(2E,2′E)-1,1′-(1,4-Phenyl­ene)bis­[3-(3-chloro­phen­yl)prop-2-en-1-one]

Rajendraprasad, S.; Chidan Kumar, C.S.; Chandraju, S.; Lokanath, N.K.; Quah, C.K.; Naveen, S.; Abdoh, M.

doi:10.1107/S2414314617002127

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170212

https://doi.org/10.1107/S2414314617002127

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(2E,2′E)-1,1′-(1,4-Phenylene)bis[3-(3-chlorophenyl)prop-2-en-1-one]

S. Rajendraprasad,^a C. S. Chidan Kumar,^b S. Chandraju,^a N. K. Lokanath,^c Ching Kheng Quah,^d S. Naveen ^e ^* and Muneer Abdoh ^f ^*

^aDepartment of Chemistry, Sir M.V. PG Center, University of Mysore, Tubinakere, Mandya 571 402, India, ^bDepartment of Engineering Chemistry, Vidya Vikas Institute of Engineering and Technology, Visvesvaraya Technological University, Alanahalli, Mysuru 570 028, India, ^cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, Penang 11800 USM, Malaysia, ^eInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^fDepartment of Physics, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, muneer@najah.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 7 February 2017; accepted 9 February 2017; online 14 February 2017)

The title bis-chalcone compound, C₂₄H₁₆Cl₂O₂, crystallizes with one half-molecule in the asymmetric unit. The molecule has crystallographic inversion symmetry and lies about an inversion centre at the centroid of the central benzene ring. The olefinic double bonds adopt E configurations. The s-trans conformation of the central C—C bond of the enone group is confirmed by a C—C—C=C torsion angle of −162.88 (17)°.

Keywords: crystal structure; bis-chalcone; mirror symmetry.

CCDC reference: 1449583

Structure description

The title compound is a bis-chalcone and a diketone. Numerous studies have shown that bis-chalcones possess multiple pharmacological properties (Nowakowska, 2007 ). Crystalline chalcone derivatives are also of interest due to their second and third harmonic generation properties (Chidan et al., 2015 ). The optical properties of the molecules are also associated with their molecular geometry (Kumar et al. 2013 ) and, as a part of our ongoing work on such molecules (Naveen et al. 2017 ), we report here the crystal structure of the title compound.

The title compound crystallizes with one half-molecule in the asymmetric unit and its structure is shown in Fig. 1. The molecule has crystallographic inversion symmetry and lies about an inversion centre at the centroid of the central benzene ring. The olefinic double bond adopts an E configuration. The s-trans conformation of the central C—C bond of the enone group is confirmed by the C10—C9—C8=C7 torsion angle of −162.88 (17)°. This value is less than that reported for the related compound 2,5-bis(4-chlorobenzylidene)cyclopentanone (Samshuddin et al., 2016 ).

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. Labelled atoms are related to unlabelled atoms by the symmetry operation −x + 1, −y, −z + 1.

Synthesis and crystallization

1,4-Diacetylbenzene (1.62 g, 0.01 mol) was mixed with 3-chlorobenzaldehyde (2.80 g, 0.01 mol) and dissolved in methanol (30 ml). To this, 3 ml of NaOH (50%) was added. The reaction mixture was stirred for 6 h. The resulting crude solid was filtered, washed successively with distilled water and finally recrystallized from methanol (95%) to give the pure bis-chalcone. Single crystals suitable for X-ray diffraction studies were grown by slow evaporation of an acetone-methanol (1:1) solution (m.p. 413–415 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₄H₁₆Cl₂O₂
M_r	407.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	22.6336 (13), 7.0895 (4), 5.9515 (3)
β (°)	95.485 (2)
V (Å³)	950.61 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.44 × 0.26 × 0.14

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku, 1999 )
T_min, T_max	0.859, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	27758, 3656, 2542
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.772

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.166, 1.04
No. of reflections	3656
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.21
Computer programs: CrystalClear SM-Expert (Rigaku, 2011 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1449583

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617002127/sj4088sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002127/sj4088Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002127/sj4088Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear SM-Expert (Rigaku, 2011); cell refinement: CrystalClear SM-Expert (Rigaku, 2011); data reduction: CrystalClear SM-Expert (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: Mercury (Macrae et al., 2008).

