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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o179.
Published online 2007 December 6. doi:  10.1107/S1600536807063209
PMCID: PMC2915242

Ethyl 3-(6-phenyl-4λ4-1,2-dithiolo[1,5-b][1,2,4]dithia­zol-2-yl)propanoate

Abstract

The title compound, C15H15NO2S3, exists in a bicyclic form, with resonance contributions from two monocyclic forms, each without a second S—S bond. The trithiapentalene heterocyclic ring system is planar, with a mean deviation of 0.014 (2) Å from the mean plane, and is inclined to the plane of the attached phenyl ring at an angle of 17.24 (7)°.

Related literature

For related compounds, see: Rašović et al. (2007 [triangle]); Yokoyama et al. (1985 [triangle]). For related literature, see: Lozac’h (1984 [triangle]); Marković et al. (2004 [triangle]); Terem (1996 [triangle]); Allen (2002 [triangle]).

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Object name is e-64-0o179-scheme1.jpg

Experimental

Crystal data

  • C15H15NO2S3
  • M r = 337.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o179-efi1.jpg
  • a = 4.5830 (8) Å
  • b = 15.550 (3) Å
  • c = 21.858 (4) Å
  • β = 91.579 (2)°
  • V = 1557.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.48 mm−1
  • T = 168 (2) K
  • 0.56 × 0.15 × 0.14 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2002 [triangle]) T min = 0.776, T max = 0.936
  • 18585 measured reflections
  • 3154 independent reflections
  • 2496 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.081
  • S = 1.04
  • 3154 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063209/ga2023sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063209/ga2023Isup2.hkl

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

Acknowledgments

PJS thanks the Royal Society of New Zealand for the award of a James Cook Research Fellowship.

supplementary crystallographic information

Comment

The title compound (1) was prepared in the course of a study of the thionation of thiazolidine enaminones (Marković et al., 2004). It could potentially exist in any of three forms (1 A - 1 C) as shown in Scheme 1. The X-ray structure reveals that it exists in the bicyclic form (1 A). However, comparison of the S—S bond lengths (Table 1) with the average value (2.07 Å) for the 31 1,2-dithiolanes and the 11 3-imino-3H-1,2-dithioles (as in 1B) in the Cambridge Structural Database (Allen, 2002) along with consideration of the S—C bond lengths suggests that resonance forms (1B) and (1 C) make some contribution to the overall structure. These results are consistent with two structurally related compounds that have been published previously (Rašović et al., 2007; Yokoyama et al., 1985) and with the known resonance behaviour of 1,6,6a-trithiapentalenes (Lozac'h, 1984; Terem, 1996; Rašović et al., 2007).

The whole molecule is remarkably close to being planar with both substituents lying in the same plane as the trithiaazapentalene ring system. This bicyclic system is planar [mean deviation = 0.014 (3) Å] and the attached phenyl ring is inclined to this plane at an angle of 17.4 (1) °. Inspection of the packing shows that there are short intermolecular contacts [3.491 (1) Å] between sulfur atoms of molecules related by a crystallographic centre of inversion, as well as other weak C–H···O and C–H···π interactions.

Experimental

The title compound was prepared as previously described (Marković et al., 2004).

Refinement

All H atoms were introduced in calculated positions as riding atoms, with Uiso(H) = 1.5Ueq(C) for the methyl group and Uiso(H) = 1.2Ueq(C) for other carbons.

Figures

Fig. 1.
The molecular structure of (1), showing displacement ellipsoids at the 50% probability level.
Fig. 2.
Forms of the title compound.

Crystal data

C15H15NO2S3F000 = 704
Mr = 337.46Dx = 1.440 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4889 reflections
a = 4.5830 (8) Åθ = 2.3–26.3º
b = 15.550 (3) ŵ = 0.48 mm1
c = 21.858 (4) ÅT = 168 (2) K
β = 91.579 (2)ºBlock, red
V = 1557.1 (5) Å30.56 × 0.15 × 0.14 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3154 independent reflections
Radiation source: fine-focus sealed tube2496 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 168(2) Kθmax = 26.4º
phi and ω scansθmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)h = −5→3
Tmin = 0.776, Tmax = 0.936k = −19→19
18585 measured reflectionsl = −27→27

