4,6,7,9,10,12-Hexahydro-1,3-dithiolo[4,5-f][1,4,9]oxadithia­cyclo­undecine-2-thione

Hou, R.-B.; Li, B.; Yin, B.-Z.; Wu, L.-X.

doi:10.1107/S1600536809024003

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1710

doi:10.1107/S1600536809024003

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4,6,7,9,10,12-Hexahydro-1,3-dithiolo[4,5-f][1,4,9]oxadithiacycloundecine-2-thione

Rui-Bin Hou,^a Bao Li,^b Bing-Zhu Yin ^a ^* and Li-Xin Wu ^b

^aKey Laboratory of Organism Functional Factors of Changbai Mountain, Yanbian University, Ministry of Education, Yanji 133002, People's Republic of China, and ^bState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China
^*Correspondence e-mail: zqcong@ybu.edu.cn

(Received 10 June 2009; accepted 23 June 2009; online 27 June 2009)

In the title molecule, C₉H₁₂S₅O, the five-membered ring and attached S atom are essentially coplanar [mean deviation from the mean plane = 0.020 (1) Å]. The two S atoms belonging to the macrocycle deviate from this plane by 1.005 (1) and 1.337 (2) Å. In the crystal, π–π interactions link the molecules into centrosymmetric dimers with a short distance of 3.753 (5) Å between the centroids of the five-membered rings.

Related literature

The title compound was prepared according to Chen et al. (2005 ). For background literature concerning crown-ether-annulated 1,3-dithiol-2-thione derivatives, see: Hansen et al. (1992 ); Trippé et al. (2002 ).

Experimental

Crystal data

C₉H₁₂OS₅
M_r = 296.49
Triclinic, $[P \overline 1]$
a = 8.3425 (17) Å
b = 8.9611 (18) Å
c = 9.820 (2) Å
α = 98.10 (3)°
β = 106.58 (3)°
γ = 112.74 (3)°
V = 622.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 291 K
0.15 × 0.12 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.877, T_max = 0.900
6141 measured reflections
2813 independent reflections
2560 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.106
S = 1.06
2813 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024003/cv2573sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024003/cv2573Isup2.hkl

checkCIF report

Comment top

Crown ether annulated 1,3-dithiol-2-thione derivatives have been intensively investigated as key intermediate of the crowned tetrathiafulvalenes because the latter molecules show electrochemical signaling for various metal cations (Hansen et al.,1992; Trippé et al., 2002). We report hererin the crystal structure of the title compound, (I).

In (I) (Fig. 1), five-membered ring and attached S2 atom are essentially coplanar with the mean deviation of 0.020 (1) Å from the mean plane P. The plane defined by the rest non-hydrogen atoms forms an angle of 70.25 (4) ° with P. The π-π interactions with the short distance of 3.753 (5) Å between the centroids of five-membered rings link the molecules into centrosymmetric dimers.

Related literature top

The title compound was prepared according to Chen et al. (2005). For background literature concerning crown-ether-annulated 1,3-dithiol-2-thione derivatives, see: Hansen et al. (1992); Trippé et al. (2002).

Experimental top

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 at room temperatue.

Computing details top

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

Figures top

Fig. 1. The molecular structure of (I) showing the atom numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

4,6,7,9,10,12-Hexahydro-1,3- dithiolo[4,5-f][1,4,9]oxadithiacycloundecine-2-thione top

Crystal data top

C₉H₁₂OS₅	Z = 2
M_r = 296.49	F(000) = 308
Triclinic, P1	D_x = 1.583 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3425 (17) Å	Cell parameters from 5678 reflections
b = 8.9611 (18) Å	θ = 3.4–27.0°
c = 9.820 (2) Å	µ = 0.90 mm⁻¹
α = 98.10 (3)°	T = 291 K
β = 106.58 (3)°	Block, yellow
γ = 112.74 (3)°	0.15 × 0.12 × 0.12 mm
V = 622.2 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2813 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.877, T_max = 0.900	k = −11→11
6141 measured reflections	l = −12→12

