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

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

doi:10.1107/S2414314617002383

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170238

https://doi.org/10.1107/S2414314617002383

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

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

^aDepartment of Engineering Chemistry, Vidya Vikas Institute of Engineering and Technology, Visvesvaraya Technological University, Alanahalli, Mysuru 570 028, India, ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, Penang 11800 USM, Malaysia, ^cDepartment of Chemistry, Sir M.V. PG Center, University of Mysore, Tubinakere, Mandya 571 402, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^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 9 February 2017; accepted 12 February 2017; online 17 February 2017)

The title bis-chalcone compound, C₂₄H₁₆F₂O₂, crystallizes with one half-molecule in the asymmetric unit. The molecule lies about an inversion centre at the centroid of the central benzene ring. The olefinic double bonds adopt E conformations. In the crystal, C—H⋯O hydrogen bonds form sheets of molecules in the ac plane and C—H⋯F hydrogen bonds form zigzag chains along the a-axis direction. These combine to generate a three-dimensional network of molecules stacked along the c-axis direction.

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

CCDC reference: 1449627

Structure description

Numerous studies have shown that bis-chalcones possess multiple pharmacological properties (Nowakowska, 2007 ). Materials with large non-linear optical (NLO) susceptibilities are of current interest in the area of harmonic generation and optical modulation. There is also considerable interest in the synthesis of new NLO materials because of their potential applications in technologies such as optical computing and optical communication (Chidan et al., 2015 ) and because such materials play an important role in fields such as photonics and optoelectronics (Kumar et al. 2013 ). As a part of our ongoing work on such molecules (Naveen et al., 2017 ; Rajendraprasad et al., 2017 ), we report here the crystal structure of the title bis-chalcone derivative.

The title compound crystallizes with one half-molecule in the asymmetric unit and its structure is shown in Fig. 1. The molecule lies about an inversion centre at the centroid of the central C10–C12/C10ⁱ–C12ⁱ, benzene ring [symmetry code: (i) −x + 1, −y + 2, −z + 2]. The olefinic double bond adopts an E conformation. The trans conformation of the C=C double bond in the central enone group is confirmed by the C10—C9—C8=C7 torsion angle of −178.3 (2)°. This value is larger than that reported previously for the related compound (2E,2′E)-1,1′-(1,4-phenylene)bis(3-(3-chlorophenyl)prop-2-en-1-one) (Rajendraprasad et al., 2017).

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme. Labelled atoms are related to unlabelled atoms by the symmetry operation (−x + 1, −y + 2, −z + 2). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

In the crystal, C5—H5A⋯O1 and C8—H8A⋯O1 hydrogen bonds link molecules into sheets in the ac plane, Fig. 2, while C2—H2A⋯F1 hydrogen bonds form zigzag chains along the a-axis direction (Table 1). These contacts combine to generate a three-dimensional network with molecules stacked along the c-axis direction, Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯F1ⁱ	0.95	2.50	3.392 (3)	155
C5—H5A⋯O1ⁱⁱ	0.95	2.59	3.515 (3)	166
C8—H8A⋯O1ⁱⁱ	0.95	2.63	3.577 (3)	171
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A sheet of molecules in the ac plane viewed along the b axis, with C—H⋯O hydrogen bonds drawn as dashed lines.

Figure 3
Packing of the molecules viewed along the c axis, showing the zigzag arrangement of molecules and layered stacking.

Synthesis and crystallization

Terephthalaldehyde (1.06 g, 0.01 mol) was mixed with 4-fluoroacetophenone (2.76 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 (90%) to give the pure bis-chalcone. Single crystals suitable for X-ray diffraction studies were grown by the slow evaporation of an acetone-methanol (1:1) solution (m.p. 402–405 K).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₆F₂O₂
M_r	374.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	20.405 (6), 3.8237 (11), 11.233 (3)
β (°)	93.989 (5)
V (Å³)	874.3 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.15 × 0.13

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku, 1999 )
T_min, T_max	0.977, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	6328, 1963, 1379
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.203, 1.09
No. of reflections	1963
No. of parameters	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37
Computer programs: CrystalClear SM-Expert (Rigaku, 2011 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1449627

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617002383/sj4089sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002383/sj4089Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002383/sj4089Isup3.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)-3,3'-(1,4-Phenylene)bis[1-(4-fluorophenyl)prop-2-en-1-one] top

