4,6,7,9,10,12,13,15,16,18-Decahydro-1,3-dithiolo[4,5-l][1,4,7,10,15]trioxadithia­cyclo­hepta­decine-2-thione

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

doi:10.1107/S1600536810016946

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1335

https://doi.org/10.1107/S1600536810016946

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4,6,7,9,10,12,13,15,16,18-Decahydro-1,3-dithiolo[4,5-l][1,4,7,10,15]trioxadithiacycloheptadecine-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 the Changbai Moutain, 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 29 March 2010; accepted 10 May 2010; online 15 May 2010)

The title compound, C₁₃H₂₀O₃S₅, is bisected by a crystallographic twofold rotation axis, which relates the two halves of the molecule to one another: one S, one C and one O atom lie on the axis. The thione S atom lies in the plane of the five-membered rings with an r.m.s. deviation of 0.0042 (5) Å. Parts of the 17-membered macrocycle were refined using a two-part disorder model [occupancies of 0.553 (14) and 0.447 (14)]. There are no noteworthy intermolecular interactions.

Related literature

Thiacrown ether annulated 1,3-dithiol-2-thione is a key intermediate of the crown ether-bearing redox-active tetrathiafulvalene moiety, see: Moore et al. (2000 ). For details of the synthesis, see: Chen et al. (2005 ). For a related structure, see: Hou et al. (2009 )

Experimental

Crystal data

C₁₃H₂₀O₃S₅
M_r = 384.59
Monoclinic, C 2/c
a = 14.040 (3) Å
b = 13.616 (3) Å
c = 10.004 (2) Å
β = 110.89 (3)°
V = 1786.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 290 K
0.13 × 0.13 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.920, T_max = 0.926
8683 measured reflections
2054 independent reflections
1795 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.103
S = 1.05
2054 reflections
116 parameters
31 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.40 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: https://doi.org/10.1107/S1600536810016946/nk2030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016946/nk2030Isup2.hkl

checkCIF report

Comment top

Thiacrown ether annulated 1,3-dithiol-2-thione has been intensively investigated because it is a key intermediate of the crown ether bearing redox-active tetrathiafulvalene moiety (Moore et al., 2000). Herein, we report the crystal structure of the title compound, (I).

The molecule structure of title compound, C₁₃H₂₀O₃S₅, is shown in Fig. 1. All bond lengths and angles are unexceptional and comparable with the related structure (Hou et al., 2009). The C6, C7 and C6', C7' atoms were refined using a two-part disorder model with a major:minor occupancy ratio of 55:45.

Related literature top

Thiacrown ether annulated 1,3-dithiol-2-thione is a key intermediate of the crown ether-bearing redox-active tetrathiafulvalene moiety, see: Moore et al. (2000). For details of the synthesis, see: Chen et al. (2005). For a related structure, see: Hou et al. (2009)

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 evaperation a mixture of dichloromethane and petroleum (60-90 °C) at room temperature.

Structure description top

Thiacrown ether annulated 1,3-dithiol-2-thione is a key intermediate of the crown ether-bearing redox-active tetrathiafulvalene moiety, see: Moore et al. (2000). For details of the synthesis, see: Chen et al. (2005). For a related structure, see: Hou et al. (2009)

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 asymmetric of title compound, with the atom numbering. The disordered C6', C7' and their attached H atoms are omitted for clarity. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

4,6,7,9,10,12,13,15,16,18-Decahydro-1,3-dithiolo[4,5- l][1,4,7,10,15]trioxadithiacycloheptadecine-2-thione top

