Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009504/na6230sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009504/na62302sup2.hkl |
CCDC reference: 214819
A solution of indene (2.92 ml, 25 mmol) in 1,2-dichloroethane was added dropwise to a stirred suspension of K-10/ZnCl2 (15.92 g) (Clark et al., 1994) and DMDS (2.25 ml, 25 mmol) in dichloroethane (35 ml). After the mixture had been stirred for 3 h, the clay catalyst was removed by filtration and the filtrate was washed with aqueous edta (2 × 100 ml) toremove traces of ZnCl2 from the organic phase. The organic solution was then washed with water (1 × 100 ml) and was dried over anhydrous MgSO4. Evaporation of the solvents and excess DMDS left an oil which on distillation under high vacuum yielded the dithio adduct (1) as a pale-yellow oil (2.14 g, 41%, b.p. 379 K at 0.01 mm H g). Oxidation of this product (Aitken et al., 1994) gave the disulfone (2) in quantitative yield as colorless crystals (m.p. 415 K).
The H atoms were located from a difference Fourier map and were included in the refinement at idealized positions with isotropic displacement parameters 1.5 (CH3) and 1.2 (CH & CH2) times the equivalent displacement parameters of the atoms to which they were bonded, with C—H distances in the range 0.98–1.00 Å.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. ORTEPII (Johnson, 1976) drawing of (2), with displacement ellipsoids plotted at the 50% probability level. | |
Fig. 2. Unit-cell packing diagram of (2). |
C11H14O4S2 | F(000) = 576 |
Mr = 274.34 | Dx = 1.518 Mg m−3 |
Monoclinic, P21/a | Melting point: 415 K |
Hall symbol: -P 2yab | Mo Kα radiation, λ = 0.71069 Å |
a = 11.138 (6) Å | Cell parameters from 12 reflections |
b = 8.102 (2) Å | θ = 15.0–30.0° |
c = 13.307 (2) Å | µ = 0.44 mm−1 |
β = 91.82 (2)° | T = 170 K |
V = 1200.2 (7) Å3 | Plate, colorless |
Z = 4 | 0.40 × 0.30 × 0.07 mm |
Rigaku AFC-6S diffractometer | 1034 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 25.1°, θmin = 2.9° |
ω/2θ scans | h = 0→13 |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | k = 0→9 |
Tmin = 0.843, Tmax = 0.970 | l = −15→15 |
2249 measured reflections | 3 standard reflections every 200 reflections |
2128 independent reflections | intensity decay: 1.4% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.402P] where P = (Fo2 + 2Fc2)/3 |
2128 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C11H14O4S2 | V = 1200.2 (7) Å3 |
Mr = 274.34 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 11.138 (6) Å | µ = 0.44 mm−1 |
b = 8.102 (2) Å | T = 170 K |
c = 13.307 (2) Å | 0.40 × 0.30 × 0.07 mm |
β = 91.82 (2)° |
Rigaku AFC-6S diffractometer | 1034 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | Rint = 0.042 |
Tmin = 0.843, Tmax = 0.970 | 3 standard reflections every 200 reflections |
2249 measured reflections | intensity decay: 1.4% |
2128 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.33 e Å−3 |
2128 reflections | Δρmin = −0.34 e Å−3 |
