(E)-3-(3-Methyl­thio­phen-2-yl)-1-p-tolyl­prop-2-en-1-one

Naveen, S.; Al-Maqtari, H.M.; Jamalis, J.; Sirat, H.M.; Lokanath, N.K.; Abdoh, M.

doi:10.1107/S2414314617002346

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170234

https://doi.org/10.1107/S2414314617002346

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ADDENDA AND ERRATA
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(E)-3-(3-Methylthiophen-2-yl)-1-p-tolylprop-2-en-1-one

S. Naveen,^a Helmi Muhammed Al-Maqtari,^b Joazaizulfazli Jamalis,^b Hasnah Mohd Sirat,^b N. K. Lokanath ^c ^* and Muneer Abdoh ^d ^*

^aInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^bFaculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai Johor, Malaysia, ^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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 February 2017; accepted 11 February 2017; online 17 February 2017)

In the title compound, C₁₅H₁₄OS, the dihedral angle between the thiophene and benzene rings is 31.34 (13)°. The thiophene S atom and enone C=O group are approximately in an anti orientation. In the crystal, molecules are linked via pairs of very weak C—H-⋯O hydrogen bonds, forming inversion dimers with R₂²(16) ring motifs.

Keywords: crystal structure; bis-chalcone; π-conjugation.

CCDC reference: 1532444

Structure description

Chalcones and heterocyclic chalcone derivatives play important roles against diverse human diseases due to their anti-inflammatory, anti-leishmanial (Aponte et al., 2010 ) and other properties. As part of our ongoing studies of such molecules (Tejkiran et al., 2016 ; Karthik et al., 2016 ), we report herein the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

The molecule is non-planar, with a dihedral angle of 31.34 (13)° between the methyl-thiophene and the p-toluene rings that are bridged by the enone group. This value is larger than the 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 thiophene ring is affected by π conjugation. This can be explained by the longer C—S bond lengths of 1.738 (3) Å and 1.704 (3) Å for C11—S1 and C14—S1, respectively. The bond angles about C8 [119.7 (3), 121.3 (3) and 119.0 (3) for O1—C8—C6, O1—C8—C9 and C9—C8—C6, respectively] indicate that this carbon atom is in a distorted trigonal planar conformation, which may be due to the steric bulk of the oxygen atom.

In the crystal, the molecules are linked via pairs of very weak C—H⋯O hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (16) ring motif (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1ⁱ	0.96	2.63	3.554 (4)	163
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 2
C—H⋯O hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (16) ring motif.

Synthesis and crystallization

A mixture of 3-methyl-2-thiophenecarboxaldehyde (1 mol) with 4-methylacetophenone (1 mol) was dissolved in methanol (25 ml) and aqueous potassium hydroxide (15 ml) was added drop wise. The reaction mixture was stirred overnight at room temperature. The solid product obtained was separated, filtered and washed with cold methanol. Pure yellow crystals of the title compound were obtained by recrystallization from methanol solution (yield 78%, m.p. 350–353 K).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₄OS
M_r	242.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	6.9231 (4), 27.7148 (16), 7.1228 (5)
β (°)	114.774 (4)
V (Å³)	1240.89 (14)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.14
Crystal size (mm)	0.30 × 0.25 × 0.14

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.566, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	8610, 2031, 1598
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.586

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.174, 1.03
No. of reflections	2031
No. of parameters	156
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1532444

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617002346/hb4125sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002346/hb4125Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002346/hb4125Isup3.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)-3-(3-Methylthiophen-2-yl)-1-p-tolylprop-2-en-1-one top

Crystal data top

C₁₅H₁₄OS	F(000) = 512
M_r = 242.33	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 1598 reflections
a = 6.9231 (4) Å	θ = 7.0–64.7°
b = 27.7148 (16) Å	µ = 2.14 mm⁻¹
c = 7.1228 (5) Å	T = 296 K
β = 114.774 (4)°	Prism, yellow
V = 1240.89 (14) Å³	0.30 × 0.25 × 0.14 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	2031 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1598 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.070
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.7°, θ_min = 7.0°
φ and ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −32→30
T_min = 0.566, T_max = 0.754	l = −7→8
8610 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.1125P)²] where P = (F_o² + 2F_c²)/3
2031 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Special details top

Experimental. IR (cm^-1): 3116 (C-H-sp² stretching of aromatic ring), 2919 (CH-sp³) 1646 (C═O ), 1565, 1423 ( C═C aromatic Ring).

¹H NMR (400 MHz, CDCl₃): δ 2.40 ( s, 3H, H-7') , 2.45 ( s, 3H, H-6), 6.94 ( d, 1H, H-4, J = 5.20 Hz), 7.28-7.36 (m, 4H, H-5, H-α, H-3', H-5'), 7.95 (d, 2H, H-2', H-6', J = 8.40 Hz), 8.07(d, 1H, H-β, J = 14.80 Hz).

