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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1044.
Published online 2010 April 10. doi:  10.1107/S160053681001192X
PMCID: PMC2979097

6,7-Bis(methyl­sulfan­yl)-2,3-[(3,6,9-trioxaundecane-1,11-di­yl)bis­(sulfanediylmethyl­ene)]-1,4,5,8-tetra­thia­fulvalene

Abstract

In the title compound, C18H26O3S8, the two five-membered rings exhibit envelope conformations. The two S atoms in the 17-membered macrocycle deviate from the plane of the fused five-membered ring by 1.429 (3) and −1.434 (3) Å in opposite directions.

Related literature

For background to dithia­crown ether annulated tetra­thia­fulvalenes, see: Otsubo & Ogura (1985 [triangle]); Moore et al. (2000 [triangle]). For details of the synthesis, see: Chen et al. (2005 [triangle]). For a related structure, see Hou et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1044-scheme1.jpg

Experimental

Crystal data

  • C18H26O3S8
  • M r = 546.87
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1044-efi1.jpg
  • a = 9.715 (5) Å
  • b = 11.585 (7) Å
  • c = 12.548 (5) Å
  • α = 98.37 (2)°
  • β = 112.112 (18)°
  • γ = 103.94 (2)°
  • V = 1225.3 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.75 mm−1
  • T = 290 K
  • 0.13 × 0.11 × 0.11 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.909, T max = 0.922
  • 12067 measured reflections
  • 5535 independent reflections
  • 4519 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.125
  • S = 1.09
  • 5535 reflections
  • 264 parameters
  • H-atom parameters constrained
  • Δρmax = 1.19 e Å−3
  • Δρmin = −0.84 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001192X/cv2706sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001192X/cv2706Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20662010), the Specialized Research Fund for the Doctoral Program of Higher Education (grant No. 2006184001) and the Open Project of the State Key Laboratory of Supra­molecular Structure and Materials, Jilin University.

supplementary crystallographic information

Comment

Dithiacrown ether annulated tetrathiafulvalenes (TTF) have been received great attention as sensor molecules for various metal cations (Otsubo & Ogura, 1985; Moore et al., 2000). These sensors can recognize selectively the various metal cations to signal electrochemical information. We fused TTF unit with a extended dithiacrown ether to synthesize the title compound, (I). Herewith we report its crystal structure.

In (I) (Fig. 1), all bond lengths and angles are normal and comparable to those observed in the related structure (Hou et al., 2009). Two five-membered rings have an envelope conformation. Two S atoms in the 17-membered macrocycle deviate from the plane of the fused five-membered ring in opposite directions at 1.429 (3) and -1.434 (3) Å, respectively. The mean planes of two five-membered rings form a dihedral angle of 29.84 (10) °.

Experimental

The title compound was prepared according to the literature (Chen et al., 2005). Single crystals suitable for X-ray diffraction were prepared by slow evaporation a mixture of dichloromethane and petroleum (60-90 °C) at room temperature.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.96 and 0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.5 or 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure of (I) showing the atom numbering and 30% probability displacement ellipsoids.

Crystal data

C18H26O3S8Z = 2
Mr = 546.87F(000) = 572
Triclinic, P1Dx = 1.482 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.715 (5) ÅCell parameters from 8201 reflections
b = 11.585 (7) Åθ = 3.1–27.5°
c = 12.548 (5) ŵ = 0.75 mm1
α = 98.37 (2)°T = 290 K
β = 112.112 (18)°Block, yellow
γ = 103.94 (2)°0.13 × 0.11 × 0.11 mm
V = 1225.3 (11) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer5535 independent reflections
Radiation source: fine-focus sealed tube4519 reflections with I > 2σ(I)
graphiteRint = 0.021
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −12→11
Tmin = 0.909, Tmax = 0.922k = −14→15
12067 measured reflectionsl = −15→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0606P)2 + 0.6546P] where P = (Fo2 + 2Fc2)/3
5535 reflections(Δ/σ)max = 0.004
264 parametersΔρmax = 1.19 e Å3
0 restraintsΔρmin = −0.84 e Å3

