Crystal structure and Hirshfeld surface analysis of (E)-3-(2-chloro­phen­yl)-1-(2,5-di­chloro­thio­phen-3-yl)prop-2-en-1-one

Murthy, T.N.S.; Atioğlu, Z.; Akkurt, M.; Veeraiah, M.K.; Quah, C.K.; Chidan Kumar, C.S.; Siddaraju, B.P.

doi:10.1107/S2056989018018066

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 124-128

https://doi.org/10.1107/S2056989018018066

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Crystal structure and Hirshfeld surface analysis of (E)-3-(2-chlorophenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one

T. N. Sanjeeva Murthy,^a Zeliha Atioğlu,^b Mehmet Akkurt,^c ^* M. K. Veeraiah,^d Ching Kheng Quah,^e C. S. Chidan Kumar ^f and B. P. Siddaraju ^g

^aDepartment of Chemistry, Sri Siddhartha Academy of Higher Education, Tumkur 572 107, Karnataka, India, ^bİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^dDepartment of Chemistry, Sri Siddhartha Institute of Technology, Tumkur 572 105, Karnataka, India, ^eX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^fDepartment of Engineering Chemistry, Vidya Vikas Institute of Engineering & Technology, Visvesvaraya Technological University, Alanahalli, Mysuru 570028, Karnataka, India, and ^gDepartment of Chemistry, Cauvery Institute of Technology, Mandya 571 402, Karnataka, India
^*Correspondence e-mail: akkurt@erciyes.edu.tr

Edited by P. McArdle, National University of Ireland, Ireland (Received 17 December 2018; accepted 20 December 2018; online 4 January 2019)

The molecular structure of the title compound, C₁₃H₇Cl₃OS, consists of a 2,5- dichlorothiophene ring and a 2-chlorophenyl ring linked via a prop-2-en-1-one spacer. The dihedral angle between the 2,5-dichlorothiophene and 2-chlorophenyl rings is 9.69 (12)°. The molecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The molecular conformation is stabilized by two intramolecular C—H⋯Cl contacts and one intramolecular C—H⋯O contact, forming S(5)S(5)S(6) ring motifs. In the crystal, the molecules are linked along the a-axis direction through van der Waals forces and along the b axis by face-to-face π-stacking between the thiophene rings and between the benzene rings of neighbouring molecules, forming corrugated sheets lying parallel to the bc plane. The intermolecular interactions in the crystal packing were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are Cl⋯H/ H⋯Cl (28.6%), followed by C⋯H/H⋯C (11.9%), C⋯C (11.1%), H⋯H (11.0%), Cl⋯Cl (8.1%), O⋯H/H⋯O (8.0%) and S⋯H/H⋯S (6.6%).

Keywords: crystal structure; 2,5- dichlorothiophene ring; 2-chlorophenyl ring; E configuration; Hirshfeld surface analysis; crystal structure.

CCDC reference: 1036796

1. Chemical context

Chalcone is an aromatic ketone that forms a central core for a variety of biological compounds, which are collectively known as chalcones. Chalcones, considered to be the precursors of flavonoids and isoflavonoids, are abundant in edible plants. They consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon α,β-unsaturated carbonyl system. Chalcone was first isolated from Chinese liquorice (Glycyrrhizae inflata) (Rao et al., 2004 ). It has a 1,3-diaryl-1-one skeletal system, which was recognized as the main pharmacophore for chalcones. The introduction of various substituents into the two aryl rings is also an area of interest for investigating structure–activity relationships. Chalcones are coloured compounds because of the presence of the –CO—CH=CH– chromophore. Different methods have been reported for the preparation of chalcones, the most convenient method being the Claisen-Schimdt condensation of equimolar quantities of an aryl methylketone with an aryl aldehyde in the presence of alcoholic alkali. The synthesis and antimicrobial evaluation of new chalcones containing a 2,5-dichlorothiophene moiety have been reported (Tomar et al., 2007 ). Recently, chalcones have been used in the field of materials science as non-linear optical devices (Raghavendra et al., 2017 ; Chandra Shekhara Shetty et al., 2016 ). The crystal structures of (E)-1-(2,5-dichloro-3-thienyl)-3-[4-(dimethylamino)phenyl]prop-2-en-1-one (Dutkiewicz et al., 2010 ), (2E)-1-(2,5-dichloro-3-thienyl)-3-(6-methoxy-2-naphthyl)prop-2-en-1-one (Jasinski et al., 2010 ), (E)-1-(2,5-dichloro-3-thienyl)-3-(3,4-dimethoxyphenyl)prop-2-en-1-one (Harrison et al., 2010a ), (E)-3-(2-chloro-4-fluorophenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (Sanjeeva Murthy et al., 2018 ) and (2E)-3-(2,4-dichlorophenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (Murthy et al., 2018 ) have previously been reported.

