Ethyl (2E)-2-cyano-3-(1-methyl-1H-pyrrol-2-yl)prop-2-enoate

Asiri, A.M.; Al-Youbi, A.O.; Alamry, K.A.; Faidallah, H.M.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811031941

organic compounds

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Volume 67| Part 9| September 2011| Page o2315

doi:10.1107/S1600536811031941

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Ethyl (2E)-2-cyano-3-(1-methyl-1H-pyrrol-2-yl)prop-2-enoate

Abdullah M. Asiri,^a,^b ‡ Abdulrahman O. Al-Youbi,^a Khalid A. Alamry,^a Hassan M. Faidallah,^a Seik Weng Ng ^c,^a and Edward R. T. Tiekink ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, PO Box 80203, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 6 August 2011; accepted 7 August 2011; online 11 August 2011)

The 15 non-H atoms of the title compound, C₁₁H₁₂N₂O₂, are approximately coplanar, the r.m.s. deviation being 0.145 Å. The major deviation from coplanarity is seen in a twist between the ethene (E configuration) and pyrrole rings [C—C—N—C torsion angle = −8.26 (18)°]. The carbonyl O and cyano N atoms are syn to each other. In the crystal, supramolecular linear tapes linked by C—H⋯O and C—H⋯N interactions are further connected by C—H⋯π(pyrrole) interactions.

Related literature

For background to the biological activity of 2(1H)pyridone compounds, see: Aly et al. (1991 ); Al-Saadi et al. (2005 ); Rostom et al. (2011 ).

Experimental

Crystal data

C₁₁H₁₂N₂O₂
M_r = 204.23
Triclinic, $[P \overline 1]$
a = 7.6145 (3) Å
b = 8.4964 (6) Å
c = 9.7023 (6) Å
α = 64.898 (7)°
β = 89.859 (4)°
γ = 71.517 (5)°
V = 532.69 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.955, T_max = 1.000
4049 measured reflections
2336 independent reflections
1912 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.106
S = 1.04
2336 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N2,C7—C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11a⋯O2ⁱ	0.98	2.31	3.241 (2)	158
C9—H9⋯N1ⁱⁱ	0.95	2.62	3.557 (2)	171
C11—H11b⋯Cg1ⁱⁱⁱ	0.98	2.69	3.5332 (17)	144
Symmetry codes: (i) x-1, y+1, z; (ii) -x+1, -y+2, -z; (iii) -x+1, -y+2, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); 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: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811031941/hb6354sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031941/hb6354Isup2.hkl

checkCIF report

Comment top

The title compound (I) was studied in connection with the known biological activity of 2(1H)pyridone compounds (Aly et al., 1991; Al-Saadi et al., 2005; Rostom et al., 2011), and was prepared from the condensation of the N-methylpyrrole-2-carboxaldehyde with ethyl cyanoacetate during an attempt to prepare a 2(1H)pyridone derivative.

The molecular structure of (I), Fig. 1, is, to a first approximation, planar with the r.m.s. deviation for all 15 non-H atoms being 0.145 Å. The major deviations from the least-squares plane are 0.214 (2) and -0.337 (2) Å for the C9 and C11 atoms, respectively, reflecting a small twist between the ethene and pyrrole rings [the C11—N2—C7—C6 torsion angle = -8.26 (18) °]. The conformation about the ethene [C4═C7 = 1.3594 (18) Å] bond is E. The carbonyl-O and cyano-N atoms are syn to each other.

In the crystal packing, molecules are linked into chains via C—H···O interactions involving a N-bound methyl-H and carbonyl-O, Table 1. Chains are linked into a linear tape via C—H···N interactions involving a pyrrole-H and cyano-N, Fig. 2. The tapes are consolidated into the three-dimensional architecture by C—H···π interactions, Fig. 3, involving another N-bound methyl-H as the donor to the pyrrole ring.

Related literature top

For background to the biological activity of 2(1H)pyridone compounds, see: Aly et al. (1991); Al-Saadi et al. (2005); Rostom et al. (2011).

