organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Bigi, F., Chesini, L., Maggi, R. & Sartori, G. (1999). J. Org. Chem. 64, 1033-1035.]); Yu et al. (2000[Yu, N., Aramini, J. M. M., Germann, W. & Huang, Z. (2000). Tetrahedron Lett. 41, 6993-6996.]). For the synthesis, see: Knoevenagel (1898[Knoevenagel, E. (1898). Berichte, 31, 2585-2596.]); Yadav et al. (2004[Yadav, J. S., Subba Reddy, B. V., Basak, A. K., Visali, B., Narsaiah, A. V. & Nagaiah, K. (2004). Eur. J. Org. Chem. pp. 546-551.]).

[Scheme 1]

Experimental

Crystal data
  • C9H9N3O2

  • Mr = 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[Bruker (2001). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.980, Tmax = 0.984

  • 7118 measured reflections

  • 1436 independent reflections

  • 1189 reflections with ( > 2σ(I)

  • Rint = 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

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2001). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

Friedel pairs were merged in the absence of any anamalous scatterers in the molecule. The absolute structure in the present model has been chosen arbitrarily. All H-atoms were refined using a riding model with d(C—H) = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic, 0.97 Å, Uiso = 1.2Ueq (C) for CH2 and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms

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
[Figure 1] Fig. 1. The molecular structure of title compound, showing 30% probability displacement ellipsoids.
[Figure 2] 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
C9H9N3O2F(000) = 400
Mr = 191.19Dx = 1.359 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acθ = 2.6–25.0°
a = 10.0768 (7) ŵ = 0.10 mm1
b = 12.0387 (8) ÅT = 293 K
c = 7.7047 (6) ÅNeedle, pale yellow
V = 934.67 (12) Å30.4 × 0.23 × 0.2 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1436 independent reflections
Radiation source: fine-focus sealed tube1189 reflections with ( > 2σ(I)
Graphite monochromatorRint = 0.033
phi and ω scansθmax = 30.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1314
Tmin = 0.980, Tmax = 0.984k = 1612
7118 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 0.83 w = 1/[σ2(Fo2) + (0.1215P)2 + 0.160P]
where P = (Fo2 + 2Fc2)/3
1436 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.33 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C9H9N3O2V = 934.67 (12) Å3
Mr = 191.19Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 10.0768 (7) ŵ = 0.10 mm1
b = 12.0387 (8) ÅT = 293 K
c = 7.7047 (6) Å0.4 × 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)
Tmin = 0.980, Tmax = 0.984Rint = 0.033
7118 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0491 restraint
wR(F2) = 0.145H-atom parameters constrained
S = 0.83Δρmax = 0.33 e Å3
1436 reflectionsΔρmin = 0.22 e Å3
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
xyzUiso*/Ueq
C10.1765 (3)0.1284 (2)0.3293 (4)0.0457 (6)
H10.14470.19560.37190.055*
C20.3054 (2)0.0942 (2)0.3241 (4)0.0447 (6)
H20.37700.13550.36470.054*
C30.1905 (2)0.03689 (18)0.2134 (3)0.0364 (5)
C40.1407 (2)0.13759 (19)0.1392 (4)0.0394 (5)
H40.04870.14160.13080.047*
C50.20598 (19)0.22724 (19)0.0798 (4)0.0366 (4)
C60.1238 (2)0.32086 (19)0.0127 (4)0.0416 (5)
C70.1271 (3)0.4938 (2)0.1330 (5)0.0623 (9)
H7A0.06240.52200.05090.075*
H7B0.08060.47010.23680.075*
C80.2242 (4)0.5808 (3)0.1760 (6)0.0696 (10)
H8A0.29170.55030.24990.104*
H8B0.18020.64060.23500.104*
H8C0.26410.60820.07130.104*
C90.3471 (2)0.23680 (19)0.0740 (4)0.0421 (5)
N10.10482 (18)0.04511 (16)0.2601 (3)0.0420 (5)
H1A0.02000.04400.24770.050*
N20.31525 (19)0.00888 (17)0.2512 (3)0.0396 (5)
N30.4589 (2)0.2480 (2)0.0668 (5)0.0642 (8)
O10.00530 (18)0.32337 (16)0.0221 (4)0.0626 (7)
O20.19908 (17)0.40053 (15)0.0574 (3)0.0515 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0384 (11)0.0307 (12)0.0680 (15)0.0007 (9)0.0019 (11)0.0053 (12)
C20.0371 (11)0.0332 (12)0.0637 (15)0.0045 (9)0.0035 (10)0.0040 (12)
C30.0309 (9)0.0250 (10)0.0533 (13)0.0030 (8)0.0008 (8)0.0027 (9)
C40.0323 (9)0.0308 (11)0.0551 (12)0.0001 (8)0.0024 (10)0.0029 (9)
C50.0348 (9)0.0251 (9)0.0500 (12)0.0025 (7)0.0003 (9)0.0015 (9)
C60.0371 (10)0.0286 (11)0.0591 (14)0.0003 (8)0.0065 (10)0.0011 (10)
C70.0554 (16)0.0366 (14)0.095 (2)0.0014 (11)0.0195 (16)0.0130 (15)
C80.086 (3)0.0436 (15)0.079 (2)0.0112 (15)0.017 (2)0.0204 (16)
C90.0397 (11)0.0264 (10)0.0602 (14)0.0028 (8)0.0018 (11)0.0017 (10)
N10.0291 (8)0.0292 (9)0.0677 (13)0.0027 (7)0.0001 (9)0.0027 (10)
N20.0323 (9)0.0297 (10)0.0566 (11)0.0022 (7)0.0014 (9)0.0001 (8)
N30.0388 (10)0.0502 (14)0.103 (2)0.0028 (9)0.0041 (14)0.0151 (15)
O10.0395 (9)0.0418 (10)0.1065 (19)0.0051 (8)0.0059 (10)0.0154 (11)
O20.0434 (9)0.0291 (8)0.0819 (15)0.0001 (6)0.0067 (9)0.0126 (9)
Geometric parameters (Å, º) top
C1—N11.346 (3)C6—O11.197 (3)
C1—C21.363 (3)C6—O21.337 (3)
C1—H10.9300C7—C81.472 (5)
C2—N21.366 (3)C7—O21.458 (3)
C2—H20.9300C7—H7A0.9700
C3—N21.334 (3)C7—H7B0.9700
C3—N11.360 (3)C8—H8A0.9600
C3—C41.431 (3)C8—H8B0.9600
C4—C51.344 (3)C8—H8C0.9600
C4—H40.9300C9—N31.135 (3)
C5—C91.428 (3)N1—H1A0.8600
C5—C61.491 (3)
N1—C1—C2105.9 (2)C8—C7—O2107.9 (3)
N1—C1—H1127.0C8—C7—H7A110.1
C2—C1—H1127.0O2—C7—H7A110.1
N2—C2—C1110.8 (2)C8—C7—H7B110.1
N2—C2—H2124.6O2—C7—H7B110.1
C1—C2—H2124.6H7A—C7—H7B108.4
N2—C3—N1110.9 (2)C7—C8—H8A109.5
N2—C3—C4129.2 (2)C7—C8—H8B109.5
N1—C3—C4119.9 (2)H8A—C8—H8B109.5
C5—C4—C3130.1 (2)C7—C8—H8C109.5
C5—C4—H4114.9H8A—C8—H8C109.5
C3—C4—H4114.9H8B—C8—H8C109.5
C4—C5—C9124.3 (2)N3—C9—C5177.6 (3)
C4—C5—C6116.95 (19)C1—N1—C3107.74 (18)
C9—C5—C6118.8 (2)C1—N1—H1A126.1
O1—C6—O2124.9 (2)C3—N1—H1A126.1
O1—C6—C5123.5 (2)C3—N2—C2104.54 (19)
O2—C6—C5111.56 (19)C6—O2—C7115.6 (2)
N1—C1—C2—N20.6 (4)C2—C1—N1—C30.5 (3)
N2—C3—C4—C54.1 (5)N2—C3—N1—C10.2 (3)
N1—C3—C4—C5177.9 (3)C4—C3—N1—C1178.6 (3)
C3—C4—C5—C92.6 (5)N1—C3—N2—C20.1 (3)
C3—C4—C5—C6178.8 (3)C4—C3—N2—C2178.1 (3)
C4—C5—C6—O16.1 (5)C1—C2—N2—C30.4 (3)
C9—C5—C6—O1175.1 (3)O1—C6—O2—C72.7 (5)
C4—C5—C6—O2174.2 (3)C5—C6—O2—C7177.6 (3)
C9—C5—C6—O24.5 (4)C8—C7—O2—C6170.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O10.932.382.771 (3)105
N1—H1A···N2i0.862.112.951 (3)167
C1—H1···O1ii0.932.453.328 (4)158
Symmetry codes: (i) x1/2, y, z; (ii) x, y, z1/2.

