(Z)-Ethyl 2-cyano-3-(1H-imidazol-2-yl)acrylate

Kalkhambkar, R.G.; Kumar, M.; Gayathri, D.; Oh, J.; Jeong, Y.T.

doi:10.1107/S1600536813018278

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1223

doi:10.1107/S1600536813018278

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(Z)-Ethyl 2-cyano-3-(1H-imidazol-2-yl)acrylate

Rajesh G. Kalkhambkar,^a Mahesh Kumar,^a D. Gayathri,^b Jeongsu Oh ^c and Yeon Tae Jeong ^c ^*

^aDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad 580 001, Karnatak, India, ^bDepartment of Biotechnology, Dr. M.G.R Educational and Research Institute University, Periyar E.V.R. High Road, Maduravoyal, Chennai 600 095, India, and ^cDepartment of Image Science and Engineering, Pukyong National University, Busan 608 739, Republic of Korea
^*Correspondence e-mail: ytjeong@pknu.ac.kr

(Received 8 June 2013; accepted 2 July 2013; online 10 July 2013)

The crystal structure of the title compound, C₉H₉N₃O₂, features N—H⋯N and C—H⋯O interactions. The N—H⋯N interaction generates a chain running along the a axis and the C—H⋯O interaction generates a chain along the c axis. An intramolecular C—H⋯O interaction is also observed.

Related literature

For background references and the biological importance of related compounds, see: Bigi et al. (1999 ); Yu et al. (2000 ). For the synthesis, see: Knoevenagel (1898 ); Yadav et al. (2004 ).

Experimental

Crystal data

C₉H₉N₃O₂
M_r = 191.19
Orthorhombic, P c a 2₁
a = 10.0768 (7) Å
b = 12.0387 (8) Å
c = 7.7047 (6) Å
V = 934.67 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.4 × 0.23 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.980, T_max = 0.984
7118 measured reflections
1436 independent reflections
1189 reflections with ( > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.145
S = 0.83
1436 reflections
128 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1	0.93	2.38	2.771 (3)	105
N1—H1A⋯N2ⁱ	0.86	2.11	2.951 (3)	167
C1—H1⋯O1ⁱⁱ	0.93	2.45	3.328 (4)	158
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y, z]$ ; (ii) $[-x, -y, z-{\script{1\over 2}}]$ .

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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813018278/fj2635sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018278/fj2635Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813018278/fj2635Isup3.cml

checkCIF report

Comment top

The Knoevenagel condensation is an important carbon-carbon bond-forming reaction in organic synthesis (Knoevenagel, 1898; Yadav et al., 2004). This reaction has been widely used in organic synthesis to prepare many biologically active derivatives, and in the synthesis of cosmetics, perfumes and pharmaceuticals (Bigi et al., 1999; Yu et al., 2000). With the view of biological importance, the series of compounds are synthesized and here we report the crystal structure of the title compound.

The bond lengths and bond angles are within the normal ranges. The imidazole ring is planar and the acrylate moiety is nearly planar with torsion angles C4—C5—C6—O1 and C4—C5—C6—O2 being -6.1 (5) and 174.2 (3)°, respectively. Atoms C6, C9, N3 and O1 deviate from the planarity of the title compound with maximum deviation of 0.31 (3) Å by O1 atom. The crystal structure is stabilized by C(4)—H(4)···O1 intramolecuar interaction generating S(5) motif. The crystal packing is stabilized by N—H···N and C—H···O intermolecular interaction network. Atom N1 acts as a donor to N2 generating chain of C(4) along a axis and atom C1 acts as a donor to O1 generating C(8) chain running along c axis.

Related literature top

For background references and the biological importance of related compounds, see: Bigi et al. (1999); Yu et al. (2000). For the synthesis, see: Knoevenagel (1898); Yadav et al. (2004).

Experimental top

A solution of 1H-Imidazole-2-aldehyde (1 mol), ethyl cyanoacetate (1.2 mol) and piperidine (0.1 ml) in ethanol (20 ml) was stirred at room temperature for 4 h. After removal of the volatiles in vacuo, yellow solid was obtained in quantitative yield. A sample for analysis was obtained by recrystallization from EtOAc as pale yellow needles.

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The molecular packing of (I). For clarity, hydrogen atoms which are not involved in hydrogen bonding are omitted.