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) = 0.106	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0645P)² + 0.2783P] where P = (F_o² + 2F_c²)/3
2813 reflections	(Δ/σ)_max = 0.003
136 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₉H₁₂OS₅	γ = 112.74 (3)°
M_r = 296.49	V = 622.2 (2) Å³
Triclinic, P1	Z = 2
a = 8.3425 (17) Å	Mo Kα radiation
b = 8.9611 (18) Å	µ = 0.90 mm⁻¹
c = 9.820 (2) Å	T = 291 K
α = 98.10 (3)°	0.15 × 0.12 × 0.12 mm
β = 106.58 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2813 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2560 reflections with I > 2σ(I)
T_min = 0.877, T_max = 0.900	R_int = 0.017
6141 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
2813 reflections	Δρ_min = −0.36 e Å⁻³
136 parameters

Special details top

Experimental. (See detailed section in the paper)

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	U_iso*/U_eq
C1	0.3295 (3)	0.6916 (3)	0.4927 (2)	0.0376 (4)
C2	0.2130 (3)	0.8764 (2)	0.3463 (2)	0.0300 (4)
C3	0.1113 (3)	0.9792 (2)	0.3073 (2)	0.0354 (4)
H3A	0.1194	1.0051	0.2161	0.042*
H3B	0.1724	1.0851	0.3848	0.042*
C4	−0.2203 (3)	0.6799 (3)	0.1413 (3)	0.0408 (5)
H4A	−0.1445	0.6233	0.1746	0.049*
H4B	−0.3469	0.6075	0.1315	0.049*
C5	−0.2231 (3)	0.6956 (3)	−0.0092 (3)	0.0486 (5)
H5A	−0.2975	0.5852	−0.0811	0.058*
H5B	−0.2805	0.7677	−0.0378	0.058*
C6	−0.0193 (3)	0.6766 (3)	−0.1285 (3)	0.0466 (5)
H6A	−0.1108	0.6664	−0.2208	0.056*
H6B	−0.0423	0.5639	−0.1211	0.056*
C7	0.1742 (3)	0.7686 (3)	−0.1276 (2)	0.0439 (5)
H7A	0.1991	0.8846	−0.1229	0.053*
H7B	0.1754	0.7190	−0.2215	0.053*
C8	0.4004 (3)	0.9279 (2)	0.1782 (2)	0.0367 (4)
H8A	0.5328	1.0056	0.2243	0.044*
H8B	0.3342	0.9920	0.1443	0.044*
C9	0.3363 (2)	0.8552 (2)	0.2922 (2)	0.0294 (4)
O1	−0.0377 (2)	0.7650 (2)	−0.0088 (2)	0.0600 (5)
S1	0.43959 (7)	0.73453 (6)	0.36855 (5)	0.03533 (15)
S2	0.36763 (14)	0.58331 (12)	0.60929 (8)	0.0708 (3)
S3	0.17163 (8)	0.77394 (7)	0.48048 (6)	0.03867 (15)
S4	−0.13328 (7)	0.87314 (7)	0.28369 (6)	0.04162 (16)
S5	0.36387 (8)	0.77082 (7)	0.01819 (6)	0.04019 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0448 (11)	0.0454 (11)	0.0277 (9)	0.0247 (9)	0.0138 (8)	0.0110 (8)
C2	0.0293 (8)	0.0333 (9)	0.0239 (8)	0.0121 (7)	0.0089 (7)	0.0061 (7)
C3	0.0375 (10)	0.0361 (9)	0.0347 (10)	0.0190 (8)	0.0136 (8)	0.0087 (8)
C4	0.0313 (9)	0.0420 (10)	0.0486 (12)	0.0163 (8)	0.0140 (9)	0.0140 (9)
C5	0.0318 (10)	0.0615 (14)	0.0431 (12)	0.0164 (10)	0.0121 (9)	0.0057 (10)
C6	0.0439 (11)	0.0526 (12)	0.0361 (11)	0.0199 (10)	0.0127 (9)	0.0023 (9)
C7	0.0506 (12)	0.0565 (13)	0.0329 (10)	0.0266 (10)	0.0214 (9)	0.0172 (9)
C8	0.0388 (10)	0.0339 (9)	0.0361 (10)	0.0107 (8)	0.0200 (8)	0.0097 (8)
C9	0.0283 (8)	0.0289 (8)	0.0276 (9)	0.0101 (7)	0.0105 (7)	0.0059 (7)
O1	0.0356 (8)	0.0692 (11)	0.0481 (10)	0.0048 (8)	0.0198 (7)	−0.0146 (8)
S1	0.0340 (3)	0.0422 (3)	0.0348 (3)	0.0204 (2)	0.0152 (2)	0.0112 (2)
S2	0.1147 (7)	0.0990 (6)	0.0578 (4)	0.0820 (6)	0.0517 (4)	0.0521 (4)
S3	0.0443 (3)	0.0543 (3)	0.0322 (3)	0.0285 (2)	0.0224 (2)	0.0188 (2)
S4	0.0399 (3)	0.0544 (3)	0.0438 (3)	0.0303 (2)	0.0214 (2)	0.0135 (2)
S5	0.0468 (3)	0.0511 (3)	0.0357 (3)	0.0300 (2)	0.0217 (2)	0.0135 (2)