Special details

Experimental. (See detailed section in the paper)
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
C10.8329 (4)0.2619 (3)−0.0795 (3)0.0673 (8)
H1A0.91000.3281−0.01220.101*
H1B0.87970.2016−0.09630.101*
H1C0.74720.2243−0.06200.101*
C20.6741 (3)0.4211 (2)−0.1600 (2)0.0461 (6)
C30.6468 (3)0.6002 (2)−0.0284 (2)0.0378 (5)
C40.6879 (3)0.7034 (2)0.0568 (2)0.0375 (5)
C50.8608 (3)0.9048 (2)0.2248 (2)0.0377 (5)
C61.0049 (3)0.9939 (2)0.3263 (2)0.0453 (6)
H6A1.02220.96410.39700.054*
H6B0.98751.07240.34170.054*
C71.1338 (4)1.0744 (4)0.1696 (3)0.0672 (9)
H7A1.19461.05220.12870.081*
H7B1.02381.03240.11670.081*
C81.1631 (4)1.2111 (4)0.1912 (4)0.0809 (11)
H8A1.26681.25510.25480.097*
H8B1.15771.23620.11970.097*
C91.0704 (4)1.3669 (3)0.2552 (3)0.0717 (9)
H9A1.07451.40250.19060.086*
H9B1.16881.40800.32530.086*
C100.9373 (4)1.3834 (3)0.2801 (3)0.0631 (8)
H10A0.94451.46960.29480.076*
H10B0.83831.33650.21240.076*
C110.8268 (4)1.3533 (3)0.4170 (3)0.0631 (8)
H11A0.72451.31750.34970.076*
H11B0.84271.43960.44780.076*
C120.8366 (4)1.2872 (3)0.5112 (3)0.0684 (9)
H12A0.94381.31570.57240.082*
H12B0.77011.30600.54790.082*
C130.6293 (4)1.0953 (3)0.4346 (3)0.0646 (8)
H13A0.57001.15240.42050.077*
H13B0.62151.06420.50060.077*
C140.5624 (4)0.9902 (3)0.3249 (3)0.0579 (7)
H14A0.46590.93490.31910.070*
H14B0.63580.94450.33350.070*
C150.7020 (3)1.0495 (2)0.1709 (2)0.0424 (5)
H15A0.69481.07920.10110.051*
H15B0.78951.10950.23980.051*
C160.7328 (3)0.9291 (2)0.1574 (2)0.0369 (5)
C170.5549 (3)0.4512 (3)−0.2335 (2)0.0542 (7)
C180.2899 (5)0.2958 (4)−0.4241 (4)0.0993 (14)
H18A0.30420.2321−0.38390.149*
H18B0.23540.2598−0.50860.149*
H18C0.22960.3380−0.39830.149*
O11.0472 (3)1.2390 (2)0.2231 (2)0.0649 (6)
O20.9459 (2)1.3412 (2)0.38150 (17)0.0585 (5)
O30.7891 (2)1.1573 (2)0.46389 (19)0.0605 (5)
S10.76152 (11)0.32107 (7)−0.20652 (7)0.0659 (2)
S20.75246 (8)0.49614 (6)−0.00808 (5)0.04786 (17)
S30.85994 (8)0.75086 (6)0.19036 (5)0.04658 (17)
S41.18116 (8)1.01831 (8)0.30089 (7)0.0583 (2)
S50.52206 (8)1.03736 (6)0.18849 (6)0.04905 (17)
S60.57706 (7)0.80320 (6)0.04603 (6)0.04656 (17)