156 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.75311 (11) | 0.35653 (16) | 0.13360 (9) | 0.0258 (3) | |
S2 | 0.49376 (11) | 0.69883 (16) | 0.20879 (10) | 0.0260 (3) | |
O1 | 0.8827 (3) | 0.3594 (5) | 0.1467 (2) | 0.0325 (9) | |
O2 | 0.7027 (3) | 0.4036 (5) | 0.0362 (2) | 0.0384 (10) | |
O3 | 0.5510 (3) | 0.7965 (4) | 0.2866 (3) | 0.0373 (9) | |
O4 | 0.3639 (3) | 0.6850 (4) | 0.2074 (3) | 0.0354 (9) | |
C1 | 0.6907 (4) | 0.4931 (6) | 0.2246 (3) | 0.0217 (11) | |
H1 | 0.7204 | 0.6076 | 0.2122 | 0.026* | |
C2 | 0.5516 (4) | 0.4934 (6) | 0.2164 (3) | 0.0219 (11) | |
H2 | 0.5241 | 0.4295 | 0.1556 | 0.026* | |
C3 | 0.5074 (4) | 0.4075 (6) | 0.3119 (3) | 0.0277 (12) | |
H3A | 0.4426 | 0.4722 | 0.3426 | 0.033* | |
H3B | 0.4771 | 0.2953 | 0.2963 | 0.033* | |
C4 | 0.6170 (4) | 0.3999 (6) | 0.3812 (4) | 0.0252 (12) | |
C5 | 0.6245 (4) | 0.3530 (6) | 0.4814 (3) | 0.0307 (13) | |
H5 | 0.5546 | 0.3181 | 0.5146 | 0.037* | |
C6 | 0.7346 (4) | 0.3577 (6) | 0.5326 (4) | 0.0294 (12) | |
H6 | 0.7399 | 0.3272 | 0.6016 | 0.035* | |
C7 | 0.8369 (5) | 0.4063 (6) | 0.4844 (4) | 0.0303 (13) | |
H7 | 0.9119 | 0.4082 | 0.5205 | 0.036* | |
C8 | 0.8312 (4) | 0.4523 (6) | 0.3839 (4) | 0.0278 (12) | |
H8 | 0.9013 | 0.4862 | 0.3507 | 0.033* | |
C9 | 0.7199 (4) | 0.4474 (6) | 0.3329 (3) | 0.0224 (11) | |
C10 | 0.7020 (4) | 0.1593 (6) | 0.1642 (4) | 0.0347 (13) | |
H10A | 0.7353 | 0.0783 | 0.1180 | 0.052* | |
H10B | 0.6141 | 0.1567 | 0.1585 | 0.052* | |
H10C | 0.7280 | 0.1323 | 0.2333 | 0.052* | |
C11 | 0.5370 (5) | 0.7714 (7) | 0.0911 (4) | 0.0362 (14) | |
H11A | 0.5060 | 0.8835 | 0.0805 | 0.054* | |
H11B | 0.5044 | 0.6986 | 0.0382 | 0.054* | |
H11C | 0.6249 | 0.7728 | 0.0889 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0222 (7) | 0.0295 (7) | 0.0259 (7) | 0.0012 (6) | 0.0033 (5) | −0.0040 (6) |
S2 | 0.0230 (7) | 0.0268 (7) | 0.0282 (7) | 0.0031 (6) | 0.0007 (5) | −0.0033 (6) |
O1 | 0.0173 (18) | 0.043 (2) | 0.037 (2) | 0.0013 (17) | 0.0032 (15) | −0.0048 (18) |
O2 | 0.036 (2) | 0.056 (3) | 0.0240 (19) | 0.0071 (19) | −0.0002 (16) | −0.0003 (18) |
O3 | 0.037 (2) | 0.036 (2) | 0.038 (2) | 0.0039 (18) | −0.0063 (17) | −0.0153 (19) |
O4 | 0.0201 (19) | 0.040 (2) | 0.046 (2) | 0.0050 (17) | 0.0030 (16) | 0.0030 (18) |
C1 | 0.019 (3) | 0.020 (3) | 0.026 (3) | 0.000 (2) | 0.002 (2) | 0.002 (2) |
C2 | 0.020 (3) | 0.023 (3) | 0.022 (3) | −0.001 (2) | 0.000 (2) | −0.003 (2) |
C3 | 0.022 (3) | 0.030 (3) | 0.031 (3) | −0.004 (2) | 0.001 (2) | 0.006 (2) |
C4 | 0.021 (3) | 0.026 (3) | 0.029 (3) | 0.002 (2) | 0.000 (2) | −0.003 (2) |
C5 | 0.037 (3) | 0.030 (3) | 0.025 (3) | −0.004 (3) | 0.006 (2) | 0.002 (2) |
C6 | 0.038 (3) | 0.026 (3) | 0.023 (3) | 0.002 (3) | −0.006 (2) | 0.005 (2) |
C7 | 0.030 (3) | 0.031 (3) | 0.029 (3) | 0.003 (2) | −0.008 (2) | −0.003 (2) |
C8 | 0.023 (3) | 0.026 (3) | 0.034 (3) | −0.001 (2) | 0.003 (2) | −0.008 (2) |
C9 | 0.020 (3) | 0.021 (3) | 0.027 (3) | 0.001 (2) | 0.001 (2) | −0.003 (2) |