(2E,2'E)-1,1'-(1,4-Phenylene)bis[3-(3-chlorophenyl)prop-2-en-1-one] top

Crystal data top

C₂₄H₁₆Cl₂O₂	F(000) = 420
M_r = 407.27	D_x = 1.423 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2542 reflections
a = 22.6336 (13) Å	θ = 2.7–33.3°
b = 7.0895 (4) Å	µ = 0.36 mm⁻¹
c = 5.9515 (3) Å	T = 294 K
β = 95.485 (2)°	Rectangle, white
V = 950.61 (9) Å³	0.44 × 0.26 × 0.14 mm
Z = 2

Data collection top

Rigaku Saturn724+ diffractometer	3656 independent reflections
Radiation source: fine-focus sealed tube	2542 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 18.4 pixels mm^-1	θ_max = 33.3°, θ_min = 2.7°
profile data from ω–scans	h = −34→34
Absorption correction: multi-scan (NUMABS; Rigaku, 1999)	k = −10→10
T_min = 0.859, T_max = 0.951	l = −9→9
27758 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0803P)² + 0.2606P] where P = (F_o² + 2F_c²)/3
3656 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.21 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	0.04854 (2)	0.08183 (9)	0.31155 (9)	0.0694 (2)
O1	0.36614 (6)	0.0056 (3)	0.7913 (2)	0.0676 (6)
C1	0.16738 (6)	0.0708 (2)	0.3479 (2)	0.0351 (4)
C2	0.11601 (6)	0.0359 (2)	0.2094 (3)	0.0404 (4)
C3	0.11768 (7)	−0.0401 (2)	−0.0040 (3)	0.0447 (5)
C4	0.17253 (8)	−0.0790 (2)	−0.0789 (3)	0.0428 (5)
C5	0.22454 (7)	−0.0476 (2)	0.0578 (3)	0.0399 (4)
C6	0.22246 (6)	0.0251 (2)	0.2750 (2)	0.0343 (4)
C7	0.27480 (6)	0.0426 (2)	0.4386 (3)	0.0390 (4)
C8	0.32993 (6)	−0.0063 (3)	0.4068 (3)	0.0446 (5)
C9	0.37737 (6)	−0.0004 (3)	0.5956 (3)	0.0427 (4)
C10	0.44036 (6)	−0.0027 (2)	0.5403 (2)	0.0368 (4)
C11	0.45674 (6)	0.0564 (2)	0.3326 (3)	0.0399 (4)
C12	0.51588 (6)	0.0598 (2)	0.2924 (3)	0.0402 (4)
H1A	0.16530	0.12460	0.48940	0.0420*
H3A	0.08280	−0.06450	−0.09520	0.0540*
H4A	0.17440	−0.12700	−0.22350	0.0510*
H5A	0.26100	−0.07490	0.00500	0.0480*
H7A	0.26880	0.09300	0.57880	0.0470*
H8A	0.33880	−0.04460	0.26450	0.0540*
H11A	0.42780	0.09370	0.22000	0.0480*
H12A	0.52660	0.10040	0.15330	0.0480*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0279 (2)	0.1097 (5)	0.0716 (3)	0.0012 (2)	0.0101 (2)	−0.0044 (3)
O1	0.0364 (6)	0.1204 (14)	0.0466 (7)	0.0026 (7)	0.0066 (5)	0.0003 (8)
C1	0.0278 (6)	0.0424 (7)	0.0354 (6)	0.0011 (5)	0.0044 (5)	−0.0001 (5)
C2	0.0273 (6)	0.0482 (8)	0.0456 (8)	−0.0009 (5)	0.0038 (5)	0.0042 (6)
C3	0.0387 (8)	0.0496 (9)	0.0440 (8)	−0.0044 (6)	−0.0055 (6)	0.0008 (6)
C4	0.0496 (9)	0.0444 (8)	0.0340 (7)	0.0013 (6)	0.0014 (6)	−0.0025 (6)
C5	0.0364 (7)	0.0446 (8)	0.0396 (7)	0.0032 (6)	0.0082 (5)	−0.0006 (6)
C6	0.0280 (6)	0.0378 (7)	0.0371 (6)	−0.0001 (5)	0.0035 (5)	0.0012 (5)
C7	0.0289 (6)	0.0471 (8)	0.0407 (7)	0.0004 (5)	0.0023 (5)	−0.0023 (6)
C8	0.0275 (6)	0.0599 (10)	0.0463 (8)	0.0002 (6)	0.0025 (5)	−0.0070 (7)
C9	0.0271 (6)	0.0542 (9)	0.0467 (8)	−0.0004 (6)	0.0029 (5)	−0.0019 (7)
C10	0.0249 (6)	0.0423 (7)	0.0425 (7)	0.0000 (5)	0.0001 (5)	−0.0021 (6)
C11	0.0276 (6)	0.0482 (8)	0.0426 (7)	0.0025 (5)	−0.0035 (5)	0.0046 (6)
C12	0.0312 (6)	0.0505 (8)	0.0385 (7)	−0.0006 (6)	0.0010 (5)	0.0028 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.7277 (15)	C10—C11	1.389 (2)
O1—C9	1.216 (2)	C10—C12ⁱ	1.396 (2)
C1—C2	1.382 (2)	C11—C12	1.382 (2)
C1—C6	1.3967 (19)	C1—H1A	0.9300
C2—C3	1.384 (2)	C3—H3A	0.9300
C3—C4	1.386 (2)	C4—H4A	0.9300
C4—C5	1.384 (2)	C5—H5A	0.9300
C5—C6	1.397 (2)	C7—H7A	0.9300
C6—C7	1.465 (2)	C8—H8A	0.9300
C7—C8	1.326 (2)	C11—H11A	0.9300
C8—C9	1.479 (2)	C12—H12A	0.9300
C9—C10	1.4936 (19)