S70.48777 (8)0.55840 (7)−0.16902 (6)0.05239 (18)
S80.47241 (13)0.40014 (12)−0.39012 (7)0.0970 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.070 (2)0.0609 (19)0.077 (2)0.0254 (16)0.0397 (18)0.0044 (16)
C20.0520 (15)0.0406 (13)0.0391 (12)−0.0002 (11)0.0261 (11)−0.0012 (10)
C30.0382 (12)0.0360 (12)0.0364 (11)0.0085 (9)0.0153 (9)0.0096 (9)
C40.0378 (12)0.0352 (11)0.0389 (11)0.0118 (9)0.0159 (9)0.0096 (9)
C50.0369 (12)0.0373 (12)0.0380 (11)0.0115 (9)0.0178 (10)0.0038 (9)
C60.0406 (13)0.0497 (14)0.0390 (12)0.0129 (11)0.0150 (10)0.0013 (10)
C70.0522 (17)0.100 (3)0.0579 (17)0.0260 (17)0.0347 (15)0.0127 (17)
C80.059 (2)0.110 (3)0.091 (3)0.019 (2)0.0487 (19)0.045 (2)
C90.078 (2)0.0544 (18)0.069 (2)−0.0044 (16)0.0316 (17)0.0209 (15)
C100.081 (2)0.0383 (14)0.0566 (16)0.0106 (14)0.0199 (15)0.0147 (12)
C110.0613 (19)0.0534 (17)0.0645 (18)0.0204 (15)0.0203 (15)0.0021 (14)
C120.064 (2)0.081 (2)0.0460 (15)0.0117 (17)0.0222 (14)−0.0003 (14)
C130.0501 (16)0.091 (2)0.0611 (18)0.0179 (16)0.0329 (14)0.0263 (17)
C140.0535 (17)0.0573 (17)0.078 (2)0.0194 (14)0.0388 (15)0.0305 (15)
C150.0411 (13)0.0337 (12)0.0526 (14)0.0112 (10)0.0212 (11)0.0106 (10)
C160.0335 (11)0.0338 (11)0.0437 (12)0.0084 (9)0.0193 (10)0.0076 (9)
C170.0500 (15)0.0618 (17)0.0353 (12)−0.0017 (13)0.0199 (12)−0.0028 (11)
C180.090 (3)0.098 (3)0.070 (2)0.000 (2)0.016 (2)0.008 (2)
O10.0606 (13)0.0569 (12)0.0870 (15)0.0080 (10)0.0468 (12)0.0237 (11)
O20.0605 (12)0.0613 (12)0.0532 (11)0.0206 (10)0.0208 (10)0.0212 (9)
O30.0486 (11)0.0760 (14)0.0617 (12)0.0191 (10)0.0265 (10)0.0257 (11)
S10.0891 (6)0.0546 (4)0.0623 (4)0.0167 (4)0.0508 (4)−0.0005 (3)
S20.0601 (4)0.0414 (3)0.0366 (3)0.0208 (3)0.0156 (3)0.0012 (2)
S30.0475 (4)0.0435 (3)0.0412 (3)0.0221 (3)0.0095 (3)0.0030 (2)
S40.0325 (3)0.0715 (5)0.0582 (4)0.0171 (3)0.0114 (3)0.0018 (3)
S50.0395 (3)0.0518 (4)0.0557 (4)0.0219 (3)0.0173 (3)0.0103 (3)
S60.0351 (3)0.0367 (3)0.0556 (4)0.0113 (2)0.0094 (3)0.0050 (3)
S70.0433 (4)0.0610 (4)0.0404 (3)0.0105 (3)0.0102 (3)0.0091 (3)
S80.0877 (7)0.1331 (10)0.0378 (4)−0.0061 (6)0.0267 (4)−0.0001 (5)