C10 | 0.029 (3) | 0.026 (3) | 0.050 (3) | −0.001 (2) | 0.009 (3) | −0.009 (3) |
C11 | 0.042 (3) | 0.033 (3) | 0.034 (3) | 0.001 (3) | 0.007 (3) | 0.007 (3) |
S1—O2 | 1.448 (3) | C4—C9 | 1.387 (6) |
S1—O1 | 1.448 (3) | C4—C5 | 1.386 (6) |
S1—C10 | 1.749 (5) | C5—C6 | 1.385 (7) |
S1—C1 | 1.797 (5) | C5—H5 | 0.9500 |
S2—O3 | 1.436 (3) | C6—C7 | 1.383 (7) |
S2—O4 | 1.450 (3) | C6—H6 | 0.9500 |
S2—C11 | 1.755 (5) | C7—C8 | 1.388 (7) |
S2—C2 | 1.786 (5) | C7—H7 | 0.9500 |
C1—C9 | 1.513 (6) | C8—C9 | 1.394 (6) |
C1—C2 | 1.549 (6) | C8—H8 | 0.9500 |
C1—H1 | 1.0000 | C10—H10A | 0.9800 |
C2—C3 | 1.543 (6) | C10—H10B | 0.9800 |
C2—H2 | 1.0000 | C10—H10C | 0.9800 |
C3—C4 | 1.507 (6) | C11—H11A | 0.9800 |
C3—H3A | 0.9900 | C11—H11B | 0.9800 |
C3—H3B | 0.9900 | C11—H11C | 0.9800 |
O2—S1—O1 | 117.4 (2) | C9—C4—C5 | 119.8 (4) |
O2—S1—C10 | 109.2 (2) | C9—C4—C3 | 111.7 (4) |
O1—S1—C10 | 108.5 (2) | C5—C4—C3 | 128.5 (4) |
O2—S1—C1 | 107.1 (2) | C6—C5—C4 | 119.4 (5) |
O1—S1—C1 | 108.3 (2) | C6—C5—H5 | 120.3 |
C10—S1—C1 | 105.7 (2) | C4—C5—H5 | 120.3 |
O3—S2—O4 | 118.1 (2) | C7—C6—C5 | 120.6 (4) |
O3—S2—C11 | 109.3 (2) | C7—C6—H6 | 119.7 |
O4—S2—C11 | 108.4 (2) | C5—C6—H6 | 119.7 |
O3—S2—C2 | 108.7 (2) | C6—C7—C8 | 120.7 (5) |
O4—S2—C2 | 106.7 (2) | C6—C7—H7 | 119.7 |
C11—S2—C2 | 104.7 (2) | C8—C7—H7 | 119.7 |
C9—C1—C2 | 104.6 (4) | C7—C8—C9 | 118.3 (5) |
C9—C1—S1 | 114.5 (3) | C7—C8—H8 | 120.8 |
C2—C1—S1 | 111.1 (3) | C9—C8—H8 | 120.8 |
C9—C1—H1 | 108.8 | C4—C9—C8 | 121.1 (4) |
C2—C1—H1 | 108.8 | C4—C9—C1 | 110.7 (4) |
S1—C1—H1 | 108.8 | C8—C9—C1 | 128.1 (4) |
C3—C2—C1 | 106.6 (4) | S1—C10—H10A | 109.5 |
C3—C2—S2 | 110.1 (3) | S1—C10—H10B | 109.5 |
C1—C2—S2 | 111.3 (3) | H10A—C10—H10B | 109.5 |
C3—C2—H2 | 109.6 | S1—C10—H10C | 109.5 |
C1—C2—H2 | 109.6 | H10A—C10—H10C | 109.5 |
S2—C2—H2 | 109.6 | H10B—C10—H10C | 109.5 |
C4—C3—C2 | 104.4 (4) | S2—C11—H11A | 109.5 |
C4—C3—H3A | 110.9 | S2—C11—H11B | 109.5 |
C2—C3—H3A | 110.9 | H11A—C11—H11B | 109.5 |
C4—C3—H3B | 110.9 | S2—C11—H11C | 109.5 |
C2—C3—H3B | 110.9 | H11A—C11—H11C | 109.5 |
H3A—C3—H3B | 108.9 | H11B—C11—H11C | 109.5 |
O2—S1—C1—C9 | 171.9 (3) | C2—C3—C4—C9 | −8.7 (6) |
O1—S1—C1—C9 | −60.5 (4) | C2—C3—C4—C5 | 171.4 (5) |
C10—S1—C1—C9 | 55.5 (4) | C9—C4—C5—C6 | 1.4 (8) |
O2—S1—C1—C2 | 53.7 (4) | C3—C4—C5—C6 | −178.8 (5) |
O1—S1—C1—C2 | −178.8 (3) | C4—C5—C6—C7 | −0.9 (8) |
C10—S1—C1—C2 | −62.7 (4) | C5—C6—C7—C8 | 0.4 (8) |
C9—C1—C2—C3 | −13.5 (5) | C6—C7—C8—C9 | −0.3 (7) |
S1—C1—C2—C3 | 110.6 (4) | C5—C4—C9—C8 | −1.3 (8) |
C9—C1—C2—S2 | 106.6 (4) | C3—C4—C9—C8 | 178.8 (4) |
S1—C1—C2—S2 | −129.3 (3) | C5—C4—C9—C1 | −180.0 (4) |
O3—S2—C2—C3 | 69.6 (3) | C3—C4—C9—C1 | 0.1 (6) |
O4—S2—C2—C3 | −58.8 (4) | C7—C8—C9—C4 | 0.8 (7) |
C11—S2—C2—C3 | −173.6 (3) | C7—C8—C9—C1 | 179.2 (5) |
O3—S2—C2—C1 | −48.3 (4) | C2—C1—C9—C4 | 8.5 (5) |
O4—S2—C2—C1 | −176.7 (3) | S1—C1—C9—C4 | −113.4 (4) |
C11—S2—C2—C1 | 68.4 (4) | C2—C1—C9—C8 | −170.1 (5) |
C1—C2—C3—C4 | 13.5 (5) | S1—C1—C9—C8 | 68.0 (6) |
