(E)-3-(2,3-Di­chloro­phen­yl)-1-(2-meth­oxy­phen­yl)prop-2-en-1-one

Sunitha, V.M.; Naveen, S.; Vagish, C.B.; Ajay Kumar, K.; Lokanath, N.K.; Manjunath, H.R.

doi:10.1107/S2414314616020563

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162056

https://doi.org/10.1107/S2414314616020563

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(E)-3-(2,3-Dichlorophenyl)-1-(2-methoxyphenyl)prop-2-en-1-one

V. M. Sunitha,^a,^b S. Naveen,^c ^* C. B. Vagish,^d K. Ajay Kumar,^d N. K. Lokanath ^e and H. R. Manjunath ^f ^*

^aDepartment of Physics, Shri Pillappa College of Engineering, Bengaluru 560 089, India, ^bDepartment of Physics, Prist University, Vallam, Tanjavur 513 403, India, ^cInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^dDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^eDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^fDepartment of Physics, Acharya Institute of Technology, Soldevanahalli, Bengaluru 560 107, India
^*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, manjunathhr@acharya.ac.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 23 December 2016; accepted 28 December 2016; online 6 January 2017)

In the title compound, C₁₆H₁₂Cl₂O₂, the olefinic double bond adopts an E configuration. The molecule is non-planar, as shown by the dihedral angle of 15.40 (19)° between the 2,3-dichlorophenyl ring and the 2-methoxyphenyl ring. In the crystal, molecules are linked via weak C—H⋯O hydrogen bonds, forming zigzag chains propagating along the c axis.

Keywords: crystal structure; bis-chalcone; weak C—H⋯O hydrogen bonds.

CCDC reference: 1524698

Structure description

Chalcones form the central core for the construction of a variety of bioactive compounds. The usual method for the synthesis of chalcones involves the condensation of 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 anti-diabetic, anti-neoplastic, anti-hypertensive, anti-inflammatory, anti-malarial, anti-oxidant, anti-fungal, etc. (Mahapatra et al., 2015 ). The α,β-unsaturated carbonyl system of chalcones makes them useful as building blocks in organic synthesis. They have been efficiently employed as precursors in the synthesis of biologically potent benzothiazepines (Naveen et al., 2016b ). In view of the diverse applications of 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 non-planar, with a dihedral angle of 15.40 (19)° between the dichlorophenyl (C1–C6) and methoxyphenyl (C10–C15) rings that are bridged by the olefinic double bond C7=C8. This is comparable to the value of 19.13 (15)° reported for the related chalcone derivative (E)-3-(2,3-dichlorophenyl)-1-(4-fluorophenyl)prop-2-en-1-one (Naveen et al., 2016a). The trans configuration of the C7=C8 double bond in the central enone group is confirmed by the C7=C8—C9—C10 torsion angle value of 162.3 (4)°. The carbonyl group at C9 lies nearly in the plane of the benzene ring (C10–C15), as indicated by the torsion angle values of −10.4 (5)° and −19.3 (6)° for O1—C9—C10—C11 and C7—C8—C9—O1, respectively. The methoxy group at C15 also lies in the plane of the benzene ring (C10–C15), as indicated by the torsion angle value of 0.7 (5)° for C16—O2—C15—C14.

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 via weak C—H⋯O hydrogen bonds, forming zigzag 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
C14—H14⋯O1ⁱ	0.93	2.40	3.315 (5)	167
C16—H16A⋯O1ⁱⁱ	0.96	2.51	3.443 (5)	164
Symmetry codes: (i) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound. The dashed lines represent hydrogen bonds (see Table 1

) and, for clarity, only H atoms H14 and H16A have been included.

