The title compound, C
15H
16O
2S
2, was prepared by the Lewis acid-catalysed reaction of 2-methylresorcinol with α-chloro-α-(methylsulfanyl)acetone. The benzo[1,2-
b:5,4-
b′]difuran group is almost planar. The crystal structure is stabilized by aromatic π–π stacking and —CH
2—H
π interactions.
Supporting information
CCDC reference: 636718
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.046
- wR factor = 0.135
- Data-to-parameter ratio = 17.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.65 mm
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
2,6,8-Trimethyl-3,5-bis(methylsulfanyl)benzo[1,2 - b:5,4 - b']difuran
top
Crystal data top
C15H16O2S2 | F(000) = 616 |
Mr = 292.40 | Dx = 1.347 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p_2ybc | Cell parameters from 5039 reflections |
a = 7.895 (3) Å | θ = 2.7–28.2° |
b = 13.008 (5) Å | µ = 0.36 mm−1 |
c = 14.498 (6) Å | T = 173 K |
β = 104.479 (7)° | Block, colorless |
V = 1441.6 (10) Å3 | 0.65 × 0.58 × 0.54 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD diffractometer | 2702 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.070 |
Graphite monochromator | θmax = 27.0°, θmin = 2.1° |
Detector resolution: 10.00 pixels mm-1 | h = −10→9 |
φ and ω scans | k = −16→13 |
8031 measured reflections | l = −18→18 |
3097 independent reflections | |
Refinement top
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0664P)2 + 1.1009P] where P = (Fo2 + 2Fc2)/3 |
3097 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Special details top
Experimental. Spectroscopic analysis: 1H NMR (CDCl3): δ 2.34 (s, 6H), 2.57 (s, 6H), 2.61
(s, 3H), 7.52 (s, 1H); 13C NMR (CDCl3): δ 8.4, 12.6, 18.6, 104.6, 104.8,
108.6, 126.1, 150.8, 158.1; MS: 292 [M+]. |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.16417 (8) | 0.13072 (5) | 0.01430 (4) | 0.03434 (18) | |
S2 | 0.19226 (7) | 0.64068 (4) | 0.04782 (4) | 0.03309 (18) | |
O2 | 0.67414 (19) | 0.55739 (11) | 0.17686 (10) | 0.0264 (3) | |
O1 | 0.64796 (19) | 0.18436 (11) | 0.16212 (10) | 0.0270 (3) | |
C1 | 0.3653 (3) | 0.17953 (16) | 0.07964 (13) | 0.0266 (4) | |
C2 | 0.4143 (3) | 0.28718 (15) | 0.09559 (13) | 0.0230 (4) | |
C3 | 0.3269 (3) | 0.38103 (15) | 0.07452 (13) | 0.0249 (4) | |
H3 | 0.2094 | 0.3845 | 0.0423 | 0.030* | |
C4 | 0.4261 (3) | 0.46921 (15) | 0.10468 (13) | 0.0234 (4) | |