As part of our studies in this area, we report the crystal and molecular structures of the title compound.

2. Structural commentary

As shown in Fig. 1, the title compound is constructed from two aromatic rings (2,5-dichlorothiophene and terminal 2-chlorophenyl rings), which are linked by a C=C—C(=O)—C enone bridge. The C3—C4—C5—O1 and O1—C5—C6—C7 torsion angles about the enone bridge are 6.7 (4) and 4.3 (4)°, respectively, probably as a result of steric repulsion between the chlorine atoms of adjacent molecules. The dihedral angle between the 2-chlorothiophene and 2,4-dichlorophenyl rings is 9.69 (12)°. The bond lengths and angles in the title compound are comparable with those in the related compounds (2E)-3-(2,4-dichlorophenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (Sanjeeva Murthy et al., 2018), (E)-3-(3,4-dimethoxyphenyl)-1-(1-hydroxynaphthalen-2yl)prop-2-en-1-one (Ezhilarasi et al., 2015 ), (E)-1-(3-bromophenyl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one (Escobar et al., 2012 ) and (E)-3-(2-bromophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (Li et al., 2012 ). The molecular conformation is stabilized by two intramolecular C—H⋯Cl contacts and one intramolecular C—H⋯O contact (Table 1), forming S(5)S(5)S(6) ring motifs.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cl1	0.93	2.54	3.245 (3)	133
C7—H7A⋯Cl3	0.93	2.59	3.043 (3)	110
C7—H7A⋯O1	0.93	2.46	2.790 (3)	101

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. Intramolecular hydrogen bonds (Table 1

) are shown as dashed lines.

3. Supramolecular features

In the crystal, conventional hydrogen bonds are not observed. Molecules are linked along the a-axis direction through van der Waals forces. π-stacking is observed between thiophene rings (S1/C1–C4, centroid Cg1) of adjacent molecules in alternating sheets along the [100] direction [Cg1⋯Cg1^i,ii: centroid–centroid distance = 3.902 (2) Å, shortest perpendicular distance for the centroid of one ring to the plane of the other = 3.597 (1) Å, ring-centroid offset = 1.512 Å; symmetry codes: (i) −1 + x, y, z; (ii) 1 + x, y, z] and between the benzene rings (C8–C13, centroid Cg2) of the same molecules [Cg2⋯Cg2^i,ii: centroid–centroid distance = 3.902 (2) Å, shortest perpendicular distance = 3.482 (1) Å, offset = 1.760 Å]. The molecules are packed into corrugated sheets lying parallel to (011) (Figs. 2 and 3). Details of Cl⋯H and O⋯H contacts are given in Table 2.

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	distance	Symmetry operation
Cl1⋯Cl1	3.2876 (11)	2 − x, 1 − y, 1 − z
Cl2⋯C10	3.618 (3)	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
Cl2⋯H10A	3.06	1 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H3A⋯Cl2	3.01	2 − x, 1 − y, 2 − z
H3A⋯Cl2	2.98	3 − x, 1 − y, 2 − z
Cl3⋯H12A	3.11	x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
C6⋯C7	3.504 (4)	1 + x, y, z
O1⋯H10A	2.85	1 + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z

Figure 2
View along the b-axis direction of the zigzag sheets lying parallel to (011). π-stacking is observed between the thiophene rings (centroid Cg1) of adjacent molecules in alternating sheets along the [100] direction and between the benzene rings (centroid Cg2) of the same molecules.