(Z)-Ethyl 2-cyano-3-(1H-imidazol-2-yl)acrylate top

Crystal data top

C₉H₉N₃O₂	F(000) = 400
M_r = 191.19	D_x = 1.359 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	θ = 2.6–25.0°
a = 10.0768 (7) Å	µ = 0.10 mm⁻¹
b = 12.0387 (8) Å	T = 293 K
c = 7.7047 (6) Å	Needle, pale yellow
V = 934.67 (12) Å³	0.4 × 0.23 × 0.2 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1436 independent reflections
Radiation source: fine-focus sealed tube	1189 reflections with ( > 2σ(I)
Graphite monochromator	R_int = 0.033
phi and ω scans	θ_max = 30.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→14
T_min = 0.980, T_max = 0.984	k = −16→12
7118 measured reflections	l = −10→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.1215P)² + 0.160P] where P = (F_o² + 2F_c²)/3
1436 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.33 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₉N₃O₂	V = 934.67 (12) Å³
M_r = 191.19	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 10.0768 (7) Å	µ = 0.10 mm⁻¹
b = 12.0387 (8) Å	T = 293 K
c = 7.7047 (6) Å	0.4 × 0.23 × 0.2 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1436 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1189 reflections with ( > 2σ(I)
T_min = 0.980, T_max = 0.984	R_int = 0.033
7118 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.145	H-atom parameters constrained
S = 0.83	Δρ_max = 0.33 e Å⁻³
1436 reflections	Δρ_min = −0.22 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	0.1765 (3)	−0.1284 (2)	−0.3293 (4)	0.0457 (6)
H1	0.1447	−0.1956	−0.3719	0.055*
C2	0.3054 (2)	−0.0942 (2)	−0.3241 (4)	0.0447 (6)
H2	0.3770	−0.1355	−0.3647	0.054*
C3	0.1905 (2)	0.03689 (18)	−0.2134 (3)	0.0364 (5)
C4	0.1407 (2)	0.13759 (19)	−0.1392 (4)	0.0394 (5)
H4	0.0487	0.1416	−0.1308	0.047*
C5	0.20598 (19)	0.22724 (19)	−0.0798 (4)	0.0366 (4)
C6	0.1238 (2)	0.32086 (19)	−0.0127 (4)	0.0416 (5)
C7	0.1271 (3)	0.4938 (2)	0.1330 (5)	0.0623 (9)
H7A	0.0624	0.5220	0.0509	0.075*
H7B	0.0806	0.4701	0.2368	0.075*
C8	0.2242 (4)	0.5808 (3)	0.1760 (6)	0.0696 (10)
H8A	0.2917	0.5503	0.2499	0.104*
H8B	0.1802	0.6406	0.2350	0.104*
H8C	0.2641	0.6082	0.0713	0.104*
C9	0.3471 (2)	0.23680 (19)	−0.0740 (4)	0.0421 (5)
N1	0.10482 (18)	−0.04511 (16)	−0.2601 (3)	0.0420 (5)
H1A	0.0200	−0.0440	−0.2477	0.050*
N2	0.31525 (19)	0.00888 (17)	−0.2512 (3)	0.0396 (5)
N3	0.4589 (2)	0.2480 (2)	−0.0668 (5)	0.0642 (8)
O1	0.00530 (18)	0.32337 (16)	−0.0221 (4)	0.0626 (7)
O2	0.19908 (17)	0.40053 (15)	0.0574 (3)	0.0515 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0384 (11)	0.0307 (12)	0.0680 (15)	0.0007 (9)	−0.0019 (11)	−0.0053 (12)
C2	0.0371 (11)	0.0332 (12)	0.0637 (15)	0.0045 (9)	0.0035 (10)	−0.0040 (12)
C3	0.0309 (9)	0.0250 (10)	0.0533 (13)	−0.0030 (8)	0.0008 (8)	0.0027 (9)
C4	0.0323 (9)	0.0308 (11)	0.0551 (12)	−0.0001 (8)	0.0024 (10)	0.0029 (9)
C5	0.0348 (9)	0.0251 (9)	0.0500 (12)	0.0025 (7)	−0.0003 (9)	0.0015 (9)
C6	0.0371 (10)	0.0286 (11)	0.0591 (14)	−0.0003 (8)	0.0065 (10)	0.0011 (10)
C7	0.0554 (16)	0.0366 (14)	0.095 (2)	0.0014 (11)	0.0195 (16)	−0.0130 (15)
C8	0.086 (3)	0.0436 (15)	0.079 (2)	−0.0112 (15)	0.017 (2)	−0.0204 (16)
C9	0.0397 (11)	0.0264 (10)	0.0602 (14)	0.0028 (8)	−0.0018 (11)	−0.0017 (10)
N1	0.0291 (8)	0.0292 (9)	0.0677 (13)	−0.0027 (7)	0.0001 (9)	−0.0027 (10)
N2	0.0323 (9)	0.0297 (10)	0.0566 (11)	−0.0022 (7)	0.0014 (9)	0.0001 (8)
N3	0.0388 (10)	0.0502 (14)	0.103 (2)	0.0028 (9)	−0.0041 (14)	−0.0151 (15)
O1	0.0395 (9)	0.0418 (10)	0.1065 (19)	0.0051 (8)	0.0059 (10)	−0.0154 (11)
O2	0.0434 (9)	0.0291 (8)	0.0819 (15)	−0.0001 (6)	0.0067 (9)	−0.0126 (9)