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.081  w = 1/[σ2(Fo2) + (0.040P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3154 reflectionsΔρmax = 0.22 e Å3
190 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
S10.14659 (10)0.93968 (3)−0.06460 (2)0.03515 (13)
S20.45583 (10)0.88164 (3)0.01317 (2)0.03275 (13)
S30.75628 (10)0.81544 (3)0.08417 (2)0.03547 (13)
N10.1422 (3)0.77027 (9)−0.05925 (6)0.0310 (3)
O1−0.6255 (3)0.78860 (8)−0.22517 (6)0.0469 (4)
O2−0.4823 (3)0.65138 (8)−0.22943 (6)0.0374 (3)
C10.0397 (4)0.83948 (10)−0.08685 (8)0.0301 (4)
C20.3385 (4)0.77998 (10)−0.01248 (8)0.0299 (4)
C30.4558 (4)0.70707 (11)0.01639 (8)0.0323 (4)
H3A0.39160.65170.00340.039*
C40.6610 (4)0.71354 (11)0.06291 (8)0.0310 (4)
C11−0.1756 (4)0.83021 (10)−0.13943 (8)0.0321 (4)
H11A−0.09300.8571−0.17620.039*
H11B−0.35590.8619−0.12970.039*
C12−0.2545 (4)0.73746 (10)−0.15426 (8)0.0320 (4)
H12A−0.07560.7057−0.16480.038*
H12B−0.33610.7100−0.11760.038*
C13−0.4727 (4)0.73123 (11)−0.20648 (8)0.0310 (4)
C14−0.6901 (4)0.63594 (12)−0.27984 (9)0.0386 (4)
H14A−0.65790.6772−0.31350.046*
H14B−0.89240.6429−0.26590.046*
C15−0.6416 (5)0.54575 (13)−0.30130 (10)0.0502 (5)
H15A−0.77480.5333−0.33600.075*
H15B−0.67880.5056−0.26790.075*
H15C−0.43940.5394−0.31410.075*
C410.8042 (4)0.63919 (11)0.09330 (8)0.0336 (4)
C420.7975 (5)0.55824 (13)0.06601 (10)0.0565 (6)
H42A0.69560.55040.02800.068*
C430.9372 (6)0.48925 (14)0.09362 (12)0.0697 (8)
H43A0.92860.43430.07470.084*
C441.0889 (5)0.49931 (13)0.14834 (11)0.0559 (6)
H44A1.18550.45170.16720.067*
C451.0989 (5)0.57867 (13)0.17530 (10)0.0531 (6)
H45A1.20400.58620.21300.064*
C460.9578 (5)0.64779 (12)0.14830 (9)0.0451 (5)
H46A0.96620.70230.16780.054*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0389 (3)0.0220 (2)0.0444 (3)−0.00255 (17)−0.0017 (2)−0.00393 (17)
S20.0358 (3)0.0245 (2)0.0379 (2)−0.00752 (17)0.00185 (19)−0.00651 (17)
S30.0410 (3)0.0291 (2)0.0361 (2)−0.00723 (18)−0.0037 (2)−0.00541 (18)
N10.0316 (8)0.0253 (7)0.0359 (8)−0.0035 (6)−0.0013 (6)−0.0045 (6)
O10.0529 (9)0.0353 (7)0.0514 (8)0.0115 (6)−0.0168 (7)−0.0040 (6)
O20.0415 (7)0.0292 (6)0.0406 (7)0.0029 (5)−0.0119 (6)−0.0066 (5)
C10.0290 (9)0.0251 (8)0.0364 (9)−0.0006 (7)0.0045 (7)−0.0045 (7)
C20.0301 (9)0.0251 (8)0.0347 (9)−0.0071 (7)0.0029 (7)−0.0053 (7)
C30.0362 (10)0.0234 (8)0.0372 (9)−0.0059 (7)−0.0003 (8)−0.0043 (7)
C40.0336 (9)0.0281 (8)0.0315 (9)−0.0060 (7)0.0049 (7)−0.0026 (7)
C110.0335 (10)0.0243 (8)0.0384 (9)0.0020 (7)−0.0004 (7)−0.0025 (7)
C120.0349 (10)0.0257 (8)0.0351 (9)0.0015 (7)−0.0026 (7)−0.0022 (7)
C130.0316 (9)0.0278 (9)0.0336 (9)0.0006 (7)0.0022 (7)−0.0012 (7)
C140.0375 (11)0.0418 (10)0.0359 (10)0.0002 (8)−0.0071 (8)−0.0068 (8)
C150.0638 (14)0.0408 (11)0.0453 (11)−0.0062 (10)−0.0109 (10)−0.0088 (9)
C410.0365 (10)0.0306 (9)0.0337 (9)−0.0070 (7)−0.0014 (8)−0.0004 (7)
C420.0761 (17)0.0369 (11)0.0547 (13)0.0049 (10)−0.0300 (12)−0.0110 (9)
C430.103 (2)0.0333 (11)0.0707 (15)0.0070 (12)−0.0400 (15)−0.0110 (11)
C440.0726 (16)0.0341 (10)0.0596 (13)0.0006 (10)−0.0232 (12)0.0036 (9)
C450.0711 (15)0.0404 (11)0.0464 (12)−0.0049 (10)−0.0244 (11)0.0019 (9)
C460.0589 (13)0.0323 (10)0.0433 (11)−0.0069 (9)−0.0117 (10)−0.0036 (8)