Figure 3
Hirshfeld surface mapped d_norm showing the intra- and intermolecular C—H⋯Cl and C—H⋯O hydrogen-bonded contacts.

4. Hirshfeld surface analysis

Hirshfeld surfaces and fingerprint plots were generated for the title compound using CrystalExplorer (McKinnon et al., 2007 ). Hirshfeld surfaces enable the visualization of intermolecular interactions by using different colours and colour intensity to represent short or long contacts and indicate the relative strength of the interactions. The overall two-dimensional fingerprint plot for the title compound and those delineated into Cl⋯H/H⋯Cl, C⋯H/H⋯C, C⋯C, H⋯H, Cl⋯Cl, O⋯H/H⋯O and S⋯H/H⋯S contacts are illustrated in Fig. 4; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are as follows: Cl⋯H/H⋯Cl (28.6%), C⋯H/H⋯C (11.9%), C⋯C (11.1%), H⋯H (11.0%), Cl⋯Cl (8.1%), O⋯H/H⋯O (8.0%) and S⋯H/H⋯S (6.6%). The contributions of the other weak intermolecular contacts to the Hirshfeld surfaces are listed in Table 3.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the compound

Contact	Percentage contribution
Cl⋯H/H⋯Cl	28.6
C⋯H/H⋯C	11.9
C⋯C	11.1
H⋯H	11.0
Cl⋯Cl	8.1
O⋯H/H⋯O	8.0
S⋯H/H⋯S	6.6
C⋯Cl/Cl⋯C	4.7
S⋯Cl/Cl⋯S	4.1
S⋯C/C⋯S	2.1
O⋯C/C⋯O	1.6
O⋯Cl/Cl⋯O	1.0
S⋯S	0.8
O⋯O	0.3

Figure 4
The two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) Cl⋯H/H⋯Cl, (c) C⋯H/H⋯C, (d) C⋯C, (e) H⋯H, (f) Cl⋯Cl, (g) O⋯H/H⋯O and (h) S⋯H/H⋯S interactions.

The C—H⋯Cl interactions appear as two distinct spikes in the fingerprint plot [Fig. 4(b)] with d_e + d_i ≃ 2.85 Å [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively]. The C⋯H/H⋯C interactions are shown in Fig. 4(c). The scattered points show the van der Waals contacts and π–π stacking interactions. The interatomic C⋯C contacts appear as an arrow-shaped distribution of points in Fig. 4(d), with the vertex at d_e = d_i = 1.75 Å. The C⋯C contacts reflect π–π interactions between the aromatic rings. The H⋯H interactions are reflected in Fig. 4(e) as widely scattered points of high density due to the large hydrogen content of the molecule. The split spike with the tip at d_e = d_i ≃ 1.3 Å is due to the short interatomic H⋯H contacts. Cl⋯Cl contacts [Fig. 4(f)] are disfavoured when the number of H atoms on the molecular surface is large because of competition with the more attractive H⋯Cl contacts. Cl⋯Cl contacts from a parallel alignment of C—Cl bonds [C1—Cl1⋯Cl1ⁱⁱⁱ, and C2—Cl2⋯C10^iv; symmetry codes: (iii) 2 − x, 1 − y, 1 − z; (iv) 2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z] may be indicated. They are known in the literature as type-I halogen–halogen interactions (Bui et al., 2009 ), with both C—Cl⋯Cl angles equal to one another. In the present case, these angles are close to 165°. The H⋯O/O⋯H contacts [Fig. 4(g)] also have a symmetrical distribution of points, with two pairs of thin and thick edges at d_e + d_i ≃ 2.75 Å. The S⋯H contacts shown in Fig. 4(h) are contracted to a much lesser degree.

