Crystal structure and Hirshfeld surface analysis of (2E)-3-(2,4-di-chloro-phen-yl)-1-(2,5-di-chloro-thio-phen-3-yl)prop-2-en-1-one.

The mol-ecular structure of the title compound, C13H6Cl4OS, consists of a 2,5-di-chloro-thio-phene ring and a 2,4-di-chloro-phenyl ring linked via a prop-2-en-1-one spacer. The dihedral angle between the 2,5-di-chloro-thio-phene ring and the 2,4-di-chloro-phenyl ring is 12.24 (15)°. The mol-ecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The mol-ecular conformation is stabilized by intra-molecular C-H⋯Cl contacts, producing S(6) and S(5) ring motifs. In the crystal, the mol-ecules are linked along the a-axis direction through face-to-face π-stacking between the thio-phene rings and the benzene rings of the mol-ecules in zigzag sheets lying parallel to the bc plane along the c axis. The inter-molecular inter-actions in the crystal packing were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are Cl⋯H/ H⋯Cl (20.8%), followed by Cl⋯Cl (18.7%), C⋯C (11.9%), Cl⋯S/S⋯Cl (10.9%), H⋯H (10.1%), C⋯H/H⋯C (9.3%) and O⋯H/H⋯O (7.6%).

Chemical context

Compounds bearing the 1,3-diphenyl-2-propen-1-one framework and belong to the flavonoid family are commonly called by its generic name ‘chalcone’. These are abundant in nature, ranging from ferns to higher plants, and are considered to be the precursors of flavonoids and isoflavonoids, in which the two aromatic rings are joined by a three carbon α,β-unsaturated carbonyl system. In plants, chalcones are converted to the corresponding (2S)-flavanones in a stereospecific reaction catalysed by the enzyme chalcone isomerase. The chemistry of chalcones remains a fascination among researchers because of the large number of replaceable hydrogen atoms that allows a number of derivatives with a variety of promising biological activities. They are found in fruits and vegetables, which attracted attention because of their pharmacological activities such as anti-inflamatory (Yadav et al., 2011 ▸), anti­fungal (Mahapatra et al., 2015 ▸), anti­viral (Nowakowska, 2007 ▸; Chimenti et al., 2010 ▸; Elarfi &Al-Difar, 2012 ▸), anti­oxidant (Ferreira et al., 2006 ▸) and anti­cancer (Stiborova et al., 2011 ▸ activities). The synthesis and anti­microbial evaluation of new chalcones containing a 2,5-di­chloro­thio­phene moiety has been reported (Tomar et al., 2007 ▸). In recent years, 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 ▸). In view of all the above and as part of our ongoing work (Harrison et al., 2010 ▸; Jasinski et al., 2010 ▸; Dutkiewicz et al., 2010 ▸) herewith we report the crystal and mol­ecular structure of the title compound.

Structural commentary

The title compound, Fig. 1 ▸, is constructed from two aromatic rings (2,5-di­chloro­thio­phene and terminal 2,4-di­chloro­phenyl rings), which are linked by a C=C—C(=O)—C enone bridge. Probably as a result of the steric repulsion between the chlorine atoms of the adjacent mol­ecules, the C3—C4—C5—O1 and O1—C5—C6—C7 torsion angles about the enone bridge are −11.8 (5) and 0.4 (6)°, respectively. Hence, the dihedral angle between the 2,5-di­chloro­thio­phene ring and the 2,4-di­chloro­phenyl ring increases to 12.24 (15)°. The bond lengths and angles in the title compound are comparable with those of the related compounds (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 of the title compound is stabilized by intra­molecular C—H⋯Cl contacts (Table 1 ▸), producing S(6) and S(5) ring motifs.