Geometric parameters (Å, º) top

C1—S2	1.642 (2)	C5—H5A	0.9700
C1—S1	1.726 (2)	C5—H5B	0.9700
C1—S3	1.726 (2)	C6—O1	1.402 (3)
C2—C9	1.346 (3)	C6—C7	1.499 (3)
C2—C3	1.495 (3)	C6—H6A	0.9700
C2—S3	1.7471 (19)	C6—H6B	0.9700
C3—S4	1.814 (2)	C7—S5	1.796 (2)
C3—H3A	0.9700	C7—H7A	0.9700
C3—H3B	0.9700	C7—H7B	0.9700
C4—C5	1.498 (3)	C8—C9	1.497 (3)
C4—S4	1.802 (2)	C8—S5	1.820 (2)
C4—H4A	0.9700	C8—H8A	0.9700
C4—H4B	0.9700	C8—H8B	0.9700
C5—O1	1.426 (3)	C9—S1	1.747 (2)

S2—C1—S1	124.30 (13)	O1—C6—H6A	109.7
S2—C1—S3	123.21 (13)	C7—C6—H6A	109.7
S1—C1—S3	112.49 (12)	O1—C6—H6B	109.7
C9—C2—C3	127.67 (18)	C7—C6—H6B	109.7
C9—C2—S3	115.53 (15)	H6A—C6—H6B	108.2
C3—C2—S3	116.79 (14)	C6—C7—S5	117.34 (17)
C2—C3—S4	112.96 (14)	C6—C7—H7A	108.0
C2—C3—H3A	109.0	S5—C7—H7A	108.0
S4—C3—H3A	109.0	C6—C7—H7B	108.0
C2—C3—H3B	109.0	S5—C7—H7B	108.0
S4—C3—H3B	109.0	H7A—C7—H7B	107.2
H3A—C3—H3B	107.8	C9—C8—S5	114.07 (14)
C5—C4—S4	116.74 (17)	C9—C8—H8A	108.7
C5—C4—H4A	108.1	S5—C8—H8A	108.7
S4—C4—H4A	108.1	C9—C8—H8B	108.7
C5—C4—H4B	108.1	S5—C8—H8B	108.7
S4—C4—H4B	108.1	H8A—C8—H8B	107.6
H4A—C4—H4B	107.3	C2—C9—C8	127.63 (18)
O1—C5—C4	110.55 (19)	C2—C9—S1	116.14 (15)
O1—C5—H5A	109.5	C8—C9—S1	116.20 (14)
C4—C5—H5A	109.5	C6—O1—C5	113.57 (18)
O1—C5—H5B	109.5	C1—S1—C9	97.73 (10)
C4—C5—H5B	109.5	C1—S3—C2	98.01 (10)
H5A—C5—H5B	108.1	C4—S4—C3	102.59 (10)
O1—C6—C7	109.68 (19)	C7—S5—C8	103.70 (11)

Experimental details

Crystal data
Chemical formula	C₉H₁₂OS₅
M_r	296.49
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.3425 (17), 8.9611 (18), 9.820 (2)
α, β, γ (°)	98.10 (3), 106.58 (3), 112.74 (3)
V (Å³)	622.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.15 × 0.12 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.877, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	6141, 2813, 2560
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.106, 1.06
No. of reflections	2813
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.36

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

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.

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