Unexpected formation of a co-crystal containing the chalcone (E)-1-(5-chloro­thio­phen-2-yl)-3-(3-methyl­thio­phen-2-yl)prop-2-en-1-one and the keto–enol tautomer (Z)-1-(5-chloro­thio­phen-2-yl)-3-(3-methyl­thio­phen-2-yl)prop-1-en-1-ol

Al-Refai, M.; Ali, B.F.; Geyer, A.; Harms, K.; Marsch, M.

doi:10.1107/S2056989020002583

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ISSN: 2056-9890

Volume 76| Part 4| April 2020| Pages 477-480

https://doi.org/10.1107/S2056989020002583

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Unexpected formation of a co-crystal containing the chalcone (E)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-2-en-1-one and the keto–enol tautomer (Z)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-1-en-1-ol

Mahmoud Al-Refai,^a ^* Basem F. Ali,^a ^* Armin Geyer,^b Klaus Harms ^b and Michael Marsch ^b

^aDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan, and ^bFaculty of Chemistry, Philipps University Marburg, Hans-Meerwein-Strasse 4, 35032, Marburg, Germany
^*Correspondence e-mail: mahmoud_alrefai@aabu.edu.jo, bfali@aabu.edu.jo

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 February 2020; accepted 24 February 2020; online 3 March 2020)

The title crystal structure is assembled from the superposition of two molecular structures, (E)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-2-en-1-one, C₁₂H₉ClOS₂ (93%), and (Z)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-1-en-1-ol, C₁₂H₁₁ClOS₂ (7%), 0.93C₁₂H₉ClOS₂·0.07C₁₂H₁₁ClOS₂. Both were obtained from the reaction of 3-methylthiophene-2-carbaldehyde and 1-(5-chlorothiophen-2-yl)ethanone. In the extended structure of the major chalcone component, molecules are linked by a combination of C—H⋯O/S, Cl⋯Cl, Cl⋯π and π–π interactions, leading to a compact three-dimensional supramolecular assembly.

Keywords: crystal structure; chalcones; thiophene; superposition molecular structures.

CCDC reference: 1986074

1. Chemical context

Chalcones exhibit a wide spectrum of pharmacological activities, including antibacterial (Tran et al., 2012 ), anticancer (Shin et al., 2013 ), antifungal (López et al., 2001 ) and anti-inflammatory properties (Fang et al., 2015 ). On the other hand, thiophene derivatives display a wide range of biological activities such as antimicrobial (Mishra et al., 2012 ), antiallergic (Gillespie et al., 1985 ), anti-inflammatory (Molvi et al., 2007 ), antioxidant and antitumor agents (Jarak et al., 2005 ). Combining thiophenes and chalcones could result in compounds with interesting new structures and properties: Al-Maqtari et al. (2015 ) reported the synthesis of thiophene–chalcones containing two thiophene rings and their antimicrobial and anticancer activities. One of their reported structures is (E)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-2-en-1-one. However, the crystal structure of this thiophene-based chalcone has not yet been determined.

As a part of our ongoing research in this area (Ibrahim et al., 2019 ), we report herein the crystal structure of a chalcone containing two terminal-substituted thiophene rings, namely (E)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-2-en-1-one, which crystallized as a co-crystal in an unexpected superposition with the keto–enol tautomer (Z)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-1-en-1-ol as a minor component.

2. Structural commentary

The crystal structure (Fig. 1) exhibits two superimposed molecules with occupancies of 93% and 7%: this was surprising since the formation of the minor (enol) component was quite unexpected. A possible mechanism for the formation of this component is shown in Fig. 2. Equilibria between keto and enol isomers are regularly observed in solution but not in crystals. This issue needs a thorough exploration, which is beyond the scope of this report.

Figure 1
(a) The molecular structure of the title co-crystal showing the superposition of the two components, whose occupancies are 93% (black bonds) and 7% (white bonds), (b) the molecular structure with the atom-labelling scheme of the major component and (c) the minor component. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Possible mechanism for the formation of the minor enol component.

