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The X-ray structure analysis of 2,2'-spiro­bi(1,3-benzodi­thiole), C13H8S4, has been performed. The mol­ecule has crystallographic twofold rotation symmetry, the axis passing through the spiro-C atom. The four S atoms are arranged around the spiro-C atom in two almost orthogonal CS2 planes. However, because of large bending of the two five-membered rings, close contact is present between two connected C atoms on the benzo group of each 1,3-benzodi­thiole ring and one S atom on the other 1,3-benzodi­thiole ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003528/qa0227sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003528/qa0227Isup2.hkl
Contains datablock I

CCDC reference: 144718

Comment top

In the title compound, (I), the S1—C1, S1—C2, S2—C1, S2—C7, S1*—C1, S1*—C2*, S2*—C1 and S2*—C7* bond distances [symmetry code: (i) y, x, 1 - z] are in the range 1.77–1.84 Å, which are near to the values reported so far (1.80–1.81 Å; Sutton, 1958, 1965). The C1—S1—C2, C1—S2—C7, C1—S1*—C2* and C1—S2*—C7* bond angles are in the range 94–96° and slightly smaller than the normal values (97–99°; Sutton, 1958, 1965). The S1—C1—S2 and S1*—C1—S2* planes make a dihedral angle of 93.8 (1)°. The five-membered C1—S1—C2—C7—C2 and C1—S1*—C2*—C7*—C2* rings have an envelope-like conformation, as seen from the dihedral angles between the C1/S1/2 and S1/S2/C7/C2 planes [35.0 (1)°], resulting in a dihedral angle of 79.2 (1)° between the two benzene rings. As the result of large bending of the two five-membered rings, C2 and C2* or C7 and C7* atom on the benzo group of one 1,3-benzodithiole ring and the S2 or S2* atom on the other 1,3-benzodithiole ring become closer to each other. In particular, the closest contact can be seen between S2 and C2* atoms [3.58 (1) Å]. The contact distance is near to the sum of van der Waals' radii of C (1.75 Å) and S atoms (1.85 Å; Pauling, 1960).

The 1H NMR spectrum of (I) in DMF-d7 showed each of two kinds of signals due to the ortho-protons (H3/H3* and H6/H6*) at δ 7.26 (2H, dd, J = 2.57, 3.33 Hz) and 7.46 (2H, dd, J = 2.57, 3.33 Hz), and to the meta-protons (H4/H4* and H5/H5*) at δ 7.27 (2H, t, J = 3.33 Hz) and 7.44 (2H, t, J = 3.33 Hz) on the benzo groups. The different chemical shifts between H3/H3* and H6/H6* protons and between H4/H4* and H5/H5* protons are caused by the magnetic anisotropy due to the sulfur lone pairs in close proximity to H3/H3* and H4/ H4* protons, as seen from the crystal structure. On the other hand, only three kinds of signals (138.22, 129.01 and 124.64 p.p.m.) due to the benzo C atoms were observed together with the spiro-carbon signal (90.01 p.p.m.) in the 13C NMR spectrum. This result clearly suggests that also in solution the five-membered rings maintain an envelope-like conformation without rapid flipping on the NMR time-scale (Horn et al., 1993; Setaka et al., 1999).

Experimental top

The title compound was first obtained as a by-product (<5% yield) in the thermal decomposition of 2-(n-amyloxybenzo)-1,3-dithiole (Nakayama, 1975). In order to improve the yield, the following method was now used. 2-Methylthio-1,3-benzodithiolium tetrafluoroborate was reacted with an equimolar amount of benzene-1,2-dithiol in the presence of a catalytic amount of p-toluenesulfonic acid in 1,2-dichloroethane at 356 K for 3 h. The crude product was purified by silica-gel column chromatography with an eluent of n-hexane/benzene (v/v = 3:1), followed by recrystallization from benzene/n-hexane to give colourless crystals of (I) (m.p. 393 K) in 23% yield.

