Crystal structure of 2-[bis(benzylsulfanyl)methyl]-6-methoxyphenol

Raghuvanshi, A.; Knauer, L.; Viau, L.; Knorr, M.; Strohmann, C.

doi:10.1107/S2056989020002091

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Volume 76| Part 4| April 2020| Pages 484-487

https://doi.org/10.1107/S2056989020002091

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Crystal structure of 2-[bis(benzylsulfanyl)methyl]-6-methoxyphenol

Abhinav Raghuvanshi,^a ‡ Lena Knauer,^b Lydie Viau,^a ^* Michael Knorr ^a and Carsten Strohmann ^b ^*

^aInstitut UTINAM UMR 6213 CNRS, Université Bourgogne Franche-Comté, 16, Route de Gray, 25030 Besançon Cedex, France, and ^bAnorganische Chemie, TU Dortmund University, Otto-Hahn-Str. 6/6a, D-44227 Dortmund, Germany
^*Correspondence e-mail: lydie.viau@univ-fcomte.fr, carsten.strohmann@tu-dortmund.de

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 7 February 2020; accepted 14 February 2020; online 3 March 2020)

The title compound, C₂₂H₂₂O₂S₂, 1, represents an example of an ortho-vanillin-based functionalized dithioether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. This dithioacetal 1 crystallizes in the orthorhombic space group Pbca. The phenyl rings of the benzyl groups and that of the vanillin unit form dihedral angles of 35.38 (6) and 79.77 (6)°, respectively. The crystal structure, recorded at 100 K, displays both weak intramolecular O—H⋯O and intermolecular O—H⋯S hydrogen bonding.

Keywords: crystal structure; ortho-vanillin; thioacetal; dithioether; supramolecular network.

CCDC reference: 1983985

1. Chemical context

Acyclic and cyclic dithioether compounds containing the –S–C(R)(H)–S– (R = H, alkyl, aryl) motif are synthesized by nucleophilic substitution of geminal dihalides X–C(R)(H)–X in the presence of thiolate RS⁻ (Murray et al., 1981 ). Alternatively, they are readily accessible by treatment of aldehydes and ketones with thiols RSH and dithiols HS(CH₂)_nSH (n = 2, 3), yielding geminal dithio ethers, also called acyclic and cyclic thioacetals (1,3-dithiolanes, 1,3-dithianes) (Shaterian et al., 2011 ). This type of organosulfur compound is commonly used for Corey–Seebach umpolung reactions and the Mozingo reduction of dithioketals to hydrocarbons (Seebach & Corey, 1975 ; Zhao et al., 2017 ), but there are also numerous other transformations in organic chemistry such as their oxidation to sulfoxides and sulfones (Gasparrini et al., 1984 ). They have also been used in the past as monodentate, chelating or bridging ligands to construct both simple mono- and dinuclear coordination compounds or to assemble coordination networks of varying dimensionality ranging from 1D to 3D. Selected examples are [(C₅H₅)Fe(CO)₂(κ¹-BzSCH₂SBz)]⁺, the 1:1 adduct [Hg₂(NO₃)₂·BzSCH₂SBz)], the dinuclear Pd^I complex [ClPd(μ₂-BzSCH₂SBz)₂PdCl], and the monodimensional coordination polymer [Ag₂(BzSCH₂SBz)₂](ClO₄)₂ built upon dinuclear [Ag(μ₂-BzSCH₂SBz)₂Ag]²⁺ units (Brodersen & Rölz, 1977 ; Fuchita et al., 1991 ; Kuhn & Schumann, 1986 ; Li et al., 2005 ).

In the context of our research interest in the assembly of molecular cluster compounds and coordination polymers by complexation of ArSCH₂SAr or dithiolane- and dithiane-based thiaheterocycles (Chaabéne et al., 2016 ; Knauer et al., 2020 ; Knorr et al., 2014 ; Raghuvanshi et al., 2017 , 2019 ; Schlachter et al., 2018 ) , we have developed novel functionalized dithio ether compounds such as ferrocenyl thioethers bearing a substituent at the α-carbon atom linking the two –SR groups. With the idea of designing a functionalized thioacetal ligand bearing additional harder O-donor sites along with the two soft S-donor sites, we chose 2-hydroxy-3-methoxybenzaldehyde (ortho-vanillin) as the starting material. This hydroxylated aldehyde is present in the extracts and essential oils of many plants. Several papers describe also its use (in its deprotonated vanillinato form or as a Schiff base-derived ligand) in coordination chemistry (Andruh, 2015 ; Kırpık et al., 2019 ; Yu et al., 2011 ). Its reaction with 2 equivalents of benzyl mercaptan affords the targeted dithioacetal 2-hydroxy-3-methoxyphenyl[bis(benzylthio)]methane, 1, which was isolated in high yield as a crystalline solid.

