(E)-Ethyl 2-cyano-3-[5-nitro-2-(pyrrolidin-1-yl)phen­yl]acrylate

Yapi Marcellin Yapo; Bakary Coulibaly Abou; Ané Adjou; Rita Kakou-Yao; Jules A Tenon

doi:10.1107/S1600536810033374

. 2010 Sep 4;66(Pt 10):o2497. doi: 10.1107/S1600536810033374

(E)-Ethyl 2-cyano-3-[5-nitro-2-(pyrrolidin-1-yl)phenyl]acrylate

Yapi Marcellin Yapo ^a,^*, Bakary Coulibaly Abou ^a, Ané Adjou ^b, Rita Kakou-Yao ^a, Jules A Tenon ^a

PMCID: PMC2983149 PMID: 21587494

Abstract

The title compound, C₁₆H₁₇N₃O₄, was prepared by the reaction of 5-nitro-2-(pyrrolidin-1-yl)benzaldehyde and ethyl cyanoacetate. The molecular structure adopts an E conformation with respect to the C=C double bond. The five-membered ring has a half-chair conformation, with puckering parameters Q(2)= 0.399 (2) Å and ϕ = 93.1 (3)°. In the crystal, inversion dimers , linked by pairs of C—H⋯O interactions, are further connected through C—H⋯N hydrogen bonds. Weak slipped π-π interactions occur between symmetry-related benzene rings [centroid–centroid distance = 3.785 (1)Å].

Related literature

For related structures, see: Yapo et al. (2010 ▶); Zhang et al. (2009a ▶,b ▶). For reference bond lengths, see: Allen (2002 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₆H₁₇N₃O₄
M _r = 315.33
Triclinic,
a = 8.4137 (3) Å
b = 9.9517 (4) Å
c = 10.3731 (5) Å
α = 73.065 (1)°
β = 71.388 (2)°
γ = 72.523 (4)°
V = 766.56 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 223 K
0.15 × 0.05 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
12261 measured reflections
3925 independent reflections
2436 reflections with I > 3σ(I)
R _int = 0.04

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.098
S = 1.01
2436 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810033374/dn2594sup1.cif

e-66-o2497-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033374/dn2594Isup2.hkl

e-66-o2497-Isup2.hkl^{(196.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H152⋯O2ⁱ	0.98	2.50	3.356 (2)	145
C16—H163⋯N3ⁱⁱ	0.98	2.60	3.574 (3)	172

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors wish to thank the Laboratoire de Physique des Interactions Ioniques et Moléculaires of Provence University (France) for the use of the diffractometer.

supplementary crystallographic information

Comment

Recently, the synthesis and structure of tricyclic quinoline derivative have been widely investigated (Yapo et al., 2010). We report herein the crystal structure of the title compound C₁₆H₁₇N₃O₄(I). In fact, it is an intermediate compound on which chemical reactions will be made to obtain tricyclic quinoline derivative containing in its molecular structure two coupled rings: quinoline ring and pyrrolidine ring.

The molecular structure of the title complex displays a E conformation with respect to the C11═C12 double bond. The bond distance C12— C13=1.436 (2)Å agrees with recently reported structures (Zhang et al., 2009a; Zhang et al., 2009b) and is characteristic of single bond occuring between carbone sp¹ and carbone sp² [C(sp¹)—C(sp²)]. All other bond lengths and angles are not unusual (Allen, 2002).

The pyrrolidine ring has half-chair conformation with puckering parameters Q(2)= 0.399 (2)Å and φ= 93.1 (3)° (Cremer & Pople, 1975)

In the crystal packing, centrosymmetrically related molecules are linked by intermolecular C—H···O hydrogen bonding interactions building pseudo dimers which are further connected through C-H···N hydrogen bonds (Table 1 and Figure 2). Weak π-π interactions occur between symmetry related phenyl rings (Centroid-to-centroid = 3.785 (1)Å, interplanar distance= 3.509Å and a slippage of 1.417Å with symmetry code: (i) 2-x,1-y,-z).

Experimental

To a solution of 5-nitro-2-(pyrrolidin-1-yl)benzaldehyde (2, 9.03 mmol) in anhydrous ethanol (25 ml), ethyl cyanoacetate (2.1 ml, 10.1 mmol) was added. Maintained at room temperature and under magnetic agitation, triethylamine (3 ml) was dropped into the solution. The reaction mixture was maintained at room temperature for 30 min then heated to ethanol reflux during 2 h. After cooling, the precipitate was filtred and then washed with ethanol to obtain yellow crystals in 77% yield. The melting point is 457–458 K.