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. The two intra­molecular C—H⋯Cl contacts (see Table1) are shown as dashed lines.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cl1	0.93	2.48	3.220 (3)	136
C7—H7A⋯Cl3	0.93	2.65	3.075 (3)	108

Supra­molecular features and Hirshfeld surface analysis

In the crystal, conventional hydrogen bonds are not observed. π-stacking is observed between the thio­phene rings (S1/C1–C4, centroid Cg1) of adjacent mol­ecules in the alternating sheets along the [100] direction [Cg1⋯Cg1i,ii: centroid–centroid distance = 3.987 (2) Å, shortest perpendicular distance for the centroid of one ring to the plane of the other = 3.6143 (12) Å, ring-centroid offset = 1.683 Å; symmetry codes: (i) −1 + x, y, z; (i) 1 + x, y, z] and between the benzene rings (C8–C13, centroid Cg2) of the same mol­ecules [Cg2⋯Cg2i,ii: centroid–centroid distance = 3.987 (2) Å, shortest perpendic­ular distance = 3.5213 (13) Å, offset = 1.869 Å]. As shown Fig. 2 ▸, the mol­ecules are packed to form zigzag sheets lying parallel to (011) along the c-axis direction through face-to-face π-stacking between the thio­phene and benzene rings of pairs of adjacent mol­ecules along the [100] direction (Cl⋯S and Cl⋯H inter­actions; Table 2 ▸ and Fig. 2 ▸). The Cl⋯S contact, at 3.660 (1) Å, is equal to the sum of the van der Waals radii of S and Cl atoms (3.65 Å; Pauling, 1960 ▸).

Figure 2

A view of the offset face-to-face π-stacking in the title compound, with the thick dashed lines indicating centroid-to-centroid inter­actions. The Cl⋯H and Cl⋯S inter­actions are also shown as dashed lines.

Table 2

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

Contact	Distance	Symmetry operation
Cl2⋯S1	3.660 (1)	+ x,  − y, 2 − z
H10A⋯Cl4	3.03	− + x,  − y, 1 − z
C8⋯C9	3.573 (4)	1 + x, y, z

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 different colours and colour intensity, representing short or long contacts and indicating the relative strength of the inter­actions. The overall two-dimensional fingerprint plot for the title compound and those delineated into Cl⋯H/ H⋯Cl, Cl⋯Cl, C⋯C, Cl⋯S/S⋯Cl, H⋯H, C⋯H/H⋯C and O⋯H/H⋯O contacts are illus­trated in Fig. 3 ▸; the percentage contributions from the different inter­atomic contacts to the Hirshfeld surfaces are as follows: Cl⋯H/ H⋯Cl (20.8%), Cl⋯Cl (18.7%), C⋯C (11.9%), Cl⋯S/S⋯Cl (10.9%), H⋯H (10.1%), C⋯H/H⋯C (9.3%) and O⋯H/H⋯O (7.6%). The contributions of the other weak inter­molecular contacts to the Hirshfeld surfaces are Cl⋯C/C⋯Cl (3.6%), S⋯C/C⋯S (2.8%), Cl⋯O/O⋯Cl (2.3%), S⋯S (0.9%), O⋯O (0.6%) and C⋯O/O⋯C (0.6%).

Figure 3

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

The C—H⋯Cl inter­actions appear as two distinct spikes in the fingerprint plot (Fig. 3 ▸ b) of the title compound, where the sum of Cl⋯H/H⋯Cl inter­actions comprises 20.8% of the total Hirshfeld surface area of the mol­ecule. The Cl⋯H/H⋯Cl inter­actions represented by the spikes in the bottom right and left region (d e + d i ≃ 2.83 Å) indicate that the hydrogen atoms are in contact with the Cl atoms to build the two-dimensional supra­molecular framework [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]. Cl⋯Cl contacts (Fig. 3 ▸ c; 18.7%) 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 (C10—H10A⋯Cl4iii; (iii) − + x,  − y, 1 − 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 C⋯C contacts (Fig. 3 ▸ d); 11.9%) reflect π–π inter­actions between the above-mentioned aromatic rings. The S⋯Cl contacts (Fig. 3 ▸ e; 10.9%) contracted to a much lesser degree. The C⋯H/H⋯C inter­actions (Fig. 3 ▸ g) account for 9.3% of the total Hirshfeld surface of the mol­ecules. The scattered points in the breakdown of the fingerprint plot show the π–π stacking inter­actions. In the fingerprint plot delineated into H⋯O/O⋯H contacts (Fig. 3 ▸ h), the 7.6% contribution to the Hirshfeld surface arises from inter­molecular C=O⋯H hydrogen bonding and is viewed as pair of spikes with the tip at de + di ∼ 2.9 Å.

