(2E)-1-(2,5-Dimethyl­thio­phen-3-yl)-3-(3-nitro­phen­yl)prop-2-en-1-one

Abdullah M Asiri; Abdulrahman O Al-Youbi; Salman A Khan; M Nawaz Tahir

doi:10.1107/S1600536811047933

. 2011 Nov 16;67(Pt 12):o3333. doi: 10.1107/S1600536811047933

(2E)-1-(2,5-Dimethylthiophen-3-yl)-3-(3-nitrophenyl)prop-2-en-1-one

Abdullah M Asiri ^a,^b, Abdulrahman O Al-Youbi ^a, Salman A Khan ^a, M Nawaz Tahir ^c,^*

PMCID: PMC3238980 PMID: 22199829

Abstract

In the title compound, C₁₅H₁₃NO₃S, the benzene ring and the five-membered heterocyclic ring are oriented at a dihedral angle of 12.00 (6)°. In the crystal, C—H⋯O interactions generate two types of cyclic motifs, R ₂ ²(14) and R ₂ ²(26), connecting the molecules into tapes extending along [101]. In addition, there are π–π stacking interactions between the benzene and thiophene rings with centroid-centroid distances of 3.7263 (14) and 3.7487 (14) Å.

Related literature

For the synthesis of similar compounds, see: Asiri & Khan (2010 ▶, 2011 ▶); Kalirajan et al. (2009 ▶); Patil et al. (2009 ▶); Sarojini et al. (2006 ▶). For related structures and background references, see: Asiri et al. (2010a ▶,b ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₃NO₃S
M _r = 287.32
Monoclinic,
a = 7.3802 (5) Å
b = 13.7973 (9) Å
c = 13.4638 (8) Å
β = 96.997 (3)°
V = 1360.77 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.20 mm

Data collection

Bruker KAPPA APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.945, T _max = 0.955
10732 measured reflections
2466 independent reflections
1493 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.117
S = 1.03
2466 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) text, I. DOI: 10.1107/S1600536811047933/gk2432sup1.cif

e-67-o3333-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047933/gk2432Isup2.hkl

e-67-o3333-Isup2.hkl^{(118.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047933/gk2432Isup3.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
C6—H6⋯O3ⁱ	0.93	2.46	3.373 (3)	168
C15—H15B⋯O2ⁱⁱ	0.96	2.59	3.339 (4)	135

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

Acknowledgments

The authors would like to thank the Chemistry Department, King Abdulaziz University, Jeddah, Saudi Arabia, for providing research facilities.

supplementary crystallographic information

Comment

Claisen–Schmidt reaction is one of the most important reactions for the formation of α, β-unsaturated ketone by condensation between acetophenone and benzaldehyde (Asiri & Khan, 2010). The reaction is catalysed by bases, acids (Patil et al., 2009). It is widely used in the synthesis of important intermediates (Asiri & Khan, 2011) or end-products, pharmaceuticals (Kalirajan et al., 2009). It is also used in the field of matrial sciences such as photoelectronics, photophotonics, photodynamic therapy, electrochemical sensing, optical limiting, langmuir film and photoinitiated polymerization (Sarojini et al., 2006). The title compound (I), (Fig. 1) has been synthesized as a pharmaceutical intermediate. Similar structures to (I) have been published earlier (Asiri et al., 2010a,b and refereces therein).

In (I), the group A (C1—C6), the central propenone B (C7—C9/O3) and the group C (C10—C15/S1) are planar with r. m. s. deviation of 0.003, 0.012 and 0.008 Å, respectively. The dihedral angles between A/B, A/C and B/C are 9.88 (14), 12.00 (6) and 16.09 (12)°, respectively. The nitro group D (O1/N1/O2) is oriented at a dihedral angle of 8.4 (3)° with relation to the benzene ring A. The title compound consists of dimers due to intermolecular H-bonds of C—H···O type, where O-atom is of carbonyl and H-atom is of the nitrophenyl group. This H-bondings form a R₂²(14) (Fig. 2) ring motif (Bernstein et al., 1995). The same type of H-bonding between methyl and nitro groups consolidate the molecules in the form of one-dimensional polymers with R₂²(26) ring motifs and extending along the [1 0 1] direction. Moreover there are π···π stacking interactions between the benzene and thiophene rings with centroid-centroid distances of 3.7263 (14)–3.7487 (14) Å.

Experimental

A solution of 3-acetyl-2,5-dimethythiophene (0.38 g, 2.5 mmol) and 3-nitro-benzaldehyde (0.37 g, 2.5 mmol) in ethanolic solution of NaOH (3.0 g in 10 ml of methanol) was stirred for 16 h at room temperature. The solution was poured into ice cold water of pH=2 (pH adjusted by HCl). The solid separated was filtered and crystallized from methanol:chloroform to affoard light yellow prisms of (I).

Yield: 78%; m.p. 403–404 K.

IR (KBr) ν_max cm^-1: 3012 (Ar—H), 2926 (C—H), 1628 (C═O), 1568 (C═C).

1H NMR (DMSO-d₆) (δ/p.p.m.): 8.47 (d, J = 1.8 Hz), 8.23 (d, J = 1.2 Hz), 7.73 (d, C═CH, J = 15.6 Hz), 7.40 (d, CH═C, J = 15.6 Hz), 7.89(d, J=7.2 Hz), 7.61 (d, J = 7.8 Hz), 7.27 (s, Ar—H), 2.72 (s, CH₃), 2.39 (s, CH₃).