Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016985/sk1514sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016985/sk15141sup2.hkl |
CCDC reference: 180155
Compound 1 was obtained as a minor side product in the synthesis of 2-[(9-anthracenyl)thiomethylthio]tetrahydropyran (Sipilä et al., 2001) from 2-(acetylthio)tetrahydropyran and 9-chloromethylthioanthracene. The thioester was hydrolysed with 2.2 eq. KOH in dimethyl sulfoxide–water solution at 273 K, 9-chloromethylthioanthracene was added at the same temperature in a one-pot reaction and the mixture was allowed to reach the room temperature by stirring overnight. Water was added and the mixture was extracted with diethyl ether. The organic phase was washed with water and brine, dried with Na2SO4, evaporated to dryness and purified with flash chromatography (Silica gel, CH2Cl2). The fractions containing compound 1 were evaporated and recrystallized from CH2Cl2 – ethanol, m.p. 454–455 K.
1H, 13C, DEPT and HETCOR NMR spectra were taken for samples in CDCl3 with a Varian GEMINI 200 and a Varian Inova 300 spectrometer with SiMe4 as an internal reference. The assignments are based on DEPT and HETCOR measurements. 1H NMR: δ4.50, s, (SCH2), 4.56, s, (H8, H9), 6.8–6.9, m, (12H, arom.), 7.7–7.8, m, (4H, arom.) 13C NMR: δ 36.0 (SCH2S), 53.7 (C8, C9), 125.53, 126.55, 126.70, 127.32, 142.27, 142.34.
All hydrogen atoms in 1 are at calculated positions and they are refined using a riding model with fixed distances and angles.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf-Nonius, 1994); data reduction: WinGX (Farrugia, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C29H20S2 | Dx = 1.408 Mg m−3 |
Mr = 432.57 | Melting point = 454–455 K |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54180 Å |
a = 10.619 (2) Å | Cell parameters from 25 reflections |
b = 16.605 (3) Å | θ = 5–10° |
c = 11.966 (2) Å | µ = 2.46 mm−1 |
β = 104.67 (3)° | T = 193 K |
V = 2041.2 (7) Å3 | Prismatic, light brown |
Z = 4 | 0.24 × 0.22 × 0.21 mm |
F(000) = 904 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.044 |
Radiation source: fine-focus sealed tube | θmax = 65.0°, θmin = 4.3° |
Graphite monochromator | h = −12→0 |
ω/2θ scans | k = 0→19 |
3681 measured reflections | l = −13→14 |
3460 independent reflections | 3 standard reflections every 100 reflections |
3057 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0652P)2 + 1.5819P]
where P = (Fo2 + 2Fc2)/3 |
3460 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
C29H20S2 | V = 2041.2 (7) Å3 |