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

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 ▸] and (E)-1-(2-amino­phen­yl)-3-(thio­phen-2-yl)prop-2-en-1-one [(XI); Chantrapromma et al., 2013 ▸].

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 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. Neighboring dimers are further linked into chains along the c-axis direction by N—H⋯N hydrogen bonds.

Synthesis and crystallization

The title compound was synthesized as per the procedure reported earlier (Kumar et al., 2013a ▸,b ▸; Chidan Kumar et al., 2014 ▸). 1-(2,5-Di­chloro­thio­phen-3-yl)ethanone (0.01 mol) (Harrison et al., 2010 ▸) and 2,4-di­chloro­benzaldehyde (0.01 mol) was dissolved in 20 ml methanol. A catalytic amount of NaOH was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 2 h at room temperature. The formed crude products were filtered, washed successively with distilled water and recrystallized from methanol to get the title chalcone. The melting point (381–383 K) was determined by Stuart Scientific (UK) apparatus.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U iso(H) = 1.2U eq(C) for C—H. Owing to poor agreement between observed and calculated intensities, twelve outliers (2 7 2, 2 8 0, 2 8 1, 0 1 28, 2 8 23, 0 14 8, 0 0 6, 3 0 29, 1 0 8, 0 17 4, 1 3 27, 2 12 19) were omitted in the final cycles of refinement.

Table 3

Experimental details

Crystal data
Chemical formula	C13H6Cl4OS
M r	352.04
Crystal system, space group	Orthorhombic, P212121
Temperature (K)	294
a, b, c (Å)	3.9867 (3), 13.4564 (11), 25.573 (2)
V (Å3)	1371.91 (19)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.00
Crystal size (mm)	0.63 × 0.23 × 0.11
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 ▸)
T min, T max	0.757, 0.894
No. of measured, independent and observed [I > 2σ(I)] reflections	11402, 4226, 3425
R int	0.026
(sin θ/λ)max (Å−1)	0.720
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.102, 1.03
No. of reflections	4226
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.25, −0.20
Absolute structure	Flack x determined using 1124 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.04 (5)

Computer programs: APEX2 and SAINT (Bruker, 2007 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018010976/dx2006sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018010976/dx2006Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018010976/dx2006Isup3.cml

CCDC reference: 1036797

Additional supporting information: crystallographic information; 3D view; checkCIF report

C13H6Cl4OS	Dx = 1.704 Mg m−3
Mr = 352.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4362 reflections
a = 3.9867 (3) Å	θ = 2.2–28.5°
b = 13.4564 (11) Å	µ = 1.00 mm−1
c = 25.573 (2) Å	T = 294 K
V = 1371.91 (19) Å3	Block, yellow
Z = 4	0.63 × 0.23 × 0.11 mm
F(000) = 704

Bruker APEXII CCD diffractometer	3425 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 30.8°, θmin = 1.6°
Tmin = 0.757, Tmax = 0.894	h = −5→2
11402 measured reflections	k = −19→19
4226 independent reflections	l = −36→36

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.0581P)2 + 0.011P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.25 e Å−3
4226 reflections	Δρmin = −0.20 e Å−3
172 parameters	Absolute structure: Flack x determined using 1124 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.04 (5)

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.

