Crystal structures of 4,4′-(disulfane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one) and 4,4′-(diselanane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one)

Trentin, I.; Schindler, C.; Schulzke, C.

doi:10.1107/S2056989018007454

research communications

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ISSN: 2056-9890

Volume 74| Part 6| June 2018| Pages 840-845

https://doi.org/10.1107/S2056989018007454

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Crystal structures of 4,4′-(disulfane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one) and 4,4′-(diselanane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one)

Ivan Trentin,^a Claudia Schindler ^a ^* and Carola Schulzke ^a ^*

^aErnst-Moritz-Arndt-Universität Greifswald; Institut für Biochemie, Felix-Hausdorff-Strasse 4, 17487 Greifswald, Germany
^*Correspondence e-mail: claudia.schindler@uni-greifswald.de, carola.schulzke@uni-greifswald.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 26 April 2018; accepted 17 May 2018; online 22 May 2018)

The two title compounds, C₈H₆O₂S₆ and C₈H₆O₂S₄Se₂, are isotypic with very similar cell parameters. The complete molecules constitute the asymmetric units, despite being chemically perfectly symmetric. The most prominant differences in the metrical parameters arise from the distinct sizes of sulfur and selenium in the dichalcogenide bridges, with C—S—S—C and C—Se—Se—C torsion angles of 70.70 (5) and 68.88 (3)°, respectively. The crystal packing is determined by weak non-classical hydrogen-bonding interactions. One carbonyl oxygen but not the other participates in C—H⋯O interactions zigzagging along the b axis, forming infinite chains. This is complemented by an intramolecular C—H⋯S interaction and further intermolecular C—H⋯S (C—H⋯Se) interactions, resulting in a three-dimensional network. The interactions involving the bridging chalcogenides form chains protruding along the c axis.

Keywords: crystal structure; catenation; 1,3-ene-dithiol-2-ones; disulfide; diselenide.

CCDC references: 1843766; 1843765

1. Chemical context

Selenium- and sulfur-containing compounds play an important role in nature. Sulfur-rich compounds, in particular derivatives of tetrathiafulvalene and dithiolene, comprise chemically interesting compounds with exceptional electronic structural characteristics. Selenium is an essential trace element in the active sites of several enzymes and plays inter alia an important role in antioxidant selenoproteins for protection against oxidative stress such as in thioredoxin reductase (Lee et al., 1999 ; Lescure et al., 1999 ; Mustacich & Powis, 2000 ; Watabe et al., 1999 ; Williams et al., 2000 ). In the disulfide isomerase protein family, thioredoxin-like domains are rich in cysteine residues. A diselenide from selenocysteins was shown to be structurally very similar to the respective disulfide from two cysteins (Görbitz et al., 2015 ). As a consequence, disulfide and diselenide compounds were developed as catalysts for oxidative protein folding and refolding reactions (Arai et al., 2018 ). Here we report the serendipitous synthesis and structural characterization of bis[3-methyl-1,3-ene-dithiol-2-one] disulfide and bis[3-methyl-1,3-ene-dithiol-2-one] diselenide via unprecedented routes. Instead of the targeted products, the applied order of reactions yielded the novel disulfide and its diselenide analogue, which have potential applications in redox chemistry and as biologically interesting compounds. By in situ oxidation, S—S or Se—Se moieties are formed, replacing the ⁿBu₃Sn substituents of alkene carbon atoms of two distinct and consequently linked 1,3-ene-dithiol-2-one units. As this constitutes a substitution of a ⁿBu₃Sn functional group, it is quite likely that this method can be applied to a variety of respective different precursors.

2. Structural commentary

The two title compounds are isotypic. One complete molecule constitutes the asymmetric unit despite being chemically perfectly symmetric: i.e. no symmetry operation is used to generate the whole molecular structure. In both compounds, two 3-methyl-1,3-ene-dithiol-2-one moieties are linked by a dichalcogenide bridge (S₂²⁻ or Se₂²⁻), which is attached to one of the ene carbon atoms, while the other ene carbon is bound to a methyl group (Figs. 1 and 2). Both structures constitute the first examples of crystallographically characterized disulfides and diselenides in which two 1,3-ene-dithiol-2-one moieties are linked by a dichalcogenide bridge. While related bridged 1,3-ene-dithiol-2-thione moieties are reported for disulfides and also one compound in which the disulfide is part of a heterocycle with the 1,3-ene-dithiol-2-one moiety (Chou et al., 1998 ), no such analogues are known in the case of the diselenide bridge.

Figure 1
The molecular structure of bis[4-methyl-1,3-ene-dithiol-2-one] disulfide. Displacement ellipsoids are shown at the 50% probability level.

Figure 2
The molecular structure of [bis[4-methyl-1,3-ene-dithiol-2-one] diselenide. Displacement ellipsoids are shown at the 50% probability level.

The metrical parameters of both molecules are nearly identical (see Fig. 3 for an overlay of the molecules), with the largest differences found for the dichalcogenide bridge itself. The Se—Se distance [2.3397 (7) Å] is longer by ca 0.27 Å than the S—S distance [2.0723 (7) Å], matching almost exactly the difference in the respective covalent radii (0.13 Å; Pyykkö & Atsumi, 2009 ) multiplied by two. Similarly, the average C—Se distance [1.897 (4) Å] is longer by 0.15 Å than the average C—S distance [1.749 (2) Å]. Unusual electronic effects upon exchanging selenium for sulfur can, hence, be excluded. The average C—Se—Se angle [98.8 (6)°] is slightly more acute than the C—S—S angle [101.8 (6)°], which necessarily results from the longer distances involving the Se atom and the nearly identical atom positions of the 1,3-ene-dithiol-2-thione moieties. All other differences in the metrical parameters between the two molecular structures are marginal. All observed distances and angles also fall into or close to the expected/previously reported ranges. The S—S distances of the most closely related compounds range from 2.078 Å in an Fe(CO)₂Cp-coordinating species (Matsubayashi et al., 2002 ) to 2.160 Å in the [C₆S₁₀]²⁻ dianion crystallized as an ammonium salt (Breitzer et al., 2001 ). The observed S—S distance [S3—S4; 2.0723 (7) Å] here is slightly shorter than the former, though not shorter than the lower limit of ca 2.00 Å when generally evaluating C—S—S—C linkages (Comerlato et al., 2010 ; Aida & Nagata, 1986 ). Se—Se distances in compounds in which one Se₂²⁻ unit binds to alkene carbon atoms and bridges two identical ene-moieties range from 2.303 Å (Biswas et al., 2017 ) to 2.389 Å (Ruban et al., 1981 ), with the Se—Se distance observed here [2.3397 (7) Å] falling right in the center of this range.

Figure 3
An overlay (Mercury; Macrae et al., 2006

) of the molecular structures of bis[4-methyl-1,3-ene-dithiol-2-one] disulfide (yellow bridge) and bis[4-methyl-1,3-ene-dithiol-2-one] diselenide (orange bridge). The root-mean-square deviation (r.m.s.d.) and the maximum distance between atom positions are 0.078 and 0.171 Å, respectively.

The structurally most notable features are the C—S—S—C and C—Se—Se—C torsion angles [70.70 (5) and 68.86 (3)°, respectively] which bring the two 1,3-ene-dithiol-2-thione moieties in rather close proximity. In related disulfides they range from 52.08 to 109.82° (Breitzer et al., 2001). C—S—S—C torsion angles near 90° were found in silico to stabilize structures by an overlap of one σ*S—C orbital with the 3p lone pair of the other sulfur atom, which is maximized in such an arrangement (Aida & Nagata, 1986). The observed C—Se—Se—C torsion angles of diselenide-bridged alkenes as the closest relatives of the title diselenide range from 73.03° (Ruban et al., 1981) to 92.04° (Biswas et al., 2017). In the crystalline solid state, apparently packing effects, steric bulk, hydrogen-bonding interactions, and π–π-stacking can influence the relative orientations of the two substituents on the disulfide unit significantly, whereas the values for alkene bridging diselenides observed to date are less varied.

The four 1,3-ene-dithiol-2-one moieties (two in each structure) are essentially planar, with maximum deviations from the least-squares plane of 0.028 and 0.022 Å for the disulfide and for the diselenide, respectively, corresponding to the distances from atom S1 to the O1—S1—S2—C1—C2—C3 plane in both cases. The dihedral angles between the O1—S1—S2—C1—C2—C3 and the O2—S5—S6—C6—C7—C8 planes are 33.8 (2)° for the disulfide and 28.89 (11)° for the diselenide. Here, a smaller torsion angle around the dichalcogenide bridge is accompanied by a smaller angle between the two planes of the 1,3-ene-dithiol-2-one moieties.

3. Supramolecular features

In the crystals, molecules are linked by C—H⋯O, C—H⋯S, and C—H⋯Se non-classical hydrogen-bonding interactions, some of which being comparably weak (Tables 1 and 2). One carbonyl oxygen but not the other participates in C4—H4B⋯O1ⁱ interactions zigzagging along the b axis, forming infinite chains (Fig. 4, left). The respective D⋯A distances are 3.345 (2) Å for the disufide and 3.369 (5) Å for the diselenide. This is complemented by two intramolecular interactions between the two chalcogens of the dichalcogenide bridges and the adjacent methyl substituents (C4—H4A⋯S3/Se1 and C5—H5A⋯S4/Se2) with D⋯A distances of 3.244 (2) for S3, of 3.234 (2) for S4, of 3.354 (4) for Se1, and of 3.341 (4) for Se2. Further intermolecular C—H⋯S and C—H⋯Se interactions contribute to the formation of a three-dimensional network. The interactions involving the bridging chalcogenides form chains protruding along the c axis (Fig. 4, center and right). The closest 3-methyl-1,3-ene-dithiol-2-one moieties of two adjacent molecules are perfectly coplanar with the carbonyl oxygen atoms pointing into opposite directions. The respective distances between the planes are 3.55 and 3.58 Å for pairs of S1—S2—C1—C2—C3 heterocycles for the disulfide and diselenide, and 3.64 and 3.66 Å for pairs of S5—S6—C6—C7—C8 heterocycles. This arrangement fosters weak symmetric bidirectional C5—H5C⋯S5ⁱⁱⁱ and C4—H4C⋯S2^iv hydrogen-bonding interactions between methyl hydrogen atoms and S2 and S5 ring atoms, connecting adjacent chains and forming a three-dimensional network (Fig. 4, right).

Table 1
Hydrogen-bond geometry (Å, °) for C₈H₆O₂S₆

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯S3	0.98	2.76	3.244 (2)	111
C5—H5A⋯S4	0.98	2.75	3.234 (2)	111
C4—H4B⋯O1ⁱ	0.98	2.53	3.345 (2)	141
C5—H5C⋯S3ⁱⁱ	0.98	3.14	3.8063 (19)	126
C5—H5C⋯S5ⁱⁱⁱ	0.98	3.01	3.825 (2)	142
C4—H4C⋯S2^iv	0.98	3.12	4.021 (2)	153
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1; (iv) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °) for C₈H₆O₂S₄Se₂

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯Se1	0.98	2.84	3.354 (4)	114
C5—H5A⋯Se2	0.98	2.83	3.341 (4)	114
C4—H4B⋯O1ⁱ	0.98	2.55	3.369 (5)	141
C5—H5C⋯Se1ⁱⁱ	0.98	3.14	3.801 (4)	126
C5—H5C⋯S5ⁱⁱⁱ	0.98	3.04	3.850 (4)	141
C4—H4C⋯S2^iv	0.98	3.13	3.992 (4)	148
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1; (iv) -x+1, -y+2, -z+1.

Figure 4
Packing and non-classical hydrogen-bonding motifs for the crystal structures of bis[4-methyl-1,3-ene-dithiol-2-one] disulfide and bis[4-methyl-1,3-ene-dithiol-2-one] diselenide. Left: C4—H4B⋯O1ⁱ interactions zigzagging along the b axis shown for the diselenide; center: hydrogen-bonding interactions of the diselenide bridge C5—H5C⋯Se1ⁱⁱ protruding along the c axis; right: additional symmetric hydrogen-bonding interactions between coplanar 1,3-ene-dithiol-2-one moieties connecting adjacent chains shown for the disulfide (C4—H4C⋯S2^iv and C5—H5C⋯S5ⁱⁱⁱ). For symmetry codes, see Tables 1

and 2

4. Database survey

In the literature to date, only S—S-bridged 1,3-ene-dithiol-2-thione compounds have been reported but no analogous 1,3-ene-dithiol-2-one compounds (excluding those in which the `link' is part of a heterocycle). The first such thione crystal structure was reported in 1999 by Cerrada et al., which comprises an S—S-linked [C₃S₅—C₃S₅]²⁻ dianion (Cerrada et al., 1999 ). Ten years later, Cerrada et al. described the S—S coupling via dithiolate transfer from tin to nickel complexes where they isolated an S—S-bridged 1,3-dithiol-2-thione with different substituents as a crystalline byproduct (Cerrada et al., 2009 ). Rauchfuss and co-workers described the isolation and structural characterization of an S—S-linked dianion [C₆S₁₀]²⁻ as the tetramethylammonium salt (Breitzer et al., 2001). In 2002, Matsubayashi et al. reported the formation of an S—S-linked [C₃S₅—C₃S₅]²⁻ system bridging two Fe(CO)₂Cp complexes by coordination of thiolate sulfur to iron (Matsubayashi et al., 2002). Wardell and coworkers carried out the controlled oxidation of cesium 4-benzoylthio-1,3-dithiole-2-thione-5-thiolate using iodine as oxidant and obtained bis(4-benzoylthio-1,3-dithiole-2-thione)-5,5-disulfide, in two polymorphic forms (Comerlato et al., 2010). Recently the formation of a disulfide with a 4-(methylsulfanyl)-2H-1,3-dithiole-2-thione unit was reported from the reaction of a Cs complex with MCl₂ (M = Pt, Pd) by Kumar et al. (2017 ). Notably, such compounds predominantly constitute unanticipated side products and the focus of the respective characterization lies in crystallographic analyses with respect to solid-state intermolecular interactions and packing motifs. More in-depth studies have focused predominatly on their interesting redox properties (Breitzer et al., 2001; Matsubayashi et al., 2002).