Mr = 432.57 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 10.619 (2) Å | µ = 2.46 mm−1 |
b = 16.605 (3) Å | T = 193 K |
c = 11.966 (2) Å | 0.24 × 0.22 × 0.21 mm |
β = 104.67 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.044 |
3681 measured reflections | 3 standard reflections every 100 reflections |
3460 independent reflections | intensity decay: none |
3057 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.61 e Å−3 |
3460 reflections | Δρmin = −0.47 e Å−3 |
280 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.28760 (5) | 1.05662 (3) | 0.11707 (5) | 0.02406 (16) | |
S3 | 0.27661 (5) | 0.92906 (3) | −0.04435 (4) | 0.02488 (16) | |
C2 | 0.1955 (2) | 1.01884 (14) | −0.01808 (19) | 0.0274 (5) | |
H2B | 0.1927 | 1.0588 | −0.0801 | 0.033* | |
H2C | 0.1053 | 1.0067 | −0.0148 | 0.033* | |
C3a | 0.29629 (19) | 0.88556 (12) | 0.09968 (17) | 0.0185 (4) | |
C3b | 0.42299 (18) | 0.83649 (12) | 0.12984 (18) | 0.0187 (4) | |
C4 | 0.5245 (2) | 0.84691 (14) | 0.0766 (2) | 0.0251 (5) | |
H4B | 0.5159 | 0.8847 | 0.0155 | 0.030* | |
C5 | 0.6379 (2) | 0.80241 (14) | 0.1124 (2) | 0.0292 (5) | |
H5B | 0.7059 | 0.8094 | 0.0748 | 0.035* | |
C6 | 0.6533 (2) | 0.74802 (14) | 0.2021 (2) | 0.0293 (5) | |
H6B | 0.7317 | 0.7181 | 0.2268 | 0.035* | |
C7 | 0.5531 (2) | 0.73757 (13) | 0.25552 (19) | 0.0239 (5) | |
H7B | 0.5630 | 0.7002 | 0.3172 | 0.029* | |
C7a | 0.43861 (19) | 0.78101 (12) | 0.22010 (18) | 0.0192 (4) | |
C8 | 0.33196 (18) | 0.77423 (12) | 0.28210 (18) | 0.0188 (4) | |
H8B | 0.3427 | 0.7220 | 0.3251 | 0.023* | |
C9 | 0.34004 (18) | 0.84602 (12) | 0.37335 (17) | 0.0185 (4) | |
H9A | 0.3539 | 0.8221 | 0.4522 | 0.022* | |
C9a | 0.45069 (19) | 0.90322 (13) | 0.37410 (17) | 0.0192 (4) | |
C10 | 0.5668 (2) | 0.90078 (14) | 0.46031 (19) | 0.0245 (5) | |
H10C | 0.5768 | 0.8629 | 0.5214 | 0.029* | |
C11 | 0.6675 (2) | 0.95283 (15) | 0.4579 (2) | 0.0288 (5) | |
H11A | 0.7461 | 0.9510 | 0.5174 | 0.035* | |
C12 | 0.6536 (2) | 1.00771 (15) | 0.3686 (2) | 0.0278 (5) | |
H12A | 0.7229 | 1.0433 | 0.3664 | 0.033* | |
C13 | 0.5384 (2) | 1.01081 (14) | 0.28227 (19) | 0.0239 (5) | |
H13A | 0.5298 | 1.0483 | 0.2208 | 0.029* | |
C13a | 0.43593 (18) | 0.95988 (13) | 0.28469 (17) | 0.0183 (4) | |
C13b | 0.30394 (19) | 0.96045 (12) | 0.19461 (17) | 0.0178 (4) | |
C14 | 0.18304 (19) | 0.82842 (12) | 0.10234 (18) | 0.0186 (4) | |
C15 | 0.06354 (19) | 0.82889 (13) | 0.02061 (19) | 0.0227 (5) | |
H15A | 0.0488 | 0.8662 | −0.0416 | 0.027* | |
C16 | −0.0341 (2) | 0.77566 (14) | 0.0289 (2) | 0.0283 (5) | |