The large number of Cl⋯H/H⋯Cl, C⋯H/H⋯C, C⋯C, H⋯H, Cl⋯Cl, O⋯H/H⋯O and S⋯H/H⋯S interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Database survey

The closest related compounds with the same skeleton and containing a similar bis-chalcone moiety to the title compound but with different substituents on the aromatic rings are: (2E)- 1-(5-chlorothiophen-2-yl)-3-(4-ethylphenyl)prop-2-en-1-one [(I); Naik et al., 2015 ], (2E)-1-(5-bromothiophen-2-yl)-3-(4-ethylphenyl)prop- 2-en-1-one [(II); Naik et al., 2015], (2E)-1-(5-chlorothiophen-2-yl)-3-(4-ethoxyphenyl)prop-2-en-1-one [(III); Naik et al., 2015], (2E)-1-(5-bromothiophen-2-yl)-3-(4- ethoxyphenyl)prop-2-en-1-one [(IV); Naik et al., 2015], (2E)- 3-(4-bromophenyl)-1-(5-chlorothiophen-2-yl)prop-2-en-1-one [(V); Naik et al., 2015], (2E)-1-(5-bromothiophen-2-yl)-3-(3- methoxyphenyl)prop-2-en-1-one [(VI); Naik et al., 2015], (E)- 1-(5-chlorothiophen-2-yl)-3-(p-tolyl)prop-2-en-1-one [(VII); Kumara et al., 2017 ], (E)-1-(5-chlorothiophen-2-yl)-3-(2,4-dimethylphenyl) prop-2-en-1-one [(VIII); Naveen et al., 2016 ], (2E)-1-(5-bromothiophen- 2-yl)-3-(2-chlorophenyl)prop-2-en- 1-one [(IX); Anitha et al., 2015 ], (2E)-1-[4-hydroxy-3- (morpholin-4-ylmethyl)phenyl]-3-(thiophen-2-yl)prop-2-en-1- one [(X); Yesilyurt et al., 2018 ], (E)-1-(2-aminophenyl)-3- (thiophen-2-yl)prop-2-en-1-one [(XI); Chantrapromma et al., 2013 ] and (2E)-3-(2,4-dichlorophenyl)-1-(2,5-dichlorothiophen- 3-yl)prop-2-en-1-one [(XII); Sanjeeva Murthy et al., 2018]. In (I) and (II), the structures are isostructural in space group P1, while (III) and (IV) are isostructural in space group P2₁/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the molecules are linked into C(7) chains by means of C—H⋯O hydrogen bonds. In (V), there are again no hydrogen bonds nor any π–π stacking interactions but in (VI), the molecules are linked into C(5) chains by C—H⋯O hydrogen bonds. In each of compounds (I)–(VI), the molecular skeletons are close to planarity, and there are short halogen–halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). In (VII), the molecule is non-planar, with a dihedral angle of 22.6 (2)° between the aromatic rings. The molecules are linked by pairs of C—H⋯π interactions, forming inversion dimers. There are no other significant intermolecular interactions present. In (VIII), the molecule is nearly planar, the dihedral angle between the thiophene and phenyl rings being 9.07 (8)°. The molecules are linked via weak C—H⋯O and C—H⋯S hydrogen bonds, forming chains propagating along the c-axis direction. In (IX), the thienyl ring is not coplanar with the benzene ring, their planes forming a dihedral angle of 13.2 (4)°. In the crystal, molecules stack along the a-axis direction, with the interplanar separation between the thienyl rings and between the benzene rings being 3.925 (6) Å. In (X), the thiophene ring forms a dihedral angle of 26.04 (9)° with the benzene ring. The molecular conformation is stabilized by an O—H⋯N hydrogen bond. The molecules are connected through C—H⋯O hydrogen bonds, forming wave-like layers parallel to the ab plane, which are further linked into a three-dimensional network by C—H⋯π interactions. In (XI), the molecule is almost planar with a dihedral angle of 3.73 (8)° between the phenyl and thiophene rings. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. Adjacent molecules are linked into dimers in an anti-parallel face-to-face manner by pairs of C—H⋯O interactions. Neighbouring dimers are further linked into chains along the c-axis direction by N—H⋯N hydrogen bonds. In (XII), the dihedral angle between the thiophene and benzene rings increases to12.24 (15)°. The molecular conformation is stabilized by intramolecular C—H⋯Cl contacts, forming S(6) and S(5) ring motifs. In the crystal, the molecules are linked through face-to-face π-stacking between the thiophene rings and the benzene rings of the molecules into zigzag sheets lying parallel to the bc plane.

