(E)-1-(5-Chloro­thio­phen-2-yl)-3-(2,4-di­methyl­phen­yl)prop-2-en-1-one

Naveen, S.; Prabhudeva, M.G.; Ajay Kumar, K.; Lokanath, N.K.; Abdoh, M.

doi:10.1107/S241431461601974X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161974

https://doi.org/10.1107/S241431461601974X

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(E)-1-(5-Chlorothiophen-2-yl)-3-(2,4-dimethylphenyl)prop-2-en-1-one

S. Naveen,^a M. G. Prabhudeva,^b K. Ajay Kumar,^b N. K. Lokanath ^c ^* and Muneer Abdoh ^d ^*

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

Edited by J. Simpson, University of Otago, New Zealand (Received 6 December 2016; accepted 10 December 2016; online 13 December 2016)

In the title compound, C₁₅H₁₃ClOS, the olefinic double bond adopts an E configuration. The molecule is nearly planar, as seen by the dihedral angle of 9.07 (8)° between the thiophene and phenyl rings. The trans configuration of the C=C double bond in the central enone group is confirmed by the C—C=C—C torsion angle of 177.6 (2)°. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯S hydrogen bonds, forming chains propagating along the c axis.

Keywords: crystal structure; bis-chalcone; hydrogen bonds.

CCDC reference: 1522076

Structure description

Chalcones form the central cores for the construction of variety of bioactive molecules (Naveen et al., 2016 ). The most commonly employed method for the synthesis of chalcones involves the condensation of an aromatic aldehyde and an aromatic ketone in the presence of aqueous alkaline bases (Mahapatra et al., 2015 ). 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 ), we report here the synthesis and crystal structure of the title compound.

The title molecule (Fig. 1) is nearly planar, with a dihedral angle of 9.07 (8)° between the thiophene and phenyl rings that are bridged by the olefinic double bond. This value is less than 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., 2016). The trans configuration about the C6=C7 double bond in the central enone group is confirmed by the C5—C6=C75—C8 torsion angle, 177.6 (2)°. The carbonyl group at C5 lies in the plane of the olefinic double bond and thiophene ring as indicated by the S1—C4—C5—O1 [1.2 (3)°] and O1—C5—C6—C7 [−4.7 (3)°] torsion angles.

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

In the crystal, the molecules are linked via weak C—H⋯O and C—H⋯S hydrogen bonds, forming chains propagating along the c axis (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.48	3.400 (3)	169
C3—H3⋯S1ⁱ	0.93	2.90	3.459 (2)	120
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Packing of the molecules viewed along the b axis, with hydrogen bonds drawn as dashed lines.

Synthesis and crystallization

A mixture of 1-(5-chlorothiophen-2-yl)ethanone (5 mmol), 2,4-dimethylbenzaldehyde (5 mmol) and potassium 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, the reaction mixture was poured in to ice-cold water and kept in the refrigerator overnight. The solid that formed was filtered, and washed with cold methanol (5%) to obtain the crude product. Pure green crystals of the title compound were obtained by crystallization from methanol by the slow evaporation technique, m.p. 98–100°C.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₃ClOS
M_r	276.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	15.588 (2), 7.4306 (11), 11.4165 (17)
β (°)	94.293 (3)
V (Å³)	1318.6 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.90
Crystal size (mm)	0.29 × 0.26 × 0.23

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.397, 0.467
No. of measured, independent and observed [I > 2σ(I)] reflections	9075, 2149, 2120
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.584

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.148, 1.11
No. of reflections	2149
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.87
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1522076

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461601974X/sj4076sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461601974X/sj4076Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461601974X/sj4076Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); 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: Mercury (Macrae et al., 2008).