The molecular structures show similar conformations but differ in bond lengths and the carbon-atom geometry (hybridization), which we will describe for the major component in more detail. The molecular structure (Fig. 1) is composed of two substituted thiophene rings, 5-chlorothiophen-2-yl and 3-methylthiophen-2-yl, which are linked by the central –CO—CH=CH– spacer. The configuration about the C=C bond [1.344 (3) Å] is E and the carbonyl group is syn with respect to the C=C bond. The molecule is effectively planar as indicated by the torsion angles O1—C1—C10—C14 = 175.0 (3), C2—C1—C10—C14 = −5.2 (3), C10—C1—C2—C3 = 176.41 (19), O1—C1—C2—C3 = −3.8 (3), C1—C2—C3—C4 = 179.37 (19) and C2—C3—C4—C8 = −177.5 (2)°. The hydrogen atoms of the propenone unit are trans configured and each is involved in an intramolecular short contact that forms an S(5) motif (Fig. 1, Table 1). The bond lengths and angles are consistent with those in related structures (Vu Quoc et al., 2019 ; Yesilyurt et al., 2018 ; Sreenatha et al., 2018 ). The S atoms of the terminal 5-chlorothiophen-2-yl (S11/C10/C12–C14) and 3-methylthiophen-2-yl (S5/C4/C6–C8) rings are anti and the rings are inclined slightly to each other [dihedral angle = 6.92 (13)°].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1	0.95	2.48	2.818 (3)	101
C2—H2⋯S5	0.95	2.80	3.166 (2)	104
C13—H13⋯O1ⁱ	0.95	2.35	3.184 (4)	146
C9—H9C⋯O1ⁱⁱ	0.98	2.58	3.488 (4)	154
C6—H6⋯S11ⁱⁱⁱ	0.95	3.04	3.948 (2)	160
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y, -z+1; (iii) x, y, z-1.

3. Supramolecular features

The extended structure exhibits several hydrogen-bonding contacts (Table 1). The hydrogen bonds involve a carbonyl O atom serving as a double-acceptor with H atoms from the chlorothiophenyl unit, and a methyl group from the methylthiophenyl unit of a neighbouring molecule. Additional C—H⋯S contacts are also present (Table 1). Further interactions are detected, namely Cl⋯Cl [C12—Cl1⋯Cl1ⁱ of 3.3907 (8) Å and 142.92 (8)°; symmetry code: (i) −x, 2 − y, 2 − z], C—Cl⋯π [C12—Cl15⋯Cgⁱⁱ = 3.6536 (14) Å]; symmetry code: (ii) 1 − x, 1 − y, 1 − z; Cg1 is the centroid of the S5/C4/C6–C8 ring] as well as π–π contacts [Cg1⋯Cg2ⁱⁱⁱ of 4.0139 (15) Å; symmetry code: (iii) −x, 1 − y, 1 − z; Cg2 is the centroid of the S11/C10/C12–C14 ring], which connect neighbouring molecules, consolidating a rather compact three-dimensional supramolecular network (Fig. 3).

Figure 3
Overall packing of the major component with all intermolecular interactions (dotted and dashed lines) shown.

4. Database survey

Similar structures to the title compound (major component) with the same chalcone skeleton and one or two thiophenyl rings include the following, which are identified by their CSD (Groom et al., 2016 ) reference codes. In all compounds, the molecular skeletons are approximately planar, and have an E configuration about the C=C bond.

The structures containing one thiophenyl rings include: 1-(5-chloro-2-thienyl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-one (refcode LOVHAH; Chidan Kumar et al., 2015 ), where the molecular structure features intramolecular C—H⋯O interactions. The molecules in 1-(4-bromophenyl)-3-(3-methyl-2-thienyl)prop-2-en-1-one (XICNON; Fun et al., 2007 ), feature short intramolecular C—H⋯O/S contacts, which form S(5) rings. In the crystal structure, the molecules are linked into layers by weak C—H⋯O hydrogen bonds, and short Br⋯O contacts are also observed. In 1-(2-hydroxyphenyl)-3-(5-methylthiophen-2-yl)prop-2-en-1-one (AGEFUQ; Sreenatha et al., 2018), the structure exhibits O—H⋯O and C—H⋯O/S intramolecular interactions.

