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

Heshmatpour, F.; Darviche, F.; Emdadi, Z.; Neumueller, B.

doi:10.1107/S1600536807068833

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o402

doi:10.1107/S1600536807068833

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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

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

^aChemistry Department, K. N. Toosi University of Technology, PO Box 15875-4416, Tehran 15418, Iran, and ^bFachbereich Chemie der Universität Marburg, Marburg, Germany
^*Correspondence e-mail: darvish@kntu.ac.ir

(Received 9 December 2007; accepted 31 December 2007; online 9 January 2008)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.031
wR(F²) = 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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For general bakground, 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 top

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).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); 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).

Figures top

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

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

Crystal data top

C₁₂H₁₈S₅	F(000) = 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 = 1.9–25.9°
b = 13.067 (1) Å	µ = 0.76 mm⁻¹
c = 20.446 (2) Å	T = 173 K
β = 97.07 (1)°	Plates, yellow
V = 1481.6 (3) Å³	0.2 × 0.18 × 0.07 mm
Z = 4

Data collection top

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

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.011P)²P] where P = (F_o² + 2F_c²)/3
2866 reflections	(Δ/σ)_max = 0.002
155 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₈S₅	V = 1481.6 (3) Å³
M_r = 322.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.588 (1) Å	µ = 0.76 mm⁻¹
b = 13.067 (1) Å	T = 173 K
c = 20.446 (2) Å	0.2 × 0.18 × 0.07 mm
β = 97.07 (1)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.046	H-atom parameters constrained
S = 0.90	Δρ_max = 0.20 e Å⁻³
2866 reflections	Δρ_min = −0.21 e Å⁻³
155 parameters

Special details top

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.

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

	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₈S₅
M_r	322.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	5.588 (1), 13.067 (1), 20.446 (2)
β (°)	97.07 (1)
V (Å³)	1481.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.2 × 0.18 × 0.07

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	Numerical (shape of crystal determined optically; X-RED32 and X-SHAPE; Stoe & Cie, 2005)
T_min, T_max	0.856, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	20411, 2866, 1423
R_int	0.107
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.046, 0.90
No. of reflections	2866
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED32 (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Acknowledgements

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

References

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