6. Synthesis and crystallization

The title compound was synthesized by a reported procedure (Kumar et al., 2013a ,b ). 1-(2,5-Dichlorothiophen-3-yl)ethanone (0.01 mol) (Harrison et al., 2010b ) and 2-chlorobenzaldehyde (0.01 mol) were dissolved in 20 ml of methanol. A catalytic amount of NaOH was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 4 h at room temperature. The formed crude products were filtered, washed successively with distilled water and recrystallized from methanol. The melting point (352–363 K) was determined using a Stuart Scientific (UK) apparatus.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. H atoms were positioned geometrically and refined using riding model, with C—H = 0.93–0.96 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₃H₇Cl₃OS
M_r	317.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	3.9017 (6), 22.038 (3), 15.127 (2)
β (°)	96.998 (3)
V (Å³)	1291.0 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.85
Crystal size (mm)	0.56 × 0.10 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007 )
T_min, T_max	0.907, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	10683, 2669, 1977
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.099, 1.08
No. of reflections	2669
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1036796

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018066/qm2131sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018066/qm2131Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018018066/qm2131Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

(E)-3-(2-chlorophenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one top

Crystal data top

C₁₃H₇Cl₃OS	F(000) = 640
M_r = 317.60	D_x = 1.634 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.9017 (6) Å	Cell parameters from 2207 reflections
b = 22.038 (3) Å	θ = 2.7–23.3°
c = 15.127 (2) Å	µ = 0.85 mm⁻¹
β = 96.998 (3)°	T = 294 K
V = 1291.0 (3) Å³	Needle, colourless
Z = 4	0.56 × 0.10 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1977 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	θ_max = 26.6°, θ_min = 1.6°
T_min = 0.907, T_max = 0.953	h = −4→4
10683 measured reflections	k = −25→27
2669 independent reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0397P)² + 0.3125P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2669 reflections	Δρ_max = 0.30 e Å⁻³
163 parameters	Δρ_min = −0.32 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.19136 (18)	0.57814 (3)	0.76052 (4)	0.0475 (2)
O1	0.7421 (6)	0.37898 (9)	0.81944 (13)	0.0729 (7)