The structures of bis-thiophenyl chalcones include 2,6-(E,E)-bis[(thiophene-2-yl)methylene]cyclohexanone (BOQYAK; Yakalı et al., 2019 ) in which the terminal thiophene rings adopt a syn orientation. In the structure, the molecules display weak C—H⋯S and C—H⋯O intramolecular and only C—H⋯O intermolecular hydrogen bonds. In addition, π–π interactions are found between the thiophene rings. In 1,5-bis(3-methyl-2-thienyl)penta-1,4-dien-3-one (RUZCIZ; Contreras et al., 2009 ), the molecule consists of terminal methylthiophenyl rings with the two S atoms being in a syn arrangement and trans to the carbonyl oxygen atom. The molecule is almost planar, with a slight twist along the bridging unit, leading to a small rotation between the terminal thiophenyl rings. The molecules are connected via various types of intermolecular interactions, namely C—H⋯O, C—H⋯π and π–π, leading to a three-dimensional supramolecular network. The molecule of (2E,6E)-2,6-bis[(5-methylthiophen-2-yl)methylene]cyclohexanone (XILXUM; Liang et al., 2007 ) displays two slightly twisted syn terminal methylthiophenyl rings in an anti-arrangement with respect to the carbonyl oxygen atom. In 1,5-bis(thiophen-3-yl)penta-1,4-dien-3-one (AYUPIU; Shalini et al., 2011 ), the dihedral angle between the thiophenyl rings is 15.45 (10)°. The molecules features both C—H⋯O and C—H⋯π interactions. Both thiophene rings in 3-hydroxy-1-(thiophen-2-yl)-3-(thiophen-3-yl)prop-2-en-1-one (IBIRUJ; Oyarce et al., 2017 ) are disordered with the major-disorder components inclined to each other by 12.1 (3)°. In the crystal, the molecules are connected through C—H⋯O interactions. In the crystal of 1,3-bis(3-thienyl)prop-2-en-1-one (UNAJIE; Baggio et al., 2016 ), the thiophene rings are inclined to each other by a dihedral angle of 8.88 (10)°. The structure exhibits π–π interactions together with C—H⋯O interactions and short S⋯S contacts also occur.

5. Synthesis and crystallization

The synthesis was carried out using a reported method (Al-Maqtari et al., 2015). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at room temperature, of a solution in ethanol.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were included in calculated positions (C—H = 0.95–0.98 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl). Methyl groups were allowed to rotate about the bond to their next atom to fit the electron density.

Table 2
Experimental details

Crystal data
Chemical formula	0.93C₁₂H₉ClOS₂·0.07C₁₂H₁₁ClOS₂
M_r	268.90
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.3709 (4), 7.5063 (4), 12.4247 (6)
α, β, γ (°)	84.126 (4), 76.694 (4), 62.372 (4)
V (Å³)	592.69 (6)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	5.93
Crystal size (mm)	0.25 × 0.21 × 0.14

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (LANA; Stoe, 2016 )
T_min, T_max	0.079, 0.352
No. of measured, independent and observed [I > 2σ(I)] reflections	10865, 2398, 2221
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.06
No. of reflections	2398
No. of parameters	291
No. of restraints	754
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.28
Computer programs: X-AREA (Stoe & Cie, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and DIAMOND (Putz & Brandenburg, 2014 ).

The crystal structure was refined as a superposition of two molecular structures with formulae C₁₂H₉ClOS₂ (93% occupancy component) and C₁₂H₁₁ClOS₂ (7% occupancy component), respectively. Restraints were necessary during the refinement of geometric and anisotropic displacement parameters.

Supporting information

CCDC reference: 1986074

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020002583/hb7894sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020002583/hb7894Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2016); cell refinement: X-AREA (Stoe & Cie, 2016); data reduction: X-AREA (Stoe & Cie, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: X-AREA (Stoe & Cie, 2016).

(E)-1-(5-Chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-2-en-1-\ one–(Z)-1-(5-chlorothiophen-2-yl)-3-(3-methylthiophen-2-yl)prop-\ 1-en-1-ol (0.93/0/07) top

Crystal data top

0.93C₁₂H₉ClOS₂·0.07C₁₂H₁₁ClOS₂	Z = 2
M_r = 268.90	F(000) = 276
Triclinic, P1	D_x = 1.507 Mg m⁻³
a = 7.3709 (4) Å	Cu Kα radiation, λ = 1.54186 Å
b = 7.5063 (4) Å	Cell parameters from 17498 reflections
c = 12.4247 (6) Å	θ = 3.7–76.0°
α = 84.126 (4)°	µ = 5.93 mm⁻¹
β = 76.694 (4)°	T = 100 K
γ = 62.372 (4)°	Plate, yellow
V = 592.69 (6) Å³	0.25 × 0.21 × 0.14 mm

Data collection top

Stoe Stadivari diffractometer	2398 independent reflections
Radiation source: GeniX 3D HF Cu	2221 reflections with I > 2σ(I)
Detector resolution: 5.81 pixels mm^-1	R_int = 0.024
rotation method, ω scans	θ_max = 75.5°, θ_min = 6.7°
Absorption correction: multi-scan (LANA; Stoe, 2016)	h = −5→9
T_min = 0.079, T_max = 0.352	k = −8→9
10865 measured reflections	l = −13→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.048P)² + 0.4005P] where P = (F_o² + 2F_c²)/3
2398 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.27 e Å⁻³
754 restraints	Δρ_min = −0.28 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.