H16A | −0.1152 | 0.7769 | −0.0274 | 0.034* | |
C17 | −0.0146 (2) | 0.72079 (14) | 0.1184 (2) | 0.0285 (5) | |
H17A | −0.0816 | 0.6843 | 0.1237 | 0.034* | |
C18 | 0.1044 (2) | 0.71963 (13) | 0.2006 (2) | 0.0249 (5) | |
H18A | 0.1186 | 0.6821 | 0.2624 | 0.030* | |
C19 | 0.20260 (18) | 0.77288 (12) | 0.19294 (18) | 0.0193 (4) | |
C20 | 0.21582 (19) | 0.89387 (12) | 0.34745 (18) | 0.0187 (4) | |
C21 | 0.1227 (2) | 0.88262 (13) | 0.40882 (18) | 0.0231 (5) | |
H21A | 0.1360 | 0.8429 | 0.4677 | 0.028* | |
C22 | 0.0107 (2) | 0.92867 (15) | 0.3852 (2) | 0.0287 (5) | |
H22A | −0.0535 | 0.9201 | 0.4267 | 0.034* | |
C23 | −0.0073 (2) | 0.98713 (15) | 0.3009 (2) | 0.0292 (5) | |
H23A | −0.0832 | 1.0198 | 0.2855 | 0.035* | |
C24 | 0.0853 (2) | 0.99856 (14) | 0.23817 (18) | 0.0229 (5) | |
H24A | 0.0718 | 1.0389 | 0.1801 | 0.027* | |
C25 | 0.19644 (19) | 0.95182 (12) | 0.25945 (17) | 0.0173 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0265 (3) | 0.0192 (3) | 0.0249 (3) | −0.0018 (2) | 0.0035 (2) | 0.0037 (2) |
S3 | 0.0289 (3) | 0.0276 (3) | 0.0189 (3) | 0.0039 (2) | 0.0074 (2) | 0.0037 (2) |
C2 | 0.0257 (11) | 0.0259 (12) | 0.0272 (12) | −0.0005 (9) | 0.0007 (9) | 0.0016 (9) |
C3a | 0.0155 (10) | 0.0209 (10) | 0.0191 (10) | 0.0023 (8) | 0.0046 (8) | 0.0012 (8) |
C3b | 0.0147 (10) | 0.0192 (10) | 0.0228 (11) | 0.0018 (8) | 0.0057 (8) | −0.0012 (8) |
C4 | 0.0233 (11) | 0.0261 (11) | 0.0297 (12) | 0.0013 (9) | 0.0139 (9) | 0.0010 (9) |
C5 | 0.0203 (11) | 0.0317 (12) | 0.0406 (13) | 0.0015 (9) | 0.0172 (10) | −0.0030 (10) |
C6 | 0.0189 (11) | 0.0299 (12) | 0.0397 (13) | 0.0083 (9) | 0.0084 (9) | −0.0021 (11) |
C7 | 0.0207 (10) | 0.0226 (11) | 0.0281 (11) | 0.0056 (9) | 0.0057 (9) | 0.0009 (9) |
C7a | 0.0156 (10) | 0.0187 (10) | 0.0235 (11) | 0.0023 (8) | 0.0056 (8) | −0.0006 (8) |
C8 | 0.0162 (10) | 0.0166 (10) | 0.0241 (11) | 0.0017 (8) | 0.0062 (8) | 0.0036 (8) |
C9 | 0.0150 (9) | 0.0229 (11) | 0.0181 (10) | 0.0035 (8) | 0.0048 (8) | 0.0038 (8) |
C9a | 0.0118 (9) | 0.0253 (11) | 0.0207 (10) | 0.0036 (8) | 0.0044 (8) | −0.0018 (8) |
C10 | 0.0181 (10) | 0.0316 (12) | 0.0219 (11) | 0.0078 (9) | 0.0015 (8) | −0.0020 (9) |
C11 | 0.0123 (10) | 0.0407 (13) | 0.0306 (12) | 0.0028 (9) | 0.0001 (9) | −0.0101 (10) |
C12 | 0.0132 (10) | 0.0375 (13) | 0.0331 (12) | −0.0053 (9) | 0.0064 (9) | −0.0087 (10) |
C13 | 0.0186 (10) | 0.0297 (12) | 0.0255 (11) | −0.0027 (9) | 0.0091 (9) | −0.0034 (9) |
C13a | 0.0117 (9) | 0.0231 (10) | 0.0203 (10) | 0.0018 (8) | 0.0042 (8) | −0.0020 (8) |