Synthesis and crystallization

A mixture of 2,4,5-trimethoxybenzaldehyde (5 mmol), 1-(benzo[d][1,3]dioxol-5-yl)ethanone (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 the completion of the reaction, the mixture was poured in to ice-cold water and kept in the refrigerator overnight. The solid that formed was filtered off, and washed with cold hydrochloric acid (5%). Yellow block-like crystals were obtained by slow evaporation of a solution in methanol (yield 89%, m.p. 399–401 K).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₂O₂
M_r	307.16
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	24.7531 (9), 3.9036 (2), 14.3360 (6)
V (Å³)	1385.23 (10)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.20
Crystal size (mm)	0.28 × 0.26 × 0.25

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.386, 0.420
No. of measured, independent and observed [I > 2σ(I)] reflections	7897, 2175, 1893
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.586

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.127, 1.03
No. of reflections	2175
No. of parameters	182
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37
Absolute structure	971 (86%) Friedel pairs; Flack (1983 )
Absolute structure parameter	0.03 (2)
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1524698

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616020563/su4118sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020563/su4118Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616020563/su4118Isup3.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: SHELXL97 (Sheldrick, 2008).

(E)-3-(2,3-Dichlorophenyl)-1-(2-methoxyphenyl)prop-2-en-1-one top

Crystal data top

C₁₆H₁₂Cl₂O₂	F(000) = 632
M_r = 307.16	D_x = 1.473 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 1893 reflections
a = 24.7531 (9) Å	θ = 3.6–64.6°
b = 3.9036 (2) Å	µ = 4.20 mm⁻¹
c = 14.3360 (6) Å	T = 296 K
V = 1385.23 (10) Å³	Block, yellow
Z = 4	0.28 × 0.26 × 0.25 mm

Data collection top

Bruker X8 Proteum diffractometer	2175 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1893 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.067
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.6°, θ_min = 3.6°
φ and ω scans	h = −28→27
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −4→4
T_min = 0.386, T_max = 0.420	l = −16→16
7897 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0694P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2175 reflections	Δρ_max = 0.33 e Å⁻³
182 parameters	Δρ_min = −0.37 e Å⁻³
1 restraint	Absolute structure: 971 (86%) Friedel pairs; Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (2)

