organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

(E)-1-(5-Chloro­thio­phen-2-yl)-3-(p-tol­yl)prop-2-en-1-one

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aDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, cDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, and dDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in, khalil.i@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 6 January 2017; accepted 9 January 2017; online 13 January 2017)

In the title compound, C14H11ClOS, the trans conformation of the C=C double bond in the central enone group is confirmed by the C—C=C—C torsion angle of 178.3 (4)°. The mol­ecule is non-planar as seen by the dihedral angle of 22.6 (2)° between the chloro­thio­phene and the p-toluene rings. In the crystal, mol­ecules are linked by pairs of C—H⋯π inter­actions, forming inversion dimers. There are no other significant inter­molecular inter­actions present.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The usual method for the synthesis of chalcones involves the condensation of an aromatic aldehyde and aromatic ketone in the presence of aqueous alkaline bases (Naveen et al., 2016a[Naveen, S., Dileep Kumar, A., Ajay Kumar, K., Manjunath, H. R., Lokanath, N. K. & Warad, I. (2016a). IUCrData, 1, x161800.]). Chalcones and their derivatives demonstrate a wide range of biological activities such as anti­diabetic, anti­neoplastic, anti­tubercular, anti­arrhythmic, hypnotic, anti­angiogenic, anti­protozoal, anti­bacterial, anti­steroidal, cardioprotective. In view of the broad spectrum of applications associated with chalcones and as a part of our ongoing work on such mol­ecules (Tejkiran et al., 2016[Tejkiran, P. J., Brahma Teja, M. S., Sai Siva Kumar, P., Sankar, P., Philip, R., Naveen, S., Lokanath, N. K. & Nageswara Rao, G. (2016). J. Photochem. Photobiol. Chem. A, 324, 33-39.]; Naveen et al., 2016b[Naveen, S., Prabhudeva, M. G., Ajay Kumar, K., Lokanath, N. K. & Abdoh, M. (2016b). IUCrData, 1, x161974.]), we report herein the synthesis and crystal structure of the title compound.

The mol­ecular structure of the title compound is shown in Fig. 1[link]. The mol­ecule is non-planar, with a dihedral angle of 22.6 (2)° between the chloro­thio­phene and p-toluene rings that are bridged by the olefinic double bond. This value is in good agreement with the value of 19.13 (15)° reported earlier between the aromatic rings in the related chalcone derivative (E)-3-(2,3-di­chloro­phen­yl)-1-(4-fluoro­phen­yl)prop-2-en-1-one (Naveen et al., 2016b[Naveen, S., Prabhudeva, M. G., Ajay Kumar, K., Lokanath, N. K. & Abdoh, M. (2016b). IUCrData, 1, x161974.]). The trans conformation about the C6=C7 double bond in the central enone group is confirmed by the C5—C6=C7—C8 torsion angle of 178.3 (4)°. The carbonyl group at C5 lies in the plane of the olefinic double bond and chloro-thio­phene rings as indicated by the O1—C5—C4—C3 and O1—C5—C6—C7 torsion angle values of 177.9 (5)° and −11.7 (6)°, respectively.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, mol­ecules are linked by pairs of C—H⋯π inter­actions, forming inversion dimers (Table 1[link] and Fig. 2[link]). There are no other significant inter­molecular inter­actions present.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C8–C13 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C14—H14ACgi 0.96 2.77 3.576 (6) 141
Symmetry code: (i) -x+2, -y-1, -z+1.
[Figure 2]
Figure 2
A view along the c axis of the crystal packing of the title compound. The C—H⋯π inter­actions (Table 1[link]) are represented by dashed lines, and only H atom H14A (grey ball) has been included.

Synthesis and crystallization

A mixture of 4-methyl­benzaldehyde (5 mmol), 5-chloro-2-acetyl­thio­phene (5 mmol) and sodium hydroxide (5 mmol) in 95% ethyl alcohol (25 ml) was stirred at room temperature for 3 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into ice-cold water and kept in the refrigerator overnight. The solid formed was filtered, and washed with cold hydro­chloric acid (5%). Block-like colourless crystals of the title compound were obtained by crystallization from methanol by the slow evaporation technique (yield 84%, m.p. 403–405 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C14H11ClOS
Mr 262.75
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 293
a, b, c (Å) 6.000 (2), 9.718 (4), 10.936 (4)
α, β, γ (°) 94.268 (17), 93.83 (3), 96.97 (2)
V3) 629.3 (4)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.45
Crystal size (mm) 0.39 × 0.31 × 0.27
 
Data collection
Diffractometer Rigaku Saturn724+
Absorption correction Multi-scan (NUMABS; Rigaku, 1999[Rigaku. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.])
Tmin, Tmax 0.972, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections 3635, 2808, 1279
Rint 0.071
(sin θ/λ)max−1) 0.651
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.264, 0.90
No. of reflections 2808
No. of parameters 155
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.51, −0.65
Computer programs: CrystalClear (Rigaku, 2011[Rigaku. (2011). CrystalClear. Rigaku Corporation, Tokyo, Japan.]), SHELXS97and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Structural data


