Ethyl 1,4-bis­(4-chloro­phen­yl)-2-methyl-1H-pyrrole-3-carboxyl­ate

K N Nandeesh; Chandra; M Mahendra; K Palani; K Mantelingu

doi:10.1107/S1600536813019247

. 2013 Jul 17;69(Pt 8):o1269. doi: 10.1107/S1600536813019247

Ethyl 1,4-bis(4-chlorophenyl)-2-methyl-1H-pyrrole-3-carboxylate

K N Nandeesh ^a, Chandra ^b, M Mahendra ^b, K Palani ^c, K Mantelingu ^a,^*

PMCID: PMC3793764 PMID: 24109351

Abstract

In the title molecule, C₂₀H₁₇Cl₂NO₂, the pyrrole moiety makes dihedral angles of 63.42 (11) and 70.43 (12)° with the chlorobenzene rings. The ethoxycarbonyl unit is present in a synperiplanar conformation with respect to the pyrrole ring, as indicated by the dihedral angle of 14.5 (3)°. In the crystal, molecules are linked into chains parallel to the a-axis direction by weak C—H⋯O hydrogen bonds.

Related literature

For the biological importance of pyrroles, see: Banwell et al. (2006 ▶); Mohamed et al. (2009 ▶); Sosa et al. (2002 ▶). graphic file with name e-69-o1269-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₇Cl₂NO₂
M _r = 374.25
Triclinic,
a = 8.037 (2) Å
b = 9.797 (3) Å
c = 12.510 (4) Å
α = 72.774 (16)°
β = 86.838 (16)°
γ = 76.804 (16)°
V = 915.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 K
0.15 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.947, T _max = 0.947
15843 measured reflections
4196 independent reflections
2759 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.125
S = 1.03
4196 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019247/fb2292sup1.cif

e-69-o1269-sup1.cif^{(27.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019247/fb2292Isup2.hkl

e-69-o1269-Isup2.hkl^{(205.6KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813019247/fb2292Isup3.cml

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
C2—H2⋯O8ⁱ	0.93	2.58	3.453 (3)	157
C6—H6C⋯O8	0.96	2.42	3.041 (3)	122

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Symmetry code: (i) Inline graphic .

Acknowledgments

C and KNN would like to thank the University of Mysore for awarding RFSMS fellowships [DV5/Physics/389/RFSMS/2009–2010/10.07.2012 and No. F4–1/2006(BSR)/7–131/2007, respectively].

supplementary crystallographic information

Comment

Pyrrole is a five-membered heterocyclic ring with one nitrogen atom. Its derivatives exhibit a variety of biological activities such as antitumor (Banwell et al., 2006) and antimicrobial (Mohamed et al., 2009) activities. They also inhibit protein kinase (Sosa et al., 2002). With this background of pyrrole derivatives, we have synthesized the title compound in order to study its crystal structure.

In the molecular structure of the title compound (Fig. 1), the dihedral angle between the pyrrole ring (N1/C2/C3/C4/C5) with phenyl rings (C19/C20/C21/C22/C23/C24) and (C12/C13/C14/C15/C16/C17) are 63.42 (11)° and 70.43 (12)°, respectively. The ethoxycarbonyl unit is in syn-periplanar conformation with respect to the pyrrole moiety, as indicated by the dihedral angle value of 14.5 (3)° (C3/C4/C7/O9). There are no classical hydrogen bonds and the crystal structure is stabilized by C—H···O hydrogen bonds only (see Table 1). C6—H6C···O8 forms an intramolecular hydrogen bond, while C2—H2···O8 links molecules which are parallel to the axis a. The packing of the molecules is shown in Fig. 2.

Experimental

To a stirred solution of para-chloroaniline (1.5 mmol), para-chlorobenzaldehyde (1.0 mmol) and ethyl acetoacetate (1.0 mmol) in nitromethane (1.5 ml), ferric chloride (FeCl₃) (0.1 mmol) was added. The mixture was refluxed at 90–100°C for 6 hrs and then cooled to room temperature. The excess of solvent was removed under vacuum and the residue was directly purified by column chromatography using 60–120 silica gel with ethyl acetate in hexane (1:9) as eluent which afforded the desired product as yellow solid with 88% yield. The crude product has been recrystallized from hot ethanol. Typical size of the block-shaped crystals was 0.20 × 0.15 × 0.10 mm.