¹³C NMR (75 MHz, CDCl₃): δ 14.33, 21.70, 119.79, 127.14, 128.52, 129.31, 131.44, 134.64, 135.21, 135.69, 142.63, 143.54, 189.35.

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
S1	0.16726 (11)	0.78110 (3)	0.19824 (12)	0.0348 (3)
O1	0.7151 (3)	0.63224 (7)	0.3438 (3)	0.0352 (7)
C1	0.4738 (4)	0.54657 (10)	0.2368 (4)	0.0283 (9)
C2	0.3694 (5)	0.50372 (10)	0.2248 (4)	0.0313 (9)
C3	0.1868 (5)	0.50153 (10)	0.2602 (4)	0.0303 (9)
C4	0.1105 (5)	0.54441 (11)	0.3021 (4)	0.0316 (10)
C5	0.2131 (4)	0.58790 (10)	0.3123 (4)	0.0273 (9)
C6	0.3991 (4)	0.58970 (10)	0.2829 (4)	0.0250 (8)
C7	0.0761 (6)	0.45430 (11)	0.2523 (5)	0.0426 (11)
C8	0.5255 (4)	0.63491 (10)	0.3072 (4)	0.0279 (9)
C9	0.4192 (5)	0.68178 (10)	0.2859 (4)	0.0276 (9)
C10	0.5260 (5)	0.72348 (10)	0.3183 (4)	0.0286 (9)
C11	0.4400 (4)	0.77137 (10)	0.2968 (4)	0.0269 (9)
C12	0.5471 (5)	0.81482 (10)	0.3461 (4)	0.0309 (10)
C13	0.4087 (5)	0.85438 (11)	0.3060 (5)	0.0335 (10)
C14	0.2008 (5)	0.84200 (11)	0.2269 (4)	0.0343 (10)
C15	0.7838 (5)	0.81953 (11)	0.4367 (6)	0.0474 (13)
H1	0.59650	0.54680	0.21390	0.0340*
H2	0.42210	0.47560	0.19230	0.0380*
H4	−0.01280	0.54400	0.32400	0.0380*
H5	0.15690	0.61620	0.33920	0.0330*
H7A	0.16060	0.43520	0.37080	0.0640*
H7B	0.05750	0.43720	0.12860	0.0640*
H7C	−0.06030	0.46040	0.25240	0.0640*
H9	0.27350	0.68250	0.24870	0.0330*
H10	0.67210	0.72120	0.35930	0.0340*
H13	0.45570	0.88620	0.33140	0.0400*
H14	0.08970	0.86400	0.19240	0.0410*
H15A	0.83880	0.81980	0.58480	0.0710*
H15B	0.82160	0.84910	0.39000	0.0710*
H15C	0.84320	0.79270	0.39350	0.0710*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0330 (5)	0.0269 (5)	0.0420 (5)	0.0017 (3)	0.0132 (4)	−0.0031 (3)
O1	0.0274 (12)	0.0299 (12)	0.0449 (13)	0.0026 (9)	0.0117 (9)	0.0026 (9)
C1	0.0265 (15)	0.0290 (16)	0.0274 (16)	0.0063 (12)	0.0094 (12)	0.0009 (11)
C2	0.0406 (18)	0.0225 (15)	0.0236 (15)	0.0071 (13)	0.0063 (13)	0.0001 (11)
C3	0.0353 (17)	0.0294 (16)	0.0168 (14)	−0.0041 (13)	0.0018 (12)	0.0028 (11)
C4	0.0291 (15)	0.0389 (19)	0.0255 (16)	−0.0042 (13)	0.0101 (12)	0.0012 (12)
C5	0.0290 (15)	0.0270 (16)	0.0223 (15)	0.0052 (12)	0.0072 (12)	−0.0022 (11)
C6	0.0265 (14)	0.0282 (16)	0.0144 (13)	0.0024 (12)	0.0028 (11)	0.0005 (10)
C7	0.055 (2)	0.0318 (18)	0.0275 (17)	−0.0094 (15)	0.0039 (15)	0.0044 (12)
C8	0.0309 (16)	0.0305 (17)	0.0203 (14)	0.0023 (13)	0.0089 (12)	0.0002 (11)
C9	0.0285 (15)	0.0268 (16)	0.0273 (15)	0.0034 (12)	0.0115 (12)	−0.0013 (11)
C10	0.0326 (16)	0.0312 (17)	0.0229 (15)	0.0005 (13)	0.0126 (13)	−0.0007 (11)
C11	0.0333 (16)	0.0279 (15)	0.0224 (15)	0.0007 (12)	0.0145 (13)	−0.0008 (11)
C12	0.0405 (18)	0.0284 (17)	0.0286 (16)	−0.0006 (13)	0.0193 (13)	0.0012 (11)
C13	0.0474 (19)	0.0242 (16)	0.0343 (17)	−0.0019 (14)	0.0224 (14)	0.0009 (12)
C14	0.046 (2)	0.0234 (16)	0.0367 (17)	0.0071 (13)	0.0204 (15)	0.0041 (12)
C15	0.042 (2)	0.0305 (18)	0.073 (3)	−0.0043 (15)	0.0273 (18)	0.0001 (16)