This acyclic thioacetal contains, in addition to the benzylic thio ether groups and the methoxy group prone to ligate metal centres, a phenolic hydroxyl group, which may allow additional interactions through hydrogen bonding.

2. Structural commentary

Compound 1 crystallizes from CH₂Cl₂/hexane in the orthorhombic crystal system, space group Pbca. The C1—S1 and C1—S2 bond lengths of 1.8132 (12) and 1.8189 (12) Å are comparable with those of [BzSC(H)(C₆H₄NO₂-p)SBz] [1.823 (3) and 1.8262 (19) Å], but are elongated compared with those of bis(benzylsulfanyl)methane (CSD TUQPAX) [1.7988 (13) and 1.8013 (13) Å; Yang et al., 2010 ). The angle S1—C1—S2 is almost identical with that of 4-nitrophenyl-bis(benzylsulfanyl)methane [107.26 (6) versus 107.76°], but considerably more acute than in [BzSCH₂SBz] [117.33 (7)°]. There is a weak intramolecular O1⋯H2 contact of 2.17 (2) Å between the H atom of the phenolic hydroxyl group and the O-atom of the methoxy group (Table 1). For the starting material, 2-hydroxy-3-methoxybenzaldehyde, a similar intramolecular hydrogen bond seems to be absent; instead, a rather strong intramolecular hydrogen bond between the O—H group and the carbonyl oxygen was found (Iwasaki et al., 1976 ). The phenyl rings of the benzyl groups (C10–C15) and (C17–C22) and the phenyl ring of the vanillin unit (C2–C7) form dihedral angles of 35.38 (6) and 79.77 (6)°, respectively. Compared to the structurally very closely related compound 4-nitrophenyl-bis(benzylsulfanyl)methane [BzSC(H)(C₆H₄NO₂-p)SBz] (SUNMAQ; Binkowska et al., 2009 ), the coplanar and perpendicular arrangement of the phenyl rings is thus lost in 1 (Figs. 1 and 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯S1ⁱ	0.85 (2)	2.44 (2)	3.1315 (13)	139.0 (17)
O2—H2⋯O1	0.85 (2)	2.17 (2)	2.6469 (16)	115.4 (16)
C9—H9A⋯C20ⁱⁱ	0.99	2.86	3.528 (2)	125
C5—H5⋯Cg1ⁱⁱⁱ	0.95	2.84	3.7487 (15)	160
C16—H16A⋯Cg1^iv	0.99	2.71	3.6316 (15)	154
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iv) x-1, y, z.

Figure 1
The molecular structure of 1 with displacement ellipsoids drawn at the 50% probability level.

Figure 2
A view of the crystal packing of the title compound. For clarity, H atoms have been omitted. The intramolecular O1⋯H2 contacts are shown as dashed lines. For clarity, only H atoms involved in these interactions are presented. The intermolecular contacts are shown in Fig. 3

3. Supramolecular features

In the crystal, there is an O—H⋯S hydrogen bond between the H2 atom of the phenolic hydroxyl group and the S1 atom of a neighbouring molecule with distances [H2⋯S1 = 2.44 (2), O2⋯S1 = 3.1315 (13) Å] similar to those reported for 4-(1,3-dithian-2-yl)-1,2-benzenediol [H⋯S = 2.44, O⋯S = 3.2417 (13) Å], while the O—H⋯S angle is more acute [139.0 (17) versus 159.2°] (Fig. 3 and Table 1). This O2—H2⋯S1 interaction results in the formation of chains running along the b-axis direction.

Figure 3
Intermolecular contacts for compound 1. Symmetry codes as in Table 1

The benzylic methylene group on sulfur atom S2 interacts with the π-cloud of the phenyl part of the vanillin unit through a C—H⋯π interaction (Table 1). The second phenyl ring of the dithiane unit also exhibits a C—H⋯π interaction: the second methylene group on sulfur atom S1 interacts with a phenyl carbon. The third C—H⋯π contact is between adjacent vanillin units.

