Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003528/qa0227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003528/qa0227Isup2.hkl |
CCDC reference: 144718
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.
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.
C13H8S4 | Mo Kα radiation, λ = 0.7107 Å |
Mr = 292.45 | Cell parameters from 25 reflections |
Tetragonal, P41212 | θ = 10.4–11.9° |
a = 6.287 (6) Å | µ = 0.72 mm−1 |
c = 31.93 (1) Å | T = 293 K |
V = 1261.9 (8) Å3 | Prismatic, colorless |
Z = 4 | 0.20 × 0.20 × 0.10 mm |
Dx = 1.539 Mg m−3 |
Rigaku AFC-7R diffractometer | θmax = 27.3° |
ω–2θ scans | h = 0→8 |
934 measured reflections | k = 0→5 |
934 independent reflections | l = 0→41 |
755 reflections with F2 > 2.0σ(F2) | 3 standard reflections every 150 reflections |
Rint = 0.000 | intensity decay: 0.7% |
Refinement on F | H-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 = 1.33 | Δρmax = 0.17 e Å−3 |
803 reflections | Δρmin = −0.17 e Å−3 |
77 parameters |
C13H8S4 | Z = 4 |
Mr = 292.45 | Mo Kα radiation |
Tetragonal, P41212 | µ = 0.72 mm−1 |
a = 6.287 (6) Å | T = 293 K |
c = 31.93 (1) Å | 0.20 × 0.20 × 0.10 mm |
V = 1261.9 (8) Å3 |
Rigaku AFC-7R diffractometer | Rint = 0.000 |
934 measured reflections | 3 standard reflections every 150 reflections |
934 independent reflections | intensity decay: 0.7% |
755 reflections with F2 > 2.0σ(F2) |
R[F2 > 2σ(F2)] = 0.035 | 77 parameters |
wR(F2) = 0.045 | H-atom parameters not refined |
S = 1.33 | Δρmax = 0.17 e Å−3 |
803 reflections | Δρmin = −0.17 e Å−3 |
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). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.1054 (1) | −0.2270 (1) | 0.48960 (2) | 0.0547 (2) | |
S2 | 0.1294 (1) | 0.2026 (1) | 0.45266 (2) | 0.0552 (2) | |
C1 | 0.0530 (5) | 0.0530 | 0.5000 | 0.0458 (5) | |
C2 | 0.3241 (6) | −0.1776 (5) | 0.45604 (8) | 0.0483 (7) | |
C3 | 0.4784 (5) | −0.3292 (6) | 0.44682 (9) | 0.0595 (9) | |
C4 | 0.6392 (6) | −0.2769 (6) | 0.4181 (1) | 0.071 (1) | |
C5 | 0.6436 (6) | −0.0777 (7) | 0.3994 (1) | 0.073 (1) | |
C6 | 0.4950 (6) | 0.0756 (6) | 0.40939 (8) | 0.0630 (10) | |
C7 | 0.3346 (5) | 0.0258 (5) | 0.43777 (8) | 0.0496 (7) | |
H3 | 0.4805 | −0.4698 | 0.4590 | 0.0677* | |
H4 | 0.7515 | −0.3800 | 0.4101 | 0.0808* | |
H5 | 0.7566 | −0.0450 | 0.3782 | 0.0908* | |
H6 | 0.5063 | 0.2184 | 0.3959 | 0.0767* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0610 (5) | 0.0464 (4) | 0.0566 (4) | −0.0118 (4) | 0.0138 (4) | −0.0012 (3) |
S2 | 0.0648 (5) | 0.0538 (4) | 0.0471 (4) | −0.0072 (4) | 0.0039 (4) | 0.0060 (4) |
C1 | 0.047 (1) | 0.0467 | 0.044 (2) | 0.0000 | 0.0000 | 0.0000 |
C2 | 0.050 (2) | 0.055 (1) | 0.040 (1) | −0.013 (1) | −0.001 (1) | −0.008 (1) |
C3 | 0.059 (2) | 0.067 (2) | 0.053 (2) | 0.000 (1) | −0.006 (1) | −0.015 (2) |
C4 | 0.053 (2) | 0.090 (2) | 0.068 (2) | −0.005 (2) | 0.009 (2) | −0.032 (2) |
C5 | 0.063 (2) | 0.101 (2) | 0.055 (2) | −0.021 (2) | 0.017 (2) | −0.020 (2) |
C6 | 0.068 (2) | 0.082 (2) | 0.039 (1) | −0.027 (2) | 0.011 (1) | −0.005 (2) |
C7 | 0.053 (2) | 0.059 (1) | 0.037 (1) | −0.015 (1) | −0.003 (1) | −0.005 (1) |
S1—C1 | 1.821 (3) | C2—C7 | 1.407 (5) |