C2—C1—C6	119.89 (12)	C10—C11—C12	120.31 (15)
Cl1—C2—C1	118.55 (12)	C10ⁱ—C12—C11	120.29 (15)
Cl1—C2—C3	119.94 (12)	C2—C1—H1A	120.00
C1—C2—C3	121.47 (13)	C6—C1—H1A	120.00
C2—C3—C4	118.46 (15)	C2—C3—H3A	121.00
C3—C4—C5	121.11 (16)	C4—C3—H3A	121.00
C4—C5—C6	120.11 (15)	C3—C4—H4A	119.00
C1—C6—C5	118.89 (12)	C5—C4—H4A	119.00
C1—C6—C7	117.58 (12)	C4—C5—H5A	120.00
C5—C6—C7	123.35 (13)	C6—C5—H5A	120.00
C6—C7—C8	126.53 (16)	C6—C7—H7A	117.00
C7—C8—C9	120.60 (16)	C8—C7—H7A	117.00
O1—C9—C8	121.71 (14)	C7—C8—H8A	120.00
O1—C9—C10	120.17 (14)	C9—C8—H8A	120.00
C8—C9—C10	118.12 (14)	C10—C11—H11A	120.00
C9—C10—C11	122.31 (13)	C12—C11—H11A	120.00
C9—C10—C12ⁱ	118.24 (13)	C11—C12—H12A	120.00
C11—C10—C12ⁱ	119.40 (13)	C10ⁱ—C12—H12A	120.00

C6—C1—C2—Cl1	176.37 (11)	C6—C7—C8—C9	−173.15 (16)
C6—C1—C2—C3	−1.5 (2)	C7—C8—C9—O1	17.4 (3)
C2—C1—C6—C5	2.9 (2)	C7—C8—C9—C10	−162.88 (17)
C2—C1—C6—C7	−172.42 (13)	O1—C9—C10—C11	−156.71 (19)
Cl1—C2—C3—C4	−178.63 (12)	O1—C9—C10—C12ⁱ	20.8 (3)
C1—C2—C3—C4	−0.8 (2)	C8—C9—C10—C11	23.5 (3)
C2—C3—C4—C5	1.7 (2)	C8—C9—C10—C12ⁱ	−158.96 (16)
C3—C4—C5—C6	−0.2 (2)	C9—C10—C11—C12	177.09 (15)
C4—C5—C6—C1	−2.1 (2)	C12ⁱ—C10—C11—C12	−0.4 (2)
C4—C5—C6—C7	172.97 (14)	C9—C10—C12ⁱ—C11ⁱ	−177.19 (15)
C1—C6—C7—C8	174.96 (17)	C11—C10—C12ⁱ—C11ⁱ	0.4 (2)
C5—C6—C7—C8	−0.1 (2)	C10—C11—C12—C10ⁱ	0.4 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors extend their appreciation to Vidya Vikas Research & Development Center for the facilities and encouragement. CKQ thanks the Malaysian Government and USM for a Research University Individual (RUI) Grant (1001/PFIZIK/811278).

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