6,7,8,9,10,11,12,13-Octa­hydro-5H-1,3-dithiole[4,5-b][1,4]dithia­cyclo­tridecine-2-thione

Felora Heshmatpour; Fatemeh Darviche; Zeynab Emdadi; Bernhard Neumueller

doi:10.1107/S1600536807068833

. 2008 Jan 9;64(Pt 2):o402. doi: 10.1107/S1600536807068833

6,7,8,9,10,11,12,13-Octahydro-5H-1,3-dithiole[4,5-b][1,4]dithiacyclotridecine-2-thione

Felora Heshmatpour ^a, Fatemeh Darviche ^a,^*, Zeynab Emdadi ^a, Bernhard Neumueller ^b

PMCID: PMC2960369 PMID: 21201430

Abstract

In the crystal structure of the title compound, C₁₂H₁₈S₅, no significant intermolecular π–π interactions are found. Weak intermolecular C—S⋯π [S⋯centroid = 3.787 (1) Å] interactions and van der Waals forces may be effective in the stabilization of the structure.

Related literature

For general background, see: Ferraris et al. (1973 ▶); Williams et al. (1992 ▶); Bechgaard et al. (1975 ▶); Engler et al. (1977 ▶); Kini et al. (1999 ▶); Li et al. (2000 ▶); Svenstrup & Becher (1995 ▶). For related literature, see: Kumar et al. (1998 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₈S₅
M _r = 322.56
Monoclinic,
a = 5.588 (1) Å
b = 13.067 (1) Å
c = 20.446 (2) Å
β = 97.07 (1)°
V = 1481.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 173 (2) K
0.2 × 0.18 × 0.07 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: numerical (shape of crystal determined optically; X-RED32 and X-SHAPE; Stoe & Cie, 2005 ▶) T _min = 0.856, T _max = 0.948
20411 measured reflections
2866 independent reflections
1423 reflections with I > 2σ(I)
R _int = 0.107

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.046
S = 0.90
2866 reflections
155 parameters
H-atom paramteres constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068833/hk2410sup1.cif

e-64-0o402-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068833/hk2410Isup2.hkl

e-64-0o402-Isup2.hkl^{(137.8KB, hkl)}

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

Acknowledgments

The authors acknowledge K. N. Toosi University of Technology for financial support.

supplementary crystallographic information

Comment

Since the discovery of the first organic metal TTF-TCNQ (TTF: tetrathiafulvalene TCNQ: 7,7,8,8-tetracyanoquinodimethane) (Ferraris et al., 1973) organic electron donors with a TTF backbone have been widely investigated in terms of synthetic and structural as well as physical aspects (Williams et al., 1992). The most conventional route to these electron donors is based on the coupling of 1,3-thiole-2-thione (one) derivatives promoted by trialkyl phosphite (Bechgaard et al., 1975; Engler et al., 1977; Kini et al., 1999; Li et al., 2000). Thus, the key precursors to these TTF-based electron donors are 1,3-thiole-2-thione (one) derivatives. Among them, 4,5-bisalkylthio-1,3-dithiole-2-thione can be routinely prepared by the reaction between a zinc complex of 1,3-dithiole-2 -thione-4,5-dithiolate or the anion 1,3-dithiole-2-thione-4,5-dithiolate generated in situ and suitable electrophilic reagents (Svenstrup & Becher, 1995). Thus the interest in the synthesis of various 1,3-dithiole-2-chalcogenone is evident and promoted us to take up this project. In continuation of our work in this field, we report herein the crystal structure of title ligand, (I).

In the molecule of (I) (Fig. 1), the bond lengths are within normal ranges (Allen et al., 1987).

In the crystal structure, no significant intermolecular π–π interactions are observed. Weak intermolecular C—S···π interactions, with S1···Cg1 = 3.787 (1) Å [Cg1 denotes centroid of cyclotridecine ring; (S1/S4/C1/C2/C12), symmetry code: -1 + x, y, z] and van der Waals forces stabilize the crystal structure.

Experimental

The synthesis of (I) was carried out via the coupling of 1,9-dibromooctane (1 mmol) with the zinc complex of 1,3-dithiole-2-thione-4,5-dithiolate (0.5 mmol) in acetone (5 ml) at 293 K. The color of the mixture was turned from red to yellow. The pure compound was obtained in 32% yield by washing of the crude product with chloroform, in which it is highly soluble (Kumar et al., 1998).