Only two analogous diselenide compounds with Se—Se moieties linking two 1,3-ene-dithiol-2-thione moieties are reported in the literature, albeit without crystallographic data (Cerrada et al., 1999; Takimiya et al., 2002 ). To date, no such compounds are known with 1,3-ene-dithiol-2-one moieties. A few examples are available for distantly related compounds in which cyclic alkenes are bridged by a diselenide moiety. Already in 1981, the synthesis, characterization and crystal structure of such a diselenide was described by Ruban et al.: bis{4-(2-thienyl)selenolo[3,4-b]thiophen-6-yl}diselenide was formed unexpectedly by the reaction of 2-[(triphenylphosphonio)methyl] thiophene chloride with sodium hydrogen selenite (Ruban et al., 1981). In 2000, Oilunkaniemi et al. published a procedure for the synthesis of thienyl- and furyl diselenide compounds, which was confirmed by respective crystal structures and selenium NMR spectra (Oilunkaniemi et al., 2000 ). Kumar & Nangia (2000 ) published the crystal structure of 2,2`-diselenobis(4,4-diphenylcyclo-hexa-2,5-dienone). In 2003, Thaler et al. synthesized cyclopentadienyl selenium compounds as multifunctional ligand systems with a varied number of selenium atoms in the Se_n bridge (Thaler et al., 2003 ). Recently, the formation of a diselenide as a byproduct during the synthesis of heliannuol C (as confirmed by X-ray diffraction) was described by Biswas et al. (2017). The crystal structures of bis[4-methyl-1,3-dithiol-2-one] disulfide and diselenide described in the current work are the first in which two 1,3-ene-dithiol-2-one moieties are linked by an S—S and an Se—Se bridge, respectively. For the latter, even the chemical structure is entirely unprecedented.

5. Synthesis and crystallization

Preparation of bis[4-methyl-1,3-dithiol-2-one] disulfide: This was undertaken by a modification of a published procedure (Dinsmore et al., 1998 ). 4-Methyl-1,3-dithiol-2-one (0.95 g, 7.2 mmol) and tributyltin chloride (2.92 ml, 8.63 mmol) in dry THF (10 ml) under nitrogen were cooled to 169 K (N₂/MeOH:Et₂O or dry ice/Et₂O), and LDA (9.8 ml, 7.9 mmol, 10% solution in hexane) was added dropwise over 5 min. The mixture was allowed to stand for 35 min, warmed to ice-bath temperature and after a further 10 minutes quenched with a saturated aqueous solution of NH₄Cl (around 20 ml). The organic phase was diluted with EtOAc, separated and the aqueous phase re-extracted with Et₂O (2 × 15 ml). The combined organic phases were washed with brine, dried and the solvent evaporated in vacuo to give a yellowish oil as crude product. This was purified by chromatography (silica gel), eluting with EtOAc/petroleum ether (40/60) 3:97 v/v to give 4-methyl-5-tri-n-butylstannyl-1,3-dithiol-2-one as the major product. During purification, a yellowish oily fraction was isolated and subsequently stored at 253 K, forming large yellow crystals. Crystallographic evaluation of these crystals reveals the formation of the side product bis[4-methyl-1,3-dithiol-2-one] disulfide.

Preparation of bis[4-methyl-1,3-dithiol-2-one] diselenide: The synthesis was carried out under an inert gas atmosphere of nitrogen, whereas the purification steps were carried out in air. To a solution of 4-methyl-5-tri-n-butylstannyl-1,3-dithiol-2-one (352.5 mg, 0.84 mmol) in freshly distilled dioxane (5 ml) was added freshly sublimed selenium dioxide (134.2 mg, 1.21 mmol). The reaction mixture was heated at reflux temperature for 6 h. After cooling, the solution was filtered through celite. Solvent removal gave an orange solid (188.0 mg, 0.38 mmol, 45%). Yellow crystals suitable for crystallographic analysis were obtained by recrystallization from acetone.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The six methyl hydrogen atoms of each structure were included in calculated positions and treated as riding with C—H = 0.98 Å and U_i_so(H) = 1.5U_eq(C).

Table 3
Experimental details

	C₈H₆O₂S₆	C₈H₆O₂S₄Se₂
Crystal data
M_r	326.49	420.29
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	170	170
a, b, c (Å)	10.845 (2), 9.0387 (18), 13.370 (3)	10.960 (2), 9.1348 (18), 13.495 (3)
β (°)	108.95 (3)	108.29 (3)
V (Å³)	1239.6 (4)	1282.8 (5)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.08	6.40
Crystal size (mm)	0.50 × 0.20 × 0.001	0.48 × 0.43 × 0.41

Data collection
Diffractometer	STOE IPDS2T	Stoe IPDS2T
Absorption correction	Numerical face indexed	Numerical face indexed
T_min, T_max	0.771, 0.942	0.393, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	13324, 3344, 2636	10805, 2733, 2009
R_int	0.034	0.063
(sin θ/λ)_max (Å⁻¹)	0.687	0.636

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.03	0.029, 0.058, 0.97
No. of reflections	3344	2733
No. of parameters	147	147
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.34	0.41, −0.51
Computer programs: X-AREA (Stoe & Cie, 2010 ), SIR92 (Altomare et al., 1994 ), SHELXS2016/6 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ), XP (Bruker, 1998 ), DIAMOND (Brandenburg, 2001 ), Mercury (Macrae et al., 2006 ) and CIFTAB (Sheldrick, 2015).

Supporting information

CCDC references: 1843766; 1843765

Crystal structure: contains datablocks CSV72a12, it14ii. DOI: https://doi.org/10.1107/S2056989018007454/wm5446sup1.cif

Structure factors: contains datablock CSV72a12. DOI: https://doi.org/10.1107/S2056989018007454/wm5446CSV72a12sup2.hkl

Structure factors: contains datablock it14ii. DOI: https://doi.org/10.1107/S2056989018007454/wm5446it14iisup3.hkl

checkCIF report

Computing details top

For both structures, data collection: X-AREA (Stoe & Cie, 2010); cell refinement: X-AREA (Stoe & Cie, 2010); data reduction: X-AREA (Stoe & Cie, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994), SHELXS2016/6 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: XP (Bruker, 1998), DIAMOND (Brandenburg, 2001), Mercury (Macrae et al., 2006); software used to prepare material for publication: CIFTAB (Sheldrick, 2015).

4,4'-(Disulfane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one) (CSV72a12) top

Crystal data top

C₈H₆O₂S₄Se₂	F(000) = 808
M_r = 420.29	D_x = 2.176 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.960 (2) Å	Cell parameters from 11124 reflections
b = 9.1348 (18) Å	θ = 3.2–53.8°
c = 13.495 (3) Å	µ = 6.40 mm⁻¹
β = 108.29 (3)°	T = 170 K
V = 1282.8 (5) Å³	Block, yellow
Z = 4	0.48 × 0.43 × 0.41 mm

Data collection top

Stoe IPDS2T diffractometer	2733 independent reflections
Radiation source: fine-focus sealed tube	2009 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.063
ω scans	θ_max = 26.9°, θ_min = 2.0°
Absorption correction: numerical face indexed	h = −13→13
T_min = 0.393, T_max = 0.786	k = −11→11
10805 measured reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0249P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
2733 reflections	Δρ_max = 0.41 e Å⁻³
147 parameters	Δρ_min = −0.51 e Å⁻³

Special details top

Experimental. (X-RED32 and X-SHAPE; Stoe, 2010)

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
C1	0.5603 (4)	0.9723 (4)	0.2588 (3)	0.0330 (8)
C2	0.6767 (3)	0.9491 (4)	0.4583 (3)	0.0283 (7)
C3	0.5772 (3)	0.8578 (4)	0.4418 (3)	0.0292 (7)
C4	0.5451 (4)	0.7610 (4)	0.5199 (3)	0.0407 (9)
H4A	0.610175	0.773264	0.588334	0.061*
H4B	0.543631	0.658702	0.497773	0.061*
H4C	0.460552	0.787918	0.524643	0.061*
C5	0.8143 (4)	0.6153 (5)	0.3661 (3)	0.0430 (10)
H5A	0.857954	0.708541	0.364796	0.064*
H5B	0.722081	0.626480	0.330068	0.064*
H5C	0.849415	0.539960	0.331030	0.064*
C6	0.8349 (3)	0.5707 (4)	0.4771 (3)	0.0300 (7)
C7	0.8914 (3)	0.6483 (4)	0.5642 (3)	0.0288 (7)
C8	0.8162 (4)	0.4074 (4)	0.6323 (3)	0.0333 (8)
O1	0.5276 (3)	1.0021 (3)	0.16730 (19)	0.0441 (7)
O2	0.7920 (3)	0.3109 (3)	0.6837 (2)	0.0445 (7)
S1	0.47447 (9)	0.85051 (10)	0.31380 (8)	0.0387 (2)
S2	0.69642 (9)	1.04502 (9)	0.35303 (6)	0.02911 (19)
S5	0.89572 (10)	0.57233 (10)	0.68357 (7)	0.0345 (2)
S6	0.77748 (10)	0.39942 (10)	0.49537 (7)	0.0368 (2)
Se1	0.80328 (4)	0.98085 (4)	0.58945 (3)	0.03435 (11)
Se2	0.96657 (4)	0.83504 (4)	0.56427 (3)	0.03646 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (2)	0.0238 (17)	0.0322 (19)	0.0044 (15)	0.0063 (16)	−0.0015 (14)
C2	0.0338 (19)	0.0256 (16)	0.0271 (17)	0.0018 (14)	0.0116 (15)	−0.0010 (13)
C3	0.0321 (19)	0.0247 (17)	0.0331 (18)	0.0017 (14)	0.0135 (16)	−0.0005 (13)
C4	0.045 (2)	0.036 (2)	0.048 (2)	−0.0067 (17)	0.026 (2)	0.0043 (17)
C5	0.050 (3)	0.049 (2)	0.032 (2)	0.0010 (19)	0.0172 (19)	−0.0009 (16)
C6	0.0266 (18)	0.0348 (18)	0.0300 (18)	0.0022 (15)	0.0108 (15)	−0.0002 (14)
C7	0.0258 (18)	0.0295 (17)	0.0308 (18)	0.0004 (14)	0.0085 (15)	0.0014 (14)
C8	0.037 (2)	0.0308 (18)	0.0375 (19)	0.0024 (16)	0.0188 (17)	−0.0044 (16)
O1	0.0597 (18)	0.0337 (14)	0.0289 (13)	−0.0022 (13)	−0.0007 (13)	−0.0016 (11)
O2	0.0629 (19)	0.0320 (14)	0.0475 (15)	−0.0064 (13)	0.0303 (15)	−0.0005 (12)
S1	0.0328 (5)	0.0319 (5)	0.0450 (5)	−0.0072 (4)	0.0030 (4)	0.0015 (4)
S2	0.0334 (5)	0.0295 (4)	0.0240 (4)	−0.0052 (4)	0.0082 (4)	−0.0003 (3)
S5	0.0448 (6)	0.0306 (4)	0.0256 (4)	−0.0044 (4)	0.0075 (4)	−0.0008 (3)
S6	0.0432 (6)	0.0337 (5)	0.0331 (5)	−0.0064 (4)	0.0116 (4)	−0.0095 (4)
Se1	0.0484 (2)	0.02951 (19)	0.02304 (17)	−0.00266 (16)	0.00823 (15)	−0.00313 (14)
Se2	0.0296 (2)	0.0350 (2)	0.0410 (2)	−0.00724 (16)	0.00564 (16)	0.00402 (16)

Geometric parameters (Å, º) top

C1—O1	1.203 (4)	C5—H5A	0.9800
C1—S2	1.759 (4)	C5—H5B	0.9800
C1—S1	1.765 (4)	C5—H5C	0.9800
C2—C3	1.335 (5)	C6—C7	1.346 (5)
C2—S2	1.739 (3)	C6—S6	1.733 (4)
C2—Se1	1.898 (4)	C7—S5	1.741 (3)
C3—C4	1.499 (5)	C7—Se2	1.895 (3)
C3—S1	1.742 (4)	C8—O2	1.202 (4)
C4—H4A	0.9800	C8—S6	1.763 (4)
C4—H4B	0.9800	C8—S5	1.769 (4)
C4—H4C	0.9800	Se1—Se2	2.3397 (7)
C5—C6	1.498 (5)

O1—C1—S2	124.6 (3)	C6—C5—H5C	109.5
O1—C1—S1	123.2 (3)	H5A—C5—H5C	109.5
S2—C1—S1	112.15 (19)	H5B—C5—H5C	109.5
C3—C2—S2	118.9 (3)	C7—C6—C5	127.9 (3)
C3—C2—Se1	124.8 (3)	C7—C6—S6	116.0 (3)
S2—C2—Se1	116.29 (19)	C5—C6—S6	116.1 (3)
C2—C3—C4	127.6 (3)	C6—C7—S5	118.1 (3)
C2—C3—S1	115.4 (3)	C6—C7—Se2	123.7 (3)
C4—C3—S1	117.0 (3)	S5—C7—Se2	118.23 (18)
C3—C4—H4A	109.5	O2—C8—S6	123.4 (3)
C3—C4—H4B	109.5	O2—C8—S5	124.7 (3)
H4A—C4—H4B	109.5	S6—C8—S5	111.8 (2)
C3—C4—H4C	109.5	C3—S1—C1	97.42 (17)
H4A—C4—H4C	109.5	C2—S2—C1	96.07 (17)
H4B—C4—H4C	109.5	C7—S5—C8	96.36 (17)
C6—C5—H5A	109.5	C6—S6—C8	97.68 (17)
C6—C5—H5B	109.5	C7—Se2—Se1	99.23 (10)
H5A—C5—H5B	109.5	C2—Se1—Se2	98.40 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Se1	0.98	2.84	3.354 (4)	114
C5—H5A···Se2	0.98	2.83	3.341 (4)	114
C4—H4B···O1ⁱ	0.98	2.55	3.369 (5)	141
C5—H5C···Se1ⁱⁱ	0.98	3.14	3.801 (4)	126
C5—H5C···S5ⁱⁱⁱ	0.98	3.04	3.850 (4)	141
C4—H4C···S2^iv	0.98	3.13	3.992 (4)	148

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

4,4'-(Diselanane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one) (it14ii) top

Crystal data top

C₈H₆O₂S₆	F(000) = 664
M_r = 326.49	D_x = 1.749 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13753 reflections
a = 10.845 (2) Å	θ = 6.4–58.5°
b = 9.0387 (18) Å	µ = 1.08 mm⁻¹
c = 13.370 (3) Å	T = 170 K
β = 108.95 (3)°	Plate, yellow
V = 1239.6 (4) Å³	0.50 × 0.20 × 0.001 mm
Z = 4

Data collection top

STOE IPDS2T diffractometer	3344 independent reflections
Radiation source: fine-focus sealed tube	2636 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.034
ω scans	θ_max = 29.2°, θ_min = 3.2°
Absorption correction: numerical face indexed	h = −14→11
T_min = 0.771, T_max = 0.942	k = −12→12
13324 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.031P)² + 0.2272P] where P = (F_o² + 2F_c²)/3
3344 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Special details top

Experimental. (X-RED32 and X-SHAPE; Stoe, 2010)

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.56140 (18)	0.97691 (18)	0.25987 (13)	0.0303 (3)
C2	0.68624 (16)	0.94540 (18)	0.46161 (11)	0.0264 (3)
C3	0.58060 (16)	0.85986 (19)	0.44516 (12)	0.0283 (3)
C4	0.54816 (19)	0.7632 (2)	0.52398 (15)	0.0377 (4)
H4A	0.616846	0.771796	0.592700	0.057*
H4B	0.541661	0.660179	0.500052	0.057*
H4C	0.464737	0.794436	0.530838	0.057*
C5	0.8123 (2)	0.6221 (2)	0.36279 (14)	0.0432 (4)
H5A	0.856072	0.716664	0.361746	0.065*
H5B	0.718458	0.633249	0.326446	0.065*
H5C	0.847281	0.546622	0.326768	0.065*
C6	0.83515 (16)	0.5762 (2)	0.47454 (13)	0.0310 (3)
C7	0.89133 (16)	0.6551 (2)	0.56261 (13)	0.0298 (3)
C8	0.82334 (18)	0.4069 (2)	0.63253 (14)	0.0345 (4)
O1	0.52663 (15)	1.00821 (15)	0.16765 (9)	0.0419 (3)
O2	0.80246 (16)	0.30792 (16)	0.68404 (11)	0.0476 (3)
S1	0.47149 (4)	0.85968 (5)	0.31651 (4)	0.03579 (11)
S2	0.70545 (4)	1.04272 (5)	0.35471 (3)	0.02809 (9)
S3	0.80927 (5)	0.96538 (5)	0.58353 (3)	0.03365 (10)
S4	0.95479 (4)	0.83296 (5)	0.56233 (4)	0.03649 (11)
S5	0.89988 (5)	0.57621 (5)	0.68428 (3)	0.03564 (11)
S6	0.78190 (5)	0.40033 (5)	0.49318 (3)	0.03672 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0363 (9)	0.0215 (8)	0.0301 (7)	0.0009 (6)	0.0065 (6)	−0.0033 (6)
C2	0.0309 (8)	0.0246 (8)	0.0253 (7)	0.0014 (6)	0.0113 (6)	−0.0017 (6)
C3	0.0306 (8)	0.0246 (8)	0.0321 (7)	0.0016 (6)	0.0136 (6)	−0.0012 (6)
C4	0.0428 (10)	0.0325 (9)	0.0453 (9)	−0.0018 (8)	0.0247 (8)	0.0031 (7)
C5	0.0495 (11)	0.0536 (12)	0.0298 (8)	0.0029 (9)	0.0174 (8)	−0.0026 (8)
C6	0.0253 (8)	0.0377 (9)	0.0321 (7)	0.0022 (7)	0.0125 (6)	−0.0032 (7)
C7	0.0232 (7)	0.0338 (9)	0.0313 (7)	0.0011 (6)	0.0075 (6)	−0.0001 (6)
C8	0.0353 (9)	0.0333 (9)	0.0383 (8)	0.0016 (7)	0.0164 (7)	−0.0036 (7)
O1	0.0567 (9)	0.0324 (7)	0.0277 (6)	−0.0020 (6)	0.0014 (6)	−0.0005 (5)
O2	0.0646 (10)	0.0338 (7)	0.0514 (8)	−0.0031 (7)	0.0285 (7)	0.0010 (6)
S1	0.0296 (2)	0.0294 (2)	0.0422 (2)	−0.00548 (17)	0.00317 (17)	0.00138 (17)
S2	0.0311 (2)	0.0284 (2)	0.02544 (17)	−0.00528 (16)	0.01009 (15)	−0.00122 (14)
S3	0.0417 (2)	0.0317 (2)	0.02435 (17)	−0.00303 (18)	0.00641 (16)	−0.00476 (15)
S4	0.0255 (2)	0.0372 (2)	0.0426 (2)	−0.00639 (17)	0.00532 (17)	0.00179 (18)
S5	0.0422 (2)	0.0332 (2)	0.02811 (18)	−0.00173 (18)	0.00668 (16)	−0.00185 (16)
S6	0.0386 (2)	0.0352 (2)	0.0367 (2)	−0.00491 (18)	0.01269 (18)	−0.01011 (17)