(E)-1-(5-Chlorothiophen-2-yl)-3-(2,4-dimethylphenyl)prop-2-en-1-one top

Crystal data top

C₁₅H₁₃ClOS	F(000) = 576
M_r = 276.77	D_x = 1.394 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2120 reflections
a = 15.588 (2) Å	θ = 5.7–64.2°
b = 7.4306 (11) Å	µ = 3.90 mm⁻¹
c = 11.4165 (17) Å	T = 296 K
β = 94.293 (3)°	Rectangle, green
V = 1318.6 (3) Å³	0.29 × 0.26 × 0.23 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	2149 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	2120 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.050
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.2°, θ_min = 5.7°
φ and ω scans	h = −18→17
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −7→8
T_min = 0.397, T_max = 0.467	l = −12→13
9075 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1085P)² + 0.5955P] where P = (F_o² + 2F_c²)/3
2149 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.87 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	0.22467 (3)	0.94779 (7)	0.40476 (4)	0.0210 (2)
S1	0.39687 (3)	0.81834 (7)	0.35033 (4)	0.0179 (2)
O1	0.57439 (10)	0.7025 (2)	0.32391 (14)	0.0240 (5)
C1	0.32622 (13)	0.8762 (3)	0.45189 (19)	0.0163 (6)
C2	0.36001 (14)	0.8625 (3)	0.56508 (19)	0.0181 (6)
C3	0.44560 (15)	0.8010 (3)	0.5701 (2)	0.0174 (6)
C4	0.47497 (13)	0.7695 (3)	0.46152 (19)	0.0155 (6)
C5	0.56000 (14)	0.7119 (3)	0.42881 (19)	0.0170 (6)
C6	0.62517 (14)	0.6691 (3)	0.5239 (2)	0.0172 (6)
C7	0.70203 (14)	0.6053 (3)	0.49961 (19)	0.0179 (7)
C8	0.77481 (14)	0.5622 (3)	0.58247 (19)	0.0163 (7)
C9	0.77421 (14)	0.6023 (3)	0.7026 (2)	0.0187 (6)
C10	0.84389 (15)	0.5652 (3)	0.7802 (2)	0.0192 (7)
C11	0.91834 (14)	0.4879 (3)	0.7412 (2)	0.0185 (6)
C12	0.91894 (14)	0.4460 (3)	0.6227 (2)	0.0185 (7)
C13	0.84913 (14)	0.4818 (3)	0.5421 (2)	0.0173 (6)
C14	0.85383 (15)	0.4288 (3)	0.4153 (2)	0.0218 (7)
C15	0.99642 (15)	0.4547 (3)	0.8251 (2)	0.0232 (7)
H2	0.33040	0.89010	0.63050	0.0220*
H3	0.47900	0.78340	0.64010	0.0210*
H6	0.61300	0.68640	0.60160	0.0210*
H7	0.71000	0.58610	0.42070	0.0210*
H9	0.72560	0.65510	0.73040	0.0220*
H10	0.84140	0.59190	0.85950	0.0230*
H12	0.96760	0.39200	0.59600	0.0220*
H14A	0.90930	0.37800	0.40460	0.0330*
H14B	0.84510	0.53310	0.36630	0.0330*
H14C	0.81000	0.34140	0.39420	0.0330*
H15A	1.02790	0.35360	0.79840	0.0350*
H15B	0.97840	0.43010	0.90200	0.0350*
H15C	1.03260	0.55950	0.82810	0.0350*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0149 (4)	0.0250 (4)	0.0222 (4)	0.0028 (2)	−0.0046 (2)	0.0022 (2)
S1	0.0155 (4)	0.0266 (4)	0.0112 (4)	0.0009 (2)	−0.0024 (2)	−0.0011 (2)
O1	0.0188 (9)	0.0397 (10)	0.0134 (9)	0.0036 (7)	0.0011 (6)	−0.0022 (6)
C1	0.0136 (10)	0.0163 (11)	0.0185 (11)	−0.0008 (8)	−0.0014 (8)	0.0001 (8)
C2	0.0175 (11)	0.0218 (11)	0.0151 (11)	0.0002 (9)	0.0013 (8)	−0.0008 (9)
C3	0.0175 (11)	0.0199 (11)	0.0141 (11)	−0.0009 (8)	−0.0025 (9)	0.0031 (8)
C4	0.0152 (11)	0.0147 (10)	0.0160 (11)	−0.0026 (8)	−0.0022 (8)	0.0004 (8)
C5	0.0171 (11)	0.0177 (10)	0.0159 (11)	−0.0031 (8)	−0.0011 (9)	−0.0018 (8)
C6	0.0171 (11)	0.0201 (11)	0.0142 (11)	−0.0006 (8)	0.0006 (9)	−0.0006 (8)
C7	0.0202 (12)	0.0187 (11)	0.0148 (11)	−0.0020 (9)	0.0014 (9)	0.0005 (9)
C8	0.0155 (12)	0.0150 (11)	0.0182 (11)	−0.0034 (8)	−0.0005 (9)	0.0016 (8)
C9	0.0179 (11)	0.0194 (11)	0.0189 (11)	−0.0003 (8)	0.0027 (9)	−0.0007 (9)
C10	0.0221 (12)	0.0192 (11)	0.0161 (11)	−0.0040 (8)	0.0001 (9)	0.0001 (8)
C11	0.0182 (11)	0.0131 (10)	0.0237 (12)	−0.0046 (8)	−0.0021 (9)	0.0036 (9)
C12	0.0155 (11)	0.0143 (11)	0.0258 (13)	−0.0005 (8)	0.0016 (9)	0.0009 (8)
C13	0.0175 (11)	0.0143 (10)	0.0202 (12)	−0.0035 (8)	0.0022 (9)	0.0001 (8)
C14	0.0204 (12)	0.0241 (12)	0.0211 (12)	0.0015 (8)	0.0032 (10)	−0.0031 (9)
C15	0.0228 (12)	0.0198 (12)	0.0258 (13)	−0.0007 (9)	−0.0060 (10)	0.0011 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.718 (2)	C11—C15	1.512 (3)
S1—C1	1.713 (2)	C12—C13	1.397 (3)
S1—C4	1.730 (2)	C13—C14	1.507 (3)
O1—C5	1.237 (3)	C2—H2	0.9300
C1—C2	1.362 (3)	C3—H3	0.9300
C2—C3	1.407 (3)	C6—H6	0.9300
C3—C4	1.373 (3)	C7—H7	0.9300
C4—C5	1.468 (3)	C9—H9	0.9300
C5—C6	1.465 (3)	C10—H10	0.9300
C6—C7	1.337 (3)	C12—H12	0.9300
C7—C8	1.457 (3)	C14—H14A	0.9600
C8—C9	1.404 (3)	C14—H14B	0.9600
C8—C13	1.411 (3)	C14—H14C	0.9600
C9—C10	1.377 (3)	C15—H15A	0.9600
C10—C11	1.397 (3)	C15—H15B	0.9600
C11—C12	1.389 (3)	C15—H15C	0.9600