S2—C2—C3—C4 | −107.3 (4) |
Experimental details
Crystal data | |
Chemical formula | C11H14O4S2 |
Mr | 274.34 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 170 |
a, b, c (Å) | 11.138 (6), 8.102 (2), 13.307 (2) |
β (°) | 91.82 (2) |
V (Å3) | 1200.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.40 × 0.30 × 0.07 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.843, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2249, 2128, 1034 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.134, 0.98 |
No. of reflections | 2128 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.34 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
S1—O2 | 1.448 (3) | S2—O3 | 1.436 (3) |
S1—O1 | 1.448 (3) | S2—O4 | 1.450 (3) |
S1—C10 | 1.749 (5) | S2—C11 | 1.755 (5) |
S1—C1 | 1.797 (5) | S2—C2 | 1.786 (5) |
O2—S1—O1 | 117.4 (2) | O3—S2—O4 | 118.1 (2) |
O2—S1—C10 | 109.2 (2) | O3—S2—C11 | 109.3 (2) |
O1—S1—C10 | 108.5 (2) | O4—S2—C11 | 108.4 (2) |
O2—S1—C1 | 107.1 (2) | O3—S2—C2 | 108.7 (2) |
O1—S1—C1 | 108.3 (2) | O4—S2—C2 | 106.7 (2) |
C10—S1—C1 | 105.7 (2) | C11—S2—C2 | 104.7 (2) |
Compounds with extended delocalization of π-electrons through sulfur-containing structures such as tetrathiafulvalene become electrical conductors at low temperatures when in crystalline arrays with electron-accepting systems. These observations have resulted in considerable research aimed at producing organic conductors. Synthesis of these systems requires precursors containing vicinal sulfur substitution. In this paper, we report the facile synthesis of such a precursor derived from diene which was prepared in one-step by reaction of indene with dimethyl disulfide (DMDS) in the presence of a zinc-promoted montmorillonite clay. Since the stereochemistry of the oily 1,2-diSCH3 adduct, (1), could not be determined unequivocally using NMR spectroscopy, (1) was oxidized to the crystalline disulfone, trans-2,3-bis(methylsulfonyl)indane, (2), for characterization using X-ray diffraction methods.
The crystal structure is composed of discrete molecules of (2) (Fig. 1) separated by normal van der Waals distances. The two sulfonyl groups are trans-fused to the five-membered indane ring. The C1/C2/C3/C4/C9 five-membered ring adopts a C2-envelope conformation, with C2 0.224 (8) Å out of the plane formed by the rest of the atoms in the ring; the maximum deviation of any atom from this plane being 0.001 (3) Å. The molecular dimensions in (2) are in agreement with the reported values for the corresponding dimensions (Orpen et al., 1994). It is interesting to note that the S—C distances involving the terminal methyl groups are significantly shorter [average 1.752 (3) Å] than the S—C bonds involving indyl group [average 1.792(5 Å]. The molecules of (2) lie about inversion centers with indyl moieties parallel to each other, as presented in Fig. 2, thus forming a hydrocarbon zone in the middle of the unit cell along the b axis.