Cl1	0.8918 (3)	0.51901 (4)	0.59796 (4)	0.0767 (3)
Cl2	1.37875 (18)	0.58175 (3)	0.95615 (4)	0.0553 (2)
Cl3	0.18192 (19)	0.21002 (3)	0.65287 (4)	0.0547 (2)
C1	1.0021 (6)	0.51465 (11)	0.71070 (15)	0.0419 (6)
C2	1.2074 (6)	0.54379 (11)	0.86299 (15)	0.0405 (6)
C3	1.0742 (6)	0.48785 (11)	0.85791 (16)	0.0409 (6)
H3A	1.062770	0.463252	0.907420	0.049*
C4	0.9511 (6)	0.46945 (11)	0.76907 (15)	0.0368 (5)
C5	0.7905 (7)	0.40836 (12)	0.75452 (17)	0.0432 (6)
C6	0.6952 (7)	0.38479 (12)	0.66419 (17)	0.0498 (7)
H6A	0.750113	0.407394	0.615933	0.060*
C7	0.5354 (7)	0.33292 (12)	0.64948 (16)	0.0442 (6)
H7A	0.484449	0.311865	0.699544	0.053*
C8	0.4278 (6)	0.30426 (11)	0.56358 (16)	0.0383 (5)
C9	0.2658 (6)	0.24794 (11)	0.55730 (16)	0.0389 (6)
C10	0.1648 (7)	0.22027 (12)	0.47628 (17)	0.0478 (6)
H10A	0.058424	0.182449	0.474158	0.057*
C11	0.2228 (8)	0.24897 (13)	0.39919 (17)	0.0548 (7)
H11A	0.153881	0.230816	0.344393	0.066*
C12	0.3828 (8)	0.30463 (13)	0.40288 (18)	0.0568 (7)
H12A	0.423175	0.324019	0.350527	0.068*
C13	0.4827 (7)	0.33156 (12)	0.48330 (17)	0.0503 (7)
H13A	0.590560	0.369228	0.484531	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0609 (4)	0.0364 (4)	0.0465 (4)	−0.0055 (3)	0.0117 (3)	−0.0010 (3)
O1	0.1185 (19)	0.0477 (12)	0.0502 (11)	−0.0279 (12)	0.0013 (12)	0.0062 (10)
Cl1	0.1343 (8)	0.0581 (5)	0.0363 (4)	−0.0125 (5)	0.0043 (4)	0.0020 (3)
Cl2	0.0611 (4)	0.0495 (4)	0.0514 (4)	−0.0053 (3)	−0.0085 (3)	−0.0104 (3)
Cl3	0.0722 (5)	0.0451 (4)	0.0472 (4)	−0.0141 (3)	0.0086 (3)	0.0062 (3)
C1	0.0527 (15)	0.0377 (15)	0.0357 (12)	0.0016 (12)	0.0069 (11)	−0.0030 (10)
C2	0.0395 (13)	0.0417 (15)	0.0395 (13)	0.0005 (11)	0.0013 (10)	−0.0045 (11)
C3	0.0456 (14)	0.0375 (14)	0.0382 (12)	−0.0001 (11)	0.0001 (11)	0.0019 (11)
C4	0.0366 (12)	0.0349 (14)	0.0387 (12)	0.0033 (10)	0.0029 (10)	−0.0009 (10)
C5	0.0476 (14)	0.0356 (14)	0.0452 (14)	0.0002 (11)	0.0010 (11)	0.0000 (11)
C6	0.0636 (17)	0.0416 (16)	0.0434 (14)	−0.0111 (13)	0.0028 (12)	−0.0013 (12)
C7	0.0496 (15)	0.0376 (15)	0.0448 (13)	−0.0028 (12)	0.0031 (11)	0.0013 (11)
C8	0.0373 (13)	0.0332 (14)	0.0440 (13)	−0.0011 (10)	0.0037 (10)	0.0006 (10)
C9	0.0414 (13)	0.0340 (14)	0.0412 (13)	0.0004 (11)	0.0042 (10)	0.0023 (10)
C10	0.0518 (15)	0.0399 (15)	0.0508 (15)	−0.0081 (12)	0.0023 (12)	−0.0030 (12)
C11	0.0685 (19)	0.0525 (18)	0.0419 (14)	−0.0038 (15)	0.0011 (13)	−0.0041 (13)
C12	0.0710 (19)	0.0553 (19)	0.0434 (15)	−0.0100 (15)	0.0043 (13)	0.0090 (13)
C13	0.0586 (17)	0.0383 (15)	0.0532 (15)	−0.0082 (13)	0.0041 (13)	0.0068 (12)