Experimental top

A mixture of the N-methylpyrrole-2-carboxaldehyde (1.0 g,1 0 mmol), 2-methylcyclohexanone (1.12 g, 10 mmol), ethyl cyanoacetate (1.1 g, 10 mmol) and ammonium acetate (6.2 g, 80 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction mixture was allowed to cool, the formed precipitate was filtered, washed with water, dried and recrystallized from ethanol to form yellow blocks. M.pt. 420–421 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular tape in (I) mediated by C—H···O and C—H···N interactions shown as orange and blue dashed lines, respectively.
	Fig. 3. A view in projection down the b axis of the unit-cell contents of (I). The C—H···O, C—H···N and C—H···π interactions shown as orange, blue and purple dashed lines, respectively.

Ethyl (2E)-2-cyano-3-(1-methyl-1H-pyrrol-2-yl)prop-2-enoate top

Crystal data top

C₁₁H₁₂N₂O₂	Z = 2
M_r = 204.23	F(000) = 216
Triclinic, P1	D_x = 1.273 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6145 (3) Å	Cell parameters from 2042 reflections
b = 8.4964 (6) Å	θ = 2.3–29.2°
c = 9.7023 (6) Å	µ = 0.09 mm⁻¹
α = 64.898 (7)°	T = 100 K
β = 89.859 (4)°	Block, yellow
γ = 71.517 (5)°	0.30 × 0.25 × 0.10 mm
V = 532.69 (5) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2336 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1912 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −8→11
T_min = 0.955, T_max = 1.000	l = −12→11
4049 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.043P)² + 0.1378P] where P = (F_o² + 2F_c²)/3
2336 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₂N₂O₂	γ = 71.517 (5)°
M_r = 204.23	V = 532.69 (5) Å³
Triclinic, P1	Z = 2
a = 7.6145 (3) Å	Mo Kα radiation
b = 8.4964 (6) Å	µ = 0.09 mm⁻¹
c = 9.7023 (6) Å	T = 100 K
α = 64.898 (7)°	0.30 × 0.25 × 0.10 mm
β = 89.859 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2336 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1912 reflections with I > 2σ(I)
T_min = 0.955, T_max = 1.000	R_int = 0.030
4049 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
2336 reflections	Δρ_min = −0.21 e Å⁻³
138 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
O1	0.76560 (13)	0.39008 (13)	0.75762 (10)	0.0210 (2)
O2	0.94151 (13)	0.24631 (13)	0.62962 (11)	0.0240 (2)