4. Database survey

There are several other examples of structurally characterized related dithioethers bearing hydroxy substituents that give rise to the formation of supramolecular networks. Selected examples found in the Cambridge Structural Database (CSD, version 5.40, update August 2019; Groom et al., 2016 ) include 2-(2-hydroxyphenyl)-1,3-dithiane (WADROJ; Usman et al., 2003 ), 2-(3-hydroxyphenyl)-1,3-dithiane (KALJUD; Ganguly et al., 2005 ), 4,6-bis(1,3-dithian-2-yl)benzene-1,3-diol (DITFIX; Datta et al., 2013 ), 4-(1,3-dithian-2-yl)benzene-1,3-diol (DITFOD; Datta et al., 2013), 2-phenyl-1,3-dithiepane-5,6-diol (FIBTOC; Liu et al., 2018 ) and 2,2′-{[(4-methoxyphenyl)methylene]disulfanediyl}diethanol (YISVUT; Laskar et al., 2013 ). It is noteable that in most of these examples, the intermolecular contacts are noticeably stronger than those of 1.

Note that in dithioether compounds with phenolic aryl groups as encountered in 1, the relative position of the phenolic OH substituent seems to play a crucial role, whether the intermolecular contacts are dominated by O—H⋯H or O—H⋯S hydrogen bonds. This is nicely illustrated by the series of three isomeric hydroxyphenyl-1,3-dithianes, ortho-, meta- and para-HO–C₆H₄–C₄H₇S₂. Whereas 2-(2-hydroxyphenyl)-1,3-dithiane (WADROY) and 2-(3-hydroxyphenyl)-1,3-dithiane (KALJUD) exhibit, like 1, only intermolecular O—H⋯S hydrogen bonding, the para-derivative 2-(4-hydroxyphenyl)-1,3-dithiane (KALKAK) features solely intermolecular phenolic O—H⋯H bonding (Ganguly et al., 2005).

5. Synthesis and crystallization

The reaction scheme for the synthesis of the title compound is illustrated in Fig. 4.

Figure 4
Synthesis of 1.

3-Methoxysalicylaldehyde (1 mmol, 152 mg), benzyl mercaptan (2.5 mmol, 310 mg), and conc. HCl (2 mL) were added to a flask at 273 K. The mixture was stirred for 60 min at room temperature. After the reaction was complete, the resulting mixture was neutralized with 10% aq NaHCO₃ (10 mL) and extracted with dichloromethane (3 × 10 mL). The combined extracts were washed with H₂O (3 × 20 mL) and dried over Na₂SO₄. Evaporation of the solvent in vacuo gave a solid product, which was further purified by column chromatography. The product was obtained as a white solid, Yield: 83% (430 mg). X-ray quality crystals were obtained by keeping a dichloromethane:hexane (1:1) mixture of 1 at 278 K for 3–4 d. ¹H NMR (400 MHz, CDCl₃) δ 7.26–7.19 (m, 11H, Ph), 6.86 (t, J = 7.8 Hz, 1H, CH), 6.78 (d, J = 7.8 Hz, 1H, CH), 5.83 (s, 1H, OH), 5.13 (s, 1H CHS₂), 3.88 (s, 3H, OCH₃), 3.79 (d, J = 13.1 Hz, 2H, CH₂), 3.64 (d, J = 13.1 Hz, 2H, CH₂).¹³C{¹H} NMR (101 MHz, CDCl₃) δ 146.5 (Cq_OH), 142.8 (CqOCH₃), 137.8 (SCH₂Cq), 129.1 (SCH₂CCH), 128.4 (SCH₂CCHCH), 126.9 (SCH₂CCHCHCH), 125.3 (S₂CHCq), 120.9 (S₂CHCqCH), 119.9 (S₂CHCqCHCH), 110.0 (CHCqOCH₃), 56.1 (OCH₃), 44.8 (S₂CH), 36.7 (S₂CH₂). IR (ATR) cm⁻¹: 3419 (O—H), 1430-1612 (C=C). 1054 and 1264 (C—O), 766 (C—S). HRMS: (ESI) m/z calculated for C₂₂H₂₂O₂S₂Na [M + Na]⁺ 405.0953, found 405.0965.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C) for CH₂ and CH hydrogen atoms and U_iso(H) = 1.5U_eq(C-methyl). The phenolic proton H2 was refined independently.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₂₂O₂S₂
M_r	382.51
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	7.7418 (8), 13.856 (3), 36.197 (5)
V (Å³)	3882.9 (10)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.29
Crystal size (mm)	0.49 × 0.42 × 0.25