Refinement. The crystal structure is an overlay of two molecular structure with ratio 93:7.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.3137 (4)	0.2710 (3)	0.5851 (2)	0.0314 (5)	0.93
C1	0.2726 (3)	0.4337 (3)	0.53882 (16)	0.0247 (4)	0.93
C2	0.2535 (3)	0.4652 (3)	0.42238 (15)	0.0259 (4)	0.93
H2	0.213137	0.595628	0.391242	0.031*	0.93
C3	0.2928 (3)	0.3105 (3)	0.35969 (16)	0.0259 (4)	0.93
H3	0.334120	0.182539	0.394094	0.031*	0.93
C4	0.2784 (3)	0.3201 (3)	0.24557 (16)	0.0256 (4)	0.93
S5	0.21123 (9)	0.54296 (8)	0.17199 (4)	0.03242 (16)	0.93
C6	0.2248 (4)	0.4291 (4)	0.05595 (18)	0.0348 (5)	0.93
H6	0.198313	0.496677	−0.011889	0.042*	0.93
C7	0.2777 (4)	0.2310 (3)	0.07204 (18)	0.0314 (4)	0.93
H7	0.291283	0.145132	0.016418	0.038*	0.93
C8	0.3110 (3)	0.1643 (3)	0.18065 (17)	0.0262 (4)	0.93
C9	0.3748 (4)	−0.0483 (3)	0.21906 (19)	0.0312 (5)	0.93
H9A	0.422423	−0.136716	0.154993	0.047*	0.93
H9B	0.254852	−0.057161	0.268618	0.047*	0.93
H9C	0.488738	−0.090123	0.258667	0.047*	0.93
C10	0.2397 (3)	0.6067 (3)	0.60062 (16)	0.0233 (4)	0.93
S11	0.24466 (9)	0.57165 (8)	0.74011 (4)	0.02410 (15)	0.93
C12	0.1984 (3)	0.8151 (3)	0.75171 (17)	0.0251 (4)	0.93
C13	0.1837 (3)	0.9193 (3)	0.65490 (19)	0.0276 (4)	0.93
H13	0.161182	1.054853	0.646974	0.033*	0.93
C14	0.2066 (4)	0.7980 (3)	0.56787 (18)	0.0268 (4)	0.93
H14	0.199724	0.844259	0.494119	0.032*	0.93
Cl1	0.17230 (10)	0.90570 (8)	0.87916 (4)	0.03112 (15)	0.93
O1A	0.354 (6)	0.286 (4)	0.602 (3)	0.035 (6)	0.07
H1A	0.343705	0.215573	0.557340	0.053*	0.07
C1A	0.257 (5)	0.496 (4)	0.569 (2)	0.028 (3)	0.07
C2A	0.126 (4)	0.535 (4)	0.497 (2)	0.029 (3)	0.07
H2A	0.031913	0.671106	0.487244	0.035*	0.07
C3A	0.121 (5)	0.385 (4)	0.435 (2)	0.034 (3)	0.07
H3A	−0.022191	0.397317	0.458163	0.041*	0.07
H3B	0.216209	0.252274	0.460874	0.041*	0.07
C4A	0.175 (5)	0.377 (3)	0.3079 (17)	0.032 (3)	0.07
S5A	0.1043 (15)	0.6046 (12)	0.2374 (7)	0.0485 (18)	0.07
C6A	0.200 (5)	0.482 (3)	0.1107 (16)	0.034 (3)	0.07
H6A	0.209319	0.547565	0.041533	0.041*	0.07
C7A	0.260 (5)	0.281 (3)	0.1218 (18)	0.035 (3)	0.07
H7A	0.296091	0.192728	0.062046	0.042*	0.07
C8A	0.261 (5)	0.219 (3)	0.2331 (19)	0.032 (3)	0.07
C9A	0.331 (5)	0.001 (3)	0.272 (3)	0.036 (5)	0.07
H9AA	0.370744	−0.086268	0.208833	0.053*	0.07
H9AB	0.214815	−0.008058	0.325911	0.053*	0.07
H9AC	0.450522	−0.041072	0.307367	0.053*	0.07
C10A	0.262 (5)	0.615 (4)	0.6395 (18)	0.029 (2)	0.07
S11A	0.3211 (17)	0.5574 (13)	0.7707 (9)	0.0450 (19)	0.07
C12A	0.238 (5)	0.810 (3)	0.7933 (17)	0.031 (3)	0.07
C13A	0.213 (5)	0.918 (4)	0.6986 (19)	0.032 (3)	0.07
H13A	0.186143	1.054308	0.694311	0.039*	0.07
C14A	0.228 (5)	0.812 (4)	0.6075 (19)	0.029 (3)	0.07
H14A	0.217023	0.865457	0.535253	0.034*	0.07
Cl1A	0.255 (2)	0.8778 (18)	0.9186 (11)	0.067 (3)	0.07

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0477 (13)	0.0282 (8)	0.0229 (10)	−0.0213 (8)	−0.0077 (7)	0.0027 (6)
C1	0.0291 (10)	0.0248 (10)	0.0217 (10)	−0.0149 (8)	−0.0016 (8)	−0.0017 (7)
C2	0.0297 (9)	0.0260 (9)	0.0215 (9)	−0.0130 (8)	−0.0042 (7)	0.0013 (7)
C3	0.0287 (10)	0.0281 (9)	0.0216 (9)	−0.0146 (8)	−0.0034 (7)	0.0017 (7)
C4	0.0308 (10)	0.0251 (9)	0.0214 (9)	−0.0141 (8)	−0.0040 (8)	0.0013 (7)
S5	0.0476 (3)	0.0276 (3)	0.0260 (3)	−0.0194 (2)	−0.0118 (2)	0.0051 (2)
C6	0.0465 (12)	0.0405 (12)	0.0214 (9)	−0.0218 (10)	−0.0108 (9)	0.0027 (9)
C7	0.0373 (11)	0.0359 (11)	0.0224 (9)	−0.0177 (9)	−0.0050 (8)	−0.0031 (8)
C8	0.0273 (10)	0.0290 (10)	0.0221 (9)	−0.0132 (8)	−0.0025 (8)	−0.0028 (8)
C9	0.0366 (12)	0.0267 (10)	0.0285 (11)	−0.0132 (9)	−0.0047 (9)	−0.0028 (9)
C10	0.0282 (10)	0.0259 (9)	0.0156 (9)	−0.0130 (7)	−0.0027 (8)	0.0001 (8)
S11	0.0318 (3)	0.0229 (2)	0.0182 (2)	−0.0139 (2)	−0.0033 (2)	0.00121 (18)
C12	0.0315 (10)	0.0249 (9)	0.0207 (9)	−0.0146 (8)	−0.0030 (8)	−0.0036 (8)
C13	0.0327 (11)	0.0245 (9)	0.0252 (10)	−0.0136 (8)	−0.0049 (9)	0.0016 (8)
C14	0.0329 (10)	0.0280 (10)	0.0201 (9)	−0.0154 (8)	−0.0048 (8)	0.0035 (8)
Cl1	0.0378 (3)	0.0319 (3)	0.0246 (3)	−0.0173 (2)	−0.0021 (2)	−0.00631 (19)
O1A	0.045 (11)	0.024 (6)	0.034 (10)	−0.013 (7)	−0.008 (8)	−0.002 (7)
C1A	0.033 (4)	0.027 (4)	0.022 (4)	−0.013 (4)	−0.002 (4)	0.002 (4)
C2A	0.034 (4)	0.028 (4)	0.022 (4)	−0.015 (4)	−0.002 (4)	0.005 (4)
C3A	0.038 (5)	0.030 (5)	0.027 (4)	−0.011 (4)	−0.002 (4)	0.000 (4)
C4A	0.039 (4)	0.028 (4)	0.026 (4)	−0.014 (4)	−0.001 (4)	0.002 (4)
S5A	0.057 (4)	0.035 (3)	0.036 (3)	−0.014 (3)	0.006 (3)	0.005 (3)
C6A	0.047 (4)	0.032 (4)	0.022 (4)	−0.016 (4)	−0.009 (4)	−0.002 (4)
C7A	0.041 (4)	0.035 (4)	0.026 (4)	−0.015 (4)	−0.006 (4)	−0.001 (4)
C8A	0.035 (4)	0.032 (4)	0.025 (4)	−0.012 (4)	−0.005 (4)	0.000 (3)
C9A	0.031 (9)	0.035 (7)	0.039 (10)	−0.014 (7)	−0.007 (9)	−0.002 (7)
C10A	0.034 (4)	0.027 (3)	0.023 (4)	−0.013 (3)	−0.004 (3)	0.000 (3)
S11A	0.045 (4)	0.040 (3)	0.044 (4)	−0.018 (3)	−0.005 (3)	0.008 (3)
C12A	0.036 (4)	0.031 (4)	0.027 (4)	−0.018 (4)	−0.004 (4)	0.001 (4)
C13A	0.038 (5)	0.029 (4)	0.024 (4)	−0.012 (4)	−0.004 (4)	0.001 (4)
C14A	0.035 (4)	0.028 (4)	0.020 (4)	−0.014 (4)	−0.003 (4)	0.002 (4)
Cl1A	0.059 (6)	0.068 (6)	0.070 (7)	−0.030 (5)	−0.004 (5)	−0.001 (5)

Geometric parameters (Å, º) top

O1—C1	1.227 (3)	O1A—H1A	0.8400
C1—C10	1.470 (3)	C1A—C10A	1.328 (10)
C1—C2	1.470 (3)	C1A—C2A	1.38 (4)
C2—C3	1.344 (3)	C2A—C3A	1.44 (4)
C2—H2	0.9500	C2A—H2A	0.9500
C3—C4	1.438 (3)	C3A—C4A	1.54 (3)
C3—H3	0.9500	C3A—H3A	0.9900
C4—C8	1.385 (3)	C3A—H3B	0.9900
C4—S5	1.734 (2)	C4A—C8A	1.386 (18)
S5—C6	1.711 (2)	C4A—S5A	1.744 (16)
C6—C7	1.356 (3)	S5A—C6A	1.734 (18)
C6—H6	0.9500	C6A—C7A	1.367 (18)
C7—C8	1.425 (3)	C6A—H6A	0.9500
C7—H7	0.9500	C7A—C8A	1.414 (18)
C8—C9	1.499 (3)	C7A—H7A	0.9500
C9—H9A	0.9800	C8A—C9A	1.531 (17)
C9—H9B	0.9800	C9A—H9AA	0.9800
C9—H9C	0.9800	C9A—H9AB	0.9800
C10—C14	1.374 (3)	C9A—H9AC	0.9800
C10—S11	1.732 (2)	C10A—C14A	1.412 (18)
S11—C12	1.712 (2)	C10A—S11A	1.743 (18)
C12—C13	1.364 (3)	S11A—C12A	1.735 (17)
C12—Cl1	1.722 (2)	C12A—C13A	1.356 (18)
C13—C14	1.415 (3)	C12A—Cl1A	1.732 (17)
C13—H13	0.9500	C13A—C14A	1.399 (19)
C14—H14	0.9500	C13A—H13A	0.9500
O1A—C1A	1.453 (10)	C14A—H14A	0.9500

O1—C1—C10	119.75 (19)	C10A—C1A—O1A	112 (2)
O1—C1—C2	122.7 (2)	C2A—C1A—O1A	113 (2)
C10—C1—C2	117.52 (17)	C1A—C2A—C3A	126 (3)
C3—C2—C1	120.42 (18)	C1A—C2A—H2A	117.2
C3—C2—H2	119.8	C3A—C2A—H2A	117.2
C1—C2—H2	119.8	C2A—C3A—C4A	123 (2)
C2—C3—C4	126.27 (19)	C2A—C3A—H3A	106.7
C2—C3—H3	116.9	C4A—C3A—H3A	106.7
C4—C3—H3	116.9	C2A—C3A—H3B	106.7
C8—C4—C3	127.20 (18)	C4A—C3A—H3B	106.7
C8—C4—S5	111.23 (14)	H3A—C3A—H3B	106.6
C3—C4—S5	121.56 (15)	C8A—C4A—C3A	132.5 (18)
C6—S5—C4	91.72 (10)	C8A—C4A—S5A	110.0 (13)
C7—C6—S5	112.16 (16)	C3A—C4A—S5A	117.4 (16)
C7—C6—H6	123.9	C6A—S5A—C4A	91.4 (10)
S5—C6—H6	123.9	C7A—C6A—S5A	112.2 (15)
C6—C7—C8	113.4 (2)	C7A—C6A—H6A	123.9
C6—C7—H7	123.3	S5A—C6A—H6A	123.9
C8—C7—H7	123.3	C6A—C7A—C8A	111.7 (18)
C4—C8—C7	111.53 (18)	C6A—C7A—H7A	124.2
C4—C8—C9	124.48 (19)	C8A—C7A—H7A	124.2
C7—C8—C9	123.99 (19)	C4A—C8A—C7A	113.9 (16)
C8—C9—H9A	109.5	C4A—C8A—C9A	121.3 (19)
C8—C9—H9B	109.5	C7A—C8A—C9A	125 (2)
H9A—C9—H9B	109.5	C8A—C9A—H9AA	109.5
C8—C9—H9C	109.5	C8A—C9A—H9AB	109.5
H9A—C9—H9C	109.5	H9AA—C9A—H9AB	109.5
H9B—C9—H9C	109.5	C8A—C9A—H9AC	109.5
C14—C10—C1	131.62 (19)	H9AA—C9A—H9AC	109.5
C14—C10—S11	111.50 (16)	H9AB—C9A—H9AC	109.5
C1—C10—S11	116.88 (14)	C1A—C10A—C14A	120 (2)
C12—S11—C10	90.29 (10)	C1A—C10A—S11A	128.3 (19)
C13—C12—S11	114.16 (16)	C14A—C10A—S11A	111.9 (14)
C13—C12—Cl1	126.56 (16)	C12A—S11A—C10A	89.6 (10)
S11—C12—Cl1	119.28 (12)	C13A—C12A—Cl1A	129.0 (16)
C12—C13—C14	110.72 (18)	C13A—C12A—S11A	111.6 (14)
C12—C13—H13	124.6	Cl1A—C12A—S11A	117.7 (12)
C14—C13—H13	124.6	C12A—C13A—C14A	115.1 (17)
C10—C14—C13	113.32 (18)	C12A—C13A—H13A	122.4
C10—C14—H14	123.3	C14A—C13A—H13A	122.4
C13—C14—H14	123.3	C13A—C14A—C10A	109.6 (17)
C1A—O1A—H1A	109.5	C13A—C14A—H14A	125.2
C10A—C1A—C2A	131 (3)	C10A—C14A—H14A	125.2

