(E)-Ethyl 2-cyano-3-(1H-pyrrol-2-yl)acrylate

Yuvaraj, H.; Gayathri, D.; Kalkhambkar, R.G.; Gupta, V.K.; Rajnikant

doi:10.1107/S1600536811028790

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2135

doi:10.1107/S1600536811028790

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(E)-Ethyl 2-cyano-3-(1H-pyrrol-2-yl)acrylate

Haldorai Yuvaraj,^a ^* D. Gayathri,^b Rajesh G. Kalkhambkar,^c Vivek K. Gupta ^d and Rajnikant ^d

^aSchool of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749, Republic of Korea, ^bDepartment of Physics, Dr. M.G.R Educational and Research Institute University, Periyar E.V.R High Road, Maduravoyal, Chennai 600 095, India, ^cDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad 580 001, Karnataka, India, and ^dPost Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India
^*Correspondence e-mail: yuvraj_pd@yahoo.co.in

(Received 12 July 2011; accepted 17 July 2011; online 23 July 2011)

All the non-H atoms of the title compound, C₁₀H₁₀N₂O₂, are nearly in the same plane with a maximum deviation of 0.093 (1) Å. In the crystal, adjacent molecules are linked by pairs of intermolecular N—H⋯O hydrogen bonds, generating inversion dimers with R₂²(14) ring motifs.

Related literature

For background to and applications of pyrrole derivatives, see: Fischer & Orth (1934 ). For the Knoevenagel condensation reaction and its applications, see: Knoevenagel (1898 ); Bigi et al. (1999 ). For the synthesis of related compounds, see: Knizhnikov et al. (2007 ); Sarda et al. (2009 ). For related structures, see: Ye et al. (2009 ); Wang & Jian (2008 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₁₀H₁₀N₂O₂
M_r = 190.20
Monoclinic, P 2₁ /n
a = 6.2811 (2) Å
b = 9.4698 (3) Å
c = 16.3936 (5) Å
β = 92.645 (3)°
V = 974.06 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.971, T_max = 0.986
18157 measured reflections
1908 independent reflections
1574 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.113
S = 1.06
1908 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.09	2.874 (2)	151
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028790/is2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028790/is2752Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028790/is2752Isup3.cml

checkCIF report

Comment top

The chemistry of pyrrole compounds and biological activities of the related compounds has been extensively studied (Fischer & Orth, 1934). The Knoevenagel condensation is an important carbon–carbon bond forming reaction in organic synthesis (Knoevenagel, 1898). Ever since its discovery, the Knoevenagel reaction has been widely used in organic synthesis to prepare coumarins and their derivatives, which are important intermediates in the synthesis of cosmetics, perfumes and pharmaceuticals (Bigi et al., 1999). With the view of biological importance the title compound was synthesized and reported here its crystal structure.

Bond lengths and bond angles are comparable with the similar crystal structures solved earlier (Ye et al., 2009; Wang & Jian, 2008; Zhang et al., 2009). All the non-hydrogen atoms in the molecule are nearly in the same plane with the maximum out-of-plane deviation of 0.093 (1) Å (r.m.s. deviation = 0.04 Å). The crystal packing is stabilized by N—H···O intermolecular interactions, generating a centrosymmetric dimer of R₂²(14) ring.

Related literature top

For background to and applications of pyrrole derivatives, see: Fischer & Orth (1934). For the Knoevenagel condensation and its applications, see: Knoevenagel (1898); Bigi et al. (1999). For the synthesis of related compounds, see: Knizhnikov et al. (2007); Sarda et al. (2009). For related structures, see: Ye et al. (2009); Wang & Jian (2008); Zhang et al. (2009).

Experimental top

A solution of pyrrole-2-aldehyde (1 mol), ethyl cyanoacetate (1.2 mol) and piperidine (0.1 ml) in ethanol (20 ml) was stirred at room temperature for 8 h. After removal of the volatiles in vacuo, orange solid was obtained in quantitative yield. A sample for analysis was obtained by recrystallization from EtOAc as pale yellow needles: ¹H NMR (300 MHz, CDCl₃) δ p.p.m.: 1.38 t (3H, CH₃), 4.35 q (2H, CH₂), 6.41 m (1H, CH), 6.92 m (1H, CH), 7.22 m (1H, CH), 7.98 s (1H, HC=C), 9.92 s (1H, NH).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. A molecular packing view of the title compound, showing intermolecular interactions. For clarity, hydrogen atoms which are not involved in hydrogen bonding have been omitted.