Experimental details

Crystal data
Chemical formulaC9H9N3O2
Mr191.19
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)293
a, b, c (Å)10.0768 (7), 12.0387 (8), 7.7047 (6)
V3)934.67 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.4 × 0.23 × 0.2
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.980, 0.984
No. of measured, independent and
observed [( > 2σ(I)] reflections
7118, 1436, 1189
Rint0.033
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.145, 0.83
No. of reflections1436
No. of parameters128
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C4—H4···O10.932.382.771 (3)105
N1—H1A···N2i0.862.112.951 (3)167
C1—H1···O1ii0.932.453.328 (4)158
Symmetry codes: (i) x1/2, y, z; (ii) x, y, z1/2.
 

Acknowledgements

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

References

First citationBigi, F., Chesini, L., Maggi, R. & Sartori, G. (1999). J. Org. Chem. 64, 1033–1035.  Web of Science CrossRef PubMed CAS
First citationBruker (2001). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationKnoevenagel, E. (1898). Berichte, 31, 2585–2596.  CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals
First citationYadav, J. S., Subba Reddy, B. V., Basak, A. K., Visali, B., Narsaiah, A. V. & Nagaiah, K. (2004). Eur. J. Org. Chem. pp. 546–551.  Web of Science CrossRef
First citationYu, N., Aramini, J. M. M., Germann, W. & Huang, Z. (2000). Tetrahedron Lett. 41, 6993–6996.  Web of Science CrossRef CAS

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ISSN: 2056-9890
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