C13b | 0.0140 (9) | 0.0188 (10) | 0.0198 (10) | 0.0007 (7) | 0.0030 (8) | 0.0005 (8) |
C14 | 0.0151 (9) | 0.0194 (10) | 0.0221 (10) | 0.0014 (8) | 0.0059 (8) | −0.0028 (8) |
C15 | 0.0169 (10) | 0.0240 (11) | 0.0258 (11) | 0.0062 (8) | 0.0030 (8) | −0.0021 (9) |
C16 | 0.0140 (10) | 0.0331 (13) | 0.0363 (13) | 0.0026 (9) | 0.0038 (9) | −0.0093 (10) |
C17 | 0.0172 (10) | 0.0309 (12) | 0.0412 (14) | −0.0054 (9) | 0.0145 (10) | −0.0087 (10) |
C18 | 0.0210 (10) | 0.0259 (11) | 0.0315 (12) | −0.0013 (9) | 0.0134 (9) | −0.0019 (9) |
C19 | 0.0142 (10) | 0.0205 (10) | 0.0245 (11) | 0.0020 (8) | 0.0074 (8) | −0.0020 (8) |
C20 | 0.0137 (9) | 0.0217 (11) | 0.0212 (10) | −0.0015 (8) | 0.0052 (8) | −0.0021 (8) |
C21 | 0.0206 (10) | 0.0271 (11) | 0.0236 (11) | −0.0025 (9) | 0.0089 (9) | −0.0012 (9) |
C22 | 0.0172 (10) | 0.0409 (14) | 0.0322 (12) | −0.0011 (9) | 0.0139 (9) | −0.0061 (10) |
C23 | 0.0164 (10) | 0.0379 (13) | 0.0333 (12) | 0.0077 (9) | 0.0065 (9) | −0.0054 (10) |
C24 | 0.0178 (10) | 0.0269 (11) | 0.0224 (11) | 0.0038 (8) | 0.0024 (8) | −0.0016 (9) |
C25 | 0.0132 (9) | 0.0191 (10) | 0.0189 (10) | −0.0012 (8) | 0.0029 (8) | −0.0030 (8) |
S1—C2 | 1.779 (2) | C10—H10C | 0.9500 |
S1—C13b | 1.833 (2) | C11—C12 | 1.384 (4) |
S3—C2 | 1.789 (2) | C11—H11A | 0.9500 |
S3—C3a | 1.831 (2) | C12—C13 | 1.387 (3) |
C2—H2B | 0.9900 | C12—H12A | 0.9500 |
C2—H2C | 0.9900 | C13—C13a | 1.385 (3) |
C3a—C3b | 1.536 (3) | C13—H13A | 0.9500 |
C3a—C14 | 1.539 (3) | C13a—C13b | 1.537 (3) |
C3a—C13b | 1.672 (3) | C13b—C25 | 1.541 (3) |
C3b—C4 | 1.395 (3) | C14—C15 | 1.392 (3) |
C3b—C7a | 1.397 (3) | C14—C19 | 1.398 (3) |
C4—C5 | 1.385 (3) | C15—C16 | 1.385 (3) |
C4—H4B | 0.9500 | C15—H15A | 0.9500 |
C5—C6 | 1.380 (3) | C16—C17 | 1.381 (3) |
C5—H5B | 0.9500 | C16—H16A | 0.9500 |
C6—C7 | 1.384 (3) | C17—C18 | 1.391 (3) |
C6—H6B | 0.9500 | C17—H17A | 0.9500 |
C7—C7a | 1.385 (3) | C18—C19 | 1.388 (3) |
C7—H7B | 0.9500 | C18—H18A | 0.9500 |
C7a—C8 | 1.507 (3) | C20—C21 | 1.386 (3) |
C8—C19 | 1.511 (3) | C20—C25 | 1.403 (3) |
C8—C9 | 1.604 (3) | C21—C22 | 1.382 (3) |
C8—H8B | 1.0000 | C21—H21A | 0.9500 |
C9—C20 | 1.503 (3) | C22—C23 | 1.378 (3) |
C9—C9a | 1.509 (3) | C22—H22A | 0.9500 |
C9—H9A | 1.0000 | C23—C24 | 1.393 (3) |
C9a—C10 | 1.393 (3) | C23—H23A | 0.9500 |
C9a—C13a | 1.403 (3) | C24—C25 | 1.382 (3) |
C10—C11 | 1.381 (3) | C24—H24A | 0.9500 |
C2—S1—C13b | 96.47 (10) | C12—C11—H11A | 120.1 |
C2—S3—C3a | 96.24 (10) | C11—C12—C13 | 120.1 (2) |
S1—C2—S3 | 106.00 (12) | C11—C12—H12A | 119.9 |
S1—C2—H2B | 110.5 | C13—C12—H12A | 119.9 |