(E)-Ethyl 2-cyano-3-(1H-pyrrol-2-yl)acrylate top

Crystal data top

C₁₀H₁₀N₂O₂	F(000) = 400
M_r = 190.20	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7544 reflections
a = 6.2811 (2) Å	θ = 3.5–29.0°
b = 9.4698 (3) Å	µ = 0.09 mm⁻¹
c = 16.3936 (5) Å	T = 293 K
β = 92.645 (3)°	Rectangular, light yellow
V = 974.06 (5) Å³	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1908 independent reflections
Radiation source: fine-focus sealed tube	1574 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
T_min = 0.971, T_max = 0.986	l = −20→20
18157 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0623P)² + 0.1138P] where P = (F_o² + 2F_c²)/3
1908 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₀H₁₀N₂O₂	V = 974.06 (5) Å³
M_r = 190.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2811 (2) Å	µ = 0.09 mm⁻¹
b = 9.4698 (3) Å	T = 293 K
c = 16.3936 (5) Å	0.30 × 0.20 × 0.15 mm
β = 92.645 (3)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1908 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1574 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.986	R_int = 0.032
18157 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	Δρ_max = 0.12 e Å⁻³
1908 reflections	Δρ_min = −0.19 e Å⁻³
128 parameters

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
C1	−0.1517 (2)	0.73171 (17)	0.56284 (9)	0.0557 (4)
H1	−0.2260	0.7170	0.6099	0.067*
C2	−0.2045 (3)	0.82705 (18)	0.50230 (9)	0.0596 (4)
H2	−0.3208	0.8879	0.5007	0.072*
C3	−0.0526 (2)	0.81600 (16)	0.44393 (9)	0.0522 (4)
H3	−0.0488	0.8687	0.3962	0.063*
C4	0.0926 (2)	0.71274 (13)	0.46903 (7)	0.0403 (3)
C5	0.2764 (2)	0.65298 (13)	0.43588 (8)	0.0403 (3)
H5	0.3441	0.5838	0.4679	0.048*
C6	0.36856 (19)	0.68137 (13)	0.36460 (7)	0.0390 (3)
C7	0.2877 (2)	0.78645 (15)	0.30869 (8)	0.0433 (3)
C8	0.5592 (2)	0.60070 (14)	0.34340 (7)	0.0400 (3)
C9	0.8147 (2)	0.56123 (16)	0.24473 (8)	0.0502 (4)
H9A	0.7809	0.4614	0.2415	0.060*
H9B	0.9363	0.5737	0.2827	0.060*
C10	0.8645 (3)	0.61655 (18)	0.16209 (9)	0.0593 (4)
H10A	0.7448	0.6008	0.1247	0.089*
H10B	0.9870	0.5683	0.1429	0.089*
H10C	0.8937	0.7159	0.1657	0.089*
N1	0.02503 (19)	0.66332 (12)	0.54287 (7)	0.0472 (3)
H1A	0.0873	0.5982	0.5717	0.057*
N2	0.2208 (2)	0.87126 (15)	0.26485 (8)	0.0631 (4)
O1	0.63859 (15)	0.50906 (11)	0.38609 (6)	0.0539 (3)
O2	0.63298 (14)	0.64028 (10)	0.27206 (5)	0.0454 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0510 (8)	0.0684 (10)	0.0490 (8)	0.0055 (7)	0.0159 (6)	−0.0045 (7)
C2	0.0537 (9)	0.0672 (10)	0.0587 (9)	0.0183 (7)	0.0105 (7)	0.0000 (8)
C3	0.0544 (8)	0.0562 (9)	0.0464 (8)	0.0119 (7)	0.0072 (6)	0.0048 (6)
C4	0.0420 (7)	0.0431 (7)	0.0359 (6)	−0.0008 (6)	0.0034 (5)	−0.0025 (5)
C5	0.0402 (7)	0.0420 (7)	0.0386 (7)	0.0013 (5)	0.0018 (5)	−0.0001 (5)
C6	0.0375 (7)	0.0422 (7)	0.0375 (6)	−0.0014 (5)	0.0024 (5)	0.0005 (5)
C7	0.0414 (7)	0.0477 (8)	0.0412 (7)	0.0014 (6)	0.0068 (5)	0.0012 (6)
C8	0.0388 (7)	0.0434 (7)	0.0380 (7)	−0.0012 (5)	0.0032 (5)	0.0002 (5)
C9	0.0450 (7)	0.0541 (8)	0.0526 (8)	0.0072 (6)	0.0133 (6)	0.0026 (7)
C10	0.0608 (9)	0.0625 (10)	0.0565 (9)	0.0038 (7)	0.0227 (7)	0.0043 (7)
N1	0.0487 (7)	0.0524 (7)	0.0412 (6)	0.0062 (5)	0.0091 (5)	0.0043 (5)
N2	0.0660 (9)	0.0669 (8)	0.0570 (8)	0.0129 (7)	0.0092 (6)	0.0184 (7)
O1	0.0540 (6)	0.0611 (6)	0.0474 (6)	0.0163 (5)	0.0092 (4)	0.0123 (5)
O2	0.0425 (5)	0.0507 (6)	0.0437 (5)	0.0047 (4)	0.0120 (4)	0.0066 (4)