Geometric parameters (Å, °)

S1—C11.7003 (16)C12—H12A0.9900
S1—S22.3623 (7)C12—H12B0.9900
S2—C21.7567 (16)C14—C151.497 (3)
S2—S32.2905 (7)C14—H14A0.9900
S3—C41.7047 (17)C14—H14B0.9900
N1—C11.314 (2)C15—H15A0.9800
N1—C21.351 (2)C15—H15B0.9800
O1—C131.199 (2)C15—H15C0.9800
O2—C131.339 (2)C41—C461.383 (3)
O2—C141.456 (2)C41—C421.393 (3)
C1—C111.501 (2)C42—C431.380 (3)
C2—C31.398 (2)C42—H42A0.9500
C3—C41.370 (2)C43—C441.376 (3)
C3—H3A0.9500C43—H43A0.9500
C4—C411.478 (3)C44—C451.368 (3)
C11—C121.520 (2)C44—H44A0.9500
C11—H11A0.9900C45—C461.379 (3)
C11—H11B0.9900C45—H45A0.9500
C12—C131.500 (2)C46—H46A0.9500
C1—S1—S291.04 (6)O1—C13—C12125.60 (16)
C2—S2—S389.13 (6)O2—C13—C12111.04 (14)
C2—S2—S186.66 (6)O2—C14—C15106.97 (15)
S3—S2—S1175.44 (2)O2—C14—H14A110.3
C4—S3—S295.07 (6)C15—C14—H14A110.3
C1—N1—C2118.55 (14)O2—C14—H14B110.3
C13—O2—C14116.74 (14)C15—C14—H14B110.3
N1—C1—C11119.47 (14)H14A—C14—H14B108.6
N1—C1—S1121.50 (13)C14—C15—H15A109.5
C11—C1—S1119.03 (12)C14—C15—H15B109.5
N1—C2—C3119.38 (14)H15A—C15—H15B109.5
N1—C2—S2122.25 (13)C14—C15—H15C109.5
C3—C2—S2118.38 (13)H15A—C15—H15C109.5
C4—C3—C2121.55 (15)H15B—C15—H15C109.5
C4—C3—H3A119.2C46—C41—C42117.67 (18)
C2—C3—H3A119.2C46—C41—C4121.61 (16)
C3—C4—C41124.30 (16)C42—C41—C4120.68 (16)
C3—C4—S3115.86 (13)C43—C42—C41120.72 (19)
C41—C4—S3119.82 (13)C43—C42—H42A119.6
C1—C11—C12113.71 (14)C41—C42—H42A119.6
C1—C11—H11A108.8C44—C43—C42120.6 (2)
C12—C11—H11A108.8C44—C43—H43A119.7
C1—C11—H11B108.8C42—C43—H43A119.7
C12—C11—H11B108.8C45—C44—C43119.2 (2)
H11A—C11—H11B107.7C45—C44—H44A120.4
C13—C12—C11111.93 (14)C43—C44—H44A120.4
C13—C12—H12A109.2C44—C45—C46120.60 (19)
C11—C12—H12A109.2C44—C45—H45A119.7
C13—C12—H12B109.2C46—C45—H45A119.7
C11—C12—H12B109.2C45—C46—C41121.23 (18)
H12A—C12—H12B107.9C45—C46—H46A119.4
O1—C13—O2123.33 (16)C41—C46—H46A119.4

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GA2023).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bruker (1997). SMART, SAINT and SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lozac’h, N. (1984). Comprehensive Heterocyclic Chemistry, Vol. 6, edited by A. R. Katritzky, C. W. Rees & K. T. Potts, pp. 1049–1070. Oxford: Pergamon Press.
  • Marković, R., Rašović, A., Baranac, M., Stojanović, M., Steel, P. J. & Jovetić, S. (2004). J. Serb. Chem. Soc.69, 909–918.
  • Rašović, A., Steel, P. J., Kleinpeter, E. & Marković, R. (2007). Tetrahedron, 63, 1937–1945.
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  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]
  • Sheldrick, G. M. (2002). SADABS Version 2.03. University of Göttingen, Germany.
  • Terem, B. (1996). Comprehensive Heterocyclic Chemistry II, Vol. 8, edited by A. R. Katritzky, C. W. Rees & E. F. V. Scriven, pp. 833–862. Oxford: Pergamon Press.
  • Yokoyama, M., Shiraishi, T., Hatanaka, H. & Ogata, K. (1985). J. Chem. Soc. Chem. Commun. pp. 1704–1705.

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