Geometric parameters (Å, º) top

S1—C11	1.738 (3)	C12—C15	1.494 (5)
S1—C14	1.704 (3)	C13—C14	1.352 (5)
O1—C8	1.229 (4)	C1—H1	0.9300
C1—C2	1.374 (4)	C2—H2	0.9300
C1—C6	1.395 (4)	C4—H4	0.9300
C2—C3	1.390 (5)	C5—H5	0.9300
C3—C4	1.383 (4)	C7—H7A	0.9600
C3—C7	1.506 (5)	C7—H7B	0.9600
C4—C5	1.385 (4)	C7—H7C	0.9600
C5—C6	1.389 (4)	C9—H9	0.9300
C6—C8	1.496 (4)	C10—H10	0.9300
C8—C9	1.469 (4)	C13—H13	0.9300
C9—C10	1.339 (4)	C14—H14	0.9300
C10—C11	1.436 (4)	C15—H15A	0.9600
C11—C12	1.380 (4)	C15—H15B	0.9600
C12—C13	1.404 (5)	C15—H15C	0.9600

C11—S1—C14	92.00 (15)	C1—C2—H2	119.00
C2—C1—C6	121.2 (3)	C3—C2—H2	119.00
C1—C2—C3	121.4 (3)	C3—C4—H4	119.00
C2—C3—C4	117.4 (3)	C5—C4—H4	119.00
C2—C3—C7	121.2 (3)	C4—C5—H5	120.00
C4—C3—C7	121.4 (3)	C6—C5—H5	120.00
C3—C4—C5	121.7 (3)	C3—C7—H7A	109.00
C4—C5—C6	120.7 (3)	C3—C7—H7B	109.00
C1—C6—C5	117.6 (3)	C3—C7—H7C	109.00
C1—C6—C8	119.2 (3)	H7A—C7—H7B	109.00
C5—C6—C8	123.1 (3)	H7A—C7—H7C	110.00
O1—C8—C6	119.7 (3)	H7B—C7—H7C	110.00
O1—C8—C9	121.3 (3)	C8—C9—H9	119.00
C6—C8—C9	119.0 (3)	C10—C9—H9	119.00
C8—C9—C10	121.9 (3)	C9—C10—H10	116.00
C9—C10—C11	127.2 (3)	C11—C10—H10	116.00
S1—C11—C10	121.2 (2)	C12—C13—H13	123.00
S1—C11—C12	110.1 (2)	C14—C13—H13	123.00
C10—C11—C12	128.7 (3)	S1—C14—H14	124.00
C11—C12—C13	112.4 (3)	C13—C14—H14	124.00
C11—C12—C15	124.1 (3)	C12—C15—H15A	109.00
C13—C12—C15	123.4 (3)	C12—C15—H15B	109.00
C12—C13—C14	113.8 (3)	C12—C15—H15C	109.00
S1—C14—C13	111.7 (2)	H15A—C15—H15B	109.00
C2—C1—H1	119.00	H15A—C15—H15C	109.00
C6—C1—H1	119.00	H15B—C15—H15C	110.00

C14—S1—C11—C10	179.2 (2)	C5—C6—C8—O1	157.1 (3)
C14—S1—C11—C12	−0.6 (2)	C5—C6—C8—C9	−23.1 (4)
C11—S1—C14—C13	0.4 (2)	O1—C8—C9—C10	−4.4 (4)
C6—C1—C2—C3	−0.7 (4)	C6—C8—C9—C10	175.8 (3)
C2—C1—C6—C5	−1.2 (4)	C8—C9—C10—C11	178.1 (3)
C2—C1—C6—C8	176.2 (2)	C9—C10—C11—S1	−6.1 (4)
C1—C2—C3—C4	1.8 (4)	C9—C10—C11—C12	173.7 (3)
C1—C2—C3—C7	−178.4 (3)	S1—C11—C12—C13	0.7 (3)
C2—C3—C4—C5	−1.1 (4)	S1—C11—C12—C15	179.3 (3)
C7—C3—C4—C5	179.1 (3)	C10—C11—C12—C13	−179.2 (3)
C3—C4—C5—C6	−0.8 (4)	C10—C11—C12—C15	−0.5 (5)
C4—C5—C6—C1	1.9 (4)	C11—C12—C13—C14	−0.4 (4)
C4—C5—C6—C8	−175.4 (2)	C15—C12—C13—C14	−179.0 (3)
C1—C6—C8—O1	−20.2 (4)	C12—C13—C14—S1	−0.1 (4)
C1—C6—C8—C9	159.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1ⁱ	0.96	2.63	3.554 (4)	163

Symmetry code: (i) −x+1, −y+1, −z+1.

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. JJ thanks Universiti Teknologi Malaysia (UTM) for financial support under the Fundamental Research Grant Scheme (FRGS) of vote numbers 4F122 and 4F448.

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