Geometric parameters (Å, º) top

C1—N1	1.3386 (18)	C6—C8	1.4753 (18)
C1—C2	1.371 (2)	C7—N2	1.1447 (17)
C1—H1	0.9300	C8—O1	1.2080 (15)
C2—C3	1.386 (2)	C8—O2	1.3316 (15)
C2—H2	0.9300	C9—O2	1.4528 (16)
C3—C4	1.3869 (19)	C9—C10	1.4991 (19)
C3—H3	0.9300	C9—H9A	0.9700
C4—N1	1.3827 (16)	C9—H9B	0.9700
C4—C5	1.4165 (18)	C10—H10A	0.9600
C5—C6	1.3546 (18)	C10—H10B	0.9600
C5—H5	0.9300	C10—H10C	0.9600
C6—C7	1.4301 (18)	N1—H1A	0.8600

N1—C1—C2	108.49 (12)	O1—C8—O2	124.05 (12)
N1—C1—H1	125.8	O1—C8—C6	123.60 (11)
C2—C1—H1	125.8	O2—C8—C6	112.35 (11)
C1—C2—C3	107.40 (13)	O2—C9—C10	107.37 (12)
C1—C2—H2	126.3	O2—C9—H9A	110.2
C3—C2—H2	126.3	C10—C9—H9A	110.2
C2—C3—C4	108.22 (13)	O2—C9—H9B	110.2
C2—C3—H3	125.9	C10—C9—H9B	110.2
C4—C3—H3	125.9	H9A—C9—H9B	108.5
N1—C4—C3	105.90 (12)	C9—C10—H10A	109.5
N1—C4—C5	119.30 (12)	C9—C10—H10B	109.5
C3—C4—C5	134.80 (12)	H10A—C10—H10B	109.5
C6—C5—C4	129.78 (12)	C9—C10—H10C	109.5
C6—C5—H5	115.1	H10A—C10—H10C	109.5
C4—C5—H5	115.1	H10B—C10—H10C	109.5
C5—C6—C7	122.53 (12)	C1—N1—C4	110.00 (12)
C5—C6—C8	118.95 (11)	C1—N1—H1A	125.0
C7—C6—C8	118.53 (11)	C4—N1—H1A	125.0
N2—C7—C6	178.93 (14)	C8—O2—C9	115.85 (10)

N1—C1—C2—C3	−0.38 (18)	C7—C6—C8—O1	−179.34 (12)
C1—C2—C3—C4	0.31 (18)	C5—C6—C8—O2	−179.66 (11)
C2—C3—C4—N1	−0.12 (16)	C7—C6—C8—O2	0.57 (17)
C2—C3—C4—C5	178.72 (15)	C2—C1—N1—C4	0.31 (18)
N1—C4—C5—C6	178.23 (12)	C3—C4—N1—C1	−0.11 (16)
C3—C4—C5—C6	−0.5 (3)	C5—C4—N1—C1	−179.17 (12)
C4—C5—C6—C7	1.1 (2)	O1—C8—O2—C9	2.78 (19)
C4—C5—C6—C8	−178.64 (12)	C6—C8—O2—C9	−177.13 (10)
C5—C6—C8—O1	0.4 (2)	C10—C9—O2—C8	176.96 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.09	2.874 (2)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O₂
M_r	190.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.2811 (2), 9.4698 (3), 16.3936 (5)
β (°)	92.645 (3)
V (Å³)	974.06 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.971, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	18157, 1908, 1574
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.113, 1.06
No. of reflections	1908
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.19

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.09	2.874 (2)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank the Director of the University Sophisticated Instrumentation Facility, University of Jammu, Jammu Tawi, India, for the X-ray data collection. HY gratefully acknowledges Yeungnam University for providing the opportunity to work as an International Research Professor.

References

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