	x	y	z	Uiso*/Ueq
C1	1.1673 (8)	0.77797 (19)	0.84012 (9)	0.0391 (6)
C2	1.2553 (8)	0.6794 (2)	0.91880 (10)	0.0419 (6)
C3	1.1115 (8)	0.6258 (2)	0.88062 (10)	0.0410 (6)
H3A	1.052432	0.559246	0.884223	0.049*
C4	1.0587 (8)	0.6820 (2)	0.83366 (10)	0.0382 (6)
C5	0.9016 (9)	0.6327 (2)	0.78763 (10)	0.0444 (7)
C6	0.7779 (10)	0.6938 (2)	0.74420 (11)	0.0493 (7)
H6A	0.809837	0.762158	0.746266	0.059*
C7	0.6253 (9)	0.6588 (2)	0.70264 (10)	0.0462 (7)
H7A	0.596005	0.590316	0.700760	0.055*
C8	0.4975 (8)	0.7177 (2)	0.65917 (10)	0.0386 (6)
C9	0.3384 (8)	0.67552 (19)	0.61621 (10)	0.0403 (6)
C10	0.2191 (8)	0.7316 (2)	0.57472 (10)	0.0431 (6)
H10A	0.112503	0.701315	0.546561	0.052*
C11	0.2620 (8)	0.8330 (2)	0.57612 (10)	0.0425 (7)
C12	0.4192 (9)	0.8788 (2)	0.61805 (11)	0.0465 (7)
H12A	0.447771	0.947373	0.618483	0.056*
C13	0.5316 (9)	0.8219 (2)	0.65879 (11)	0.0438 (7)
H13A	0.633719	0.852975	0.687101	0.053*
O1	0.8718 (9)	0.54311 (16)	0.78790 (9)	0.0721 (9)
S1	1.3313 (2)	0.80047 (5)	0.90119 (3)	0.04511 (19)
Cl1	1.1738 (3)	0.87633 (5)	0.79734 (3)	0.0556 (2)
Cl2	1.3606 (3)	0.63887 (6)	0.98017 (3)	0.0593 (2)
Cl3	0.2772 (3)	0.54840 (5)	0.61241 (3)	0.0639 (3)
Cl4	0.1204 (3)	0.90504 (6)	0.52453 (3)	0.0605 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0422 (17)	0.0375 (11)	0.0377 (11)	0.0021 (13)	0.0062 (12)	−0.0015 (9)
C2	0.0429 (18)	0.0443 (13)	0.0384 (12)	0.0015 (13)	−0.0020 (11)	0.0019 (10)
C3	0.0430 (18)	0.0392 (12)	0.0408 (12)	−0.0001 (13)	−0.0012 (12)	0.0003 (10)
C4	0.0376 (16)	0.0406 (12)	0.0364 (11)	0.0014 (12)	0.0021 (11)	−0.0021 (10)
C5	0.051 (2)	0.0462 (14)	0.0362 (12)	−0.0046 (14)	0.0005 (12)	−0.0046 (10)
C6	0.059 (2)	0.0451 (13)	0.0437 (13)	−0.0026 (15)	−0.0080 (14)	−0.0013 (11)
C7	0.058 (2)	0.0429 (13)	0.0382 (12)	−0.0006 (15)	0.0010 (14)	−0.0022 (10)
C8	0.0385 (16)	0.0415 (13)	0.0358 (11)	0.0001 (12)	0.0045 (11)	−0.0038 (10)
C9	0.0416 (16)	0.0380 (11)	0.0412 (12)	−0.0018 (13)	0.0027 (13)	−0.0046 (9)
C10	0.0433 (18)	0.0481 (13)	0.0378 (12)	0.0008 (13)	0.0001 (12)	−0.0066 (10)
C11	0.0387 (18)	0.0488 (14)	0.0401 (12)	0.0061 (13)	0.0018 (11)	0.0002 (10)
C12	0.048 (2)	0.0396 (13)	0.0522 (15)	−0.0007 (13)	0.0013 (14)	−0.0061 (11)
C13	0.0468 (19)	0.0422 (13)	0.0426 (13)	−0.0004 (13)	−0.0034 (13)	−0.0080 (11)
O1	0.123 (3)	0.0414 (11)	0.0517 (12)	−0.0110 (15)	−0.0209 (16)	−0.0012 (9)
S1	0.0504 (5)	0.0422 (3)	0.0427 (3)	−0.0035 (3)	−0.0008 (3)	−0.0055 (3)
Cl1	0.0766 (6)	0.0403 (3)	0.0498 (4)	−0.0043 (4)	−0.0001 (4)	0.0048 (3)
Cl2	0.0740 (6)	0.0589 (4)	0.0450 (3)	−0.0016 (4)	−0.0159 (4)	0.0056 (3)
Cl3	0.0883 (8)	0.0410 (3)	0.0625 (4)	−0.0127 (4)	−0.0148 (5)	−0.0023 (3)
Cl4	0.0684 (6)	0.0556 (4)	0.0576 (4)	0.0076 (4)	−0.0106 (4)	0.0080 (3)