S3—C2—H2B | 110.5 | C13a—C13—C12 | 120.7 (2) |
S1—C2—H2C | 110.5 | C13a—C13—H13A | 119.6 |
S3—C2—H2C | 110.5 | C12—C13—H13A | 119.6 |
H2B—C2—H2C | 108.7 | C13—C13a—C9a | 119.26 (19) |
C3b—C3a—C14 | 108.11 (16) | C13—C13a—C13b | 124.32 (19) |
C3b—C3a—C13b | 110.24 (15) | C9a—C13a—C13b | 116.42 (18) |
C14—C3a—C13b | 110.38 (15) | C13a—C13b—C25 | 107.86 (16) |
C3b—C3a—S3 | 108.35 (14) | C13a—C13b—C3a | 110.52 (15) |
C14—C3a—S3 | 111.05 (14) | C25—C13b—C3a | 110.98 (15) |
C13b—C3a—S3 | 108.68 (13) | C13a—C13b—S1 | 108.25 (14) |
C4—C3b—C7a | 118.72 (19) | C25—C13b—S1 | 110.41 (14) |
C4—C3b—C3a | 124.01 (19) | C3a—C13b—S1 | 108.78 (13) |
C7a—C3b—C3a | 117.19 (17) | C15—C14—C19 | 118.58 (19) |
C5—C4—C3b | 120.3 (2) | C15—C14—C3a | 124.07 (19) |
C5—C4—H4B | 119.8 | C19—C14—C3a | 117.35 (17) |
C3b—C4—H4B | 119.8 | C16—C15—C14 | 120.8 (2) |
C6—C5—C4 | 120.8 (2) | C16—C15—H15A | 119.6 |
C6—C5—H5B | 119.6 | C14—C15—H15A | 119.6 |
C4—C5—H5B | 119.6 | C17—C16—C15 | 120.6 (2) |
C5—C6—C7 | 119.2 (2) | C17—C16—H16A | 119.7 |
C5—C6—H6B | 120.4 | C15—C16—H16A | 119.7 |
C7—C6—H6B | 120.4 | C16—C17—C18 | 119.2 (2) |
C6—C7—C7a | 120.7 (2) | C16—C17—H17A | 120.4 |
C6—C7—H7B | 119.6 | C18—C17—H17A | 120.4 |
C7a—C7—H7B | 119.6 | C19—C18—C17 | 120.5 (2) |
C7—C7a—C3b | 120.22 (19) | C19—C18—H18A | 119.7 |
C7—C7a—C8 | 121.42 (19) | C17—C18—H18A | 119.7 |
C3b—C7a—C8 | 118.23 (17) | C18—C19—C14 | 120.31 (19) |
C7a—C8—C19 | 108.40 (17) | C18—C19—C8 | 121.79 (19) |
C7a—C8—C9 | 111.23 (16) | C14—C19—C8 | 117.88 (18) |
C19—C8—C9 | 111.96 (16) | C21—C20—C25 | 120.11 (19) |
C7a—C8—H8B | 108.4 | C21—C20—C9 | 121.76 (19) |
C19—C8—H8B | 108.4 | C25—C20—C9 | 118.13 (18) |
C9—C8—H8B | 108.4 | C22—C21—C20 | 120.7 (2) |
C20—C9—C9a | 108.05 (16) | C22—C21—H21A | 119.7 |
C20—C9—C8 | 111.07 (16) | C20—C21—H21A | 119.7 |
C9a—C9—C8 | 112.28 (16) | C23—C22—C21 | 119.5 (2) |
C20—C9—H9A | 108.4 | C23—C22—H22A | 120.2 |
C9a—C9—H9A | 108.4 | C21—C22—H22A | 120.2 |
C8—C9—H9A | 108.4 | C22—C23—C24 | 120.3 (2) |
C10—C9a—C13a | 119.41 (19) | C22—C23—H23A | 119.9 |
C10—C9a—C9 | 121.85 (19) | C24—C23—H23A | 119.9 |
C13a—C9a—C9 | 118.74 (17) | C25—C24—C23 | 120.7 (2) |
C11—C10—C9a | 120.8 (2) | C25—C24—H24A | 119.6 |
C11—C10—H10C | 119.6 | C23—C24—H24A | 119.6 |
C9a—C10—H10C | 119.6 | C24—C25—C20 | 118.67 (19) |
C10—C11—C12 | 119.7 (2) | C24—C25—C13b | 124.22 (19) |
C10—C11—H11A | 120.1 | C20—C25—C13b | 117.09 (17) |
C13b—S1—C2—S3 | −46.59 (13) | S3—C3a—C13b—C13a | −118.02 (15) |
C3a—S3—C2—S1 | 46.98 (13) | C3b—C3a—C13b—C25 | −119.03 (18) |