Geometric parameters (Å, º) top

S1—C1	1.713 (3)	C6—H6A	0.9300
S1—C2	1.719 (2)	C7—C8	1.460 (3)
O1—C5	1.210 (3)	C7—H7A	0.9300
Cl1—C1	1.710 (2)	C8—C9	1.391 (3)
Cl2—C2	1.704 (2)	C8—C13	1.395 (3)
Cl3—C9	1.735 (2)	C9—C10	1.382 (3)
C1—C4	1.362 (3)	C10—C11	1.369 (4)
C2—C3	1.336 (3)	C10—H10A	0.9300
C3—C4	1.430 (3)	C11—C12	1.374 (4)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.490 (3)	C12—C13	1.367 (4)
C5—C6	1.467 (3)	C12—H12A	0.9300
C6—C7	1.308 (3)	C13—H13A	0.9300

C1—S1—C2	90.19 (12)	C6—C7—H7A	116.2
C4—C1—Cl1	130.5 (2)	C8—C7—H7A	116.2
C4—C1—S1	113.67 (18)	C9—C8—C13	116.2 (2)
Cl1—C1—S1	115.81 (14)	C9—C8—C7	121.7 (2)
C3—C2—Cl2	127.67 (19)	C13—C8—C7	122.0 (2)
C3—C2—S1	112.53 (18)	C10—C9—C8	122.2 (2)
Cl2—C2—S1	119.80 (15)	C10—C9—Cl3	117.64 (19)
C2—C3—C4	113.5 (2)	C8—C9—Cl3	120.21 (18)
C2—C3—H3A	123.2	C11—C10—C9	119.5 (2)
C4—C3—H3A	123.2	C11—C10—H10A	120.2
C1—C4—C3	110.1 (2)	C9—C10—H10A	120.2
C1—C4—C5	131.1 (2)	C10—C11—C12	119.9 (2)
C3—C4—C5	118.8 (2)	C10—C11—H11A	120.0
O1—C5—C6	121.3 (2)	C12—C11—H11A	120.0
O1—C5—C4	117.9 (2)	C13—C12—C11	120.2 (3)
C6—C5—C4	120.8 (2)	C13—C12—H12A	119.9
C7—C6—C5	122.0 (2)	C11—C12—H12A	119.9
C7—C6—H6A	119.0	C12—C13—C8	122.0 (2)
C5—C6—H6A	119.0	C12—C13—H13A	119.0
C6—C7—C8	127.5 (2)	C8—C13—H13A	119.0

C2—S1—C1—C4	0.4 (2)	O1—C5—C6—C7	4.3 (4)
C2—S1—C1—Cl1	177.73 (16)	C4—C5—C6—C7	−175.9 (2)
C1—S1—C2—C3	−0.3 (2)	C5—C6—C7—C8	−179.7 (2)
C1—S1—C2—Cl2	179.98 (16)	C6—C7—C8—C9	178.5 (3)
Cl2—C2—C3—C4	179.88 (19)	C6—C7—C8—C13	−1.2 (4)
S1—C2—C3—C4	0.2 (3)	C13—C8—C9—C10	0.1 (4)
Cl1—C1—C4—C3	−177.2 (2)	C7—C8—C9—C10	−179.6 (2)
S1—C1—C4—C3	−0.3 (3)	C13—C8—C9—Cl3	−179.60 (19)
Cl1—C1—C4—C5	1.6 (4)	C7—C8—C9—Cl3	0.7 (3)
S1—C1—C4—C5	178.5 (2)	C8—C9—C10—C11	−0.4 (4)
C2—C3—C4—C1	0.0 (3)	Cl3—C9—C10—C11	179.3 (2)
C2—C3—C4—C5	−178.9 (2)	C9—C10—C11—C12	0.5 (4)
C1—C4—C5—O1	−172.0 (3)	C10—C11—C12—C13	−0.3 (5)
C3—C4—C5—O1	6.7 (4)	C11—C12—C13—C8	0.0 (5)
C1—C4—C5—C6	8.1 (4)	C9—C8—C13—C12	0.1 (4)
C3—C4—C5—C6	−173.2 (2)	C7—C8—C13—C12	179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cl1	0.93	2.54	3.245 (3)	133
C7—H7A···Cl3	0.93	2.59	3.043 (3)	110
C7—H7A···O1	0.93	2.46	2.790 (3)	101

Summary of short interatomic contacts (Å) in the title compound top

Contact	distance	Symmetry operation
Cl1···Cl1	3.2876 (11)	2 - x, 1 - y, 1 - z
Cl2···C10	3.618 (3)	2 - x, 1/2 + y, 3/2 - z
Cl2···H10A	3.06	1 - x, 1/2 + y, 3/2 - z
H3A···Cl2	3.01	2 - x, 1 - y, 2 - z
H3A···Cl2	2.98	3 - x, 1 - y, 2 - z
Cl3···H12A	3.11	x, 1/2 - y, 1/2 + z
C6···C7	3.504 (4)	1 + x, y, z
O1···H10A	2.85	1 + x, 1/2 - y, 1/2 + z

Percentage contributions of interatomic contacts to the Hirshfeld surface for the compound top

Contact	Percentage contribution
Cl···H/H···Cl	28.6
C···H/H···C	11.9
C···C	11.1
H···H	11.0
Cl···Cl	8.1
O···H/H···O	8.0
S···H/H···S	6.6
C···Cl/Cl···C	4.7
S···Cl/Cl···S	4.1
S···C/C···S	2.1
O···C/C···O	1.6
O···Cl/Cl···O	1.0
S···S	0.8
O···O	0.3

Acknowledgements

The authors extend their appreciation to the Vidya Vikas Research & Development Centre for the facilities and encouragement.

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