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The tetra­thia­ne ring of the title compound, C26H16S4, has a chair conformation and the mol­ecule has approximate C2 symmetry. Each of the two fluorene ring systems is virtually planar, with the ring planes intersecting at an angle of 67.58 (5)°. This novel compound has been formed as a side product from the treatment of 9H-fluorene-9-thione with methyl N-[(benzyl­idene)­phenyl]­glycinate in the presence of LiBr and 1,6-di­aza­bi­cyclo­[5.4.0]­un­decane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005248/na1515sup1.cif
Contains datablocks HG9822, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005248/na1515IVsup2.hkl
Contains datablock IV

CCDC reference: 167001

Comment top

For many years we have been investigating reactions involving compounds containing CS groups, for example, thioketones and 1,3-thiazole-5(4H)-thiones (Heimgartner, 1986, 1991; Mloston & Heimgartner, 2000). The focus of our studies is on 1,3-dipolar cycloadditions which lead to new sulfur heterocycles. Among the 1,3-dipoles that have been used are nitrile ylides (Büchel et al., 1984), nitrile imines (Linden et al., 1999), azides (Mloston & Heimgartner, 1995; Mloston et al., 1996), diazo compounds (Kägi et al., 1996; Kelmendi et al., 2000), carbonyl ylides (Meier et al., 1997) and thiocarbonyl ylides (Mloston & Heimgartner, 2000). In some cases, such as with azides and diazo compounds under forced conditions, elemental sulfur was formed (`twofold extrusion'; Guziec & Sanfilippo, 1988), which led to the formation of products containing more than one S atom per molecule. As an example, reactions of reactive thiocarbonyl compounds, such as thiobenzophenone or 9H-fluorene-9-thione, with phenyl azide yielded the corresponding N-phenylimines and 1,2,4-trithiolanes (Mloston & Heimgartner, 1995; cf. Fabian & Senning, 1998). The intermediate formation of a thiosulfine (thiocarbonyl-S-sulfide) via sulfur transfer and a subsequent 1,3-dipolar cycloaddition is proposed as the reaction mechanism. Thiosulfines, which can also be generated by thiation of thiocarbonyl compounds with S8, can dimerize to give 1,2,4,5-tetrathianes (Franek, 1991a,b; Huisgen & Rapp, 1997; Huisgen et al., 1997; cf. Senning, 1994).

Cyclic polysulfides are a highly interesting class of sulfur heterocycles (cf. Block et al., 1988; Sato et al., 2001). Among them, several 1,2,3,4-tetrathianes have been prepared by reacting 1,2-dithiols with dichlorodisulfane (S2Cl2; Fehér & Degen, 1967; Fehér et al., 1972a,b; Kustos & Stendel, 1995). Different approaches have been developed by heating alkenes with polysulfides (Krespan & Brasen, 1962), with sulfur (S8) and catalysts (Chernyshev et al., 1984; Nekhaev et al., 1991) or by treatment of thiiranes with catalytic amounts of tris(4-bromophenyl)aminium hexachloroantimonate, an aminium radical salt, in dichloromethane, the latter reaction occurring via a SET mechanism (Kamata et al., 1990).

Recently, we became interested in the reaction of azomethine ylides with C S compounds (Mloston & Heimgartner, 1998; Gebert, 2001; Gebert et al., 2001). Among the different known routes for synthesizing reactive azomethine ylides, we followed a protocol that starts with N-benzylidene-α-amino acid esters in the presence of LiBr and 1,6-diazabicyclo[5.4.0]undecane (DBU) as the base (Grigg & Sridharan, 1993; Kanemasa & Tsuge, 1993; Barr et al., 1995). In the case of methyl N-[(benzylidene)phenyl]glycinate, (I), and 9H-fluorene-9-thione, (II), the reaction at room temperature was terminated after 2 min. In addition to the two diastereoisomeric cycloadducts of type (III), which were isolated in 82% yield (cis/trans-ratio 2.4:1) (Gebert et al., 2001), small amounts of 9H-fluoren-9-one, dispiro[fluorene-9,5'-[1,2,3,4]tetrathiane-6',9''-fluorene], (IV), and olefin (V) were isolated after chromatography. Whereas 9H-fluoren-9-one and the olefin (V) are well known side products in reactions involving (II), the tetrathiane (IV) has never been observed before. The latter was obtained in 1–3% yield after crystallization and as part of the full characterization of this compound, its low-temperature crystal structure has been determined.

The molecule of compound (IV) has approximate C2 symmetry with an r.m.s. deviation of the related atoms of 0.14 Å. The C2 axis is not parallel to any of the unit cell axes. The 1,2,3,4-tetrathiane ring has a slightly distorted chair conformation with puckering parameters (Cremer & Pople, 1975) of Q = 0.927 (1) Å, θ = 13.4 (1)° and ϕ = 85.3 (4)° for the atom sequence S1, S2, S3, S4, C14 and C1. Ideally, θ = 0° for a perfect chair and the distortions can be attributed to the heteroatomic nature of the ring. Each of the two fluorene ring-systems is nearly planar, although the phenyl rings are inclined very slightly from the plane to form a flat dish-shaped moiety. In the fluorene group defined by atoms C1 to C13, the r.m.s. deviation of these atoms from their mean plane is 0.034 Å, with a maximum deviation of 0.060 (2) Å for C3. The angle between the two phenyl ring planes is 3.91 (18)°. In the second fluorene moiety, the r.m.s. deviation of atoms C14–C26 from their mean plane is 0.060 Å, with a maximum deviation of 0.104 (2) Å for C17, and the angle between the two phenyl ring planes is 6.49 (15)°. The mean planes of the two fluorene ring systems intersect at an angle of 67.58 (5)°.

Atoms C3 and H3 have short intramolecular contacts with S2 and S4, while atoms C25 and H25 have similar contacts with S1 and S3 (Table 2). These contacts are only 0.06–0.15 Å shorter than the sum of the van der Waals radii of the respective atoms and it may be inappropriate to describe them as weak hydrogen-bonding interactions because the C—H···S angles are less than 120°. Distortions in the conformation of the molecule suggest that the contacts are probably causing repulsive interactions and that the lack of sufficient conformational flexibility in the molecule prevents these atoms from being able to increase their interatomic separation any further. The C3—H3 bond nestles neatly between S2 and S4 of the 1,2,3,4-tetrathiane ring and is virtually equidistant from these S atoms. In this position and in the absence of steric strain, C3 and H3 would come too close to S2 and S4. The repulsive interactions cause the fluorene ring to be tipped back slightly on its C2—C1—C13 pivot, so that the plane defined by S1, C1 and C14 does not intersect the C7—C8 bond at its midpoint, but at a point much closer to C7. The distances of C7 and C8 from this plane are 0.451 (10) and 1.003 (10) Å, respectively. The interactions of C25 and H24 with S1 and S3 cause the second fluorene moiety to be tipped in a similar manner, with C21 and C20 being 0.435 (10) and 1.019 (10) Å, respectively, from the plane defined by C1, C14 and S4.

The Cambridge Structural Database (CSD, October 2000 release; Allen & Kennard, 1993) cites three structures containing 1,2,3,4-tetrathiane rings, these being simply substituted derivatives, namely 1,1-dimethylsila-4,5,6,7-tetrathiabicyclo[4.3.0]nonane (Chernyshev et al., 1984), trans-5,6-diphenyl-1,2,3,4-tetrathiane (Kamata et al., 1990) and 1,2,3,4-tetrathiadecalin (Fehér et al., 1972). In each case, the tetrathiane ring adopts a slightly distorted chair conformation and the bond lengths and angles around the ring are in close agreement with those observed for compound (IV) (Table 1). For all four compounds, the intra-ring angles involving S atoms are several degrees smaller than the ideal tetrahedral angle, with the S—S—S angles being the smallest, while those involving C atoms are slightly larger than the ideal tetrahedral angle. Such distortions are consistent with the ring strain introduced by the presence of two elements with significantly different covalent radii in the ring.

Experimental top

The title compound, (IV), was obtained in 1–3% yield by reacting methyl N-[(benzylidene)phenyl]glycinate, (I) (253 mg, 1.0 mmol), with 9H-fluorene-9-thione, (II) (394 mg, 2.0 mmol), in a mixture of acetonitrile (5 ml) and toluene (1 ml) for 2 min at room temperature. After chromatography (silica gel, hexane/ethyl acetate 30:1) and crystallization from chloroform/hexane, (IV) was isolated as colourless prisms (m.p. 445–449 K). Suitable single crystals of (IV) were obtained by recrystallization from chloroform/hexane.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the molecule of the title compound, (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
Dispiro[fluorene-9,5'-[1,2,3,4]tetrathiane-6',9''-fluorene] top
Crystal data top
C26H16S4Dx = 1.484 Mg m3
Mr = 456.65Melting point = 445–449 K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2n 2abCell parameters from 22 reflections
a = 13.510 (3) Åθ = 15.0–20.0°
b = 18.014 (7) ŵ = 0.48 mm1
c = 16.795 (5) ÅT = 173 K
V = 4087 (2) Å3Prism, colourless
Z = 80.45 × 0.25 × 0.25 mm
F(000) = 1888
Data collection top
Rigaku AFC-5R
diffractometer
3074 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generatorRint = 0.038
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
ω–2θ scansh = 117
Absorption correction: ψ scan
(North et al., 1968)
k = 123
Tmin = 0.833, Tmax = 0.888l = 210
5956 measured reflections3 standard reflections every 150 reflections
4685 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0489P)2 + 1.1375P]
where P = (Fo2 + 2Fc2)/3
4685 reflections(Δ/σ)max = 0.001
271 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C26H16S4V = 4087 (2) Å3
Mr = 456.65Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 13.510 (3) ŵ = 0.48 mm1
b = 18.014 (7) ÅT = 173 K
c = 16.795 (5) Å0.45 × 0.25 × 0.25 mm
Data collection top
Rigaku AFC-5R
diffractometer
3074 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.038
Tmin = 0.833, Tmax = 0.8883 standard reflections every 150 reflections
5956 measured reflections intensity decay: none
4685 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.02Δρmax = 0.34 e Å3
4685 reflectionsΔρmin = 0.38 e Å3
271 parameters
Special details top

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

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.4988 (0.0059) x + 9.2742 (0.0111) y + 9.7812 (0.0063) z = 5.8866 (0.0030)

* -0.0219 (0.0021) C1 * 0.0061 (0.0023) C2 * 0.0601 (0.0022) C3 * 0.0370 (0.0023) C4 * -0.0203 (0.0023) C5 * -0.0349 (0.0024) C6 * -0.0200 (0.0024) C7 * -0.0339 (0.0024) C8 * 0.0160 (0.0023) C9 * 0.0464 (0.0023) C10 * 0.0296 (0.0023) C11 * -0.0060 (0.0023) C12 * -0.0582 (0.0023) C13

Rms deviation of fitted atoms = 0.0344

- 5.6660 (0.0085) x + 14.8642 (0.0081) y + 6.3564 (0.0059) z = 0.4147 (0.0024)

Angle to previous plane (with approximate e.s.d.) = 67.58 (0.05)

* 0.0783 (0.0022) C14 * 0.0392 (0.0023) C15 * -0.0763 (0.0023) C16 * -0.1040 (0.0023) C17 * -0.0140 (0.0022) C18 * 0.0642 (0.0023) C19 * 0.0703 (0.0024) C20 * 0.0530 (0.0025) C21 * 0.0105 (0.0024) C22 * -0.0537 (0.0024) C23 * -0.0782 (0.0024) C24 * -0.0233 (0.0024) C25 * 0.0340 (0.0024) C26

Rms deviation of fitted atoms = 0.0603

8.1749 (0.0119) x + 9.6751 (0.0169) y + 9.8700 (0.0148) z = 5.8925 (0.0061)

* -0.0137 (0.0018) C2 * 0.0097 (0.0019) C3 * 0.0023 (0.0019) C4 * -0.0102 (0.0020) C5 * 0.0061 (0.0019) C6 * 0.0058 (0.0018) C7

Rms deviation of fitted atoms = 0.0088

8.8764 (0.0118) x + 8.9952 (0.0177) y + 9.4848 (0.0156) z = 5.8304 (0.0040)

Angle to previous plane (with approximate e.s.d.) = 3.91 (0.18)

* 0.0020 (0.0018) C8 * 0.0028 (0.0019) C9 * -0.0015 (0.0020) C10 * -0.0045 (0.0019) C11 * 0.0092 (0.0019) C12 * -0.0079 (0.0018) C13

Rms deviation of fitted atoms = 0.0055

- 5.4370 (0.0133) x + 15.4410 (0.0114) y + 5.3981 (0.0172) z = 0.5830 (0.0037)

* 0.0192 (0.0018) C15 * -0.0056 (0.0019) C16 * -0.0106 (0.0019) C17 * 0.0132 (0.0019) C18 * 0.0006 (0.0019) C19 * -0.0167 (0.0018) C20

Rms deviation of fitted atoms = 0.0127

- 5.5872 (0.0142) x + 14.5325 (0.0136) y + 7.0886 (0.0179) z = 0.5313 (0.0049)

Angle to previous plane (with approximate e.s.d.) = 6.49 (0.15)

* -0.0013 (0.0019) C21 * 0.0017 (0.0020) C22 * 0.0013 (0.0021) C23 * -0.0047 (0.0020) C24 * 0.0050 (0.0020) C25 * -0.0021 (0.0019) C26

Rms deviation of fitted atoms = 0.0031

9.9549 (0.0159) x + 0.7246 (0.0522) y - 11.3335 (0.0191) z = 2.8148 (0.0065)

* 0.0000 (0.0000) S1 * 0.0000 (0.0000) C1 * 0.0000 (0.0000) C14 0.4508 (0.0101) C7 - 1.0034 (0.0096) C8

Rms deviation of fitted atoms = 0.0000

3.9929 (0.0357) x - 5.6821 (0.0353) y + 15.1445 (0.0088) z = 1.3894 (0.0185)

* 0.0000 (0.0000) C1 * 0.0000 (0.0000) C14 * 0.0000 (0.0000) S4 - 1.0193 (0.0096) C20 0.4353 (0.0102) C21

Rms deviation of fitted atoms = 0.0000

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 > σ(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
xyzUiso*/Ueq
S10.45038 (5)0.22763 (4)0.16179 (4)0.02654 (16)
S20.58051 (5)0.19057 (4)0.11268 (5)0.03191 (18)
S30.54643 (6)0.08019 (4)0.09676 (5)0.03523 (19)
S40.44196 (5)0.08806 (4)0.00826 (4)0.02887 (17)
C10.35781 (19)0.22011 (14)0.07999 (15)0.0216 (5)
C20.38287 (19)0.27263 (13)0.01127 (15)0.0219 (5)
C30.4582 (2)0.26935 (15)0.04558 (16)0.0261 (6)
H30.50570.23050.04470.031*
C40.4620 (2)0.32473 (15)0.10374 (16)0.0281 (6)
H40.51230.32280.14320.034*
C50.3944 (2)0.38211 (16)0.10520 (17)0.0312 (7)
H50.39800.41860.14600.037*
C60.3209 (2)0.38693 (16)0.04746 (17)0.0297 (6)
H60.27510.42700.04770.036*
C70.31573 (19)0.33224 (14)0.01043 (15)0.0234 (6)
C80.24615 (19)0.32419 (14)0.07710 (16)0.0234 (6)
C90.1712 (2)0.37109 (16)0.10286 (17)0.0294 (6)
H90.15660.41550.07480.035*
C100.1180 (2)0.35174 (17)0.17053 (19)0.0346 (7)
H100.06640.38330.18880.042*
C110.1392 (2)0.28701 (17)0.21175 (17)0.0304 (6)
H110.10160.27450.25760.037*
C120.2152 (2)0.23992 (16)0.18673 (16)0.0274 (6)
H120.23060.19620.21590.033*
C130.26800 (19)0.25820 (14)0.11819 (15)0.0228 (6)
C140.33529 (19)0.13749 (14)0.05493 (15)0.0227 (6)
C150.2580 (2)0.13413 (14)0.01225 (15)0.0223 (5)
C160.2620 (2)0.16104 (15)0.08977 (16)0.0261 (6)
H160.31890.18670.10840.031*
C170.1810 (2)0.14963 (15)0.13972 (16)0.0279 (6)
H170.18300.16760.19290.033*
C180.0974 (2)0.11237 (15)0.11294 (16)0.0261 (6)
H180.04200.10650.14730.031*
C190.0943 (2)0.08366 (15)0.03624 (17)0.0262 (6)
H190.03750.05750.01810.031*
C200.17496 (19)0.09358 (14)0.01342 (15)0.0220 (5)
C210.1943 (2)0.06540 (14)0.09381 (16)0.0247 (6)
C220.1356 (2)0.01978 (15)0.14153 (17)0.0303 (6)
H220.07210.00400.12400.036*
C230.1720 (2)0.00205 (16)0.21490 (19)0.0349 (7)
H230.13290.03300.24820.042*
C240.2651 (2)0.02085 (16)0.24053 (17)0.0331 (7)
H240.28920.00480.29080.040*
C250.3236 (2)0.06696 (16)0.19341 (16)0.0299 (6)
H250.38660.08320.21150.036*
C260.2878 (2)0.08888 (14)0.11929 (16)0.0249 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0229 (3)0.0318 (4)0.0249 (3)0.0022 (3)0.0027 (3)0.0034 (3)
S20.0232 (4)0.0359 (4)0.0366 (4)0.0015 (3)0.0022 (3)0.0053 (3)
S30.0297 (4)0.0322 (4)0.0438 (5)0.0048 (3)0.0071 (3)0.0019 (3)
S40.0257 (3)0.0277 (3)0.0332 (4)0.0012 (3)0.0002 (3)0.0063 (3)
C10.0206 (13)0.0235 (13)0.0208 (12)0.0026 (11)0.0014 (11)0.0012 (11)
C20.0222 (13)0.0221 (13)0.0215 (13)0.0040 (10)0.0002 (11)0.0035 (11)
C30.0250 (14)0.0260 (14)0.0272 (14)0.0041 (12)0.0031 (11)0.0039 (12)
C40.0266 (14)0.0329 (15)0.0248 (14)0.0080 (12)0.0039 (12)0.0043 (12)
C50.0301 (15)0.0335 (15)0.0299 (15)0.0083 (12)0.0030 (12)0.0096 (13)
C60.0251 (14)0.0295 (14)0.0346 (16)0.0015 (12)0.0033 (12)0.0035 (12)
C70.0204 (13)0.0246 (13)0.0251 (14)0.0055 (11)0.0002 (11)0.0019 (11)
C80.0189 (12)0.0272 (14)0.0239 (13)0.0035 (11)0.0011 (11)0.0060 (11)
C90.0276 (14)0.0281 (14)0.0324 (16)0.0003 (12)0.0030 (12)0.0033 (12)
C100.0238 (14)0.0406 (17)0.0394 (17)0.0001 (13)0.0027 (13)0.0128 (14)
C110.0242 (14)0.0420 (16)0.0251 (14)0.0070 (12)0.0030 (12)0.0081 (13)
C120.0265 (14)0.0317 (15)0.0242 (14)0.0051 (12)0.0000 (11)0.0029 (12)
C130.0207 (13)0.0264 (13)0.0214 (13)0.0045 (11)0.0020 (11)0.0051 (11)
C140.0221 (13)0.0241 (13)0.0218 (13)0.0015 (11)0.0007 (11)0.0011 (11)
C150.0245 (13)0.0210 (12)0.0214 (13)0.0011 (11)0.0016 (11)0.0041 (10)
C160.0268 (14)0.0269 (14)0.0247 (13)0.0058 (12)0.0037 (12)0.0027 (11)
C170.0351 (15)0.0266 (14)0.0220 (14)0.0050 (12)0.0029 (12)0.0003 (11)
C180.0279 (14)0.0259 (13)0.0245 (13)0.0008 (11)0.0059 (12)0.0052 (12)
C190.0245 (13)0.0266 (14)0.0276 (14)0.0014 (11)0.0024 (11)0.0040 (12)
C200.0251 (13)0.0194 (12)0.0216 (13)0.0009 (11)0.0023 (11)0.0016 (10)
C210.0272 (14)0.0228 (13)0.0242 (14)0.0008 (11)0.0011 (12)0.0013 (11)
C220.0286 (15)0.0274 (14)0.0349 (16)0.0051 (12)0.0025 (13)0.0005 (12)
C230.0403 (17)0.0291 (15)0.0352 (16)0.0028 (13)0.0075 (14)0.0086 (13)
C240.0429 (17)0.0325 (15)0.0239 (14)0.0025 (14)0.0010 (13)0.0052 (12)
C250.0319 (15)0.0305 (15)0.0274 (15)0.0024 (12)0.0033 (13)0.0015 (12)
C260.0282 (14)0.0219 (13)0.0246 (14)0.0012 (11)0.0013 (11)0.0008 (11)
Geometric parameters (Å, º) top
S1—C11.863 (3)C11—H110.95
S1—S22.0534 (11)C12—C131.394 (4)
S2—S32.0585 (13)C12—H120.95
S3—S42.0546 (11)C14—C151.538 (4)
S4—C141.867 (3)C14—C261.532 (4)
C1—C21.530 (3)C15—C161.390 (4)
C1—C131.534 (4)C15—C201.407 (4)
C1—C141.576 (3)C16—C171.395 (4)
C2—C31.397 (4)C16—H160.95
C2—C71.406 (4)C17—C181.389 (4)
C3—C41.397 (4)C17—H170.95
C3—H30.95C18—C191.389 (4)
C4—C51.380 (4)C18—H180.95
C4—H40.95C19—C201.384 (4)
C5—C61.390 (4)C19—H190.95
C5—H50.95C20—C211.466 (4)
C6—C71.386 (4)C21—C221.395 (4)
C6—H60.95C21—C261.400 (4)
C7—C81.469 (4)C22—C231.384 (4)
C8—C91.388 (4)C22—H220.95
C8—C131.406 (4)C23—C241.393 (4)
C9—C101.389 (4)C23—H230.95
C9—H90.95C24—C251.393 (4)
C10—C111.386 (4)C24—H240.95
C10—H100.95C25—C261.392 (4)
C11—C121.396 (4)C25—H250.95
C1—S1—S2104.77 (9)C12—C13—C1130.1 (2)
S1—S2—S3100.06 (4)C8—C13—C1109.8 (2)
S2—S3—S4100.43 (4)C26—C14—C15102.2 (2)
S3—S4—C14105.04 (9)C26—C14—C1115.6 (2)
C2—C1—C13102.3 (2)C15—C14—C1111.3 (2)
C2—C1—C14115.2 (2)C26—C14—S4110.30 (18)
C13—C1—C14112.4 (2)C15—C14—S4101.37 (17)
C2—C1—S1111.26 (17)S4—C14—C1114.43 (18)
C13—C1—S1100.95 (17)C16—C15—C20120.0 (2)
S1—C1—C14113.28 (17)C16—C15—C14130.3 (2)
C3—C2—C7119.7 (2)C20—C15—C14109.7 (2)
C3—C2—C1130.6 (2)C15—C16—C17118.8 (2)
C7—C2—C1109.7 (2)C15—C16—H16120.6
C4—C3—C2118.3 (3)C17—C16—H16120.6
C4—C3—H3120.8C18—C17—C16121.0 (3)
C2—C3—H3120.8C18—C17—H17119.5
C5—C4—C3121.5 (3)C16—C17—H17119.5
C5—C4—H4119.2C17—C18—C19120.3 (3)
C3—C4—H4119.2C17—C18—H18119.8
C4—C5—C6120.5 (3)C19—C18—H18119.8
C4—C5—H5119.8C20—C19—C18119.2 (3)
C6—C5—H5119.8C20—C19—H19120.4
C7—C6—C5118.7 (3)C18—C19—H19120.4
C7—C6—H6120.6C19—C20—C15120.7 (2)
C5—C6—H6120.6C19—C20—C21130.6 (2)
C6—C7—C2121.2 (2)C15—C20—C21108.7 (2)
C6—C7—C8129.6 (3)C22—C21—C26121.0 (3)
C2—C7—C8109.3 (2)C22—C21—C20129.2 (3)
C9—C8—C13121.0 (3)C26—C21—C20109.7 (2)
C9—C8—C7130.1 (3)C23—C22—C21118.5 (3)
C13—C8—C7108.9 (2)C23—C22—H22120.7
C8—C9—C10118.7 (3)C21—C22—H22120.7
C8—C9—H9120.7C22—C23—C24120.8 (3)
C10—C9—H9120.7C22—C23—H23119.6
C11—C10—C9120.8 (3)C24—C23—H23119.6
C11—C10—H10119.6C25—C24—C23120.9 (3)
C9—C10—H10119.6C25—C24—H24119.6
C10—C11—C12120.9 (3)C23—C24—H24119.6
C10—C11—H11119.6C26—C25—C24118.7 (3)
C12—C11—H11119.6C26—C25—H25120.6
C13—C12—C11118.8 (3)C24—C25—H25120.6
C13—C12—H12120.6C25—C26—C21120.1 (3)
C11—C12—H12120.6C25—C26—C14130.4 (3)
C12—C13—C8119.8 (2)C21—C26—C14109.6 (2)
C1—S1—S2—S367.73 (9)C2—C1—C14—C1550.8 (3)
S1—S2—S3—S468.71 (5)C13—C1—C14—C1565.9 (3)
S2—S3—S4—C1465.78 (10)S1—C1—C14—C15179.59 (17)
S2—S1—C1—C264.79 (18)C2—C1—C14—S463.5 (3)
S2—S1—C1—C13172.79 (14)C13—C1—C14—S4179.86 (17)
S2—S1—C1—C1466.81 (18)S1—C1—C14—S466.2 (2)
C13—C1—C2—C3179.1 (3)S3—S4—C14—C2667.12 (19)
C14—C1—C2—C358.6 (4)S3—S4—C14—C15174.80 (14)
S1—C1—C2—C372.0 (3)S3—S4—C14—C165.27 (18)
C13—C1—C2—C70.3 (3)C26—C14—C15—C16173.0 (3)
C14—C1—C2—C7121.9 (2)C1—C14—C15—C1663.0 (3)
S1—C1—C2—C7107.4 (2)S4—C14—C15—C1659.1 (3)
C7—C2—C3—C42.3 (4)C26—C14—C15—C203.9 (3)
C1—C2—C3—C4178.2 (2)C1—C14—C15—C20120.1 (2)
C2—C3—C4—C50.8 (4)S4—C14—C15—C20117.80 (19)
C3—C4—C5—C61.0 (4)C20—C15—C16—C172.6 (4)
C4—C5—C6—C71.4 (4)C14—C15—C16—C17179.2 (3)
C5—C6—C7—C20.2 (4)C15—C16—C17—C180.2 (4)
C5—C6—C7—C8179.8 (3)C16—C17—C18—C192.0 (4)
C3—C2—C7—C62.0 (4)C17—C18—C19—C200.9 (4)
C1—C2—C7—C6178.4 (2)C18—C19—C20—C151.9 (4)
C3—C2—C7—C8178.3 (2)C18—C19—C20—C21175.3 (3)
C1—C2—C7—C81.3 (3)C16—C15—C20—C193.7 (4)
C6—C7—C8—C94.4 (5)C14—C15—C20—C19179.0 (2)
C2—C7—C8—C9175.9 (3)C16—C15—C20—C21174.1 (2)
C6—C7—C8—C13177.9 (3)C14—C15—C20—C213.1 (3)
C2—C7—C8—C131.8 (3)C19—C20—C21—C220.8 (5)
C13—C8—C9—C100.2 (4)C15—C20—C21—C22176.7 (3)
C7—C8—C9—C10177.3 (3)C19—C20—C21—C26178.5 (3)
C8—C9—C10—C110.1 (4)C15—C20—C21—C261.0 (3)
C9—C10—C11—C120.6 (4)C26—C21—C22—C230.1 (4)
C10—C11—C12—C131.6 (4)C20—C21—C22—C23177.4 (3)
C11—C12—C13—C81.9 (4)C21—C22—C23—C240.1 (4)
C11—C12—C13—C1175.9 (3)C22—C23—C24—C250.7 (4)
C9—C8—C13—C121.2 (4)C23—C24—C25—C261.1 (4)
C7—C8—C13—C12176.7 (2)C24—C25—C26—C210.8 (4)
C9—C8—C13—C1176.4 (2)C24—C25—C26—C14178.9 (3)
C7—C8—C13—C11.6 (3)C22—C21—C26—C250.2 (4)
C2—C1—C13—C12175.3 (3)C20—C21—C26—C25178.2 (2)
C14—C1—C13—C1260.6 (3)C22—C21—C26—C14179.5 (2)
S1—C1—C13—C1260.4 (3)C20—C21—C26—C141.6 (3)
C2—C1—C13—C80.8 (3)C15—C14—C26—C25176.5 (3)
C14—C1—C13—C8124.9 (2)C1—C14—C26—C2562.5 (4)
S1—C1—C13—C8114.1 (2)S4—C14—C26—C2569.3 (3)
C2—C1—C14—C26166.7 (2)C15—C14—C26—C213.3 (3)
C13—C1—C14—C2650.1 (3)C1—C14—C26—C21117.8 (2)
S1—C1—C14—C2663.6 (3)S4—C14—C26—C21110.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···S20.952.923.436 (3)115
C3—H3···S40.952.853.396 (3)118
C25—H25···S10.952.873.405 (3)117
C25—H25···S30.952.893.429 (3)117

Experimental details

Crystal data
Chemical formulaC26H16S4
Mr456.65
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)173
a, b, c (Å)13.510 (3), 18.014 (7), 16.795 (5)
V3)4087 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.45 × 0.25 × 0.25
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.833, 0.888
No. of measured, independent and
observed [I > 2σ(I)] reflections
5956, 4685, 3074
Rint0.038
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.116, 1.02
No. of reflections4685
No. of parameters271
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.38

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
S1—C11.863 (3)C1—C21.530 (3)
S1—S22.0534 (11)C1—C131.534 (4)
S2—S32.0585 (13)C1—C141.576 (3)
S3—S42.0546 (11)C14—C151.538 (4)
S4—C141.867 (3)C14—C261.532 (4)
C1—S1—S2104.77 (9)S3—S4—C14105.04 (9)
S1—S2—S3100.06 (4)S1—C1—C14113.28 (17)
S2—S3—S4100.43 (4)S4—C14—C1114.43 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···S20.952.923.436 (3)115
C3—H3···S40.952.853.396 (3)118
C25—H25···S10.952.873.405 (3)117
C25—H25···S30.952.893.429 (3)117
 

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