C2—S3—C3a—C3b | −147.83 (14) | C14—C3a—C13b—C25 | 0.3 (2) |
C2—S3—C3a—C14 | 93.57 (15) | S3—C3a—C13b—C25 | 122.36 (15) |
C2—S3—C3a—C13b | −28.03 (14) | C3b—C3a—C13b—S1 | 119.31 (15) |
C14—C3a—C3b—C4 | 140.8 (2) | C14—C3a—C13b—S1 | −121.32 (15) |
C13b—C3a—C3b—C4 | −98.4 (2) | S3—C3a—C13b—S1 | 0.69 (15) |
S3—C3a—C3b—C4 | 20.4 (3) | C2—S1—C13b—C13a | 147.28 (15) |
C14—C3a—C3b—C7a | −42.4 (2) | C2—S1—C13b—C25 | −94.87 (15) |
C13b—C3a—C3b—C7a | 78.3 (2) | C2—S1—C13b—C3a | 27.15 (14) |
S3—C3a—C3b—C7a | −162.84 (16) | C3b—C3a—C14—C15 | −137.7 (2) |
C7a—C3b—C4—C5 | 0.5 (3) | C13b—C3a—C14—C15 | 101.6 (2) |
C3a—C3b—C4—C5 | 177.3 (2) | S3—C3a—C14—C15 | −19.0 (2) |
C3b—C4—C5—C6 | −0.9 (4) | C3b—C3a—C14—C19 | 42.3 (2) |
C4—C5—C6—C7 | 0.7 (4) | C13b—C3a—C14—C19 | −78.3 (2) |
C5—C6—C7—C7a | −0.1 (3) | S3—C3a—C14—C19 | 161.06 (15) |
C6—C7—C7a—C3b | −0.3 (3) | C19—C14—C15—C16 | 0.2 (3) |
C6—C7—C7a—C8 | −176.1 (2) | C3a—C14—C15—C16 | −179.81 (19) |
C4—C3b—C7a—C7 | 0.1 (3) | C14—C15—C16—C17 | −0.2 (3) |
C3a—C3b—C7a—C7 | −176.88 (19) | C15—C16—C17—C18 | 0.2 (3) |
C4—C3b—C7a—C8 | 176.03 (19) | C16—C17—C18—C19 | −0.1 (3) |
C3a—C3b—C7a—C8 | −0.9 (3) | C17—C18—C19—C14 | 0.0 (3) |
C7—C7a—C8—C19 | −139.4 (2) | C17—C18—C19—C8 | 178.79 (19) |
C3b—C7a—C8—C19 | 44.7 (2) | C15—C14—C19—C18 | 0.0 (3) |
C7—C7a—C8—C9 | 97.1 (2) | C3a—C14—C19—C18 | 179.94 (18) |
C3b—C7a—C8—C9 | −78.8 (2) | C15—C14—C19—C8 | −178.89 (18) |
C7a—C8—C9—C20 | 121.80 (18) | C3a—C14—C19—C8 | 1.1 (3) |
C19—C8—C9—C20 | 0.4 (2) | C7a—C8—C19—C18 | 136.5 (2) |
C7a—C8—C9—C9a | 0.7 (2) | C9—C8—C19—C18 | −100.5 (2) |
C19—C8—C9—C9a | −120.77 (18) | C7a—C8—C19—C14 | −44.7 (2) |
C20—C9—C9a—C10 | 134.9 (2) | C9—C8—C19—C14 | 78.4 (2) |
C8—C9—C9a—C10 | −102.3 (2) | C9a—C9—C20—C21 | −135.6 (2) |
C20—C9—C9a—C13a | −45.6 (2) | C8—C9—C20—C21 | 100.8 (2) |
C8—C9—C9a—C13a | 77.2 (2) | C9a—C9—C20—C25 | 43.6 (2) |
C13a—C9a—C10—C11 | −0.7 (3) | C8—C9—C20—C25 | −80.0 (2) |
C9—C9a—C10—C11 | 178.82 (19) | C25—C20—C21—C22 | −0.7 (3) |
C9a—C10—C11—C12 | −0.4 (3) | C9—C20—C21—C22 | 178.5 (2) |
C10—C11—C12—C13 | 0.5 (3) | C20—C21—C22—C23 | −1.0 (3) |
C11—C12—C13—C13a | 0.6 (3) | C21—C22—C23—C24 | 1.4 (3) |
C12—C13—C13a—C9a | −1.7 (3) | C22—C23—C24—C25 | −0.2 (3) |
C12—C13—C13a—C13b | 178.44 (19) | C23—C24—C25—C20 | −1.5 (3) |
C10—C9a—C13a—C13 | 1.7 (3) | C23—C24—C25—C13b | −179.82 (19) |
C9—C9a—C13a—C13 | −177.78 (18) | C21—C20—C25—C24 | 1.9 (3) |
C10—C9a—C13a—C13b | −178.41 (18) | C9—C20—C25—C24 | −177.26 (18) |
C9—C9a—C13a—C13b | 2.1 (3) | C21—C20—C25—C13b | −179.64 (18) |