Crystal data top

C₁₃H₂₀O₃S₅	F(000) = 808
M_r = 384.59	D_x = 1.430 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7120 reflections
a = 14.040 (3) Å	θ = 3.0–27.5°
b = 13.616 (3) Å	µ = 0.65 mm⁻¹
c = 10.004 (2) Å	T = 290 K
β = 110.89 (3)°	Block, yellow
V = 1786.6 (6) Å³	0.13 × 0.13 × 0.12 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2054 independent reflections
Radiation source: fine-focus sealed tube	1795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→17
T_min = 0.920, T_max = 0.926	k = −15→17
8683 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0458P)² + 1.730P] where P = (F_o² + 2F_c²)/3
2054 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.38 e Å⁻³
31 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₃H₂₀O₃S₅	V = 1786.6 (6) Å³
M_r = 384.59	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.040 (3) Å	µ = 0.65 mm⁻¹
b = 13.616 (3) Å	T = 290 K
c = 10.004 (2) Å	0.13 × 0.13 × 0.12 mm
β = 110.89 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2054 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1795 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.926	R_int = 0.022
8683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	31 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	Δρ_max = 0.38 e Å⁻³
2054 reflections	Δρ_min = −0.40 e Å⁻³
116 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.0000	−0.12281 (6)	0.2500	0.0692 (3)
S2	0.05129 (4)	0.06857 (4)	0.14909 (6)	0.04829 (17)
S3	0.17462 (5)	0.26384 (5)	0.11969 (8)	0.0693 (2)
O1	0.17749 (17)	0.40044 (19)	0.3861 (3)	0.1067 (8)
O2	0.0000	0.5091 (3)	0.2500	0.1381 (16)
C1	0.0000	−0.0016 (2)	0.2500	0.0456 (6)
C2	0.02260 (13)	0.18371 (13)	0.2012 (2)	0.0390 (4)
C3	0.04873 (15)	0.27043 (15)	0.1292 (2)	0.0493 (5)
H3A	0.0440	0.3295	0.1807	0.059*
H3B	−0.0010	0.2757	0.0330	0.059*
C4	0.25511 (19)	0.2730 (2)	0.3037 (4)	0.0816 (9)
H4A	0.2278	0.2308	0.3594	0.098*
H4B	0.3221	0.2481	0.3138	0.098*
C5	0.2672 (2)	0.3743 (2)	0.3658 (4)	0.0896 (10)
H5A	0.3238	0.3758	0.4564	0.108*
H5B	0.2813	0.4205	0.3013	0.108*
C6	0.1737 (6)	0.4901 (6)	0.4396 (11)	0.092 (2)	0.553 (14)
H6A	0.2409	0.5199	0.4753	0.111*	0.553 (14)
H6B	0.1473	0.4868	0.5169	0.111*	0.553 (14)
C7	0.1044 (10)	0.5461 (6)	0.3178 (12)	0.099 (3)	0.553 (14)
H7A	0.1004	0.6126	0.3501	0.118*	0.553 (14)
H7B	0.1351	0.5497	0.2451	0.118*	0.553 (14)
C6'	0.1649 (8)	0.5194 (7)	0.3562 (16)	0.083 (3)	0.447 (14)
H6'1	0.2130	0.5549	0.4360	0.100*	0.447 (14)
H6'2	0.1785	0.5356	0.2703	0.100*	0.447 (14)
C7'	0.0574 (11)	0.5476 (8)	0.3385 (11)	0.092 (3)	0.447 (14)
H7'1	0.0459	0.5333	0.4266	0.110*	0.447 (14)
H7'2	0.0491	0.6178	0.3219	0.110*	0.447 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0894 (6)	0.0347 (4)	0.0982 (7)	0.000	0.0513 (5)	0.000
S2	0.0524 (3)	0.0401 (3)	0.0612 (3)	0.00140 (19)	0.0310 (2)	−0.0020 (2)
S3	0.0700 (4)	0.0671 (4)	0.0918 (5)	−0.0035 (3)	0.0543 (4)	0.0127 (3)
O1	0.0793 (14)	0.1025 (17)	0.142 (2)	−0.0370 (13)	0.0438 (14)	−0.0511 (16)
O2	0.110 (3)	0.067 (2)	0.225 (5)	0.000	0.044 (3)	0.000
C1	0.0432 (13)	0.0374 (13)	0.0576 (15)	0.000	0.0199 (12)	0.000
C2	0.0321 (8)	0.0354 (9)	0.0478 (9)	−0.0004 (6)	0.0123 (7)	0.0006 (7)
C3	0.0459 (10)	0.0444 (10)	0.0561 (11)	−0.0011 (8)	0.0165 (9)	0.0090 (9)
C4	0.0423 (12)	0.0699 (17)	0.122 (2)	−0.0026 (11)	0.0168 (14)	0.0213 (16)
C5	0.0518 (15)	0.086 (2)	0.115 (2)	−0.0222 (13)	0.0109 (15)	0.0036 (18)
C6	0.109 (5)	0.077 (4)	0.080 (5)	−0.023 (3)	0.021 (3)	−0.014 (3)
C7	0.112 (5)	0.054 (3)	0.126 (5)	−0.018 (4)	0.038 (5)	−0.010 (3)
C6'	0.092 (5)	0.063 (5)	0.100 (7)	−0.029 (4)	0.043 (5)	−0.029 (5)
C7'	0.108 (7)	0.081 (5)	0.094 (5)	−0.003 (5)	0.045 (5)	−0.037 (4)

