,3-benzodioxol-5-yl)acrylate

Bakthadoss, M.; Devaraj, A.; Lakshmanan, D.; Murugavel, S.

doi:10.1107/S1600536812043164

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3184

doi:10.1107/S1600536812043164

Open

access

Methyl (E)-2-cyano-3-(6-nitro-1,3-benzodioxol-5-yl)acrylate

M. Bakthadoss,^a,^b ‡ A. Devaraj,^a D. Lakshmanan ^c and S. Murugavel ^d ^*

^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

(Received 4 October 2012; accepted 16 October 2012; online 20 October 2012)

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

C₁₂H₈N₂O₆
M_r = 276.20
Monoclinic, P 2₁ /n
a = 10.8191 (9) Å
b = 7.3220 (6) Å
c = 15.4133 (13) Å
β = 91.691 (2)°
V = 1220.47 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.23 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.972, T_max = 0.979
14190 measured reflections
3567 independent reflections
2286 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 1.03
3567 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043164/hb6968sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043164/hb6968Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043164/hb6968Isup3.cml

checkCIF report

Comment top

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—Cg^v 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.

Related literature top

For a related structure and background references, see: Karthikeyan et al. (2011); Loghmani-Khouzani et al. (2009).

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I) showing C—H···O hydrogen bonds (dotted lines), with the formation of C(8) chains along [101]. [Symmetry codes: (i)1/2+x, 1/2-y, 1/2+z; (ii)1+x, y, 1+z; (iii)<3/2+x, 1/2-y, 3/2+z; (iv)2+x, y, 2+z].
	Fig. 3. A view of π—π (green dotted lines) interactions in the crystal structure of the title compound. Cg denotes the centroid of the C1/C2/C4/C5/C6/C7 benzene ring [Symmetry code:(v)1-x, 1-y, -z].

Methyl (E)-2-cyano-3-(6-nitro-1,3-benzodioxol-5-yl)acrylate top

Crystal data top

C₁₂H₈N₂O₆	F(000) = 568
M_r = 276.20	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	3567 independent reflections
Radiation source: fine-focus sealed tube	2286 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.0 pixels mm^-1	θ_max = 30.1°, θ_min = 2.3°
ω scans	h = −15→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −6→10
T_min = 0.972, T_max = 0.979	l = −21→19
14190 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0569P)² + 0.1956P] where P = (F_o² + 2F_c²)/3
3567 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₈N₂O₆	V = 1220.47 (18) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	3567 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2286 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.979	R_int = 0.027
14190 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
3567 reflections	Δρ_min = −0.18 e Å⁻³
182 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	0.34825 (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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.972, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	14190, 3567, 2286
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. 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