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The title compound, C12H8S4, has crystallographic \overline{1} symmetry, the benzene groups thus being anti with respect to the plane of the four S atoms. The S—S and C—S bond lengths of the sulfur–carbon eight-membered ring were found to be similar to those in other structures containing such sulfur–carbon rings. There is evidence for π–π inter­actions between the aromatic rings of neighboring mol­ecules, linking them into sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107040358/gd3134sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107040358/gd3134Isup2.hkl
Contains datablock I

CCDC reference: 665502

Comment top

Bis(o-phenylene) tetrasulfide, (I), was synthesized in 1961 as part of a study of organic disulfides and related compounds (Field et al., 1961). Two forms are possible, a rigid anti form with the benzene rings on opposite sides of the plane of the S atoms and a syn form with the rings on the same side. The syn form may also exist in a conformation with the rings mutually perpendicular. Because of these interesting possibilities and attendant questions concerning the nature of the C—S bonding, a single-crystal X-ray study was undertaken.

A crystal was grown from a carbon disulfide solution. Using photographic film and Buerger precession camera techniques, 591 independent reflections were recorded with Mo Kα radiation. On the basis of the method of Howells et al. (1950) and statistics proposed by Hauptman and Karle (Karle & Hauptman, 1953<; Hauptman & Karle, 1953; Karle, 1961), the space group indicated was P1 (Mitchell & Lippert, 1965; in this short communication the compound was incorrectly called bis-o-phenylene disulfide). It is now known that, although these tests are necessary, neither is sufficient. Mitchell and Lippert were unable to solve this triclinic structure in the early 1960 s. Direct methods for solution of the phase problem were in their initial stages and the necessary resources for a structure solution were not readily available. Coordinates for the S atoms were found from a Patterson map, but the structure remained incomplete (Mitchell, 1965). Using the corrected observed Fobs in Mitchell's thesis (Mitchell, 1965), the structure has now been solved in space group P1 using SHELXTL (Sheldrick, 2000). This structure was refined to R1 = 0.1083, but with bond lengths and angles unacceptable by today's standards. Since more accurate measurement and data reduction methods are now available, it was decided that the crystalline structure of (I) should be redetermined as described in the experimental and refinement sections.

The structure is the anti form (Fig. 1) with the parallel benzene rings on opposite sides of the planar sulfur group. The S—S and S—C bond lengths (Table 1) are similar to those found in seven other sulfur–carbon eight-membered rings, where the average S—S and S—C bond lengths are 2.06 and 1.78 Å (Kopf et al., 1979; Lakshmikantham et al., 1987; Chivers et al., 1998; Ogawa et al., 1999; Kimura et al., 2002; Joshi et al., 2003; Sugimoto et al., 2005), respectively. The average bond length from X-ray and neutron diffraction studies of all organic disulfide bonds is 2.048 (26) Å (Allen et al., 1987), and the average length of a disulfide bridge in macromolecular structures is 2.03 Å (Engh & Huber, 1991). For comparison, the S—S distance ranges from 2.035 to 2.060 Å in the various allotropes of sulfur (Gallacher & Pinkerton, 1993; Rettig & Trotter, 1987; Templeton et al., 1976; Goldsmith & Strouse, 1977).

A packing diagram of (I) is shown in Fig. 2. No hydrogen bonds are discernible, as all the S—H distances are greater than 3 Å. There is evidence of face-to-face ππ stacking interactions between the phenyl rings of neigbouring molecules (Hunter & Sanders, 1990; Steed & Atwood, 2000). According to the Hunter–Sanders model (Hunter & Sanders, 1990), the aromatic rings in the face-to-face mode should have an interplanar separation of about 3.4–3.6 Å and be slightly offset from one another. A direct face-to-face mode between the aromatic rings would result in a repulsion instead of an attraction between the two rings. The ring at (x, y, z), part of the molecule centred across (0, 0, 0), is parallel to the two rings at (−x, −y, 1 − z) and (1 − x, 1 − y, 1 − z), which lie in the molecules centred at (0, 0, 1/2) and (1 − x, 1 − y, 1 − z). The interplanar spacings are 3.418 (2) and 3.442 (2) Å, with ring-centroid separations of 3.768 (2) and 3.769 (2) Å, corresponding to centroid offsets of 1.585 (2) and 1.535 (2) Å respectively. Propagation of these two π-stacking interactions links the molecules into sheets parallel to (110) (Fig. 2). We also note the similarity to the packing of graphite (Nelson & Riley, 1945; Franklin, 1951; Pauling, 1966).