Crystal data top

C₂₄H₁₆F₂O₂	F(000) = 388
M_r = 374.37	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1379 reflections
a = 20.405 (6) Å	θ = 2.0–27.4°
b = 3.8237 (11) Å	µ = 0.10 mm⁻¹
c = 11.233 (3) Å	T = 100 K
β = 93.989 (5)°	Rectangle, white
V = 874.3 (4) Å³	0.22 × 0.15 × 0.13 mm
Z = 2

Data collection top

Rigaku Saturn724+ diffractometer	1963 independent reflections
Radiation source: fine-focus sealed tube	1379 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 18.4 pixels mm^-1	θ_max = 27.4°, θ_min = 2.0°
profile data from ω–scans	h = −25→26
Absorption correction: multi-scan (NUMABS; Rigaku, 1999)	k = −4→4
T_min = 0.977, T_max = 0.987	l = −14→14
6328 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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.203	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.1169P)² + 0.1724P] where P = (F_o² + 2F_c²)/3
1963 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.37 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
F1	0.02041 (7)	0.3368 (4)	0.88439 (14)	0.0309 (5)
O1	0.29100 (8)	0.6037 (5)	0.66903 (15)	0.0296 (6)
C1	0.16568 (12)	0.4078 (6)	0.7220 (2)	0.0217 (7)
C2	0.10182 (12)	0.3342 (6)	0.7470 (2)	0.0239 (8)
C3	0.08291 (11)	0.4157 (6)	0.8586 (2)	0.0223 (7)
C4	0.12399 (11)	0.5737 (6)	0.9452 (2)	0.0227 (8)
C5	0.18808 (11)	0.6453 (6)	0.9197 (2)	0.0215 (7)
C6	0.20983 (11)	0.5648 (6)	0.8074 (2)	0.0195 (7)
C7	0.27745 (12)	0.6434 (6)	0.7722 (2)	0.0218 (7)
C8	0.32763 (12)	0.7663 (6)	0.8654 (2)	0.0213 (7)
C9	0.39052 (11)	0.7978 (6)	0.8397 (2)	0.0204 (7)
C10	0.44537 (11)	0.9062 (6)	0.9229 (2)	0.0203 (7)
C11	0.43665 (12)	1.0668 (6)	1.0322 (2)	0.0219 (7)
C12	0.50979 (12)	0.8414 (6)	0.8921 (2)	0.0207 (7)
H1A	0.18000	0.35110	0.64570	0.0260*
H2A	0.07190	0.23040	0.68880	0.0290*
H4A	0.10870	0.63200	1.02070	0.0270*
H5A	0.21740	0.74970	0.97870	0.0260*
H8A	0.31510	0.82230	0.94300	0.0260*
H9A	0.40050	0.74510	0.76030	0.0250*
H11A	0.39350	1.11350	1.05480	0.0260*
H12A	0.51670	0.73270	0.81800	0.0250*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0202 (8)	0.0400 (9)	0.0327 (9)	−0.0027 (6)	0.0033 (6)	0.0003 (7)
O1	0.0271 (10)	0.0471 (12)	0.0147 (9)	−0.0049 (8)	0.0016 (7)	−0.0024 (8)
C1	0.0273 (13)	0.0205 (12)	0.0170 (12)	0.0007 (9)	−0.0015 (9)	0.0007 (9)
C2	0.0233 (13)	0.0247 (13)	0.0225 (13)	−0.0004 (10)	−0.0068 (9)	−0.0015 (10)
C3	0.0203 (12)	0.0194 (12)	0.0271 (14)	0.0010 (9)	0.0004 (9)	0.0044 (9)
C4	0.0243 (13)	0.0256 (14)	0.0180 (12)	0.0020 (10)	0.0008 (9)	0.0004 (9)
C5	0.0249 (13)	0.0230 (12)	0.0161 (12)	0.0004 (10)	−0.0013 (9)	0.0012 (9)
C6	0.0236 (12)	0.0180 (12)	0.0163 (12)	0.0009 (9)	−0.0020 (9)	0.0010 (8)
C7	0.0264 (13)	0.0226 (12)	0.0159 (12)	0.0002 (10)	−0.0019 (9)	0.0006 (9)
C8	0.0224 (12)	0.0253 (13)	0.0157 (12)	−0.0008 (9)	−0.0016 (9)	−0.0006 (9)
C9	0.0226 (13)	0.0241 (13)	0.0144 (12)	−0.0013 (9)	−0.0001 (9)	0.0003 (9)
C10	0.0213 (12)	0.0217 (12)	0.0175 (12)	−0.0029 (9)	−0.0017 (9)	0.0036 (9)
C11	0.0226 (12)	0.0238 (13)	0.0191 (12)	−0.0008 (9)	0.0007 (9)	0.0025 (9)
C12	0.0258 (13)	0.0227 (12)	0.0136 (12)	−0.0013 (9)	0.0009 (9)	0.0000 (9)