C1—C4	1.372 (4)	C7—C8	1.458 (4)
C1—Cl1	1.717 (3)	C7—H7A	0.9300
C1—S1	1.720 (3)	C8—C9	1.390 (4)
C2—C3	1.343 (4)	C8—C13	1.408 (4)
C2—Cl2	1.714 (3)	C9—C10	1.386 (4)
C2—S1	1.717 (3)	C9—Cl3	1.731 (3)
C3—C4	1.435 (4)	C10—C11	1.375 (4)
C3—H3A	0.9300	C10—H10A	0.9300
C4—C5	1.489 (4)	C11—C12	1.387 (4)
C5—O1	1.212 (4)	C11—Cl4	1.732 (3)
C5—C6	1.467 (4)	C12—C13	1.368 (4)
C6—C7	1.312 (4)	C12—H12A	0.9300
C6—H6A	0.9300	C13—H13A	0.9300
C4—C1—Cl1	130.8 (2)	C8—C7—H7A	117.1
C4—C1—S1	113.3 (2)	C9—C8—C13	116.5 (3)
Cl1—C1—S1	115.92 (16)	C9—C8—C7	122.7 (3)
C3—C2—Cl2	126.8 (2)	C13—C8—C7	120.9 (3)
C3—C2—S1	113.3 (2)	C10—C9—C8	122.6 (3)
Cl2—C2—S1	119.95 (17)	C10—C9—Cl3	116.5 (2)
C2—C3—C4	112.8 (3)	C8—C9—Cl3	120.8 (2)
C2—C3—H3A	123.6	C11—C10—C9	118.5 (3)
C4—C3—H3A	123.6	C11—C10—H10A	120.7
C1—C4—C3	110.5 (2)	C9—C10—H10A	120.7
C1—C4—C5	130.3 (2)	C10—C11—C12	121.2 (3)
C3—C4—C5	119.2 (3)	C10—C11—Cl4	119.7 (2)
O1—C5—C6	121.9 (3)	C12—C11—Cl4	119.2 (2)
O1—C5—C4	118.7 (3)	C13—C12—C11	119.2 (3)
C6—C5—C4	119.3 (3)	C13—C12—H12A	120.4
C7—C6—C5	124.6 (3)	C11—C12—H12A	120.4
C7—C6—H6A	117.7	C12—C13—C8	122.0 (3)
C5—C6—H6A	117.7	C12—C13—H13A	119.0
C6—C7—C8	125.7 (3)	C8—C13—H13A	119.0
C6—C7—H7A	117.1	C2—S1—C1	90.24 (13)
Cl2—C2—C3—C4	−179.6 (2)	C13—C8—C9—C10	0.3 (5)
S1—C2—C3—C4	0.7 (4)	C7—C8—C9—C10	−179.5 (3)
Cl1—C1—C4—C3	178.6 (3)	C13—C8—C9—Cl3	−179.3 (3)
S1—C1—C4—C3	0.2 (4)	C7—C8—C9—Cl3	0.9 (4)
Cl1—C1—C4—C5	−2.0 (6)	C8—C9—C10—C11	0.4 (5)
S1—C1—C4—C5	179.6 (3)	Cl3—C9—C10—C11	179.9 (3)
C2—C3—C4—C1	−0.6 (4)	C9—C10—C11—C12	−0.3 (5)
C2—C3—C4—C5	179.9 (3)	C9—C10—C11—Cl4	179.2 (2)
C1—C4—C5—O1	168.9 (4)	C10—C11—C12—C13	−0.3 (5)
C3—C4—C5—O1	−11.8 (5)	Cl4—C11—C12—C13	−179.9 (3)
C1—C4—C5—C6	−13.1 (5)	C11—C12—C13—C8	1.0 (5)
C3—C4—C5—C6	166.3 (3)	C9—C8—C13—C12	−1.0 (5)
O1—C5—C6—C7	0.4 (6)	C7—C8—C13—C12	178.8 (3)
C4—C5—C6—C7	−177.6 (3)	C3—C2—S1—C1	−0.5 (3)
C5—C6—C7—C8	179.5 (3)	Cl2—C2—S1—C1	179.8 (2)
C6—C7—C8—C9	179.9 (4)	C4—C1—S1—C2	0.1 (3)
C6—C7—C8—C13	0.1 (5)	Cl1—C1—S1—C2	−178.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cl1	0.93	2.48	3.220 (3)	136
C7—H7A···Cl3	0.93	2.65	3.075 (3)	108