O1—C1—C2—C3	−3.8 (3)	C10A—C1A—C2A—C3A	−171 (3)
C10—C1—C2—C3	176.41 (19)	O1A—C1A—C2A—C3A	−16 (5)
C1—C2—C3—C4	179.37 (19)	C1A—C2A—C3A—C4A	−117 (3)
C2—C3—C4—C8	−177.5 (2)	C2A—C3A—C4A—C8A	150 (3)
C2—C3—C4—S5	1.6 (3)	C2A—C3A—C4A—S5A	−35 (4)
C8—C4—S5—C6	0.42 (17)	C8A—C4A—S5A—C6A	−2 (3)
C3—C4—S5—C6	−178.88 (18)	C3A—C4A—S5A—C6A	−178 (3)
C4—S5—C6—C7	0.04 (19)	C4A—S5A—C6A—C7A	7 (3)
S5—C6—C7—C8	−0.5 (3)	S5A—C6A—C7A—C8A	−10 (4)
C3—C4—C8—C7	178.5 (2)	C3A—C4A—C8A—C7A	172 (3)
S5—C4—C8—C7	−0.7 (2)	S5A—C4A—C8A—C7A	−3 (4)
C3—C4—C8—C9	−1.9 (3)	C3A—C4A—C8A—C9A	−2 (6)
S5—C4—C8—C9	178.87 (17)	S5A—C4A—C8A—C9A	−178 (2)
C6—C7—C8—C4	0.8 (3)	C6A—C7A—C8A—C4A	9 (4)
C6—C7—C8—C9	−178.8 (2)	C6A—C7A—C8A—C9A	−177 (3)
O1—C1—C10—C14	175.0 (3)	C2A—C1A—C10A—C14A	−41 (6)
C2—C1—C10—C14	−5.2 (3)	O1A—C1A—C10A—C14A	163 (3)
O1—C1—C10—S11	−4.2 (3)	C2A—C1A—C10A—S11A	143 (3)
C2—C1—C10—S11	175.62 (15)	O1A—C1A—C10A—S11A	−13 (5)
C14—C10—S11—C12	0.86 (17)	C1A—C10A—S11A—C12A	−170 (4)
C1—C10—S11—C12	−179.83 (17)	C14A—C10A—S11A—C12A	13 (3)
C10—S11—C12—C13	−1.24 (18)	C10A—S11A—C12A—C13A	−12 (3)
C10—S11—C12—Cl1	178.05 (14)	C10A—S11A—C12A—Cl1A	−179 (2)
S11—C12—C13—C14	1.3 (3)	Cl1A—C12A—C13A—C14A	173 (3)
Cl1—C12—C13—C14	−177.96 (16)	S11A—C12A—C13A—C14A	9 (4)
C1—C10—C14—C13	−179.5 (2)	C12A—C13A—C14A—C10A	2 (4)
S11—C10—C14—C13	−0.3 (2)	C1A—C10A—C14A—C13A	172 (3)
C12—C13—C14—C10	−0.6 (3)	S11A—C10A—C14A—C13A	−11 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	0.95	2.48	2.818 (3)	101
C2—H2···S5	0.95	2.80	3.166 (2)	104
C13—H13···O1ⁱ	0.95	2.35	3.184 (4)	146
C9—H9C···O1ⁱⁱ	0.98	2.58	3.488 (4)	154
C6—H6···S11ⁱⁱⁱ	0.95	3.04	3.948 (2)	160

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

Funding information

The authors thank Al al-Bayt University (Mafraq, Jordan) for financial support.

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