Figures

Fig. 1. — The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C₁₂H₁₈S₅	F₀₀₀ = 680
M_r = 322.56	D_x = 1.446 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10000 reflections
a = 5.588 (1) Å	θ = 1.9–25.9º
b = 13.067 (1) Å	µ = 0.76 mm⁻¹
c = 20.446 (2) Å	T = 173 (2) K
β = 97.07 (1)º	Plates, yellow
V = 1481.6 (3) Å³	0.2 × 0.18 × 0.07 mm
Z = 4

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Data collection

Stoe IPDS-II diffractometer	R_int = 0.107
φ scans	θ_max = 25.9º
Absorption correction: numerical(shape of crystal determined optically; X-RED32 and X-SHAPE; Stoe & Cie, 2005)	θ_min = 1.9º
T_min = 0.856, T_max = 0.948	h = −6→6
20411 measured reflections	k = −15→16
2866 independent reflections	l = −25→25
1423 reflections with I > 2σ(I)

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Refinement

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.046	w = 1/[σ²(F_o²) + (0.011P)²P] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max = 0.002
2866 reflections	Δρ_max = 0.20 e Å⁻³
155 parameters	Δρ_min = −0.20 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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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.

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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

	x	y	z	U_iso*/U_eq
S1	0.15648 (13)	0.36424 (6)	0.20855 (4)	0.0339 (2)
S2	0.60599 (13)	0.38230 (7)	0.30580 (4)	0.0359 (2)
S3	0.55751 (13)	0.13199 (7)	0.32641 (4)	0.0384 (2)
S4	0.11036 (13)	0.14671 (6)	0.22596 (4)	0.0356 (2)
S5	−0.26751 (12)	0.25565 (8)	0.13696 (3)	0.03771 (19)
C1	−0.0162 (4)	0.2563 (3)	0.18733 (11)	0.0301 (6)
C2	0.3700 (5)	0.3076 (2)	0.26703 (13)	0.0292 (7)
C3	0.4388 (5)	0.4824 (2)	0.34333 (15)	0.0403 (8)
H31	0.5563	0.5299	0.3675	0.050 (2)*
H32	0.3447	0.5219	0.3077	0.050 (2)*
C4	0.2663 (6)	0.4446 (3)	0.39077 (15)	0.0405 (8)
H41	0.1872	0.5045	0.4086	0.050 (2)*
H42	0.1390	0.4023	0.3659	0.050 (2)*
C5	0.3895 (5)	0.3822 (3)	0.44765 (14)	0.0438 (8)
H51	0.5312	0.4206	0.4687	0.050 (2)*
H52	0.4486	0.3175	0.4303	0.050 (2)*
C6	0.2221 (5)	0.3571 (3)	0.50025 (14)	0.0458 (9)
H61	0.3242	0.3340	0.5406	0.050 (2)*
H62	0.1424	0.4214	0.5114	0.050 (2)*
C7	0.0271 (5)	0.2770 (2)	0.48280 (14)	0.0434 (9)
H71	−0.0170	0.2769	0.4344	0.050 (2)*
H72	−0.1179	0.2972	0.5030	0.050 (2)*
C8	0.0975 (6)	0.1682 (3)	0.50494 (14)	0.0470 (9)
H81	0.1614	0.1704	0.5523	0.050 (2)*
H82	−0.0507	0.1260	0.5008	0.050 (2)*
C9	0.2818 (6)	0.1145 (3)	0.46824 (14)	0.0446 (9)
H91	0.3430	0.0533	0.4936	0.050 (2)*
H92	0.4199	0.1611	0.4653	0.050 (2)*
C10	0.1780 (5)	0.0816 (2)	0.39871 (14)	0.0405 (8)
H101	0.0509	0.0298	0.4021	0.050 (2)*
H102	0.1009	0.1417	0.3753	0.050 (2)*
C11	0.3638 (5)	0.0371 (2)	0.35761 (15)	0.0376 (8)
H111	0.2777	−0.0008	0.3199	0.050 (2)*
H112	0.4656	−0.0126	0.3850	0.050 (2)*
C12	0.3500 (5)	0.2060 (2)	0.27516 (13)	0.0292 (7)

