2,5-Bis(4-chloro­benzyl­idene)cyclo­penta­none

Samshuddin, S.; Naveen, S.; Ananya, L.N.; Vishwanatha, P.; Lokanath, N.K.; Abdoh, M.

doi:10.1107/S2414314616018654

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161865

https://doi.org/10.1107/S2414314616018654

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2,5-Bis(4-chlorobenzylidene)cyclopentanone

Seranthimata Samshuddin,^a S. Naveen,^b L. N. Ananya,^c P. Vishwanatha,^d N. K. Lokanath ^e ^* and Muneer Abdoh ^f ^*

^aDepartment of Chemistry, SDM Institute of Technology, Ujire 574 240, India, ^bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^cDepartment of P.G. Studies in Chemistry, Alva's College, Moodbidri 574 227, India, ^dDepartment of Chemistry, SDM Degree College (Autonomous), Ujire 574 240, India, ^eDepartment of Studies in Physics, 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: lokanath@physics.uni-mysore.ac.in, muneer@najah.edu

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 17 November 2016; accepted 22 November 2016; online 25 November 2016)

The title bis-chalcone compound, C₁₉H₁₄Cl₂O, crystallizes with one half-molecule in the asymmetric unit. The molecule has crystallographic mirror symmetry with the C=O bond on the mirror plane. The molecule adopts an E configuration about the central olefinic bonds. In the crystal, molecules are linked via weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along the [100] direction.

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

CCDC reference: 1518584

Structure description

The development of highly efficient non-linear optical crystals is extremely important for laser spectroscopy and laser processing. Bis(arylmethylidene) cycloalkanones have been reported to exhibit promising non-linear optical properties (Yu et al., 2000 ). In addition, these compounds are widely used as precursors for the synthesis of biologically active heterocycles (Guilford et al., 1999 ). In view of the importance of bis-chalcones, we report herein on the synthesis and crystal structure of title compound.

The molecular structure of the title compound is shown in Fig. 1. The molecule has crystallographic mirror symmetry and adopts an E configuration about the central olefinic bonds, exhibiting a butterfly-shaped geometry. In the crystal, the molecules are linked via weak C—H⋯O hydrogen bonds (Table 1), forming supramolecular chains propagating along the [100] direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H5⋯O1ⁱ	0.97	2.54	3.270 (3)	132
Symmetry code: (i) x+1, y, z.

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. Unlabelled atoms are generated by the symmetry operation x, $[{3\over 2}]$ − y, z.

Synthesis and crystallization

A mixture of cyclopentanone (0.84 g, 0.01 mol) and 4-chlorobenzaldehyde (2.80 g, 0.02 mol) in 30 ml ethanolic sodium hydroxide (0.1 mol) was stirred at 278–283 K for 3 h. The precipitate formed was collected by filtration and purified by recrystallization from ethanol solution. Single crystals were grown from DMF in 86% yield by slow evaporation.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₄Cl₂O
M_r	329.20
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	6.1029 (4), 35.7084 (18), 7.2217 (6)
V (Å³)	1573.79 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	0.29 × 0.27 × 0.25

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2011 )
T_min, T_max	0.888, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	6328, 1583, 1063
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.111, 1.04
No. of reflections	1583
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2011), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1518584

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616018654/xu4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018654/xu4018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018654/xu4018Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 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,5E)-2,5-Bis(4-chlorobenzylidene)cyclopentanone top

Crystal data top

C₁₉H₁₄Cl₂O	D_x = 1.389 Mg m⁻³
M_r = 329.20	Melting point: 432 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1063 reflections
a = 6.1029 (4) Å	θ = 2.9–26.1°
b = 35.7084 (18) Å	µ = 0.41 mm⁻¹
c = 7.2217 (6) Å	T = 296 K
V = 1573.79 (18) Å³	Rectangle, colorless
Z = 4	0.29 × 0.27 × 0.25 mm
F(000) = 680

Data collection top

Bruker APEXII diffractometer	1583 independent reflections
Radiation source: Enraf Nonius FR590	1063 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 18.4 pixels mm^-1	θ_max = 26.1°, θ_min = 2.9°
CCD rotation images, thick slices scans	h = −7→5
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −43→42
T_min = 0.888, T_max = 0.902	l = −4→8
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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0447P)² + 0.4484P] where P = (F_o² + 2F_c²)/3
1583 reflections	(Δ/σ)_max = 0.001
103 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.20 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	0.78079 (13)	0.52896 (2)	1.04515 (13)	0.0841 (4)
O1	0.1615 (3)	0.75000	0.8758 (3)	0.0438 (7)
C1	0.6686 (4)	0.57327 (6)	1.0207 (3)	0.0482 (8)
C2	0.7870 (4)	0.60368 (6)	1.0815 (3)	0.0475 (8)
C3	0.7013 (3)	0.63916 (6)	1.0602 (3)	0.0425 (8)
C4	0.4964 (3)	0.64510 (5)	0.9785 (3)	0.0347 (7)
C5	0.3827 (4)	0.61340 (5)	0.9195 (3)	0.0422 (8)
C6	0.4653 (4)	0.57775 (6)	0.9402 (3)	0.0509 (9)
C7	0.3980 (3)	0.68207 (5)	0.9492 (3)	0.0341 (7)
C8	0.4771 (3)	0.71622 (5)	0.9844 (3)	0.0324 (6)
C9	0.6917 (3)	0.72845 (5)	1.0656 (3)	0.0411 (8)
C10	0.3465 (4)	0.75000	0.9390 (4)	0.0318 (9)
H1	0.78180	0.65970	1.10110	0.0510*
H2	0.38550	0.55710	0.90050	0.0610*
H3	0.24620	0.61640	0.86410	0.0510*
H4	0.25820	0.68170	0.89810	0.0410*
H5	0.81240	0.71900	0.99180	0.0490*
H7	0.92350	0.60030	1.13630	0.0570*
H8	0.70690	0.71900	1.19090	0.0490*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0893 (6)	0.0438 (4)	0.1191 (8)	0.0186 (3)	−0.0081 (5)	0.0048 (4)
O1	0.0301 (10)	0.0461 (12)	0.0551 (16)	0.0000	−0.0091 (10)	0.0000
C1	0.0577 (14)	0.0395 (12)	0.0474 (16)	0.0083 (11)	0.0044 (13)	0.0044 (10)
C2	0.0426 (12)	0.0511 (14)	0.0489 (17)	0.0045 (11)	−0.0060 (11)	0.0071 (11)
C3	0.0422 (12)	0.0399 (12)	0.0454 (16)	−0.0008 (10)	−0.0064 (11)	0.0028 (10)
C4	0.0356 (10)	0.0376 (11)	0.0308 (13)	−0.0018 (9)	0.0028 (10)	0.0018 (9)
C5	0.0413 (11)	0.0429 (13)	0.0425 (16)	−0.0042 (9)	−0.0035 (11)	−0.0005 (10)
C6	0.0593 (15)	0.0366 (12)	0.0567 (18)	−0.0069 (11)	−0.0052 (13)	−0.0023 (11)
C7	0.0293 (10)	0.0406 (12)	0.0323 (14)	−0.0015 (9)	−0.0019 (9)	0.0012 (9)
C8	0.0313 (10)	0.0388 (11)	0.0272 (12)	0.0001 (9)	0.0010 (9)	0.0027 (9)
C9	0.0364 (11)	0.0400 (12)	0.0469 (16)	−0.0004 (9)	−0.0127 (11)	0.0026 (10)
C10	0.0272 (14)	0.0429 (16)	0.0254 (18)	0.0000	0.0018 (13)	0.0000

Geometric parameters (Å, º) top

Cl1—C1	1.733 (2)	C8—C9	1.500 (3)
O1—C10	1.218 (3)	C8—C10	1.483 (2)
C1—C2	1.376 (3)	C9—C9ⁱ	1.539 (3)
C1—C6	1.380 (3)	C2—H7	0.9300
C2—C3	1.379 (3)	C3—H1	0.9300
C3—C4	1.399 (3)	C5—H3	0.9300
C4—C5	1.394 (3)	C6—H2	0.9300
C4—C7	1.466 (3)	C7—H4	0.9300
C5—C6	1.377 (3)	C9—H5	0.9700
C7—C8	1.336 (3)	C9—H8	0.9700

Cl1—C1—C2	118.72 (18)	C8—C10—C8ⁱ	108.91 (19)
Cl1—C1—C6	120.27 (17)	C1—C2—H7	120.00
C2—C1—C6	121.0 (2)	C3—C2—H7	120.00
C1—C2—C3	119.4 (2)	C2—C3—H1	119.00
C2—C3—C4	121.69 (19)	C4—C3—H1	119.00
C3—C4—C5	116.79 (18)	C4—C5—H3	119.00
C3—C4—C7	124.32 (17)	C6—C5—H3	119.00
C5—C4—C7	118.89 (18)	C1—C6—H2	121.00
C4—C5—C6	122.3 (2)	C5—C6—H2	121.00
C1—C6—C5	118.8 (2)	C4—C7—H4	115.00
C4—C7—C8	130.29 (18)	C8—C7—H4	115.00
C7—C8—C9	130.97 (17)	C8—C9—H5	110.00
C7—C8—C10	120.42 (18)	C8—C9—H8	110.00
C9—C8—C10	108.60 (15)	H5—C9—H8	109.00
C8—C9—C9ⁱ	106.93 (15)	C9ⁱ—C9—H5	110.00
O1—C10—C8	125.55 (11)	C9ⁱ—C9—H8	110.00
O1—C10—C8ⁱ	125.55 (11)

Cl1—C1—C2—C3	178.96 (17)	C4—C5—C6—C1	−0.6 (3)
C6—C1—C2—C3	−0.5 (3)	C4—C7—C8—C9	−0.1 (4)
Cl1—C1—C6—C5	−178.73 (18)	C4—C7—C8—C10	178.9 (2)
C2—C1—C6—C5	0.7 (3)	C7—C8—C9—C9ⁱ	178.0 (2)
C1—C2—C3—C4	0.1 (3)	C10—C8—C9—C9ⁱ	−1.1 (2)
C2—C3—C4—C5	0.0 (3)	C7—C8—C10—O1	3.0 (4)
C2—C3—C4—C7	−179.0 (2)	C7—C8—C10—C8ⁱ	−177.4 (2)
C3—C4—C5—C6	0.2 (3)	C9—C8—C10—O1	−177.8 (3)
C7—C4—C5—C6	179.3 (2)	C9—C8—C10—C8ⁱ	1.8 (3)
C3—C4—C7—C8	2.5 (4)	C8—C9—C9ⁱ—C8ⁱ	0.0 (2)
C5—C4—C7—C8	−176.4 (2)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H5···O1ⁱⁱ	0.97	2.54	3.270 (3)	132

Symmetry code: (ii) x+1, y, z.

Acknowledgements

The authors thank Alva's Education Foundation, Moodbidri, for proving research facilities.

References

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