C1—S1—C4	90.50 (10)	C1—C2—H2	124.00
Cl1—C1—S1	119.33 (13)	C3—C2—H2	124.00
Cl1—C1—C2	127.02 (17)	C2—C3—H3	123.00
S1—C1—C2	113.63 (16)	C4—C3—H3	123.00
C1—C2—C3	111.2 (2)	C5—C6—H6	120.00
C2—C3—C4	113.4 (2)	C7—C6—H6	120.00
S1—C4—C3	111.27 (16)	C6—C7—H7	116.00
S1—C4—C5	118.28 (16)	C8—C7—H7	116.00
C3—C4—C5	130.4 (2)	C8—C9—H9	119.00
O1—C5—C4	119.7 (2)	C10—C9—H9	119.00
O1—C5—C6	122.6 (2)	C9—C10—H10	120.00
C4—C5—C6	117.65 (19)	C11—C10—H10	120.00
C5—C6—C7	120.4 (2)	C11—C12—H12	119.00
C6—C7—C8	127.6 (2)	C13—C12—H12	119.00
C7—C8—C9	121.7 (2)	C13—C14—H14A	110.00
C7—C8—C13	120.0 (2)	C13—C14—H14B	110.00
C9—C8—C13	118.3 (2)	C13—C14—H14C	109.00
C8—C9—C10	121.6 (2)	H14A—C14—H14B	109.00
C9—C10—C11	120.7 (2)	H14A—C14—H14C	109.00
C10—C11—C12	118.0 (2)	H14B—C14—H14C	109.00
C10—C11—C15	120.9 (2)	C11—C15—H15A	109.00
C12—C11—C15	121.1 (2)	C11—C15—H15B	110.00
C11—C12—C13	122.5 (2)	C11—C15—H15C	109.00
C8—C13—C12	118.9 (2)	H15A—C15—H15B	109.00
C8—C13—C14	121.6 (2)	H15A—C15—H15C	109.00
C12—C13—C14	119.4 (2)	H15B—C15—H15C	109.00

C4—S1—C1—Cl1	179.60 (15)	C6—C7—C8—C9	−6.7 (4)
C4—S1—C1—C2	0.98 (19)	C6—C7—C8—C13	174.8 (2)
C1—S1—C4—C3	−0.93 (18)	C7—C8—C9—C10	−178.5 (2)
C1—S1—C4—C5	−178.14 (18)	C13—C8—C9—C10	0.1 (3)
Cl1—C1—C2—C3	−179.26 (17)	C7—C8—C13—C12	178.4 (2)
S1—C1—C2—C3	−0.8 (3)	C7—C8—C13—C14	−3.5 (3)
C1—C2—C3—C4	0.0 (3)	C9—C8—C13—C12	−0.2 (3)
C2—C3—C4—S1	0.7 (3)	C9—C8—C13—C14	177.9 (2)
C2—C3—C4—C5	177.5 (2)	C8—C9—C10—C11	0.8 (3)
S1—C4—C5—O1	1.2 (3)	C9—C10—C11—C12	−1.5 (3)
S1—C4—C5—C6	−179.34 (16)	C9—C10—C11—C15	177.2 (2)
C3—C4—C5—O1	−175.4 (2)	C10—C11—C12—C13	1.4 (3)
C3—C4—C5—C6	4.1 (4)	C15—C11—C12—C13	−177.3 (2)
O1—C5—C6—C7	−4.7 (3)	C11—C12—C13—C8	−0.5 (3)
C4—C5—C6—C7	175.9 (2)	C11—C12—C13—C14	−178.7 (2)
C5—C6—C7—C8	177.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.48	3.400 (3)	169
C3—H3···S1ⁱ	0.93	2.90	3.459 (2)	120

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility.

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