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Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0339 (4)	0.0324 (5)	0.0350 (4)	−0.0027 (4)	0.0022 (3)	0.0027 (4)
S2	0.0295 (4)	0.0386 (5)	0.0396 (4)	−0.0053 (4)	0.0042 (4)	−0.0042 (4)
S3	0.0312 (4)	0.0394 (5)	0.0437 (5)	0.0050 (4)	0.0013 (4)	0.0023 (4)
S4	0.0350 (5)	0.0306 (5)	0.0399 (4)	−0.0020 (4)	−0.0002 (4)	−0.0017 (4)
S5	0.0349 (4)	0.0417 (5)	0.0353 (4)	−0.0011 (4)	−0.0006 (3)	−0.0007 (4)
C1	0.0328 (15)	0.0328 (17)	0.0268 (15)	−0.0002 (15)	0.0126 (11)	−0.0026 (15)
C2	0.0277 (18)	0.034 (2)	0.0275 (16)	0.0014 (13)	0.0094 (14)	−0.0018 (14)
C3	0.0429 (18)	0.035 (2)	0.0437 (19)	−0.0040 (15)	0.0080 (15)	−0.0085 (15)
C4	0.0424 (19)	0.039 (2)	0.0399 (18)	0.0058 (15)	0.0050 (15)	−0.0045 (16)
C5	0.0462 (18)	0.043 (2)	0.0419 (18)	−0.0003 (16)	0.0042 (14)	−0.0029 (16)
C6	0.055 (2)	0.050 (2)	0.0326 (17)	0.0093 (19)	0.0065 (15)	−0.0035 (17)
C7	0.0426 (17)	0.054 (3)	0.0351 (17)	0.0132 (16)	0.0122 (14)	0.0030 (16)
C8	0.054 (2)	0.051 (2)	0.0371 (18)	0.0110 (17)	0.0114 (15)	0.0080 (15)
C9	0.050 (2)	0.043 (2)	0.0398 (18)	0.0173 (17)	0.0005 (15)	0.0056 (16)
C10	0.0394 (18)	0.046 (2)	0.0360 (18)	−0.0001 (15)	0.0055 (14)	0.0061 (15)
C11	0.0439 (19)	0.0284 (19)	0.0400 (19)	0.0005 (15)	0.0027 (15)	0.0029 (14)
C12	0.0252 (17)	0.039 (2)	0.0244 (15)	0.0002 (14)	0.0058 (13)	−0.0016 (14)

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Geometric parameters (Å, °)

S1—C1	1.734 (3)	C5—H52	0.9900
S1—C2	1.746 (3)	C6—C7	1.521 (4)
S2—C2	1.750 (3)	C6—H61	0.9900
S2—C3	1.830 (3)	C6—H62	0.9900
S3—C12	1.754 (3)	C7—C8	1.528 (4)
S3—C11	1.813 (3)	C7—H71	0.9900
S4—C1	1.743 (3)	C7—H72	0.9900
S4—C12	1.753 (3)	C8—C9	1.519 (4)
S5—C1	1.636 (2)	C8—H81	0.9900
C2—C12	1.345 (3)	C8—H82	0.9900
C3—C4	1.531 (4)	C9—C10	1.529 (4)
C3—H31	0.9900	C9—H91	0.9900
C3—H32	0.9900	C9—H92	0.9900
C4—C5	1.515 (4)	C10—C11	1.529 (4)
C4—H41	0.9900	C10—H101	0.9900
C4—H42	0.9900	C10—H102	0.9900
C5—C6	1.545 (4)	C11—H111	0.9900
C5—H51	0.9900	C11—H112	0.9900

C1—S1—C2	97.99 (14)	C6—C7—C8	114.8 (3)
C2—S2—C3	101.15 (14)	C6—C7—H71	108.6
C12—S3—C11	101.98 (14)	C8—C7—H71	108.6
C1—S4—C12	97.81 (14)	C6—C7—H72	108.6
S5—C1—S1	124.7 (2)	C8—C7—H72	108.6
S5—C1—S4	123.4 (2)	H71—C7—H72	107.5
S1—C1—S4	111.88 (12)	C9—C8—C7	116.7 (2)
C12—C2—S1	116.3 (2)	C9—C8—H81	108.1
C12—C2—S2	124.3 (2)	C7—C8—H81	108.1
S1—C2—S2	119.16 (18)	C9—C8—H82	108.1
C4—C3—S2	115.4 (2)	C7—C8—H82	108.1
C4—C3—H31	108.4	H81—C8—H82	107.3
S2—C3—H31	108.4	C8—C9—C10	112.7 (3)
C4—C3—H32	108.4	C8—C9—H91	109.0
S2—C3—H32	108.4	C10—C9—H91	109.0
H31—C3—H32	107.5	C8—C9—H92	109.0
C5—C4—C3	113.5 (3)	C10—C9—H92	109.0
C5—C4—H41	108.9	H91—C9—H92	107.8
C3—C4—H41	108.9	C11—C10—C9	114.4 (2)
C5—C4—H42	108.9	C11—C10—H101	108.7
C3—C4—H42	108.9	C9—C10—H101	108.7
H41—C4—H42	107.7	C11—C10—H102	108.7
C4—C5—C6	113.1 (2)	C9—C10—H102	108.7
C4—C5—H51	109.0	H101—C10—H102	107.6
C6—C5—H51	109.0	C10—C11—S3	114.1 (2)
C4—C5—H52	109.0	C10—C11—H111	108.7
C6—C5—H52	109.0	S3—C11—H111	108.7
H51—C5—H52	107.8	C10—C11—H112	108.7
C7—C6—C5	117.4 (2)	S3—C11—H112	108.7
C7—C6—H61	107.9	H111—C11—H112	107.6
C5—C6—H61	107.9	C2—C12—S4	115.8 (2)
C7—C6—H62	107.9	C2—C12—S3	124.0 (2)
C5—C6—H62	107.9	S4—C12—S3	120.10 (19)
H61—C6—H62	107.2