S1—C2 | 1.77 (1) | C3—C4 | 1.404 (9) |
S2—C1 | 1.843 (3) | C4—C5 | 1.388 (6) |
S2—C7 | 1.768 (10) | C5—C6 | 1.380 (8) |
C2—C3 | 1.391 (8) | C6—C7 | 1.391 (8) |
C1—S1—C2 | 94.7 (2) | S1—C2—C7 | 116.5 (3) |
C1—S2—C7 | 95.2 (2) | C3—C2—C7 | 120.1 (4) |
S1—C1—S1i | 112.5 (3) | C2—C3—C4 | 118.7 (5) |
S1—C1—S2 | 107.24 (8) | C3—C4—C5 | 120.5 (4) |
S1—C1—S2i | 108.0 (2) | C4—C5—C6 | 121.2 (4) |
S1—C1i—S2 | 107.2 (4) | C5—C6—C7 | 119.0 (5) |
S1—C1i—S2i | 108.0 (1) | S2—C7—C2 | 115.2 (3) |
S2—C1—S2i | 114.0 (4) | S2—C7—C6 | 124.2 (4) |
S1—C2—C3 | 123.3 (4) | C2—C7—C6 | 120.6 (4) |
S1—C1—S1i—C2i | 150.1 (1) | C1—S1i—C2i—C3i | 159.9 (4) |
S1—C1—S2—C7 | −31.0 (2) | C1—S1i—C2i—C7i | −21.3 (3) |
S1—C1—S2i—C7i | −152.5 (2) | C1—S2—C7—C2 | 18.7 (3) |
S1—C2—C3—C4 | 176.7 (3) | C1—S2—C7—C6 | −162.9 (3) |
S1—C2—C7—S2 | 1.7 (4) | C1—S2i—C7i—C2i | 18.7 (3) |
S1—C2—C7—C6 | −176.8 (3) | C1—S2i—C7i—C6i | −162.9 (3) |
S2—C1—S1—C2 | 31.5 (2) | C2—C3—C4—C5 | 0.1 (6) |
S2—C1—S1i—C2i | −91.8 (2) | C2—C7—C6—C5 | 0.0 (6) |
S2—C1—S2i—C7i | 88.4 (4) | C3—C2—C7—C6 | 2.0 (5) |
S2—C7—C2—C3 | −179.5 (3) | C3—C4—C5—C6 | 2.0 (6) |
S2—C7—C6—C5 | −178.3 (3) | C4—C3—C2—C7 | −2.0 (6) |
C1—S1—C2—C3 | 159.9 (3) | C4—C5—C6—C7 | −2.0 (6) |
C1—S1—C2—C7 | −21.3 (3) |
Symmetry code: (i) y, x, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H8S4 |
Mr | 292.45 |
Crystal system, space group | Tetragonal, P41212 |
Temperature (K) | 293 |
a, c (Å) | 6.287 (6), 31.93 (1) |
V (Å3) | 1261.9 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 934, 934, 755 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.646 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.045, 1.33 |
No. of reflections | 803 |
No. of parameters | 77 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 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.
S1—C1 | 1.821 (3) | C2—C7 | 1.407 (5) |
S1—C2 | 1.77 (1) | C3—C4 | 1.404 (9) |
S2—C1 | 1.843 (3) | C4—C5 | 1.388 (6) |
S2—C7 | 1.768 (10) | C5—C6 | 1.380 (8) |
C2—C3 | 1.391 (8) | C6—C7 | 1.391 (8) |
C1—S1—C2 | 94.7 (2) | S1—C2—C7 | 116.5 (3) |
C1—S2—C7 | 95.2 (2) | C3—C2—C7 | 120.1 (4) |
S1—C1—S1i | 112.5 (3) | C2—C3—C4 | 118.7 (5) |
S1—C1—S2 | 107.24 (8) | C3—C4—C5 | 120.5 (4) |
S1—C1—S2i | 108.0 (2) | C4—C5—C6 | 121.2 (4) |
S1—C1i—S2 | 107.2 (4) | C5—C6—C7 | 119.0 (5) |
S1—C1i—S2i | 108.0 (1) | S2—C7—C2 | 115.2 (3) |
S2—C1—S2i | 114.0 (4) | S2—C7—C6 | 124.2 (4) |
S1—C2—C3 | 123.3 (4) | C2—C7—C6 | 120.6 (4) |
S1—C1—S1i—C2i | 150.1 (1) | C1—S1i—C2i—C3i | 159.9 (4) |
S1—C1—S2—C7 | −31.0 (2) | C1—S1i—C2i—C7i | −21.3 (3) |
S1—C1—S2i—C7i | −152.5 (2) | C1—S2—C7—C2 | 18.7 (3) |
S1—C2—C3—C4 | 176.7 (3) | C1—S2—C7—C6 | −162.9 (3) |
S1—C2—C7—S2 | 1.7 (4) | C1—S2i—C7i—C2i | 18.7 (3) |
S1—C2—C7—C6 | −176.8 (3) | C1—S2i—C7i—C6i | −162.9 (3) |
S2—C1—S1—C2 | 31.5 (2) | C2—C3—C4—C5 | 0.1 (6) |
S2—C1—S1i—C2i | −91.8 (2) | C2—C7—C6—C5 | 0.0 (6) |
S2—C1—S2i—C7i | 88.4 (4) | C3—C2—C7—C6 | 2.0 (5) |
S2—C7—C2—C3 | −179.5 (3) | C3—C4—C5—C6 | 2.0 (6) |
S2—C7—C6—C5 | −178.3 (3) | C4—C3—C2—C7 | −2.0 (6) |
C1—S1—C2—C3 | 159.9 (3) | C4—C5—C6—C7 | −2.0 (6) |
C1—S1—C2—C7 | −21.3 (3) |
Symmetry code: (i) y, x, −z+1. |
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).