Geometric parameters (Å, º) top

C1—O1	1.200 (2)	C5—H5A	0.9800
C1—S2	1.7652 (19)	C5—H5B	0.9800
C1—S1	1.7682 (19)	C5—H5C	0.9800
C2—C3	1.340 (2)	C6—C7	1.342 (2)
C2—S2	1.7473 (16)	C6—S6	1.7363 (19)
C2—S3	1.7486 (17)	C7—S4	1.7494 (18)
C3—C4	1.496 (2)	C7—S5	1.7507 (17)
C3—S1	1.7426 (18)	C8—O2	1.195 (2)
C4—H4A	0.9800	C8—S6	1.7700 (18)
C4—H4B	0.9800	C8—S5	1.7710 (19)
C4—H4C	0.9800	S3—S4	2.0723 (7)
C5—C6	1.492 (2)

O1—C1—S2	124.61 (15)	C6—C5—H5C	109.5
O1—C1—S1	123.25 (15)	H5A—C5—H5C	109.5
S2—C1—S1	112.13 (9)	H5B—C5—H5C	109.5
C3—C2—S2	118.62 (12)	C7—C6—C5	127.68 (18)
C3—C2—S3	124.44 (12)	C7—C6—S6	115.98 (13)
S2—C2—S3	116.93 (10)	C5—C6—S6	116.34 (14)
C2—C3—C4	127.26 (16)	C6—C7—S4	123.61 (14)
C2—C3—S1	115.65 (12)	C6—C7—S5	118.09 (14)
C4—C3—S1	117.07 (13)	S4—C7—S5	118.30 (10)
C3—C4—H4A	109.5	O2—C8—S6	123.42 (15)
C3—C4—H4B	109.5	O2—C8—S5	125.06 (15)
H4A—C4—H4B	109.5	S6—C8—S5	111.52 (10)
C3—C4—H4C	109.5	C3—S1—C1	97.47 (8)
H4A—C4—H4C	109.5	C2—S2—C1	96.03 (8)
H4B—C4—H4C	109.5	C2—S3—S4	101.38 (6)
C6—C5—H5A	109.5	C7—S4—S3	102.29 (6)
C6—C5—H5B	109.5	C7—S5—C8	96.44 (8)
H5A—C5—H5B	109.5	C6—S6—C8	97.92 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···S3	0.98	2.76	3.244 (2)	111
C5—H5A···S4	0.98	2.75	3.234 (2)	111
C4—H4B···O1ⁱ	0.98	2.53	3.345 (2)	141
C5—H5C···S3ⁱⁱ	0.98	3.14	3.8063 (19)	126
C5—H5C···S5ⁱⁱⁱ	0.98	3.01	3.825 (2)	142
C4—H4C···S2^iv	0.98	3.12	4.021 (2)	153

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

Funding information

Generous financial support from the European Research Council (project MocoModels) is gratefully acknowledged.

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Volume 74| Part 6| June 2018| Pages 840-845

https://doi.org/10.1107/S2056989018007454

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of 4,4′-(disulfane-1,2-diyl)bis­(5-methyl-2H-1,3-di­thiol-2-one) and 4,4′-(diselanane-1,2-diyl)bis­(5-methyl-2H-1,3-di­thiol-2-one)

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Crystal structures of 4,4′-(disulfane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one) and 4,4′-(diselanane-1,2-diyl)bis(5-methyl-2H-1,3-dithiol-2-one)

3. Supramolecular features