C13—C13a—C13b—C25 | −137.7 (2) | C9—C20—C25—C13b | 1.2 (3) |
C9a—C13a—C13b—C25 | 42.5 (2) | C13a—C13b—C25—C24 | 133.9 (2) |
C13—C13a—C13b—C3a | 100.8 (2) | C3a—C13b—C25—C24 | −104.9 (2) |
C9a—C13a—C13b—C3a | −79.0 (2) | S1—C13b—C25—C24 | 15.8 (3) |
C13—C13a—C13b—S1 | −18.2 (2) | C13a—C13b—C25—C20 | −44.5 (2) |
C9a—C13a—C13b—S1 | 161.94 (15) | C3a—C13b—C25—C20 | 76.7 (2) |
C3b—C3a—C13b—C13a | 0.6 (2) | S1—C13b—C25—C20 | −162.55 (15) |
C14—C3a—C13b—C13a | 119.96 (18) |
Experimental details
Crystal data | |
Chemical formula | C29H20S2 |
Mr | 432.57 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 10.619 (2), 16.605 (3), 11.966 (2) |
β (°) | 104.67 (3) |
V (Å3) | 2041.2 (7) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.46 |
Crystal size (mm) | 0.24 × 0.22 × 0.21 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3681, 3460, 3057 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.113, 1.04 |
No. of reflections | 3460 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.47 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), WinGX (Farrugia, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
S1—C2 | 1.779 (2) | C3b—C7a | 1.397 (3) |
S1—C13b | 1.833 (2) | C8—C9 | 1.604 (3) |
S3—C2 | 1.789 (2) | C9a—C13a | 1.403 (3) |
S3—C3a | 1.831 (2) | C13a—C13b | 1.537 (3) |
C3a—C3b | 1.536 (3) | C13b—C25 | 1.541 (3) |
C3a—C14 | 1.539 (3) | C14—C19 | 1.398 (3) |
C3a—C13b | 1.672 (3) | C20—C25 | 1.403 (3) |
C2—S1—C13b | 96.47 (10) | C13—C13a—C13b | 124.32 (19) |
C2—S3—C3a | 96.24 (10) | C3a—C13b—S1 | 108.78 (13) |
S1—C2—S3 | 106.00 (12) | C15—C14—C3a | 124.07 (19) |
C3b—C3a—S3 | 108.35 (14) | C24—C25—C13b | 124.22 (19) |
C4—C3b—C3a | 124.01 (19) | ||
C13b—S1—C2—S3 | −46.59 (13) | S3—C3a—C3b—C4 | 20.4 (3) |
C3a—S3—C2—S1 | 46.98 (13) | C13—C13a—C13b—S1 | −18.2 (2) |
C2—S3—C3a—C3b | −147.83 (14) | C2—S1—C13b—C13a | 147.28 (15) |
C2—S3—C3a—C14 | 93.57 (15) | C2—S1—C13b—C25 | −94.87 (15) |
C2—S3—C3a—C13b | −28.03 (14) | C2—S1—C13b—C3a | 27.15 (14) |
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The title compound (1) is the only anthracene dimer reported so far where the S-atoms are bonded to the anthryl groups and additionally form a fused heterocyclic ring. According to the CA Index nomenclature (1) is called 8,9-dihydro-3a,8[1,2]:9,13b[1¨,2¨]- dibenzenodibenzo-[3,4:7,8]cycloocta[1,2-d]-1,3-dithiole. The synthesis and photochemical studies of an analogous anthracene dimer with a fused 1,3-dioxole ring have been published, but unfortunately without X-ray data (Desvergne et al., 1992, 1995).