Geometric parameters (Å, º) top

C1—N1	1.346 (3)	C6—O1	1.197 (3)
C1—C2	1.363 (3)	C6—O2	1.337 (3)
C1—H1	0.9300	C7—C8	1.472 (5)
C2—N2	1.366 (3)	C7—O2	1.458 (3)
C2—H2	0.9300	C7—H7A	0.9700
C3—N2	1.334 (3)	C7—H7B	0.9700
C3—N1	1.360 (3)	C8—H8A	0.9600
C3—C4	1.431 (3)	C8—H8B	0.9600
C4—C5	1.344 (3)	C8—H8C	0.9600
C4—H4	0.9300	C9—N3	1.135 (3)
C5—C9	1.428 (3)	N1—H1A	0.8600
C5—C6	1.491 (3)

N1—C1—C2	105.9 (2)	C8—C7—O2	107.9 (3)
N1—C1—H1	127.0	C8—C7—H7A	110.1
C2—C1—H1	127.0	O2—C7—H7A	110.1
N2—C2—C1	110.8 (2)	C8—C7—H7B	110.1
N2—C2—H2	124.6	O2—C7—H7B	110.1
C1—C2—H2	124.6	H7A—C7—H7B	108.4
N2—C3—N1	110.9 (2)	C7—C8—H8A	109.5
N2—C3—C4	129.2 (2)	C7—C8—H8B	109.5
N1—C3—C4	119.9 (2)	H8A—C8—H8B	109.5
C5—C4—C3	130.1 (2)	C7—C8—H8C	109.5
C5—C4—H4	114.9	H8A—C8—H8C	109.5
C3—C4—H4	114.9	H8B—C8—H8C	109.5
C4—C5—C9	124.3 (2)	N3—C9—C5	177.6 (3)
C4—C5—C6	116.95 (19)	C1—N1—C3	107.74 (18)
C9—C5—C6	118.8 (2)	C1—N1—H1A	126.1
O1—C6—O2	124.9 (2)	C3—N1—H1A	126.1
O1—C6—C5	123.5 (2)	C3—N2—C2	104.54 (19)
O2—C6—C5	111.56 (19)	C6—O2—C7	115.6 (2)

N1—C1—C2—N2	0.6 (4)	C2—C1—N1—C3	−0.5 (3)
N2—C3—C4—C5	−4.1 (5)	N2—C3—N1—C1	0.2 (3)
N1—C3—C4—C5	177.9 (3)	C4—C3—N1—C1	178.6 (3)
C3—C4—C5—C9	−2.6 (5)	N1—C3—N2—C2	0.1 (3)
C3—C4—C5—C6	178.8 (3)	C4—C3—N2—C2	−178.1 (3)
C4—C5—C6—O1	−6.1 (5)	C1—C2—N2—C3	−0.4 (3)
C9—C5—C6—O1	175.1 (3)	O1—C6—O2—C7	2.7 (5)
C4—C5—C6—O2	174.2 (3)	C5—C6—O2—C7	−177.6 (3)
C9—C5—C6—O2	−4.5 (4)	C8—C7—O2—C6	−170.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1	0.93	2.38	2.771 (3)	105
N1—H1A···N2ⁱ	0.86	2.11	2.951 (3)	167
C1—H1···O1ⁱⁱ	0.93	2.45	3.328 (4)	158

Symmetry codes: (i) x−1/2, −y, z; (ii) −x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₂
M_r	191.19
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	10.0768 (7), 12.0387 (8), 7.7047 (6)
V (Å³)	934.67 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.4 × 0.23 × 0.2

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.980, 0.984
No. of measured, independent and observed [( > 2σ(I)] reflections	7118, 1436, 1189
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.145, 0.83
No. of reflections	1436
No. of parameters	128
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.22

Computer programs: SMART (Bruker 2001), SAINT (Bruker, 2001), 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
C4—H4···O1	0.93	2.38	2.771 (3)	105
N1—H1A···N2ⁱ	0.86	2.11	2.951 (3)	167
C1—H1···O1ⁱⁱ	0.93	2.45	3.328 (4)	158

Symmetry codes: (i) x−1/2, −y, z; (ii) −x, −y, z−1/2.

Acknowledgements

The authors thank the Director, USIC Karnatak University Dharwad, India, for the X-ray data collection.

References

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