C5 | 0.3902 (3) | 0.57913 (16) | 0.09933 (13) | 0.0255 (4) | |
C6 | 0.5414 (3) | 0.62742 (15) | 0.14272 (14) | 0.0262 (4) | |
C7 | 0.6027 (3) | 0.46116 (15) | 0.15430 (13) | 0.0234 (4) | |
C8 | 0.6950 (3) | 0.37021 (15) | 0.18017 (14) | 0.0251 (4) | |
C9 | 0.5907 (3) | 0.28482 (16) | 0.14686 (13) | 0.0238 (4) | |
C10 | 0.5073 (3) | 0.12257 (15) | 0.12071 (14) | 0.0271 (4) | |
C11 | 0.5902 (3) | 0.73707 (17) | 0.15837 (15) | 0.0316 (5) | |
H11A | 0.6805 | 0.7532 | 0.1270 | 0.038* | |
H11B | 0.6321 | 0.7499 | 0.2254 | 0.038* | |
H11C | 0.4896 | 0.7793 | 0.1329 | 0.038* | |
C12 | 0.8811 (3) | 0.36481 (17) | 0.23901 (18) | 0.0364 (5) | |
H12A | 0.9588 | 0.3625 | 0.1976 | 0.055* | |
H12B | 0.8965 | 0.3041 | 0.2778 | 0.055* | |
H12C | 0.9066 | 0.4244 | 0.2791 | 0.055* | |
C13 | 0.5402 (3) | 0.01050 (17) | 0.13009 (16) | 0.0342 (5) | |
H13A | 0.5757 | −0.0076 | 0.1963 | 0.041* | |
H13B | 0.6311 | −0.0076 | 0.0998 | 0.041* | |
H13C | 0.4351 | −0.0260 | 0.1002 | 0.041* | |
C14 | 0.0312 (3) | 0.1401 (2) | 0.09831 (19) | 0.0424 (6) | |
H14A | −0.0842 | 0.1150 | 0.0695 | 0.064* | |
H14B | 0.0245 | 0.2107 | 0.1166 | 0.064* | |
H14C | 0.0825 | 0.0997 | 0.1537 | 0.064* | |
C15 | 0.0642 (3) | 0.6019 (2) | 0.12901 (16) | 0.0371 (5) | |
H15A | −0.0509 | 0.6310 | 0.1088 | 0.056* | |
H15B | 0.1196 | 0.6259 | 0.1920 | 0.056* | |
H15C | 0.0559 | 0.5283 | 0.1295 | 0.056* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0317 (3) | 0.0369 (3) | 0.0349 (3) | −0.0076 (2) | 0.0093 (2) | −0.0105 (2) |
S2 | 0.0309 (3) | 0.0336 (3) | 0.0348 (3) | 0.0082 (2) | 0.0082 (2) | 0.0072 (2) |
O2 | 0.0264 (7) | 0.0235 (7) | 0.0300 (7) | −0.0011 (6) | 0.0083 (5) | −0.0009 (6) |
O1 | 0.0292 (7) | 0.0229 (7) | 0.0290 (7) | 0.0028 (6) | 0.0074 (5) | 0.0012 (6) |
C1 | 0.0302 (10) | 0.0281 (11) | 0.0239 (9) | −0.0025 (8) | 0.0111 (7) | −0.0027 (8) |
C2 | 0.0252 (10) | 0.0240 (10) | 0.0209 (8) | −0.0020 (8) | 0.0080 (7) | −0.0015 (7) |
C3 | 0.0245 (10) | 0.0282 (10) | 0.0222 (9) | 0.0005 (8) | 0.0060 (7) | 0.0003 (7) |
C4 | 0.0263 (10) | 0.0234 (10) | 0.0223 (8) | 0.0022 (8) | 0.0092 (7) | 0.0012 (7) |
C5 | 0.0262 (10) | 0.0265 (10) | 0.0258 (9) | 0.0029 (8) | 0.0104 (7) | 0.0029 (7) |
C6 | 0.0317 (11) | 0.0248 (10) | 0.0255 (9) | 0.0036 (8) | 0.0136 (8) | 0.0021 (7) |