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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2410).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bechgaard, K., Cowan, D. O., Bloch, A. N. & Henriksen, L. (1975). J. Org. Chem.40, 746–749.
Engler, E. M., Scott, B. A., Etemad, S., Penney, T. & Patel, V. V. (1977). J. Am. Chem. Soc.99, 5909–5916.
Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
Ferraris, J., Walatka, V., Perlstein, J. H. & Cowan, D. O. (1973). J. Am. Chem. Soc.95, 948–949.
Kini, A. M., Parakka, J. P., Geiser, U., Wang, H.-H., Rivas, F., DiNino, E., Thomas, S., Dudek, J. D. & Williams, J. M. (1999). J. Mater. Chem.9, 883–892.
Kumar, E. V. K. S., Singh, J. D., Singh, H. B., Das, K., Yakhmi, J. V. & Butcher, R. J. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 1769–1777.
Li, H.-X., Zhang, D.-Q., Zhang, B., Yao, Y.-X., Xu, W., Zhu, D.-B. & Wang, Z.-M. (2000). J. Mater. Chem.10, 2063–2067.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Stoe & Cie (2005). X-AREA (Version 1.31), X-RED32 (Version 1.28b) and X-SHAPE (Version 2.05). Stoe & Cie, Darmstadt, Germany.
Svenstrup, N. & Becher, J. (1995). Synthesis, pp. 215–235.
Williams, J. M., Ferraro, J. R., Thorn, R. J., Carlson, K. D., Geiser, U., Wang, H. H., Kini, A. M. & Whangbo, M.-H. (1992). Organic Superconductors (including Fullerenes) Englewood Cliffs, New Jersey: Prentice Hall.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068833/hk2410sup1.cif

e-64-0o402-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068833/hk2410Isup2.hkl

e-64-0o402-Isup2.hkl^{(137.8KB, hkl)}

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

[bb1] Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

[bb2] Bechgaard, K., Cowan, D. O., Bloch, A. N. & Henriksen, L. (1975). J. Org. Chem.40, 746–749.

[bb3] Engler, E. M., Scott, B. A., Etemad, S., Penney, T. & Patel, V. V. (1977). J. Am. Chem. Soc.99, 5909–5916.

[bb4] Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.

[bb5] Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.

[bb6] Ferraris, J., Walatka, V., Perlstein, J. H. & Cowan, D. O. (1973). J. Am. Chem. Soc.95, 948–949.

[bb7] Kini, A. M., Parakka, J. P., Geiser, U., Wang, H.-H., Rivas, F., DiNino, E., Thomas, S., Dudek, J. D. & Williams, J. M. (1999). J. Mater. Chem.9, 883–892.

[bb8] Kumar, E. V. K. S., Singh, J. D., Singh, H. B., Das, K., Yakhmi, J. V. & Butcher, R. J. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 1769–1777.

[bb9] Li, H.-X., Zhang, D.-Q., Zhang, B., Yao, Y.-X., Xu, W., Zhu, D.-B. & Wang, Z.-M. (2000). J. Mater. Chem.10, 2063–2067.

[bb10] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb11] Stoe & Cie (2005). X-AREA (Version 1.31), X-RED32 (Version 1.28b) and X-SHAPE (Version 2.05). Stoe & Cie, Darmstadt, Germany.

[bb12] Svenstrup, N. & Becher, J. (1995). Synthesis, pp. 215–235.

[bb13] Williams, J. M., Ferraro, J. R., Thorn, R. J., Carlson, K. D., Geiser, U., Wang, H. H., Kini, A. M. & Whangbo, M.-H. (1992). Organic Superconductors (including Fullerenes) Englewood Cliffs, New Jersey: Prentice Hall.

PERMALINK

6,7,8,9,10,11,12,13-Octahydro-5H-1,3-dithiole[4,5-b][1,4]dithiacyclotridecine-2-thione

Felora Heshmatpour

Fatemeh Darviche

Zeynab Emdadi

Bernhard Neumueller

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

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PERMALINK

6,7,8,9,10,11,12,13-Octa­hydro-5H-1,3-dithiole[4,5-b][1,4]dithia­cyclo­tridecine-2-thione

Felora Heshmatpour

Fatemeh Darviche

Zeynab Emdadi

Bernhard Neumueller

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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6,7,8,9,10,11,12,13-Octahydro-5H-1,3-dithiole[4,5-b][1,4]dithiacyclotridecine-2-thione

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

Atomic displacement parameters (Å²)