Data collection
Diffractometer	Bruker D8 VENTURE area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.713, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	107706, 5005, 4510
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.079, 1.09
No. of reflections	5005
No. of parameters	241
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1983985

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020002091/vm2228sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989020002091/vm2228Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989020002091/vm2228Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-[Bis(benzylsulfanyl)methyl]-6-methoxyphenol top

Crystal data top

C₂₂H₂₂O₂S₂	D_x = 1.309 Mg m⁻³
M_r = 382.51	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9791 reflections
a = 7.7418 (8) Å	θ = 2.3–28.2°
b = 13.856 (3) Å	µ = 0.29 mm⁻¹
c = 36.197 (5) Å	T = 100 K
V = 3882.9 (10) Å³	Block, colourless
Z = 8	0.49 × 0.42 × 0.25 mm
F(000) = 1616

Data collection top

Bruker D8 VENTURE area detector diffractometer	5005 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	4510 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.033
Detector resolution: 10.4167 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ω and φ scans	h = −9→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −18→18
T_min = 0.713, T_max = 0.746	l = −49→45
107706 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0287P)² + 2.6399P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.003
S = 1.09	Δρ_max = 0.34 e Å⁻³
5005 reflections	Δρ_min = −0.23 e Å⁻³
241 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0017 (2)
Primary atom site location: dual