C7 | 0.0235 (9) | 0.0232 (10) | 0.0252 (9) | −0.0013 (7) | 0.0092 (7) | −0.0016 (7) |
C8 | 0.0245 (10) | 0.0255 (10) | 0.0256 (9) | 0.0014 (7) | 0.0066 (7) | 0.0008 (7) |
C9 | 0.0247 (10) | 0.0246 (10) | 0.0233 (9) | 0.0030 (7) | 0.0083 (7) | 0.0017 (7) |
C10 | 0.0348 (11) | 0.0251 (10) | 0.0245 (9) | −0.0016 (8) | 0.0132 (8) | −0.0011 (7) |
C11 | 0.0371 (12) | 0.0261 (11) | 0.0349 (11) | −0.0022 (9) | 0.0148 (9) | −0.0002 (8) |
C12 | 0.0276 (11) | 0.0320 (12) | 0.0440 (12) | 0.0026 (9) | −0.0013 (9) | −0.0002 (9) |
C13 | 0.0453 (13) | 0.0246 (11) | 0.0349 (11) | 0.0023 (9) | 0.0143 (9) | −0.0002 (9) |
C14 | 0.0336 (13) | 0.0493 (15) | 0.0480 (14) | −0.0013 (10) | 0.0175 (10) | 0.0040 (11) |
C15 | 0.0259 (11) | 0.0492 (14) | 0.0375 (11) | −0.0002 (10) | 0.0102 (8) | −0.0064 (10) |
Geometric parameters (Å, º) top
S1—C1 | 1.752 (2) | C8—C9 | 1.395 (3) |
S1—C14 | 1.800 (3) | C8—C12 | 1.505 (3) |
S2—C5 | 1.749 (2) | C10—C13 | 1.481 (3) |
S2—C15 | 1.804 (2) | C11—H11A | 0.9600 |
O2—C7 | 1.378 (2) | C11—H11B | 0.9600 |
O2—C6 | 1.383 (3) | C11—H11C | 0.9600 |
O1—C9 | 1.382 (2) | C12—H12A | 0.9600 |
O1—C10 | 1.381 (3) | C12—H12B | 0.9600 |
C1—C10 | 1.351 (3) | C12—H12C | 0.9600 |
C1—C2 | 1.456 (3) | C13—H13A | 0.9600 |
C2—C3 | 1.398 (3) | C13—H13B | 0.9600 |
C2—C9 | 1.405 (3) | C13—H13C | 0.9600 |
C3—C4 | 1.396 (3) | C14—H14A | 0.9600 |
C3—H3 | 0.9300 | C14—H14B | 0.9600 |
C4—C7 | 1.404 (3) | C14—H14C | 0.9600 |
C4—C5 | 1.456 (3) | C15—H15A | 0.9600 |
C5—C6 | 1.356 (3) | C15—H15B | 0.9600 |
C6—C11 | 1.480 (3) | C15—H15C | 0.9600 |
C7—C8 | 1.391 (3) | | |
| | | |
C1—S1—C14 | 102.27 (11) | C1—C10—C13 | 133.4 (2) |
C5—S2—C15 | 100.38 (11) | O1—C10—C13 | 115.43 (19) |
C7—O2—C6 | 106.54 (16) | C6—C11—H11A | 109.5 |
C9—O1—C10 | 106.58 (16) | C6—C11—H11B | 109.5 |
C10—C1—C2 | 107.42 (18) | H11A—C11—H11B | 109.5 |
C10—C1—S1 | 125.39 (17) | C6—C11—H11C | 109.5 |
C2—C1—S1 | 127.11 (16) | H11A—C11—H11C | 109.5 |
C3—C2—C9 | 120.28 (18) | H11B—C11—H11C | 109.5 |
C3—C2—C1 | 135.09 (19) | C8—C12—H12A | 109.5 |
C9—C2—C1 | 104.58 (17) | C8—C12—H12B | 109.5 |
C4—C3—C2 | 116.20 (18) | H12A—C12—H12B | 109.5 |
C4—C3—H3 | 121.9 | C8—C12—H12C | 109.5 |
C2—C3—H3 | 121.9 | H12A—C12—H12C | 109.5 |
C3—C4—C7 | 120.44 (18) | H12B—C12—H12C | 109.5 |
C3—C4—C5 | 134.74 (19) | C10—C13—H13A | 109.5 |