Refinement top

For the refinement 803 reflections were used with I > 0.7σ(I).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1985); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

(I) top
Crystal data top
C13H8S4Mo Kα radiation, λ = 0.7107 Å
Mr = 292.45Cell parameters from 25 reflections
Tetragonal, P41212θ = 10.4–11.9°
a = 6.287 (6) ŵ = 0.72 mm1
c = 31.93 (1) ÅT = 293 K
V = 1261.9 (8) Å3Prismatic, colorless
Z = 40.20 × 0.20 × 0.10 mm
Dx = 1.539 Mg m3
Data collection top
Rigaku AFC-7R
diffractometer
θmax = 27.3°
ω–2θ scansh = 08
934 measured reflectionsk = 05
934 independent reflectionsl = 041
755 reflections with F2 > 2.0σ(F2)3 standard reflections every 150 reflections
Rint = 0.000 intensity decay: 0.7%
Refinement top
Refinement on FH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.035 w = 1/[σ2(Fo) + 0.00040|Fo|2]
wR(F2) = 0.045(Δ/σ)max = 0.039
S = 1.33Δρmax = 0.17 e Å3
803 reflectionsΔρmin = 0.17 e Å3
77 parameters
Crystal data top
C13H8S4Z = 4
Mr = 292.45Mo Kα radiation
Tetragonal, P41212µ = 0.72 mm1
a = 6.287 (6) ÅT = 293 K
c = 31.93 (1) Å0.20 × 0.20 × 0.10 mm
V = 1261.9 (8) Å3
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.000
934 measured reflections3 standard reflections every 150 reflections
934 independent reflections intensity decay: 0.7%
755 reflections with F2 > 2.0σ(F2)
Refinement top
R[F2 > 2σ(F2)] = 0.03577 parameters
wR(F2) = 0.045H-atom parameters not refined
S = 1.33Δρmax = 0.17 e Å3
803 reflectionsΔρmin = 0.17 e Å3
Special details top

Refinement. Refinement using reflections with F2 > 0.7 σ(F2). The weighted R-factor

(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero

for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only

for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.1054 (1)0.2270 (1)0.48960 (2)0.0547 (2)
S20.1294 (1)0.2026 (1)0.45266 (2)0.0552 (2)
C10.0530 (5)0.05300.50000.0458 (5)
C20.3241 (6)0.1776 (5)0.45604 (8)0.0483 (7)
C30.4784 (5)0.3292 (6)0.44682 (9)0.0595 (9)
C40.6392 (6)0.2769 (6)0.4181 (1)0.071 (1)
C50.6436 (6)0.0777 (7)0.3994 (1)0.073 (1)
C60.4950 (6)0.0756 (6)0.40939 (8)0.0630 (10)
C70.3346 (5)0.0258 (5)0.43777 (8)0.0496 (7)
H30.48050.46980.45900.0677*
H40.75150.38000.41010.0808*
H50.75660.04500.37820.0908*
H60.50630.21840.39590.0767*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0610 (5)0.0464 (4)0.0566 (4)0.0118 (4)0.0138 (4)0.0012 (3)
S20.0648 (5)0.0538 (4)0.0471 (4)0.0072 (4)0.0039 (4)0.0060 (4)
C10.047 (1)0.04670.044 (2)0.00000.00000.0000
C20.050 (2)0.055 (1)0.040 (1)0.013 (1)0.001 (1)0.008 (1)
C30.059 (2)0.067 (2)0.053 (2)0.000 (1)0.006 (1)0.015 (2)
C40.053 (2)0.090 (2)0.068 (2)0.005 (2)0.009 (2)0.032 (2)
C50.063 (2)0.101 (2)0.055 (2)0.021 (2)0.017 (2)0.020 (2)
C60.068 (2)0.082 (2)0.039 (1)0.027 (2)0.011 (1)0.005 (2)
C70.053 (2)0.059 (1)0.037 (1)0.015 (1)0.003 (1)0.005 (1)
Geometric parameters (Å, º) top
S1—C11.821 (3)C2—C71.407 (5)
S1—C21.77 (1)C3—C41.404 (9)
S2—C11.843 (3)C4—C51.388 (6)
S2—C71.768 (10)C5—C61.380 (8)
C2—C31.391 (8)C6—C71.391 (8)
C1—S1—C294.7 (2)S1—C2—C7116.5 (3)
C1—S2—C795.2 (2)C3—C2—C7120.1 (4)
S1—C1—S1i112.5 (3)C2—C3—C4118.7 (5)
S1—C1—S2107.24 (8)C3—C4—C5120.5 (4)
S1—C1—S2i108.0 (2)C4—C5—C6121.2 (4)
S1—C1i—S2107.2 (4)C5—C6—C7119.0 (5)
S1—C1i—S2i108.0 (1)S2—C7—C2115.2 (3)
S2—C1—S2i114.0 (4)S2—C7—C6124.2 (4)
S1—C2—C3123.3 (4)C2—C7—C6120.6 (4)
S1—C1—S1i—C2i150.1 (1)C1—S1i—C2i—C3i159.9 (4)
S1—C1—S2—C731.0 (2)C1—S1i—C2i—C7i21.3 (3)
S1—C1—S2i—C7i152.5 (2)C1—S2—C7—C218.7 (3)
S1—C2—C3—C4176.7 (3)C1—S2—C7—C6162.9 (3)
S1—C2—C7—S21.7 (4)C1—S2i—C7i—C2i18.7 (3)
S1—C2—C7—C6176.8 (3)C1—S2i—C7i—C6i162.9 (3)
S2—C1—S1—C231.5 (2)C2—C3—C4—C50.1 (6)
S2—C1—S1i—C2i91.8 (2)C2—C7—C6—C50.0 (6)
S2—C1—S2i—C7i88.4 (4)C3—C2—C7—C62.0 (5)
S2—C7—C2—C3179.5 (3)C3—C4—C5—C62.0 (6)
S2—C7—C6—C5178.3 (3)C4—C3—C2—C72.0 (6)
C1—S1—C2—C3159.9 (3)C4—C5—C6—C72.0 (6)
C1—S1—C2—C721.3 (3)
Symmetry code: (i) y, x, z+1.

Experimental details

Crystal data
Chemical formulaC13H8S4
Mr292.45
Crystal system, space groupTetragonal, P41212
Temperature (K)293
a, c (Å)6.287 (6), 31.93 (1)
V3)1261.9 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.72
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [F2 > 2.0σ(F2)] reflections
934, 934, 755
Rint0.000
(sin θ/λ)max1)0.646
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.045, 1.33
No. of reflections803
No. of parameters77
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.17, 0.17

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1985), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), TEXSAN.

Selected geometric parameters (Å, º) top
S1—C11.821 (3)C2—C71.407 (5)
S1—C21.77 (1)C3—C41.404 (9)
S2—C11.843 (3)C4—C51.388 (6)
S2—C71.768 (10)C5—C61.380 (8)
C2—C31.391 (8)C6—C71.391 (8)
C1—S1—C294.7 (2)S1—C2—C7116.5 (3)
C1—S2—C795.2 (2)C3—C2—C7120.1 (4)
S1—C1—S1i112.5 (3)C2—C3—C4118.7 (5)
S1—C1—S2107.24 (8)C3—C4—C5120.5 (4)
S1—C1—S2i108.0 (2)C4—C5—C6121.2 (4)
S1—C1i—S2107.2 (4)C5—C6—C7119.0 (5)
S1—C1i—S2i108.0 (1)S2—C7—C2115.2 (3)
S2—C1—S2i114.0 (4)S2—C7—C6124.2 (4)
S1—C2—C3123.3 (4)C2—C7—C6120.6 (4)
S1—C1—S1i—C2i150.1 (1)C1—S1i—C2i—C3i159.9 (4)
S1—C1—S2—C731.0 (2)C1—S1i—C2i—C7i21.3 (3)
S1—C1—S2i—C7i152.5 (2)C1—S2—C7—C218.7 (3)
S1—C2—C3—C4176.7 (3)C1—S2—C7—C6162.9 (3)
S1—C2—C7—S21.7 (4)C1—S2i—C7i—C2i18.7 (3)
S1—C2—C7—C6176.8 (3)C1—S2i—C7i—C6i162.9 (3)
S2—C1—S1—C231.5 (2)C2—C3—C4—C50.1 (6)
S2—C1—S1i—C2i91.8 (2)C2—C7—C6—C50.0 (6)
S2—C1—S2i—C7i88.4 (4)C3—C2—C7—C62.0 (5)
S2—C7—C2—C3179.5 (3)C3—C4—C5—C62.0 (6)
S2—C7—C6—C5178.3 (3)C4—C3—C2—C72.0 (6)
C1—S1—C2—C3159.9 (3)C4—C5—C6—C72.0 (6)
C1—S1—C2—C721.3 (3)
Symmetry code: (i) y, x, z+1.
 

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