N2	0.31730 (15)	0.98384 (16)	0.40412 (13)	0.0195 (3)
C1	0.7806 (2)	0.2663 (2)	1.02981 (18)	0.0367 (4)
H1A	0.8394	0.1579	1.1287	0.055*
H1B	0.6452	0.2928	1.0165	0.055*
H1C	0.8049	0.3737	1.0280	0.055*
C2	0.8606 (2)	0.22752 (19)	0.90199 (16)	0.0239 (3)
H2A	0.9970	0.2036	0.9128	0.029*
H2B	0.8402	0.1170	0.9045	0.029*
C3	0.82056 (17)	0.37907 (18)	0.63059 (15)	0.0178 (3)
C4	0.71681 (17)	0.54814 (18)	0.48907 (15)	0.0177 (3)
C5	0.77316 (18)	0.54540 (18)	0.34926 (16)	0.0198 (3)
C6	0.57429 (17)	0.68970 (18)	0.49404 (15)	0.0176 (3)
H6	0.5455	0.6706	0.5940	0.021*
C7	0.46245 (17)	0.86137 (18)	0.37221 (15)	0.0185 (3)
C8	0.47051 (19)	0.95100 (19)	0.21554 (16)	0.0225 (3)
H8	0.5559	0.9015	0.1603	0.027*
C9	0.3314 (2)	1.1258 (2)	0.15416 (17)	0.0268 (3)
H9	0.3051	1.2171	0.0499	0.032*
C10	0.23870 (19)	1.14206 (19)	0.27246 (16)	0.0241 (3)
H10	0.1364	1.2471	0.2631	0.029*
C11	0.25065 (19)	0.9441 (2)	0.55193 (16)	0.0230 (3)
H11A	0.1556	1.0568	0.5462	0.034*
H11B	0.3559	0.9013	0.6323	0.034*
H11C	0.1956	0.8473	0.5767	0.034*
N1	0.81855 (17)	0.53952 (17)	0.23809 (14)	0.0273 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0231 (5)	0.0179 (5)	0.0169 (5)	−0.0016 (4)	0.0022 (4)	−0.0073 (4)
O2	0.0218 (5)	0.0215 (5)	0.0278 (6)	−0.0014 (4)	0.0028 (4)	−0.0145 (4)
N2	0.0176 (5)	0.0198 (6)	0.0224 (6)	−0.0041 (5)	0.0011 (4)	−0.0122 (5)
C1	0.0394 (9)	0.0389 (10)	0.0209 (8)	−0.0062 (8)	0.0046 (7)	−0.0089 (7)
C2	0.0269 (7)	0.0183 (7)	0.0187 (7)	−0.0043 (6)	−0.0005 (6)	−0.0038 (6)
C3	0.0163 (6)	0.0193 (7)	0.0206 (7)	−0.0061 (5)	0.0036 (5)	−0.0116 (6)
C4	0.0167 (6)	0.0202 (7)	0.0194 (7)	−0.0076 (5)	0.0035 (5)	−0.0108 (6)
C5	0.0183 (6)	0.0179 (7)	0.0225 (7)	−0.0044 (5)	0.0019 (5)	−0.0098 (6)
C6	0.0169 (6)	0.0211 (7)	0.0190 (7)	−0.0084 (5)	0.0037 (5)	−0.0115 (5)
C7	0.0174 (6)	0.0190 (7)	0.0208 (7)	−0.0054 (5)	0.0019 (5)	−0.0111 (6)
C8	0.0254 (7)	0.0231 (7)	0.0204 (7)	−0.0069 (6)	0.0011 (5)	−0.0120 (6)
C9	0.0305 (8)	0.0234 (8)	0.0213 (7)	−0.0055 (6)	−0.0048 (6)	−0.0082 (6)
C10	0.0211 (7)	0.0194 (7)	0.0282 (8)	−0.0012 (6)	−0.0045 (6)	−0.0115 (6)
C11	0.0199 (7)	0.0251 (8)	0.0283 (8)	−0.0059 (6)	0.0061 (6)	−0.0172 (6)
N1	0.0325 (7)	0.0267 (7)	0.0234 (7)	−0.0074 (6)	0.0076 (5)	−0.0139 (5)