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	0.80662 (4)	1.1660 (3)	0.33612 (8)	0.0407 (3)
Cl2	0.69437 (4)	0.8842 (3)	0.26987 (7)	0.0381 (3)
O1	0.51800 (11)	0.4104 (7)	0.3625 (2)	0.0379 (10)
O2	0.55245 (10)	0.1930 (7)	0.6377 (2)	0.0327 (8)
C1	0.70987 (16)	0.8885 (10)	0.3882 (3)	0.0287 (12)
C2	0.67209 (15)	0.7666 (10)	0.4528 (3)	0.0285 (11)
C3	0.68707 (15)	0.7817 (13)	0.5468 (3)	0.0328 (11)
C4	0.73578 (17)	0.9109 (11)	0.5754 (3)	0.0363 (14)
C5	0.77279 (16)	1.0284 (11)	0.5106 (3)	0.0357 (14)
C6	0.75962 (15)	1.0168 (11)	0.4167 (3)	0.0318 (11)
C7	0.62046 (16)	0.6269 (10)	0.4238 (3)	0.0307 (12)
C8	0.57938 (16)	0.5491 (11)	0.4795 (3)	0.0315 (11)
C9	0.52915 (15)	0.3920 (10)	0.4451 (3)	0.0277 (11)
C10	0.49098 (15)	0.2178 (9)	0.5104 (3)	0.0266 (11)
C11	0.44040 (15)	0.1365 (10)	0.4748 (3)	0.0313 (11)
C12	0.40200 (15)	−0.0369 (10)	0.5257 (3)	0.0352 (13)
C13	0.41414 (17)	−0.1308 (10)	0.6165 (3)	0.0383 (14)
C14	0.46347 (17)	−0.0531 (11)	0.6552 (3)	0.0360 (12)
C15	0.50218 (16)	0.1218 (9)	0.6032 (3)	0.0291 (11)
C16	0.56561 (19)	0.0802 (11)	0.7298 (3)	0.0373 (14)
H3	0.66300	0.70090	0.59150	0.0390*
H4	0.74400	0.91970	0.63870	0.0440*
H5	0.80600	1.11400	0.52980	0.0430*
H7	0.61570	0.58820	0.36030	0.0370*
H8	0.58250	0.59580	0.54290	0.0380*
H11	0.43210	0.20190	0.41410	0.0370*
H12	0.36860	−0.09000	0.49960	0.0420*
H13	0.38860	−0.24780	0.65180	0.0460*
H14	0.47100	−0.11760	0.71620	0.0430*
H16A	0.54100	0.18170	0.77370	0.0560*
H16B	0.60190	0.14790	0.74470	0.0560*
H16C	0.56270	−0.16480	0.73300	0.0560*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0297 (5)	0.0456 (6)	0.0467 (7)	−0.0055 (4)	0.0074 (4)	0.0066 (5)
Cl2	0.0386 (5)	0.0509 (6)	0.0248 (5)	−0.0053 (4)	0.0038 (4)	0.0028 (4)
O1	0.0391 (16)	0.0498 (18)	0.0248 (16)	−0.0084 (13)	−0.0048 (12)	0.0012 (12)
O2	0.0357 (15)	0.0411 (15)	0.0212 (14)	−0.0048 (13)	−0.0032 (11)	0.0045 (11)
C1	0.034 (2)	0.025 (2)	0.027 (2)	0.0053 (16)	0.0015 (17)	0.0002 (15)
C2	0.0266 (19)	0.032 (2)	0.027 (2)	0.0017 (17)	0.0019 (16)	−0.0003 (16)
C3	0.0324 (19)	0.039 (2)	0.027 (2)	−0.002 (2)	0.0010 (17)	0.0017 (16)
C4	0.035 (2)	0.046 (3)	0.028 (2)	−0.0023 (19)	−0.0037 (17)	0.0019 (19)
C5	0.030 (2)	0.035 (2)	0.042 (3)	0.0002 (17)	−0.0047 (18)	0.0006 (19)
C6	0.0274 (17)	0.028 (2)	0.040 (2)	0.0005 (17)	0.0033 (16)	0.0023 (17)
C7	0.032 (2)	0.040 (2)	0.020 (2)	−0.0046 (18)	0.0007 (15)	−0.0016 (15)
C8	0.0315 (19)	0.040 (2)	0.023 (2)	−0.0008 (19)	−0.0050 (15)	−0.0015 (16)
C9	0.0267 (18)	0.0285 (19)	0.028 (2)	0.0040 (15)	−0.0015 (16)	−0.0041 (14)
C10	0.0270 (18)	0.0244 (18)	0.0284 (19)	0.0026 (15)	0.0015 (15)	−0.0040 (16)
C11	0.0270 (19)	0.029 (2)	0.038 (2)	0.0024 (16)	−0.0014 (16)	−0.0050 (15)
C12	0.0256 (18)	0.034 (2)	0.046 (3)	0.0032 (17)	0.0018 (18)	−0.005 (2)
C13	0.035 (2)	0.036 (2)	0.044 (3)	−0.0021 (18)	0.0114 (18)	−0.0003 (18)
C14	0.037 (2)	0.037 (2)	0.034 (2)	0.001 (2)	0.0063 (17)	0.0037 (17)
C15	0.031 (2)	0.0274 (19)	0.029 (2)	0.0040 (16)	0.0007 (16)	−0.0043 (14)
C16	0.049 (3)	0.034 (2)	0.029 (2)	0.0068 (19)	−0.0054 (18)	0.0011 (16)

Geometric parameters (Å, º) top

Cl1—C6	1.740 (4)	C11—C12	1.376 (6)
Cl2—C1	1.739 (4)	C12—C13	1.385 (6)
O1—C9	1.218 (5)	C13—C14	1.375 (6)
O2—C15	1.368 (5)	C14—C15	1.393 (6)
O2—C16	1.429 (5)	C3—H3	0.9300
C1—C2	1.400 (6)	C4—H4	0.9300
C1—C6	1.391 (6)	C5—H5	0.9300
C2—C3	1.399 (6)	C7—H7	0.9300
C2—C7	1.450 (5)	C8—H8	0.9300
C3—C4	1.370 (6)	C11—H11	0.9300
C4—C5	1.383 (6)	C12—H12	0.9300
C5—C6	1.386 (6)	C13—H13	0.9300
C7—C8	1.328 (6)	C14—H14	0.9300
C8—C9	1.472 (6)	C16—H16A	0.9600
C9—C10	1.494 (6)	C16—H16B	0.9600
C10—C11	1.389 (5)	C16—H16C	0.9600
C10—C15	1.410 (6)