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	0.61115 (4)	0.82824 (2)	0.63211 (2)	0.01667 (8)
S2	0.42202 (4)	0.68918 (2)	0.67748 (2)	0.01772 (8)
O1	1.02466 (13)	0.48649 (7)	0.70693 (3)	0.0234 (2)
O2	0.76523 (13)	0.52864 (7)	0.66212 (3)	0.0228 (2)
H2	0.826 (3)	0.4778 (15)	0.6649 (5)	0.043 (5)*
C1	0.62315 (15)	0.70907 (8)	0.65265 (3)	0.0146 (2)
H1	0.631957	0.660278	0.632378	0.017*
C2	0.77100 (15)	0.69329 (8)	0.67929 (3)	0.0147 (2)
C3	0.84314 (17)	0.76632 (9)	0.70092 (3)	0.0179 (2)
H3	0.799141	0.830165	0.699171	0.022*
C4	0.97814 (17)	0.74678 (10)	0.72490 (3)	0.0202 (3)
H4	1.025853	0.797416	0.739354	0.024*
C5	1.04472 (16)	0.65382 (9)	0.72807 (3)	0.0185 (2)
H5	1.137719	0.640764	0.744446	0.022*
C6	0.97346 (16)	0.58102 (9)	0.70704 (3)	0.0172 (2)
C7	0.83624 (16)	0.60032 (9)	0.68273 (3)	0.0157 (2)
C8	1.17946 (19)	0.46331 (11)	0.72664 (5)	0.0311 (3)
H8A	1.274327	0.503799	0.717632	0.047*
H8B	1.208119	0.395191	0.722705	0.047*
H8C	1.161929	0.475073	0.753070	0.047*
C9	0.81405 (17)	0.83571 (10)	0.60670 (4)	0.0222 (3)
H9A	0.828248	0.902523	0.597491	0.027*
H9B	0.910248	0.822557	0.623999	0.027*
C10	0.82841 (17)	0.76755 (10)	0.57454 (4)	0.0216 (3)
C11	0.7673 (2)	0.79298 (12)	0.53965 (4)	0.0294 (3)
H11	0.712651	0.853694	0.536144	0.035*
C12	0.7855 (2)	0.73040 (14)	0.51001 (4)	0.0354 (4)
H12	0.742688	0.748223	0.486385	0.043*
C13	0.8656 (2)	0.64242 (14)	0.51472 (4)	0.0367 (4)
H13	0.880248	0.600256	0.494264	0.044*
C14	0.9247 (2)	0.61563 (13)	0.54931 (5)	0.0360 (4)
H14	0.978548	0.554677	0.552712	0.043*
C15	0.90510 (18)	0.67790 (11)	0.57899 (4)	0.0275 (3)
H15	0.944821	0.658858	0.602728	0.033*
C16	0.26715 (16)	0.68531 (9)	0.63950 (3)	0.0188 (2)
H16A	0.150774	0.672722	0.649760	0.023*
H16B	0.264227	0.749436	0.627453	0.023*
C17	0.30595 (16)	0.61034 (9)	0.61075 (3)	0.0176 (2)
C18	0.25087 (18)	0.51529 (10)	0.61502 (4)	0.0231 (3)
H18	0.188646	0.497061	0.636537	0.028*
C19	0.2863 (2)	0.44732 (10)	0.58807 (4)	0.0274 (3)
H19	0.246189	0.382978	0.590983	0.033*
C20	0.37995 (19)	0.47228 (11)	0.55688 (4)	0.0264 (3)
H20	0.406356	0.424957	0.538749	0.032*
C21	0.43459 (18)	0.56639 (12)	0.55233 (4)	0.0269 (3)
H21	0.498143	0.584070	0.530921	0.032*
C22	0.39681 (17)	0.63509 (10)	0.57896 (4)	0.0223 (3)
H22	0.433413	0.699893	0.575465	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01657 (15)	0.01393 (14)	0.01952 (15)	−0.00028 (11)	−0.00002 (11)	0.00077 (10)
S2	0.01469 (15)	0.02377 (16)	0.01471 (14)	−0.00302 (11)	−0.00020 (11)	0.00089 (11)
O1	0.0226 (5)	0.0196 (4)	0.0279 (5)	0.0043 (4)	−0.0075 (4)	0.0010 (4)
O2	0.0254 (5)	0.0145 (4)	0.0285 (5)	0.0022 (4)	−0.0092 (4)	−0.0048 (4)
C1	0.0133 (5)	0.0145 (5)	0.0159 (5)	−0.0009 (4)	−0.0003 (4)	0.0000 (4)
C2	0.0129 (5)	0.0164 (5)	0.0147 (5)	−0.0011 (4)	0.0002 (4)	−0.0002 (4)
C3	0.0184 (6)	0.0174 (6)	0.0180 (6)	−0.0009 (5)	−0.0005 (5)	−0.0022 (4)
C4	0.0207 (6)	0.0231 (6)	0.0169 (6)	−0.0049 (5)	−0.0014 (5)	−0.0035 (5)
C5	0.0147 (6)	0.0266 (6)	0.0141 (5)	−0.0014 (5)	−0.0013 (4)	0.0017 (5)
C6	0.0166 (6)	0.0193 (6)	0.0158 (5)	0.0013 (5)	0.0007 (4)	0.0022 (4)
C7	0.0146 (6)	0.0172 (5)	0.0154 (5)	−0.0018 (4)	0.0003 (4)	−0.0012 (4)
C8	0.0235 (7)	0.0270 (7)	0.0428 (9)	0.0027 (6)	−0.0105 (6)	0.0110 (6)
C9	0.0189 (6)	0.0261 (6)	0.0217 (6)	−0.0069 (5)	0.0026 (5)	0.0003 (5)
C10	0.0148 (6)	0.0315 (7)	0.0186 (6)	−0.0065 (5)	0.0025 (5)	−0.0010 (5)
C11	0.0307 (8)	0.0356 (8)	0.0221 (6)	−0.0084 (6)	−0.0008 (6)	0.0060 (6)
C12	0.0323 (8)	0.0572 (10)	0.0168 (6)	−0.0122 (8)	−0.0003 (6)	0.0013 (6)
C13	0.0223 (7)	0.0615 (11)	0.0264 (7)	−0.0047 (7)	0.0033 (6)	−0.0175 (7)
C14	0.0210 (7)	0.0494 (10)	0.0376 (8)	0.0090 (7)	−0.0038 (6)	−0.0153 (7)
C15	0.0167 (6)	0.0423 (8)	0.0236 (7)	0.0046 (6)	−0.0036 (5)	−0.0051 (6)
C16	0.0131 (6)	0.0258 (6)	0.0175 (6)	−0.0020 (5)	−0.0024 (5)	0.0022 (5)
C17	0.0121 (5)	0.0250 (6)	0.0157 (5)	−0.0019 (5)	−0.0037 (4)	0.0027 (5)
C18	0.0216 (6)	0.0254 (6)	0.0222 (6)	−0.0030 (5)	−0.0006 (5)	0.0061 (5)
C19	0.0304 (8)	0.0213 (6)	0.0306 (7)	−0.0009 (6)	−0.0054 (6)	0.0034 (5)
C20	0.0227 (7)	0.0319 (7)	0.0247 (7)	0.0049 (6)	−0.0067 (5)	−0.0060 (6)
C21	0.0219 (7)	0.0411 (8)	0.0177 (6)	−0.0061 (6)	0.0007 (5)	−0.0017 (6)
C22	0.0205 (6)	0.0282 (7)	0.0182 (6)	−0.0083 (5)	−0.0017 (5)	0.0022 (5)