Geometric parameters (Å, º) top

O1—C3	1.3316 (16)	C4—C5	1.4290 (19)
O1—C2	1.4570 (16)	C5—N1	1.1482 (17)
O2—C3	1.2128 (15)	C6—C7	1.4158 (18)
N2—C10	1.3542 (18)	C6—H6	0.9500
N2—C7	1.3938 (17)	C7—C8	1.3933 (19)
N2—C11	1.4568 (18)	C8—C9	1.392 (2)
C1—C2	1.494 (2)	C8—H8	0.9500
C1—H1A	0.9800	C9—C10	1.380 (2)
C1—H1B	0.9800	C9—H9	0.9500
C1—H1C	0.9800	C10—H10	0.9500
C2—H2A	0.9900	C11—H11A	0.9800
C2—H2B	0.9900	C11—H11B	0.9800
C3—C4	1.4783 (18)	C11—H11C	0.9800
C4—C6	1.3594 (18)

C3—O1—C2	115.44 (10)	N1—C5—C4	178.60 (15)
C10—N2—C7	108.92 (11)	C4—C6—C7	129.52 (13)
C10—N2—C11	125.09 (11)	C4—C6—H6	115.2
C7—N2—C11	125.83 (11)	C7—C6—H6	115.2
C2—C1—H1A	109.5	C8—C7—N2	106.74 (11)
C2—C1—H1B	109.5	C8—C7—C6	133.53 (12)
H1A—C1—H1B	109.5	N2—C7—C6	119.56 (12)
C2—C1—H1C	109.5	C9—C8—C7	107.97 (13)
H1A—C1—H1C	109.5	C9—C8—H8	126.0
H1B—C1—H1C	109.5	C7—C8—H8	126.0
O1—C2—C1	107.45 (11)	C10—C9—C8	107.48 (13)
O1—C2—H2A	110.2	C10—C9—H9	126.3
C1—C2—H2A	110.2	C8—C9—H9	126.3
O1—C2—H2B	110.2	N2—C10—C9	108.89 (12)
C1—C2—H2B	110.2	N2—C10—H10	125.6
H2A—C2—H2B	108.5	C9—C10—H10	125.6
O2—C3—O1	124.42 (12)	N2—C11—H11A	109.5
O2—C3—C4	123.32 (12)	N2—C11—H11B	109.5
O1—C3—C4	112.26 (11)	H11A—C11—H11B	109.5
C6—C4—C5	123.65 (12)	N2—C11—H11C	109.5
C6—C4—C3	121.69 (12)	H11A—C11—H11C	109.5
C5—C4—C3	114.60 (11)	H11B—C11—H11C	109.5

C3—O1—C2—C1	179.92 (11)	C10—N2—C7—C6	176.08 (11)
C2—O1—C3—O2	−0.45 (18)	C11—N2—C7—C6	−8.26 (18)
C2—O1—C3—C4	179.47 (10)	C4—C6—C7—C8	−8.2 (2)
O2—C3—C4—C6	175.93 (12)	C4—C6—C7—N2	177.34 (12)
O1—C3—C4—C6	−3.99 (17)	N2—C7—C8—C9	0.03 (15)
O2—C3—C4—C5	−1.38 (18)	C6—C7—C8—C9	−174.98 (14)
O1—C3—C4—C5	178.70 (10)	C7—C8—C9—C10	−0.29 (16)
C5—C4—C6—C7	−4.1 (2)	C7—N2—C10—C9	−0.43 (15)
C3—C4—C6—C7	178.85 (12)	C11—N2—C10—C9	−176.13 (12)
C10—N2—C7—C8	0.24 (14)	C8—C9—C10—N2	0.44 (16)
C11—N2—C7—C8	175.90 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N2,C7—C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11a···O2ⁱ	0.98	2.31	3.241 (2)	158
C9—H9···N1ⁱⁱ	0.95	2.62	3.557 (2)	171
C11—H11b···Cg1ⁱⁱⁱ	0.98	2.69	3.5332 (17)	144

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₂
M_r	204.23
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.6145 (3), 8.4964 (6), 9.7023 (6)
α, β, γ (°)	64.898 (7), 89.859 (4), 71.517 (5)
V (Å³)	532.69 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.25 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.955, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4049, 2336, 1912
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.106, 1.04
No. of reflections	2336
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N2,C7—C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11a···O2ⁱ	0.98	2.31	3.241 (2)	158
C9—H9···N1ⁱⁱ	0.95	2.62	3.557 (2)	171
C11—H11b···Cg1ⁱⁱⁱ	0.98	2.69	3.5332 (17)	144

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

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors thank King Abdulaziz University and the University of Malaya for supporting this study.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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Aly, A. S., El-Ezabawy, S. R. & Abdel-Fattah, A. M. (1991). Egypt. J. Pharm. Sci. 32, 827–834. CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Rostom, S. A. F., Faidallah, S. M. & Al Saadi, M. S. (2011). Med. Chem. Res. doi:10.1007/s00044-010-9469-0. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536811031941

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