C15—O2—C16	118.6 (3)	O2—C15—C14	122.1 (4)
Cl2—C1—C2	119.7 (3)	C10—C15—C14	120.0 (4)
Cl2—C1—C6	119.0 (3)	C2—C3—H3	119.00
C2—C1—C6	121.3 (4)	C4—C3—H3	119.00
C1—C2—C3	116.5 (4)	C3—C4—H4	120.00
C1—C2—C7	121.8 (4)	C5—C4—H4	120.00
C3—C2—C7	121.7 (4)	C4—C5—H5	120.00
C2—C3—C4	122.5 (4)	C6—C5—H5	121.00
C3—C4—C5	120.3 (4)	C2—C7—H7	117.00
C4—C5—C6	119.1 (4)	C8—C7—H7	117.00
Cl1—C6—C1	121.2 (3)	C7—C8—H8	119.00
Cl1—C6—C5	118.5 (3)	C9—C8—H8	119.00
C1—C6—C5	120.4 (4)	C10—C11—H11	119.00
C2—C7—C8	126.0 (4)	C12—C11—H11	119.00
C7—C8—C9	122.7 (4)	C11—C12—H12	121.00
O1—C9—C8	119.5 (4)	C13—C12—H12	121.00
O1—C9—C10	119.5 (3)	C12—C13—H13	120.00
C8—C9—C10	120.9 (4)	C14—C13—H13	120.00
C9—C10—C11	116.4 (4)	C13—C14—H14	120.00
C9—C10—C15	126.0 (3)	C15—C14—H14	120.00
C11—C10—C15	117.6 (4)	O2—C16—H16A	109.00
C10—C11—C12	122.7 (4)	O2—C16—H16B	110.00
C11—C12—C13	118.6 (4)	O2—C16—H16C	110.00
C12—C13—C14	120.9 (4)	H16A—C16—H16B	109.00
C13—C14—C15	120.2 (4)	H16A—C16—H16C	109.00
O2—C15—C10	117.8 (3)	H16B—C16—H16C	109.00

C16—O2—C15—C10	−176.5 (3)	C2—C7—C8—C9	−176.9 (4)
C16—O2—C15—C14	0.7 (5)	C7—C8—C9—O1	−19.3 (6)
Cl2—C1—C2—C3	−179.3 (3)	C7—C8—C9—C10	162.3 (4)
Cl2—C1—C2—C7	1.7 (5)	O1—C9—C10—C11	−10.4 (5)
C6—C1—C2—C3	0.1 (6)	O1—C9—C10—C15	167.8 (4)
C6—C1—C2—C7	−178.9 (4)	C8—C9—C10—C11	168.1 (4)
Cl2—C1—C6—Cl1	−1.0 (5)	C8—C9—C10—C15	−13.7 (6)
Cl2—C1—C6—C5	179.0 (3)	C9—C10—C11—C12	177.2 (4)
C2—C1—C6—Cl1	179.7 (3)	C15—C10—C11—C12	−1.2 (6)
C2—C1—C6—C5	−0.4 (6)	C9—C10—C15—O2	0.0 (6)
C1—C2—C3—C4	0.6 (7)	C9—C10—C15—C14	−177.2 (4)
C7—C2—C3—C4	179.6 (4)	C11—C10—C15—O2	178.3 (3)
C1—C2—C7—C8	−170.2 (4)	C11—C10—C15—C14	1.0 (5)
C3—C2—C7—C8	10.8 (7)	C10—C11—C12—C13	0.7 (6)
C2—C3—C4—C5	−1.0 (7)	C11—C12—C13—C14	0.0 (6)
C3—C4—C5—C6	0.7 (7)	C12—C13—C14—C15	−0.1 (6)
C4—C5—C6—Cl1	180.0 (3)	C13—C14—C15—O2	−177.5 (4)
C4—C5—C6—C1	0.0 (6)	C13—C14—C15—C10	−0.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1ⁱ	0.93	2.40	3.315 (5)	167
C16—H16A···O1ⁱⁱ	0.96	2.51	3.443 (5)	164

Symmetry codes: (i) −x+1, −y, z+1/2; (ii) −x+1, −y+1, 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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