Geometric parameters (Å, °)

C1—S11.790 (4)C10—O21.408 (3)
C1—H1A0.9600C10—H10A0.9700
C1—H1B0.9600C10—H10B0.9700
C1—H1C0.9600C11—O21.415 (4)
C2—C171.341 (4)C11—C121.485 (5)
C2—S11.748 (3)C11—H11A0.9700
C2—S21.753 (3)C11—H11B0.9700
C3—C41.345 (3)C12—O31.425 (4)
C3—S21.750 (3)C12—H12A0.9700
C3—S71.753 (2)C12—H12B0.9700
C4—S61.746 (2)C13—O31.420 (4)
C4—S31.756 (2)C13—C141.503 (5)
C5—C161.337 (3)C13—H13A0.9700
C5—C61.492 (3)C13—H13B0.9700
C5—S31.770 (3)C14—S51.803 (3)
C6—S41.821 (3)C14—H14A0.9700
C6—H6A0.9700C14—H14B0.9700
C6—H6B0.9700C15—C161.496 (3)
C7—C81.504 (5)C15—S51.818 (3)
C7—S41.798 (4)C15—H15A0.9700
C7—H7A0.9700C15—H15B0.9700
C7—H7B0.9700C16—S61.767 (3)
C8—O11.419 (4)C17—S81.761 (3)
C8—H8A0.9700C17—S71.765 (3)
C8—H8B0.9700C18—S81.742 (5)
C9—O11.416 (4)C18—H18A0.9600
C9—C101.487 (5)C18—H18B0.9600
C9—H9A0.9700C18—H18C0.9600
C9—H9B0.9700
S1—C1—H1A109.5O2—C11—H11B110.3
S1—C1—H1B109.5C12—C11—H11B110.3
H1A—C1—H1B109.5H11A—C11—H11B108.6
S1—C1—H1C109.5O3—C12—C11111.5 (2)
H1A—C1—H1C109.5O3—C12—H12A109.3
H1B—C1—H1C109.5C11—C12—H12A109.3
C17—C2—S1124.5 (2)O3—C12—H12B109.3
C17—C2—S2116.3 (2)C11—C12—H12B109.3
S1—C2—S2119.01 (17)H12A—C12—H12B108.0
C4—C3—S2121.99 (19)O3—C13—C14109.6 (2)
C4—C3—S7124.10 (19)O3—C13—H13A109.7
S2—C3—S7113.89 (13)C14—C13—H13A109.7
C3—C4—S6123.71 (19)O3—C13—H13B109.7
C3—C4—S3122.82 (19)C14—C13—H13B109.7
S6—C4—S3113.46 (13)H13A—C13—H13B108.2
C16—C5—C6126.9 (2)C13—C14—S5114.0 (2)
C16—C5—S3116.77 (18)C13—C14—H14A108.8
C6—C5—S3116.37 (18)S5—C14—H14A108.8
C5—C6—S4114.01 (17)C13—C14—H14B108.8
C5—C6—H6A108.7S5—C14—H14B108.8
S4—C6—H6A108.7H14A—C14—H14B107.7
C5—C6—H6B108.7C16—C15—S5112.39 (16)
S4—C6—H6B108.7C16—C15—H15A109.1
H6A—C6—H6B107.6S5—C15—H15A109.1
C8—C7—S4115.4 (2)C16—C15—H15B109.1
C8—C7—H7A108.4S5—C15—H15B109.1
S4—C7—H7A108.4H15A—C15—H15B107.9
C8—C7—H7B108.4C5—C16—C15127.2 (2)
S4—C7—H7B108.4C5—C16—S6116.68 (18)
H7A—C7—H7B107.5C15—C16—S6115.94 (18)
O1—C8—C7108.5 (3)C2—C17—S8124.0 (2)
O1—C8—H8A110.0C2—C17—S7117.57 (19)
C7—C8—H8A110.0S8—C17—S7118.18 (19)
O1—C8—H8B110.0S8—C18—H18A109.5
C7—C8—H8B110.0S8—C18—H18B109.5
H8A—C8—H8B108.4H18A—C18—H18B109.5
O1—C9—C10108.2 (2)S8—C18—H18C109.5
O1—C9—H9A110.1H18A—C18—H18C109.5
C10—C9—H9A110.1H18B—C18—H18C109.5
O1—C9—H9B110.1C9—O1—C8113.5 (3)
C10—C9—H9B110.1C10—O2—C11114.0 (2)
H9A—C9—H9B108.4C13—O3—C12113.9 (3)
O2—C10—C9107.8 (3)C2—S1—C1101.77 (14)
O2—C10—H10A110.2C3—S2—C295.28 (13)
C9—C10—H10A110.2C4—S3—C594.67 (11)
O2—C10—H10B110.2C7—S4—C6103.95 (13)
C9—C10—H10B110.2C14—S5—C15102.32 (13)
H10A—C10—H10B108.5C4—S6—C1694.86 (12)
O2—C11—C12107.1 (3)C3—S7—C1794.12 (13)
O2—C11—H11A110.3C18—S8—C17102.48 (18)
C12—C11—H11A110.3

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2706).

References

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  • Moore, A. J., Goldenberg, L. M., Bryce, M. R. & Petty, M. (2000). J. Org. Chem.65, 8269–8276. [PubMed]
  • Otsubo, T. & Ogura, F. (1985). Bull. Chem. Soc. Jpn, 58, 1343–1344.
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