An ortho­rhom­bic polymorph of (E)-1-(benzo[d][1,3]dioxol-5-yl)-3-(2,3-di­chloro­phen­yl)prop-2-en-1-one

Naveen, S.; Dileep Kumar, A.; Deepa Urs, M.V.; Ajay Kumar, K.; Lokanath, N.K.; Warad, I.

doi:10.1107/S2414314617015905

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171590

https://doi.org/10.1107/S2414314617015905

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An orthorhombic polymorph of (E)-1-(benzo[d][1,3]dioxol-5-yl)-3-(2,3-dichlorophenyl)prop-2-en-1-one

S. Naveen,^a ^* A. Dileep Kumar,^b M. V. Deepa Urs,^c K. Ajay Kumar,^b N. K. Lokanath ^d and Ismail Warad ^e ^*

^aDepartment of Physics, School of Engineering & Technology, Jain University, Bangalore 562 112, India, ^bDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^cDepartment of Physics, National Institute of Engineering, Mysuru 570 008, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^eDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: s.naveen@jainuniversity.ac.in, khalil.i@najah.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 25 October 2017; accepted 1 November 2017; online 10 November 2017)

The title compound, C₁₆H₁₀Cl₂O₃, is almost planar with a dihedral angle of 0.14 (16)° between the benzodioxole ring system and the dichlorobenzene ring that are bridged by the olefinic double bond. The corresponding value reported for the monoclinic polymorph is [5.57 (9)° (Lokeshwari et al. (2017 ). IUCrData, 2, x170103). The carbonyl group lies almost in the plane of the olefinic double bond and is twisted slightly from the benzodioxole ring plane. In the crystal, the molecules are linked by weak C—H⋯O and C—H⋯Cl hydrogen bonds, forming a chain propagating along the b-axis direction.

Keywords: crystal structure; chalcone; E configuration; hydrogen bonds.

CCDC reference: 1583520

Structure description

Chalcones and their derivatives exhibit a plethora of biological applications that include use as antioxidants, or antifungal, antibacterial and cardioprotective agents. As part of our ongoing work on such molecules (Rajendraprasad et al., 2017 ; Naveen et al., 2016a ,b ), we report here the synthesis and crystal structure of the title compound.

The structure of the title molecule is shown in Fig. 1. It is a polymorph having been reported previously in the monoclinic space-group P2₁/c (Lokeshwari et al., 2017). The molecule is nearly planar as seen by the dihedral angle of 0.14 (16)° between the benzodioxole ring system and the dichlorobenzene ring; these are bridged by an olefinic double bond that adopts an E conformation. The corresponding dihedral angle reported for the monoclinic polymorph is 5.57 (9)° (Lokeshwari et al., 2017). The trans conformation of the C=C double bond in the central enone group is confirmed by the C—C=C—C torsion angle of −174.9 (4)°. The carbonyl group at C9 lies almost in the plane of the olefinic double bond and is twisted slightly from the benzodioxole ring as indicated by the C11—C10—C9—O3 and C7—C8—C9—O3 torsion angles of 13.7 (5) and 5.0 (6)° respectively.

Figure 1
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

In the crystal, the molecules are linked by weak C—H⋯O and C—H⋯Cl hydrogen bonds (Table 1), forming a chain propagating along the b-axis direction, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.93	2.46	3.185 (5)	135
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Packing of the molecules, viewed along the b axis, with hydrogen bonds shown as blue lines.

Synthesis and crystallization

A mixture of 2,3-dichlorobenzaldehyde (5 mmol), 1-(benzo[d][1,3]dioxol-5-yl)ethanone (5 mmol) and sodium hydroxide (5 mmol) in methanol (25 ml) was stirred at room temperature for 3 h. The progress of the reaction was monitored by TLC. After completion, the mixture was poured into ice-cold water and kept in the refrigerator for 18 h. The solid formed was filtered, and washed with cold 5% hydrochloric acid. Pale-green crystals were obtained from methanol solution by using the slow solvent evaporation technique, yield 88%, m.p. 401–402 K.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₀Cl₂O₃
M_r	321.14
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	21.9756 (11), 12.7354 (6), 4.9889 (3)
V (Å³)	1396.23 (13)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.25
Crystal size (mm)	0.27 × 0.26 × 0.22

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.393, 0.455
No. of measured, independent and observed [I > 2σ(I)] reflections	6212, 1801, 1639
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.585

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.120, 1.06
No. of reflections	1801
No. of parameters	190
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.37
Absolute structure	Flack (1983 )
Absolute structure parameter	0.02 (2)
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1583520

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617015905/sj4143sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617015905/sj4143Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617015905/sj4143Isup3.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)-1-(Benzo[d][1,3]dioxol-5-yl)-3-(2,3-dichlorophenyl)prop-2-en-1-one top

Crystal data top

C₁₆H₁₀Cl₂O₃	F(000) = 656
M_r = 321.14	D_x = 1.528 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 1639 reflections
a = 21.9756 (11) Å	θ = 4.0–64.5°
b = 12.7354 (6) Å	µ = 4.25 mm⁻¹
c = 4.9889 (3) Å	T = 296 K
V = 1396.23 (13) Å³	Prism, green
Z = 4	0.27 × 0.26 × 0.22 mm

Data collection top

Bruker X8 Proteum diffractometer	1801 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1639 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.061
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.5°, θ_min = 4.0°
φ and ω scans	h = −25→24
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −13→14
T_min = 0.393, T_max = 0.455	l = −4→5
6212 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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0639P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1801 reflections	Δρ_max = 0.29 e Å⁻³
190 parameters	Δρ_min = −0.37 e Å⁻³
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (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	0.40504 (4)	0.22650 (8)	1.0103 (2)	0.0306 (3)
Cl2	0.48016 (5)	0.35770 (9)	1.4215 (3)	0.0386 (3)
O1	0.05572 (13)	0.4848 (2)	−0.3392 (7)	0.0333 (10)
O2	0.05823 (13)	0.3043 (2)	−0.2738 (7)	0.0335 (10)
O3	0.23955 (15)	0.2272 (2)	0.3436 (7)	0.0399 (11)
C1	0.38991 (17)	0.3592 (3)	1.0505 (8)	0.0229 (11)
C2	0.34376 (17)	0.4072 (3)	0.8997 (9)	0.0227 (11)
C3	0.33324 (17)	0.5145 (3)	0.9436 (9)	0.0260 (11)
C4	0.36566 (19)	0.5703 (3)	1.1311 (9)	0.0283 (12)
C5	0.41077 (18)	0.5219 (4)	1.2808 (9)	0.0300 (14)
C6	0.42298 (18)	0.4164 (4)	1.2366 (8)	0.0268 (13)
C7	0.30817 (18)	0.3496 (3)	0.7011 (9)	0.0263 (12)
C8	0.26308 (18)	0.3868 (3)	0.5549 (8)	0.0283 (12)
C9	0.22949 (17)	0.3220 (3)	0.3630 (7)	0.0232 (11)
C10	0.18281 (17)	0.3718 (3)	0.1898 (8)	0.0220 (11)
C11	0.14240 (17)	0.3059 (3)	0.0514 (8)	0.0242 (11)
C12	0.10171 (17)	0.3520 (3)	−0.1190 (9)	0.0224 (11)
C13	0.02917 (19)	0.3861 (3)	−0.4182 (9)	0.0307 (14)
C14	0.10051 (17)	0.4598 (3)	−0.1576 (8)	0.0270 (14)
C15	0.13913 (18)	0.5262 (3)	−0.0252 (9)	0.0307 (14)
C16	0.17994 (18)	0.4807 (3)	0.1541 (9)	0.0270 (12)
H3	0.30360	0.54870	0.84320	0.0310*
H4	0.35730	0.64110	1.15780	0.0340*
H5	0.43250	0.55950	1.40880	0.0360*
H7	0.31840	0.27940	0.67500	0.0320*
H8	0.25220	0.45690	0.57450	0.0340*
H11	0.14330	0.23350	0.07480	0.0290*
H13A	−0.01410	0.38620	−0.37970	0.0370*
H13B	0.03460	0.37540	−0.60930	0.0370*
H15	0.13820	0.59830	−0.05360	0.0370*
H16	0.20590	0.52370	0.25230	0.0320*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0342 (5)	0.0241 (6)	0.0335 (6)	0.0047 (4)	−0.0025 (4)	0.0021 (5)
Cl2	0.0333 (5)	0.0449 (7)	0.0375 (6)	0.0001 (5)	−0.0139 (5)	0.0056 (5)
O1	0.0329 (16)	0.0280 (17)	0.0389 (18)	0.0053 (13)	−0.0114 (13)	−0.0013 (15)
O2	0.0322 (15)	0.0252 (17)	0.0431 (19)	0.0008 (13)	−0.0158 (14)	−0.0055 (15)
O3	0.0466 (18)	0.0182 (18)	0.055 (2)	−0.0044 (14)	−0.0244 (17)	0.0006 (14)
C1	0.0237 (19)	0.021 (2)	0.024 (2)	−0.0026 (16)	0.0011 (18)	0.0057 (17)
C2	0.0239 (19)	0.024 (2)	0.0203 (19)	−0.0035 (15)	−0.0004 (16)	0.0030 (18)
C3	0.0259 (18)	0.022 (2)	0.030 (2)	0.0005 (16)	−0.0036 (17)	0.0009 (19)
C4	0.034 (2)	0.023 (2)	0.028 (2)	0.0007 (18)	−0.0004 (19)	−0.001 (2)
C5	0.028 (2)	0.039 (3)	0.023 (2)	−0.0089 (18)	−0.0015 (16)	−0.006 (2)
C6	0.0214 (18)	0.036 (3)	0.023 (2)	−0.0028 (17)	−0.0016 (17)	0.002 (2)
C7	0.029 (2)	0.018 (2)	0.032 (2)	0.0014 (16)	−0.0055 (19)	−0.0016 (19)
C8	0.031 (2)	0.024 (2)	0.030 (2)	0.0005 (17)	−0.0033 (19)	−0.0078 (19)
C9	0.0225 (18)	0.025 (2)	0.022 (2)	−0.0022 (17)	0.0014 (16)	0.0039 (18)
C10	0.0230 (19)	0.026 (2)	0.017 (2)	0.0003 (16)	0.0024 (16)	0.0018 (18)
C11	0.0275 (19)	0.021 (2)	0.024 (2)	−0.0002 (17)	0.0006 (16)	−0.0002 (18)
C12	0.0231 (18)	0.022 (2)	0.022 (2)	0.0002 (16)	0.0018 (17)	−0.0020 (18)
C13	0.029 (2)	0.032 (3)	0.031 (2)	0.0012 (18)	−0.0066 (18)	−0.001 (2)
C14	0.0249 (19)	0.028 (3)	0.028 (2)	0.0035 (18)	−0.0004 (16)	0.0006 (19)
C15	0.037 (2)	0.018 (2)	0.037 (3)	−0.0012 (18)	−0.0029 (19)	0.0009 (19)
C16	0.027 (2)	0.024 (2)	0.030 (2)	−0.0023 (17)	−0.0055 (17)	−0.004 (2)

Geometric parameters (Å, º) top

Cl1—C1	1.734 (4)	C10—C11	1.404 (5)
Cl2—C6	1.729 (4)	C10—C16	1.400 (5)
O1—C13	1.441 (5)	C11—C12	1.366 (6)
O1—C14	1.375 (5)	C12—C14	1.387 (5)
O2—C12	1.371 (5)	C14—C15	1.368 (6)
O2—C13	1.419 (5)	C15—C16	1.393 (6)
O3—C9	1.231 (5)	C3—H3	0.9300
C1—C2	1.403 (6)	C4—H4	0.9300
C1—C6	1.386 (6)	C5—H5	0.9300
C2—C3	1.403 (5)	C7—H7	0.9300
C2—C7	1.460 (6)	C8—H8	0.9300
C3—C4	1.374 (6)	C11—H11	0.9300
C4—C5	1.386 (6)	C13—H13A	0.9700
C5—C6	1.388 (7)	C13—H13B	0.9700
C7—C8	1.318 (6)	C15—H15	0.9300
C8—C9	1.464 (5)	C16—H16	0.9300
C9—C10	1.484 (5)

C13—O1—C14	105.6 (3)	O1—C14—C12	109.5 (3)
C12—O2—C13	105.9 (3)	O1—C14—C15	128.2 (3)
Cl1—C1—C2	120.1 (3)	C12—C14—C15	122.2 (4)
Cl1—C1—C6	119.3 (3)	C14—C15—C16	116.9 (4)
C2—C1—C6	120.6 (4)	C10—C16—C15	121.5 (4)
C1—C2—C3	117.4 (4)	C2—C3—H3	119.00
C1—C2—C7	122.2 (3)	C4—C3—H3	119.00
C3—C2—C7	120.5 (4)	C3—C4—H4	120.00
C2—C3—C4	121.6 (4)	C5—C4—H4	120.00
C3—C4—C5	120.5 (4)	C4—C5—H5	121.00
C4—C5—C6	118.9 (4)	C6—C5—H5	121.00
Cl2—C6—C1	120.8 (4)	C2—C7—H7	117.00
Cl2—C6—C5	118.3 (3)	C8—C7—H7	117.00
C1—C6—C5	120.9 (4)	C7—C8—H8	119.00
C2—C7—C8	126.7 (4)	C9—C8—H8	119.00
C7—C8—C9	122.6 (4)	C10—C11—H11	121.00
O3—C9—C8	120.9 (3)	C12—C11—H11	121.00
O3—C9—C10	119.8 (3)	O1—C13—H13A	110.00
C8—C9—C10	119.3 (3)	O1—C13—H13B	110.00
C9—C10—C11	117.9 (3)	O2—C13—H13A	110.00
C9—C10—C16	121.9 (3)	O2—C13—H13B	110.00
C11—C10—C16	120.1 (4)	H13A—C13—H13B	108.00
C10—C11—C12	117.6 (4)	C14—C15—H15	122.00
O2—C12—C11	128.1 (3)	C16—C15—H15	122.00
O2—C12—C14	110.3 (3)	C10—C16—H16	119.00
C11—C12—C14	121.6 (4)	C15—C16—H16	119.00
O1—C13—O2	108.6 (3)

C14—O1—C13—O2	1.6 (4)	C4—C5—C6—C1	−1.4 (6)
C13—O1—C14—C12	−1.1 (4)	C2—C7—C8—C9	−179.1 (4)
C13—O1—C14—C15	179.6 (4)	C7—C8—C9—O3	5.0 (6)
C13—O2—C12—C11	−178.6 (4)	C7—C8—C9—C10	−174.9 (4)
C13—O2—C12—C14	0.8 (4)	O3—C9—C10—C11	13.7 (5)
C12—O2—C13—O1	−1.5 (4)	O3—C9—C10—C16	−163.7 (4)
Cl1—C1—C2—C3	179.3 (3)	C8—C9—C10—C11	−166.4 (4)
Cl1—C1—C2—C7	−1.6 (6)	C8—C9—C10—C16	16.2 (6)
C6—C1—C2—C3	0.6 (6)	C9—C10—C11—C12	−176.5 (4)
C6—C1—C2—C7	179.7 (4)	C16—C10—C11—C12	1.0 (6)
Cl1—C1—C6—Cl2	1.7 (5)	C9—C10—C16—C15	174.8 (4)
Cl1—C1—C6—C5	−177.8 (3)	C11—C10—C16—C15	−2.6 (6)
C2—C1—C6—Cl2	−179.7 (3)	C10—C11—C12—O2	−179.9 (4)
C2—C1—C6—C5	0.9 (6)	C10—C11—C12—C14	0.8 (6)
C1—C2—C3—C4	−1.5 (6)	O2—C12—C14—O1	0.2 (5)
C7—C2—C3—C4	179.3 (4)	O2—C12—C14—C15	179.6 (4)
C1—C2—C7—C8	178.2 (4)	C11—C12—C14—O1	179.6 (4)
C3—C2—C7—C8	−2.8 (7)	C11—C12—C14—C15	−1.0 (6)
C2—C3—C4—C5	1.0 (7)	O1—C14—C15—C16	178.7 (4)
C3—C4—C5—C6	0.5 (6)	C12—C14—C15—C16	−0.5 (6)
C4—C5—C6—Cl2	179.1 (3)	C14—C15—C16—C10	2.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.93	2.46	3.185 (5)	135
C7—H7···Cl1	0.93	2.62	3.061 (4)	109
C7—H7···O3	0.93	2.49	2.808 (5)	100

Symmetry code: (i) −x+1/2, y+1/2, 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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