Diethyl 2-{[3-(2-meth­oxy­benz­yl)thio­phen-2-yl]methyl­idene}malonate

S Ranjith; K Sakthi Murugesan; A Subbiah Pandi; V Dhayalan; A K Mohana Krishnan

doi:10.1107/S1600536811022525

. 2011 Jun 18;67(Pt 7):o1688. doi: 10.1107/S1600536811022525

Diethyl 2-{[3-(2-methoxybenzyl)thiophen-2-yl]methylidene}malonate

S Ranjith ^a, K Sakthi Murugesan ^a, A Subbiah Pandi ^a,^*, V Dhayalan ^b, A K Mohana Krishnan ^b

PMCID: PMC3151827 PMID: 21837085

Abstract

In the title compound, C₂₀H₂₂O₅S, the dihedral angle between the mean planes through the thiophene and benzene rings is 75.2 (1)°. The methoxy group is essentially coplanar with the benzene ring, the largest deviation from the mean plane being 0.019 (2) Å for the O atom. The malonate group assumes an extended conformation.

Related literature

For the biological activities of thiophene derivatives, see: Bonini et al. (2005 ▶); Brault et al. (2005 ▶); Isloora et al. (2010 ▶); Xia et al. (2010 ▶). For a similar thiophene structure, see: Dufresne & Skene (2010 ▶).

Experimental

Crystal data

C₂₀H₂₂O₅S
M _r = 374.44
Orthorhombic,
a = 8.1680 (2) Å
b = 16.4046 (4) Å
c = 28.8651 (7) Å
V = 3867.72 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.953, T _max = 0.964
35690 measured reflections
3695 independent reflections
2687 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.145
S = 1.02
3695 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022525/nk2101sup1.cif

e-67-o1688-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022525/nk2101Isup2.hkl

e-67-o1688-Isup2.hkl^{(177.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811022525/nk2101Isup3.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
C7—H7⋯O2ⁱ	0.93	2.55	3.429 (3)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

SR and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

Thiophene derivatives exhibit anti-HIVPR inhibition (Bonini et al., 2005) and antibreast cancer (Brault et al., 2005) activity. In addition, some of the benzo[b]thiophene derivatives show significant antimicrobial and anti-inflammatory activity (Isloora et al., 2010). Thiophene derivates have been viewed as significant compounds for applications in many fields (Xia et al., 2010). Against this background, and in order to obtain detailed information on molecular conformations in the solid state, an X-ray study of the title compound was carried out.

X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The bond lengths and angles in (Fig. 1) agree with those observed in other thiophene derivative (Dufresne & Skene, 2010). The thiophene ring system make the dihedral angle of 75.2 (1)° with respect to benzene ring. The atom O1 is deviated by 0.019 (2) Å from the least-squares plane of the benzene ring. The malonate group assumes an extended conformation as can be seen from torsion angles C14—C18—O5—C19 of 178.3 (2)° and C14—C15—O3—C16 of 173.9 (2)°.

Experimental

To a solution of diethyl-2-((3-(bromomethyl)thiophen-2-yl)methylene)malonate (2.88 mmol) in dry dichloroethane (15 ml), anhydrous ZnBr₂ (2.84 mmol) and anisole (3.17 mmol) were added. The reaction mixture was stirred at room temperature for 9 h and then refluxed for 1 h under N₂ atmosphere. The solvent was removed and the residue was quenched with ice–water (50 ml) containing 1 ml of Conc. HCl, extracted with chloroform (3 × 10 ml) and dried (Na₂SO₄). Removal of solvent followed by flash column chromatographic purification (n-hexane/ethyl acetate 98:2) led to the isolation of diethyl-2-((3-(2-methoxybenzyl)thiophen-2-yl) methylene)malonate as a colorless crystal. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in methanol at room temperature.