A typical feature of the highly strained butterfly shaped anthracene dimers is the remarkable elongation of the central C–C bonds connecting the anthracene moieties compared to the C–C single bond standard of 1.54 Å (Battersby et al., 1995). Even in unsubstituted 9,9:10,10-bianthracene the central bond is reported to reach the value of 1.620 Å at 120 K (Batsanov & Howard, 2000, private communication), 1.618 Å at 198 K (Abboud et al., 1990), 1.612 Å (Ehrenberg, 1966) and 1.623 Å (Choi & Marinkas, 1980) at 295 K (DPANTH in Cambridge Structural Database (CSD), Version 5.21; Allen & Kennard, 1993). The longest reported central C–C bonds of 1.669 and 1.670 Å for 9,9:10,10-bianthracene derivatives are in the asymmetric photodimer of (Z)-1-(9-anthryloxy)-1,2-bis(9- anthryl)-2-methoxyethene (2) (HAVTAZ) (Langer & Becker, 1993a) and in symmetric 9,10-(10-methoxy-9-methylanthraceno-9-methoxy-10-methylanthracene (HAVVEF) (Langer & Becker, 1993b), respectively. The even longer C3a–C13b bond of 1.672 (3) Å in (1) (Fig. 1, Table 1) is apparently due to the greater steric demand of the fused heterocyclic 1,3-dithiole ring. The length of the other central bond (C8–C9) is only 1.604 (3) Å in (1) and 1.619 Å in (2). Similar large differences in the central bond lengths appear also in the anthracene dimer with the fused cyclobutadione ring, 1.655 (5) and 1.607 (6) Å (SIWDOR) (Becker et al., 1991) and with the fused cyclohexene ring 1.663 and 1.614 Å (REFVED) (Kammermeier et al., 1996). Several discussions based on experimental results and their comparison with theoretical calculations have been presented on the lengthening of the bridging C–C bond in anthracene dimers and related molecules (Dougherty et al., 1986; Battersby et al., 1995; Baldridge et al., 1997).
The bond angles in the 1,3-dithiole ring of (1) are rather close to those in the nonfused 4,5-tetrasubstituted 1,3-dithiole derivatives found in CSD. The main difference is the shape of the ring. They all posses more or less twisted envelope conformation but (1) is the only compound where the S atoms are in the same plane with the two C–atoms between them. This is clearly seen in the torsion angle S–C–C–S value which is only 0.69 (15)° in (1), but 38.4° in SOSHIR (Mloston et al., 1991), 49.0° in ZAMLOO (Leino et al., 1995), 44.5° in LEVFAT (Mloston et al., 1999), 52.4° in HASBIM and 53.6° in HASBEI (Kagi et al., 1993). The torsion angles C–S–C–C in (1) are 27.15 (14) and -28.03 (14)° thus proving the ring to be almost symmetric with a pseudo mirror plane.
The C–C distances of the 1,3-dithiole fragment in the above mentioned structures are mostly only slightly longer than normal, the longest being, however, 1.617 Å in LEVFAT (Mloston et al., 1999) probably due to bulky adamantyl and two phenyl groups. In compound (1) the S–C2 bonds are clearly shorter than the S–C bonds to the anthryl groups and both pairs of S–C bonds are shorter than the corresponding S–C bonds in the 1,3-dithiole structures of comparison.
In butterfly shaped dimers the anthracene moieties are typically bent at the central carbon atoms where the molecules are joined. The bent halves within each anthryl group in (1) form interplanar angles of 136.32 (8) and 130.72 (8)° which agree well with the values of 136.2 (2) and 129.7 (2)° found in SIDWOR (Becker et al., 1991). Due to the small torsion angle S–C–C–S value of 0.69° in (1) the S atoms and C2 deviate 0.029 (3), 0.056 (3) and -0.761 (4) Å from the plane defined by atoms C8, C9, C3a and C13b, respectively. According to the present data the 1,3-dithiole ring in (1) is strained.
Molecular packing of (1) shows tubular channels and separate molecule columns in the a axis direction. Molecules are oriented in such a way that the inversion related S-atoms seem to form rows of four S, one row passing the origin and the other the center of the cell through the crystal (Fig. 2).