Related literature top

For related literature, see: Allen et al. (1987); Bruker (1997); Chivers et al. (1998); Engh & Huber (1991); Field et al. (1961); Franklin (1951); Gallacher & Pinkerton (1993); Goldsmith & Strouse (1977); Karle & Hauptman (1953); Hauptman & Karle (1953); Howells et al. (1950); Hunter & Sanders (1990); Joshi et al. (2003); Karle (1961); Kimura et al. (2002); Kopf et al. (1979); Lakshmikantham et al. (1987); Mitchell (1965); Mitchell & Lippert (1965); Nelson & Riley (1945); Ogawa et al. (1999); Pauling (1966); Rettig & Trotter (1987); Sheldrick (1997, 1997, 2000); Steed & Atwood (2000); Sugimoto et al. (2005); Templeton et al. (1976).

Experimental top

The synthesis of (I) has been described in detail by Field et al. (1961). A sample of (I) retained from the 1961 synthesis was still available. Prismatic crystals were obtained from slow evaporation of a carbon disulfide solution in a glass vial.

Refinement top

Crystals of (I) are triclinic and the structure was solved and refined in space group P1. A l l H atoms were located in difference maps and their parameters were then refined, leading to C—H distances in the range 0.948 (19)–1.011 (19) Å.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures top
[Figure 1] Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a π-stacked sheet. For the sake of clarity, H atoms have been omitted.
2,3,10,11-Tetrathiatricyclo[10.4.0.04,9]hexadeca-4,6,8,12,14,16-hexaene top
Crystal data top
C12H8S4Z = 1
Mr = 280.42F(000) = 144
Triclinic, P1Dx = 1.626 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0875 (2) ÅCell parameters from 2812 reflections
b = 7.2827 (2) Åθ = 6.6–59.7°
c = 7.2971 (2) ŵ = 0.79 mm1
α = 114.534 (1)°T = 140 K
β = 95.685 (1)°Prism, yellow
γ = 116.754 (1)°0.38 × 0.34 × 0.22 mm
V = 286.37 (1) Å3
Data collection top
Bruker SMART CCD area detector
diffractometer
1649 independent reflections
Radiation source: fine-focus sealed tube1565 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 29.9°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 99
Tmin = 0.76, Tmax = 0.84k = 1010
4521 measured reflectionsl = 1010
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)] = 0.023Hydrogen site location: difference Fourier map
wR(F2) = 0.067All H-atom parameters refined
S = 1.07 w = 1/[σ2(Fo2) + (0.041P)2 + 0.0841P]
where P = (Fo2 + 2Fc2)/3
1649 reflections(Δ/σ)max < 0.001
89 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C12H8S4γ = 116.754 (1)°
Mr = 280.42V = 286.37 (1) Å3
Triclinic, P1Z = 1
a = 7.0875 (2) ÅMo Kα radiation
b = 7.2827 (2) ŵ = 0.79 mm1
c = 7.2971 (2) ÅT = 140 K
α = 114.534 (1)°0.38 × 0.34 × 0.22 mm
β = 95.685 (1)°
Data collection top
Bruker SMART CCD area detector
diffractometer
1649 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
1565 reflections with I > 2σ(I)
Tmin = 0.76, Tmax = 0.84Rint = 0.016
4521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.067All H-atom parameters refined
S = 1.07Δρmax = 0.37 e Å3
1649 reflectionsΔρmin = 0.28 e Å3
89 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.