Geometric parameters (Å, º) top

F1—C3	1.361 (3)	C10—C11	1.395 (3)
O1—C7	1.220 (3)	C10—C12	1.404 (3)
C1—C2	1.381 (3)	C11—C12ⁱ	1.383 (3)
C1—C6	1.404 (3)	C1—H1A	0.9500
C2—C3	1.373 (3)	C2—H2A	0.9500
C3—C4	1.379 (3)	C4—H4A	0.9500
C4—C5	1.385 (3)	C5—H5A	0.9500
C5—C6	1.400 (3)	C8—H8A	0.9500
C6—C7	1.492 (3)	C9—H9A	0.9500
C7—C8	1.489 (3)	C11—H11A	0.9500
C8—C9	1.340 (3)	C12—H12A	0.9500
C9—C10	1.467 (3)

C2—C1—C6	121.2 (2)	C10—C11—C12ⁱ	120.6 (2)
C1—C2—C3	117.9 (2)	C10—C12—C11ⁱ	121.1 (2)
F1—C3—C2	118.1 (2)	C2—C1—H1A	119.00
F1—C3—C4	118.7 (2)	C6—C1—H1A	119.00
C2—C3—C4	123.2 (2)	C1—C2—H2A	121.00
C3—C4—C5	118.5 (2)	C3—C2—H2A	121.00
C4—C5—C6	120.4 (2)	C3—C4—H4A	121.00
C1—C6—C5	118.7 (2)	C5—C4—H4A	121.00
C1—C6—C7	117.8 (2)	C4—C5—H5A	120.00
C5—C6—C7	123.5 (2)	C6—C5—H5A	120.00
O1—C7—C6	120.1 (2)	C7—C8—H8A	120.00
O1—C7—C8	121.2 (2)	C9—C8—H8A	120.00
C6—C7—C8	118.7 (2)	C8—C9—H9A	117.00
C7—C8—C9	119.9 (2)	C10—C9—H9A	117.00
C8—C9—C10	126.0 (2)	C10—C11—H11A	120.00
C9—C10—C11	123.1 (2)	C12ⁱ—C11—H11A	120.00
C9—C10—C12	118.6 (2)	C10—C12—H12A	119.00
C11—C10—C12	118.3 (2)	C11ⁱ—C12—H12A	119.00

C6—C1—C2—C3	−0.7 (3)	C5—C6—C7—O1	−171.6 (2)
C2—C1—C6—C5	0.3 (3)	C5—C6—C7—C8	9.1 (3)
C2—C1—C6—C7	−178.6 (2)	O1—C7—C8—C9	−7.5 (4)
C1—C2—C3—F1	−178.6 (2)	C6—C7—C8—C9	171.9 (2)
C1—C2—C3—C4	1.5 (4)	C7—C8—C9—C10	−178.3 (2)
F1—C3—C4—C5	178.3 (2)	C8—C9—C10—C11	−15.2 (4)
C2—C3—C4—C5	−1.8 (4)	C8—C9—C10—C12	163.9 (2)
C3—C4—C5—C6	1.3 (3)	C9—C10—C11—C12ⁱ	179.0 (2)
C4—C5—C6—C1	−0.6 (3)	C12—C10—C11—C12ⁱ	−0.1 (3)
C4—C5—C6—C7	178.2 (2)	C9—C10—C12—C11ⁱ	−179.1 (2)
C1—C6—C7—O1	7.2 (3)	C11—C10—C12—C11ⁱ	0.1 (3)
C1—C6—C7—C8	−172.1 (2)	C10—C11—C12ⁱ—C10ⁱ	0.1 (3)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F1ⁱⁱ	0.95	2.50	3.392 (3)	155
C5—H5A···O1ⁱⁱⁱ	0.95	2.59	3.515 (3)	166
C8—H8A···O1ⁱⁱⁱ	0.95	2.63	3.577 (3)	171

Symmetry codes: (ii) −x, y−1/2, −z+3/2; (iii) x, −y+3/2, z+1/2.

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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