C7—C4—C5 | 104.81 (17) | C10—C13—H13B | 109.5 |
C6—C5—C4 | 107.06 (18) | H13A—C13—H13B | 109.5 |
C6—C5—S2 | 125.09 (17) | C10—C13—H13C | 109.5 |
C4—C5—S2 | 127.85 (16) | H13A—C13—H13C | 109.5 |
C5—C6—O2 | 111.16 (18) | H13B—C13—H13C | 109.5 |
C5—C6—C11 | 133.0 (2) | S1—C14—H14A | 109.5 |
O2—C6—C11 | 115.79 (19) | S1—C14—H14B | 109.5 |
O2—C7—C8 | 123.56 (18) | H14A—C14—H14B | 109.5 |
O2—C7—C4 | 110.42 (17) | S1—C14—H14C | 109.5 |
C8—C7—C4 | 126.00 (18) | H14A—C14—H14C | 109.5 |
C7—C8—C9 | 111.10 (18) | H14B—C14—H14C | 109.5 |
C7—C8—C12 | 124.32 (18) | S2—C15—H15A | 109.5 |
C9—C8—C12 | 124.55 (18) | S2—C15—H15B | 109.5 |
O1—C9—C8 | 123.80 (18) | H15A—C15—H15B | 109.5 |
O1—C9—C2 | 110.27 (17) | S2—C15—H15C | 109.5 |
C8—C9—C2 | 125.92 (19) | H15A—C15—H15C | 109.5 |
C1—C10—O1 | 111.14 (18) | H15B—C15—H15C | 109.5 |
| | | |
C14—S1—C1—C10 | 102.73 (19) | C3—C4—C7—O2 | −179.98 (16) |
C14—S1—C1—C2 | −80.81 (19) | C5—C4—C7—O2 | −1.2 (2) |
C10—C1—C2—C3 | −177.3 (2) | C3—C4—C7—C8 | −1.5 (3) |
S1—C1—C2—C3 | 5.8 (3) | C5—C4—C7—C8 | 177.34 (18) |
C10—C1—C2—C9 | 0.4 (2) | O2—C7—C8—C9 | −179.25 (16) |
S1—C1—C2—C9 | −176.55 (14) | C4—C7—C8—C9 | 2.4 (3) |
C9—C2—C3—C4 | 1.8 (3) | O2—C7—C8—C12 | 2.5 (3) |
C1—C2—C3—C4 | 179.2 (2) | C4—C7—C8—C12 | −175.8 (2) |
C2—C3—C4—C7 | −0.8 (3) | C10—O1—C9—C8 | 178.53 (18) |
C2—C3—C4—C5 | −179.22 (19) | C10—O1—C9—C2 | −0.2 (2) |
C3—C4—C5—C6 | 179.5 (2) | C7—C8—C9—O1 | −179.89 (16) |
C7—C4—C5—C6 | 0.9 (2) | C12—C8—C9—O1 | −1.7 (3) |
C3—C4—C5—S2 | −0.4 (3) | C7—C8—C9—C2 | −1.3 (3) |
C7—C4—C5—S2 | −178.94 (14) | C12—C8—C9—C2 | 176.9 (2) |
C15—S2—C5—C6 | −111.48 (19) | C3—C2—C9—O1 | 177.98 (16) |
C15—S2—C5—C4 | 68.37 (19) | C1—C2—C9—O1 | −0.1 (2) |
C4—C5—C6—O2 | −0.4 (2) | C3—C2—C9—C8 | −0.7 (3) |
S2—C5—C6—O2 | 179.48 (13) | C1—C2—C9—C8 | −178.84 (18) |
C4—C5—C6—C11 | 178.4 (2) | C2—C1—C10—O1 | −0.6 (2) |
S2—C5—C6—C11 | −1.7 (3) | S1—C1—C10—O1 | 176.45 (13) |
C7—O2—C6—C5 | −0.3 (2) | C2—C1—C10—C13 | 179.1 (2) |
C7—O2—C6—C11 | −179.32 (16) | S1—C1—C10—C13 | −3.9 (3) |
C6—O2—C7—C8 | −177.59 (18) | C9—O1—C10—C1 | 0.5 (2) |
C6—O2—C7—C4 | 0.9 (2) | C9—O1—C10—C13 | −179.22 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···Cg1i | 0.96 | 2.75 | 3.480 (3) | 133 |
C13—H13A···Cg3ii | 0.96 | 2.82 | 3.586 (3) | 138 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |