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

Kumara, K.; Naveen, S.; Prabhudeva, M.G.; Ajay Kumar, K.; Lokanath, N.K.; Warad, I.

doi:10.1107/S2414314617000384

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x170038

https://doi.org/10.1107/S2414314617000384

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access

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

Karthik Kumara,^a S. Naveen,^b M. G. Prabhudeva,^c K. Ajay Kumar,^c N. K. Lokanath ^a ^* and Ismail Warad ^d ^*

^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.

Keywords: crystal structure; chalcone; trans conformation; C—H⋯π interactions.

CCDC reference: 1526365

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 ). 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 ; Naveen et al., 2016b ), we report herein the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. 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). 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
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 and Fig. 2). 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	D⋯A	D—H⋯A
C14—H14A⋯Cgⁱ	0.96	2.77	3.576 (6)	141
Symmetry code: (i) -x+2, -y-1, -z+1.

Figure 2
A view along the c axis of the crystal packing of the title compound. The C—H⋯π interactions (Table 1

) 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.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClOS
M_r	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)
V (Å³)	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 )
T_min, T_max	0.972, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	3635, 2808, 1279
R_int	0.071
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.65
Computer programs: CrystalClear (Rigaku, 2011 ), SHELXS97and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1526365

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617000384/su4122sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000384/su4122Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000384/su4122Isup3.cml

checkCIF report

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

C₁₄H₁₁ClOS	Z = 2
M_r = 262.75	F(000) = 272
Triclinic, P1	D_x = 1.387 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.000 (2) Å	Cell parameters from 3635 reflections
b = 9.718 (4) Å	θ = 3.4–27.6°
c = 10.936 (4) Å	µ = 0.45 mm⁻¹
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 tube	1279 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 18.4 pixels mm^-1	θ_max = 27.6°, θ_min = 3.4°
profile data from ω–scans	h = −7→7
Absorption correction: multi-scan (NUMABS; Rigaku, 1999)	k = −11→12
T_min = 0.972, T_max = 0.976	l = −13→14
3635 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.264	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.1466P)²] where P = (F_o² + 2F_c²)/3
2808 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cl1	0.6471 (3)	0.42181 (15)	−0.15570 (14)	0.0791 (6)
S1	0.5125 (2)	0.22896 (12)	0.03032 (11)	0.0490 (4)
O1	0.4218 (6)	0.0428 (4)	0.2208 (3)	0.0609 (12)
C1	0.7155 (8)	0.3040 (5)	−0.0540 (4)	0.0473 (16)
C2	0.9174 (9)	0.2628 (5)	−0.0289 (5)	0.0566 (17)
C3	0.9106 (8)	0.1657 (5)	0.0608 (4)	0.0494 (17)
C4	0.7015 (7)	0.1373 (4)	0.1020 (4)	0.0421 (14)
C5	0.6217 (8)	0.0486 (4)	0.1973 (4)	0.0435 (14)
C6	0.7863 (7)	−0.0282 (4)	0.2624 (4)	0.0415 (12)
C7	0.7370 (8)	−0.0886 (4)	0.3637 (4)	0.0423 (12)
C8	0.8780 (9)	−0.1707 (4)	0.4362 (4)	0.0463 (14)
C9	1.0772 (8)	−0.2111 (5)	0.3982 (4)	0.0475 (17)
C10	1.2012 (8)	−0.2947 (5)	0.4676 (4)	0.0499 (17)
C11	1.1293 (9)	−0.3381 (4)	0.5784 (4)	0.0485 (16)
C12	0.9276 (9)	−0.2947 (5)	0.6170 (4)	0.0516 (16)
C13	0.8017 (9)	−0.2132 (5)	0.5487 (4)	0.0525 (14)
C14	1.2604 (11)	−0.4281 (5)	0.6534 (5)	0.075 (2)
H2	1.04670	0.29450	−0.06610	0.0680*
H3	1.03520	0.12540	0.08890	0.0600*
H6	0.92600	−0.03400	0.23170	0.0500*
H7	0.59690	−0.07760	0.39200	0.0510*
H9	1.12970	−0.18200	0.32510	0.0570*
H10	1.33340	−0.32170	0.43930	0.0600*
H12	0.87730	−0.32190	0.69120	0.0620*
H13	0.66870	−0.18680	0.57640	0.0630*
H14A	1.26880	−0.51450	0.60630	0.1130*
H14B	1.18680	−0.44620	0.72680	0.1130*
H14C	1.40970	−0.38140	0.67500	0.1130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1032 (13)	0.0772 (10)	0.0688 (10)	0.0388 (9)	0.0066 (9)	0.0402 (8)
S1	0.0518 (8)	0.0535 (7)	0.0465 (7)	0.0221 (6)	0.0015 (6)	0.0126 (5)
O1	0.063 (2)	0.071 (2)	0.057 (2)	0.0232 (19)	0.0186 (19)	0.0236 (18)
C1	0.054 (3)	0.047 (2)	0.046 (3)	0.024 (2)	0.000 (2)	0.013 (2)
C2	0.048 (3)	0.066 (3)	0.060 (3)	0.009 (3)	0.011 (2)	0.024 (3)
C3	0.045 (3)	0.056 (3)	0.054 (3)	0.025 (2)	0.005 (2)	0.019 (2)
C4	0.050 (3)	0.040 (2)	0.037 (2)	0.009 (2)	0.002 (2)	0.0042 (18)
C5	0.055 (3)	0.041 (2)	0.036 (2)	0.011 (2)	0.003 (2)	0.0051 (18)
C6	0.035 (2)	0.047 (2)	0.045 (2)	0.0122 (19)	0.004 (2)	0.009 (2)
C7	0.041 (2)	0.041 (2)	0.046 (2)	0.0092 (19)	0.002 (2)	0.0063 (19)
C8	0.069 (3)	0.034 (2)	0.034 (2)	0.000 (2)	−0.002 (2)	0.0073 (17)
C9	0.049 (3)	0.052 (3)	0.045 (3)	0.014 (2)	0.006 (2)	0.013 (2)
C10	0.046 (3)	0.052 (3)	0.053 (3)	0.013 (2)	−0.003 (2)	0.009 (2)
C11	0.061 (3)	0.036 (2)	0.045 (3)	−0.002 (2)	−0.011 (2)	0.0065 (19)
C12	0.065 (3)	0.050 (3)	0.037 (2)	−0.004 (2)	−0.005 (2)	0.012 (2)
C13	0.069 (3)	0.048 (2)	0.038 (2)	−0.005 (2)	0.004 (2)	0.008 (2)
C14	0.115 (5)	0.048 (3)	0.056 (3)	−0.006 (3)	−0.031 (3)	0.018 (2)