Computing details top

Data collection: CrystalClear (Rigaku, 2011); cell refinement: CrystalClear (Rigaku, 2011); data reduction: CrystalClear (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

(E)-1-(5-Chlorothiophen-2-yl)-3-(p-tolyl)prop-2-en-1-one top
Crystal data top
C14H11ClOSZ = 2
Mr = 262.75F(000) = 272
Triclinic, P1Dx = 1.387 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.000 (2) ÅCell parameters from 3635 reflections
b = 9.718 (4) Åθ = 3.4–27.6°
c = 10.936 (4) ŵ = 0.45 mm1
α = 94.268 (17)°T = 293 K
β = 93.83 (3)°Block, colourless
γ = 96.97 (2)°0.39 × 0.31 × 0.27 mm
V = 629.3 (4) Å3
Data collection top
Rigaku Saturn724+
diffractometer
2808 independent reflections
Radiation source: fine-focus sealed tube1279 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
Detector resolution: 18.4 pixels mm-1θmax = 27.6°, θmin = 3.4°
profile data from ω–scansh = 77
Absorption correction: multi-scan
(NUMABS; Rigaku, 1999)
k = 1112
Tmin = 0.972, Tmax = 0.976l = 1314
3635 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.264H-atom parameters constrained
S = 0.90 w = 1/[σ2(Fo2) + (0.1466P)2]
where P = (Fo2 + 2Fc2)/3
2808 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.65 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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
xyzUiso*/Ueq
Cl10.6471 (3)0.42181 (15)0.15570 (14)0.0791 (6)
S10.5125 (2)0.22896 (12)0.03032 (11)0.0490 (4)
O10.4218 (6)0.0428 (4)0.2208 (3)0.0609 (12)
C10.7155 (8)0.3040 (5)0.0540 (4)0.0473 (16)
C20.9174 (9)0.2628 (5)0.0289 (5)0.0566 (17)
C30.9106 (8)0.1657 (5)0.0608 (4)0.0494 (17)
C40.7015 (7)0.1373 (4)0.1020 (4)0.0421 (14)
C50.6217 (8)0.0486 (4)0.1973 (4)0.0435 (14)
C60.7863 (7)0.0282 (4)0.2624 (4)0.0415 (12)
C70.7370 (8)0.0886 (4)0.3637 (4)0.0423 (12)
C80.8780 (9)0.1707 (4)0.4362 (4)0.0463 (14)
C91.0772 (8)0.2111 (5)0.3982 (4)0.0475 (17)
C101.2012 (8)0.2947 (5)0.4676 (4)0.0499 (17)
C111.1293 (9)0.3381 (4)0.5784 (4)0.0485 (16)
C120.9276 (9)0.2947 (5)0.6170 (4)0.0516 (16)
C130.8017 (9)0.2132 (5)0.5487 (4)0.0525 (14)
C141.2604 (11)0.4281 (5)0.6534 (5)0.075 (2)
H21.046700.294500.066100.0680*
H31.035200.125400.088900.0600*
H60.926000.034000.231700.0500*
H70.596900.077600.392000.0510*
H91.129700.182000.325100.0570*
H101.333400.321700.439300.0600*
H120.877300.321900.691200.0620*
H130.668700.186800.576400.0630*
H14A1.268800.514500.606300.1130*
H14B1.186800.446200.726800.1130*
H14C1.409700.381400.675000.1130*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1032 (13)0.0772 (10)0.0688 (10)0.0388 (9)0.0066 (9)0.0402 (8)
S10.0518 (8)0.0535 (7)0.0465 (7)0.0221 (6)0.0015 (6)0.0126 (5)
O10.063 (2)0.071 (2)0.057 (2)0.0232 (19)0.0186 (19)0.0236 (18)
C10.054 (3)0.047 (2)0.046 (3)0.024 (2)0.000 (2)0.013 (2)
C20.048 (3)0.066 (3)0.060 (3)0.009 (3)0.011 (2)0.024 (3)
C30.045 (3)0.056 (3)0.054 (3)0.025 (2)0.005 (2)0.019 (2)
C40.050 (3)0.040 (2)0.037 (2)0.009 (2)0.002 (2)0.0042 (18)
C50.055 (3)0.041 (2)0.036 (2)0.011 (2)0.003 (2)0.0051 (18)
C60.035 (2)0.047 (2)0.045 (2)0.0122 (19)0.004 (2)0.009 (2)
C70.041 (2)0.041 (2)0.046 (2)0.0092 (19)0.002 (2)0.0063 (19)
C80.069 (3)0.034 (2)0.034 (2)0.000 (2)0.002 (2)0.0073 (17)
C90.049 (3)0.052 (3)0.045 (3)0.014 (2)0.006 (2)0.013 (2)
C100.046 (3)0.052 (3)0.053 (3)0.013 (2)0.003 (2)0.009 (2)