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
S10.12869 (5)0.17412 (4)0.03595 (4)0.02034 (9)
S20.21536 (4)0.02171 (5)0.15050 (4)0.01966 (9)
C10.10541 (19)0.32423 (19)0.55057 (17)0.0201 (2)
C20.30637 (19)0.42551 (19)0.70973 (17)0.0223 (2)
C30.45402 (18)0.3529 (2)0.65951 (18)0.0226 (2)
C40.39857 (18)0.1747 (2)0.45066 (18)0.0206 (2)
C50.19568 (17)0.06900 (18)0.29062 (16)0.01735 (19)
C60.04836 (17)0.14666 (18)0.33996 (16)0.01724 (19)
H10.000 (3)0.381 (3)0.587 (3)0.035 (4)*
H20.348 (3)0.548 (3)0.856 (3)0.037 (5)*
H30.595 (3)0.427 (3)0.765 (3)0.039 (5)*
H40.506 (3)0.128 (3)0.414 (3)0.033 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02434 (15)0.01917 (14)0.01875 (14)0.01365 (11)0.00648 (10)0.00900 (11)
S20.01543 (14)0.02346 (14)0.01793 (14)0.00986 (11)0.00546 (10)0.00988 (11)
C10.0221 (5)0.0191 (4)0.0182 (5)0.0108 (4)0.0073 (4)0.0093 (4)
C20.0238 (5)0.0195 (5)0.0163 (4)0.0080 (4)0.0047 (4)0.0083 (4)
C30.0186 (5)0.0241 (5)0.0195 (5)0.0073 (4)0.0029 (4)0.0124 (4)
C40.0186 (5)0.0249 (5)0.0212 (5)0.0117 (4)0.0068 (4)0.0143 (4)
C50.0179 (4)0.0177 (4)0.0166 (4)0.0093 (4)0.0057 (4)0.0095 (4)
C60.0163 (4)0.0174 (4)0.0169 (4)0.0080 (4)0.0049 (3)0.0094 (4)
Geometric parameters (Å, º) top
S1—C51.7748 (10)C3—C41.3931 (16)
S1—S2i2.0655 (4)C3—H30.948 (19)
S2—C61.7734 (10)C2—C11.3916 (15)
C5—C41.3959 (14)C2—H20.965 (18)
C5—C61.4060 (14)C1—H11.011 (19)
C6—C11.3976 (14)C4—H40.983 (18)
C3—C21.3866 (17)
C5—S1—S2i104.27 (3)C4—C3—H3119.4 (11)
C6—S2—S1i103.64 (3)C3—C2—C1120.01 (10)
C4—C5—C6119.62 (9)C3—C2—H2118.2 (11)
C4—C5—S1117.21 (8)C1—C2—H2121.7 (11)
C6—C5—S1123.03 (8)C2—C1—C6120.72 (10)
C1—C6—C5119.17 (9)C2—C1—H1119.6 (10)
C1—C6—S2117.40 (8)C6—C1—H1119.6 (10)
C5—C6—S2123.38 (8)C3—C4—C5120.55 (10)
C2—C3—C4119.90 (10)C3—C4—H4119.9 (10)
C2—C3—H3120.7 (11)C5—C4—H4119.5 (10)
S2i—S1—C5—C4100.16 (8)C4—C3—C2—C11.41 (16)
S2i—S1—C5—C684.09 (9)C3—C2—C1—C60.91 (16)
C4—C5—C6—C11.74 (15)C5—C6—C1—C20.67 (15)
S1—C5—C6—C1173.91 (8)S2—C6—C1—C2178.03 (8)
C4—C5—C6—S2178.93 (8)C2—C3—C4—C50.33 (16)
S1—C5—C6—S23.28 (13)C6—C5—C4—C31.26 (16)
S1i—S2—C6—C1105.61 (8)S1—C5—C4—C3174.65 (8)
S1i—S2—C6—C577.15 (9)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formulaC12H8S4
Mr280.42
Crystal system, space groupTriclinic, P1
Temperature (K)140
a, b, c (Å)7.0875 (2), 7.2827 (2), 7.2971 (2)
α, β, γ (°)114.534 (1), 95.685 (1), 116.754 (1)
V3)286.37 (1)
Z1
Radiation typeMo Kα
µ (mm1)0.79
Crystal size (mm)0.38 × 0.34 × 0.22
Data collection
DiffractometerBruker SMART CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.76, 0.84
No. of measured, independent and
observed [I > 2σ(I)] reflections
4521, 1649, 1565
Rint0.016
(sin θ/λ)max1)0.701
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.067, 1.07
No. of reflections1649
No. of parameters89
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.37, 0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2000).

Selected bond lengths (Å) top
S1—C51.7748 (10)S2—C61.7734 (10)
S1—S2i2.0655 (4)
Symmetry code: (i) x, y, z.
 

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