Geometric parameters (Å, º) top

Cl1—C1	1.720 (5)	C11—C12	1.409 (7)
S1—C1	1.703 (5)	C11—C14	1.498 (7)
S1—C4	1.710 (4)	C12—C13	1.383 (7)
O1—C5	1.239 (6)	C2—H2	0.9300
C1—C2	1.339 (7)	C3—H3	0.9300
C2—C3	1.410 (7)	C6—H6	0.9300
C3—C4	1.365 (6)	C7—H7	0.9300
C4—C5	1.469 (6)	C9—H9	0.9300
C5—C6	1.484 (6)	C10—H10	0.9300
C6—C7	1.326 (6)	C12—H12	0.9300
C7—C8	1.466 (6)	C13—H13	0.9300
C8—C9	1.383 (7)	C14—H14A	0.9600
C8—C13	1.414 (6)	C14—H14B	0.9600
C9—C10	1.397 (7)	C14—H14C	0.9600
C10—C11	1.391 (6)

C1—S1—C4	91.1 (2)	C8—C13—C12	119.1 (5)
Cl1—C1—S1	119.3 (3)	C1—C2—H2	124.00
Cl1—C1—C2	127.7 (4)	C3—C2—H2	124.00
S1—C1—C2	113.0 (4)	C2—C3—H3	124.00
C1—C2—C3	111.9 (5)	C4—C3—H3	124.00
C2—C3—C4	112.7 (4)	C5—C6—H6	120.00
S1—C4—C3	111.2 (3)	C7—C6—H6	120.00
S1—C4—C5	117.9 (3)	C6—C7—H7	116.00
C3—C4—C5	130.9 (4)	C8—C7—H7	116.00
O1—C5—C4	118.7 (4)	C8—C9—H9	119.00
O1—C5—C6	123.1 (4)	C10—C9—H9	119.00
C4—C5—C6	118.2 (4)	C9—C10—H10	120.00
C5—C6—C7	120.9 (4)	C11—C10—H10	120.00
C6—C7—C8	127.4 (4)	C11—C12—H12	119.00
C7—C8—C9	123.2 (4)	C13—C12—H12	119.00
C7—C8—C13	117.8 (5)	C8—C13—H13	120.00
C9—C8—C13	119.0 (4)	C12—C13—H13	120.00
C8—C9—C10	121.3 (4)	C11—C14—H14A	109.00
C9—C10—C11	120.8 (4)	C11—C14—H14B	110.00
C10—C11—C12	117.4 (4)	C11—C14—H14C	109.00
C10—C11—C14	121.3 (5)	H14A—C14—H14B	109.00
C12—C11—C14	121.3 (4)	H14A—C14—H14C	109.00
C11—C12—C13	122.5 (4)	H14B—C14—H14C	110.00

C4—S1—C1—Cl1	−179.2 (3)	C4—C5—C6—C7	167.3 (4)
C4—S1—C1—C2	−0.4 (4)	C5—C6—C7—C8	178.3 (4)
C1—S1—C4—C3	0.1 (4)	C6—C7—C8—C9	−8.4 (7)
C1—S1—C4—C5	177.8 (3)	C6—C7—C8—C13	173.4 (4)
Cl1—C1—C2—C3	179.3 (4)	C7—C8—C9—C10	−177.1 (4)
S1—C1—C2—C3	0.7 (6)	C13—C8—C9—C10	1.2 (7)
C1—C2—C3—C4	−0.6 (6)	C7—C8—C13—C12	177.9 (4)
C2—C3—C4—S1	0.3 (5)	C9—C8—C13—C12	−0.5 (7)
C2—C3—C4—C5	−177.0 (4)	C8—C9—C10—C11	−1.0 (7)
S1—C4—C5—O1	0.7 (5)	C9—C10—C11—C12	0.1 (7)
S1—C4—C5—C6	−178.3 (3)	C9—C10—C11—C14	179.8 (4)
C3—C4—C5—O1	177.9 (5)	C10—C11—C12—C13	0.6 (7)
C3—C4—C5—C6	−1.1 (7)	C14—C11—C12—C13	−179.1 (5)
O1—C5—C6—C7	−11.7 (6)	C11—C12—C13—C8	−0.4 (7)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···Cgⁱ	0.96	2.77	3.576 (6)	141

Symmetry code: (i) −x+2, −y−1, −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

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. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Naveen, S., Dileep Kumar, A., Ajay Kumar, K., Manjunath, H. R., Lokanath, N. K. & Warad, I. (2016a). IUCrData, 1, x161800. Google Scholar
Naveen, S., Prabhudeva, M. G., Ajay Kumar, K., Lokanath, N. K. & Abdoh, M. (2016b). IUCrData, 1, x161974. Google Scholar
Rigaku. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku. (2011). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2414-3146

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

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

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