C110.061 (3)0.036 (2)0.045 (3)0.002 (2)0.011 (2)0.0065 (19)
C120.065 (3)0.050 (3)0.037 (2)0.004 (2)0.005 (2)0.012 (2)
C130.069 (3)0.048 (2)0.038 (2)0.005 (2)0.004 (2)0.008 (2)
C140.115 (5)0.048 (3)0.056 (3)0.006 (3)0.031 (3)0.018 (2)
Geometric parameters (Å, º) top
Cl1—C11.720 (5)C11—C121.409 (7)
S1—C11.703 (5)C11—C141.498 (7)
S1—C41.710 (4)C12—C131.383 (7)
O1—C51.239 (6)C2—H20.9300
C1—C21.339 (7)C3—H30.9300
C2—C31.410 (7)C6—H60.9300
C3—C41.365 (6)C7—H70.9300
C4—C51.469 (6)C9—H90.9300
C5—C61.484 (6)C10—H100.9300
C6—C71.326 (6)C12—H120.9300
C7—C81.466 (6)C13—H130.9300
C8—C91.383 (7)C14—H14A0.9600
C8—C131.414 (6)C14—H14B0.9600
C9—C101.397 (7)C14—H14C0.9600
C10—C111.391 (6)
C1—S1—C491.1 (2)C8—C13—C12119.1 (5)
Cl1—C1—S1119.3 (3)C1—C2—H2124.00
Cl1—C1—C2127.7 (4)C3—C2—H2124.00
S1—C1—C2113.0 (4)C2—C3—H3124.00
C1—C2—C3111.9 (5)C4—C3—H3124.00
C2—C3—C4112.7 (4)C5—C6—H6120.00
S1—C4—C3111.2 (3)C7—C6—H6120.00
S1—C4—C5117.9 (3)C6—C7—H7116.00
C3—C4—C5130.9 (4)C8—C7—H7116.00
O1—C5—C4118.7 (4)C8—C9—H9119.00
O1—C5—C6123.1 (4)C10—C9—H9119.00
C4—C5—C6118.2 (4)C9—C10—H10120.00
C5—C6—C7120.9 (4)C11—C10—H10120.00
C6—C7—C8127.4 (4)C11—C12—H12119.00
C7—C8—C9123.2 (4)C13—C12—H12119.00
C7—C8—C13117.8 (5)C8—C13—H13120.00
C9—C8—C13119.0 (4)C12—C13—H13120.00
C8—C9—C10121.3 (4)C11—C14—H14A109.00
C9—C10—C11120.8 (4)C11—C14—H14B110.00
C10—C11—C12117.4 (4)C11—C14—H14C109.00
C10—C11—C14121.3 (5)H14A—C14—H14B109.00
C12—C11—C14121.3 (4)H14A—C14—H14C109.00
C11—C12—C13122.5 (4)H14B—C14—H14C110.00
C4—S1—C1—Cl1179.2 (3)C4—C5—C6—C7167.3 (4)
C4—S1—C1—C20.4 (4)C5—C6—C7—C8178.3 (4)
C1—S1—C4—C30.1 (4)C6—C7—C8—C98.4 (7)
C1—S1—C4—C5177.8 (3)C6—C7—C8—C13173.4 (4)
Cl1—C1—C2—C3179.3 (4)C7—C8—C9—C10177.1 (4)
S1—C1—C2—C30.7 (6)C13—C8—C9—C101.2 (7)
C1—C2—C3—C40.6 (6)C7—C8—C13—C12177.9 (4)
C2—C3—C4—S10.3 (5)C9—C8—C13—C120.5 (7)
C2—C3—C4—C5177.0 (4)C8—C9—C10—C111.0 (7)
S1—C4—C5—O10.7 (5)C9—C10—C11—C120.1 (7)
S1—C4—C5—C6178.3 (3)C9—C10—C11—C14179.8 (4)
C3—C4—C5—O1177.9 (5)C10—C11—C12—C130.6 (7)
C3—C4—C5—C61.1 (7)C14—C11—C12—C13179.1 (5)
O1—C5—C6—C711.7 (6)C11—C12—C13—C80.4 (7)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C8–C13 ring.
D—H···AD—HH···AD···AD—H···A
C14—H14A···Cgi0.962.773.576 (6)141
Symmetry code: (i) x+2, y1, z+1.
 

Acknowledgements

The authors are grateful to the National Single Crystal X-ray Diffractometer facility, Department of Studies in Physics, University of Mysore, India, for providing the X-ray intensity data.

References

First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationNaveen, S., Dileep Kumar, A., Ajay Kumar, K., Manjunath, H. R., Lokanath, N. K. & Warad, I. (2016a). IUCrData, 1, x161800.  Google Scholar
First citationNaveen, S., Prabhudeva, M. G., Ajay Kumar, K., Lokanath, N. K. & Abdoh, M. (2016b). IUCrData, 1, x161974.  Google Scholar
First citationRigaku. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku. (2011). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTejkiran, P. J., Brahma Teja, M. S., Sai Siva Kumar, P., Sankar, P., Philip, R., Naveen, S., Lokanath, N. K. & Nageswara Rao, G. (2016). J. Photochem. Photobiol. Chem. A, 324, 33–39.  Web of Science CSD CrossRef CAS Google Scholar

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