Geometric parameters (Å, º) top

S1—C1	1.8132 (12)	C10—C11	1.3940 (19)
S1—C9	1.8232 (14)	C10—C15	1.386 (2)
S2—C1	1.8189 (12)	C11—H11	0.9500
S2—C16	1.8250 (13)	C11—C12	1.387 (2)
O1—C6	1.3685 (15)	C12—H12	0.9500
O1—C8	1.4312 (17)	C12—C13	1.378 (3)
O2—H2	0.85 (2)	C13—H13	0.9500
O2—C7	1.3584 (15)	C13—C14	1.383 (2)
C1—H1	1.0000	C14—H14	0.9500
C1—C2	1.5126 (16)	C14—C15	1.386 (2)
C2—C3	1.3960 (17)	C15—H15	0.9500
C2—C7	1.3893 (17)	C16—H16A	0.9900
C3—H3	0.9500	C16—H16B	0.9900
C3—C4	1.3854 (18)	C16—C17	1.5007 (18)
C4—H4	0.9500	C17—C18	1.3929 (18)
C4—C5	1.3920 (19)	C17—C22	1.3917 (17)
C5—H5	0.9500	C18—H18	0.9500
C5—C6	1.3789 (18)	C18—C19	1.383 (2)
C6—C7	1.4051 (17)	C19—H19	0.9500
C8—H8A	0.9800	C19—C20	1.385 (2)
C8—H8B	0.9800	C20—H20	0.9500
C8—H8C	0.9800	C20—C21	1.381 (2)
C9—H9A	0.9900	C21—H21	0.9500
C9—H9B	0.9900	C21—C22	1.386 (2)
C9—C10	1.5031 (19)	C22—H22	0.9500

C1—S1—C9	102.38 (6)	C15—C10—C9	120.31 (12)
C1—S2—C16	101.22 (6)	C15—C10—C11	118.51 (13)
C6—O1—C8	117.12 (11)	C10—C11—H11	119.7
C7—O2—H2	108.5 (14)	C12—C11—C10	120.54 (15)
S1—C1—S2	107.26 (6)	C12—C11—H11	119.7
S1—C1—H1	108.6	C11—C12—H12	119.9
S2—C1—H1	108.6	C13—C12—C11	120.22 (14)
C2—C1—S1	115.59 (8)	C13—C12—H12	119.9
C2—C1—S2	108.11 (8)	C12—C13—H13	120.1
C2—C1—H1	108.6	C12—C13—C14	119.86 (15)
C3—C2—C1	123.74 (11)	C14—C13—H13	120.1
C7—C2—C1	117.80 (10)	C13—C14—H14	120.1
C7—C2—C3	118.45 (11)	C13—C14—C15	119.88 (16)
C2—C3—H3	119.6	C15—C14—H14	120.1
C4—C3—C2	120.77 (12)	C10—C15—H15	119.5
C4—C3—H3	119.6	C14—C15—C10	120.96 (14)
C3—C4—H4	119.6	C14—C15—H15	119.5
C3—C4—C5	120.79 (12)	S2—C16—H16A	108.7
C5—C4—H4	119.6	S2—C16—H16B	108.7
C4—C5—H5	120.6	H16A—C16—H16B	107.6
C6—C5—C4	118.90 (12)	C17—C16—S2	114.28 (9)
C6—C5—H5	120.6	C17—C16—H16A	108.7
O1—C6—C5	125.87 (12)	C17—C16—H16B	108.7
O1—C6—C7	113.53 (11)	C18—C17—C16	121.08 (11)
C5—C6—C7	120.59 (12)	C22—C17—C16	120.27 (12)
O2—C7—C2	118.79 (11)	C22—C17—C18	118.65 (12)
O2—C7—C6	120.71 (11)	C17—C18—H18	119.8
C2—C7—C6	120.50 (11)	C19—C18—C17	120.31 (13)
O1—C8—H8A	109.5	C19—C18—H18	119.8
O1—C8—H8B	109.5	C18—C19—H19	119.7
O1—C8—H8C	109.5	C18—C19—C20	120.56 (13)
H8A—C8—H8B	109.5	C20—C19—H19	119.7
H8A—C8—H8C	109.5	C19—C20—H20	120.2
H8B—C8—H8C	109.5	C21—C20—C19	119.55 (13)
S1—C9—H9A	108.6	C21—C20—H20	120.2
S1—C9—H9B	108.6	C20—C21—H21	120.0
H9A—C9—H9B	107.6	C20—C21—C22	120.06 (13)
C10—C9—S1	114.75 (9)	C22—C21—H21	120.0
C10—C9—H9A	108.6	C17—C22—H22	119.6
C10—C9—H9B	108.6	C21—C22—C17	120.83 (13)
C11—C10—C9	121.18 (13)	C21—C22—H22	119.6

S1—C1—C2—C3	30.00 (15)	C7—C2—C3—C4	0.84 (18)
S1—C1—C2—C7	−151.09 (9)	C8—O1—C6—C5	−8.60 (19)
S1—C9—C10—C11	87.20 (15)	C8—O1—C6—C7	170.97 (12)
S1—C9—C10—C15	−93.52 (14)	C9—S1—C1—S2	−177.44 (6)
S2—C1—C2—C3	−90.18 (13)	C9—S1—C1—C2	61.92 (10)
S2—C1—C2—C7	88.73 (12)	C9—C10—C11—C12	178.27 (13)
S2—C16—C17—C18	85.08 (14)	C9—C10—C15—C14	−177.74 (14)
S2—C16—C17—C22	−95.56 (13)	C10—C11—C12—C13	−0.4 (2)
O1—C6—C7—O2	0.73 (17)	C11—C10—C15—C14	1.6 (2)
O1—C6—C7—C2	−179.12 (11)	C11—C12—C13—C14	1.4 (2)
C1—S1—C9—C10	66.89 (11)	C12—C13—C14—C15	−0.8 (2)
C1—S2—C16—C17	56.83 (10)	C13—C14—C15—C10	−0.6 (2)
C1—C2—C3—C4	179.74 (11)	C15—C10—C11—C12	−1.0 (2)
C1—C2—C7—O2	0.19 (17)	C16—S2—C1—S1	66.50 (7)
C1—C2—C7—C6	−179.95 (11)	C16—S2—C1—C2	−168.23 (8)
C2—C3—C4—C5	−0.18 (19)	C16—C17—C18—C19	179.38 (12)
C3—C2—C7—O2	179.17 (11)	C16—C17—C22—C21	179.52 (12)
C3—C2—C7—C6	−0.98 (18)	C17—C18—C19—C20	1.3 (2)
C3—C4—C5—C6	−0.34 (19)	C18—C17—C22—C21	−1.1 (2)
C4—C5—C6—O1	179.74 (12)	C18—C19—C20—C21	−1.5 (2)
C4—C5—C6—C7	0.19 (19)	C19—C20—C21—C22	0.4 (2)
C5—C6—C7—O2	−179.67 (11)	C20—C21—C22—C17	0.9 (2)
C5—C6—C7—C2	0.48 (19)	C22—C17—C18—C19	0.0 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···S1ⁱ	0.85 (2)	2.44 (2)	3.1315 (13)	139.0 (17)
O2—H2···O1	0.85 (2)	2.17 (2)	2.6469 (16)	115.4 (16)
C9—H9A···C20ⁱⁱ	0.99	2.86	3.528 (2)	125
C5—H5···Cg1ⁱⁱⁱ	0.95	2.84	3.7487 (15)	160
C16—H16A···Cg1^iv	0.99	2.71	3.6316 (15)	154

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+3/2, y+1/2, z; (iii) x+1/2, y, −z+3/2; (iv) x−1, y, z.

Footnotes

‡Current address: Discipline of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Simrol Indore 453552, MP, India.

Funding information

LK thanks the Fonds der Chemischen Industrie for a doctoral fellowship. We are grateful to the region of Franche-Comté for funding a postdoctoral fellowship for A. Raghuvanshi (grant No. RECH-MOB15–000017).

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