Geometric parameters (Å, º) top

S1—C1	1.650 (3)	C3—H3B	0.9700
S2—C1	1.7231 (16)	C4—C5	1.497 (4)
S2—C2	1.7440 (18)	C4—H4A	0.9700
S3—C4	1.788 (3)	C4—H4B	0.9700
S3—C3	1.806 (2)	C5—H5A	0.9700
O1—C6	1.342 (7)	C5—H5B	0.9700
O1—C5	1.391 (4)	C6—C7	1.472 (14)
O1—C6'	1.645 (12)	C6—H6A	0.9700
O2—C7'	1.095 (11)	C6—H6B	0.9700
O2—C7'ⁱ	1.095 (11)	C7—H7A	0.9700
O2—C7	1.467 (11)	C7—H7B	0.9700
O2—C7ⁱ	1.467 (11)	C6'—C7'	1.506 (15)
C1—S2ⁱ	1.7231 (16)	C6'—H6'1	0.9700
C2—C2ⁱ	1.340 (4)	C6'—H6'2	0.9700
C2—C3	1.495 (3)	C7'—H7'1	0.9700
C3—H3A	0.9700	C7'—H7'2	0.9700

C1—S2—C2	97.69 (10)	O1—C5—H5B	109.9
C4—S3—C3	102.32 (13)	C4—C5—H5B	109.9
C6—O1—C5	117.2 (4)	H5A—C5—H5B	108.3
C6—O1—C6'	32.8 (4)	O1—C6—C7	104.4 (8)
C5—O1—C6'	105.6 (4)	O1—C6—H6A	110.9
C7'—O2—C7'ⁱ	122.7 (13)	C7—C6—H6A	110.9
C7'—O2—C7	30.3 (5)	O1—C6—H6B	110.9
C7'ⁱ—O2—C7	122.3 (7)	C7—C6—H6B	110.9
C7'—O2—C7ⁱ	122.3 (7)	H6A—C6—H6B	108.9
C7'ⁱ—O2—C7ⁱ	30.3 (5)	O2—C7—C6	117.5 (8)
C7—O2—C7ⁱ	139.8 (8)	O2—C7—H7A	107.9
S1—C1—S2ⁱ	123.68 (8)	C6—C7—H7A	107.9
S1—C1—S2	123.68 (8)	O2—C7—H7B	107.9
S2ⁱ—C1—S2	112.65 (15)	C6—C7—H7B	107.9
C2ⁱ—C2—C3	127.72 (11)	H7A—C7—H7B	107.2
C2ⁱ—C2—S2	115.95 (6)	C7'—C6'—O1	108.1 (8)
C3—C2—S2	116.30 (14)	C7'—C6'—H6'1	110.1
C2—C3—S3	113.52 (14)	O1—C6'—H6'1	110.1
C2—C3—H3A	108.9	C7'—C6'—H6'2	110.1
S3—C3—H3A	108.9	O1—C6'—H6'2	110.1
C2—C3—H3B	108.9	H6'1—C6'—H6'2	108.4
S3—C3—H3B	108.9	O2—C7'—C6'	113.0 (9)
H3A—C3—H3B	107.7	O2—C7'—C7'ⁱ	28.7 (6)
C5—C4—S3	115.3 (2)	C6'—C7'—C7'ⁱ	125.7 (13)
C5—C4—H4A	108.4	O2—C7'—H7'1	109.0
S3—C4—H4A	108.4	C6'—C7'—H7'1	109.0
C5—C4—H4B	108.4	C7'ⁱ—C7'—H7'1	118.7
S3—C4—H4B	108.4	O2—C7'—H7'2	109.0
H4A—C4—H4B	107.5	C6'—C7'—H7'2	109.0
O1—C5—C4	108.8 (2)	C7'ⁱ—C7'—H7'2	80.4
O1—C5—H5A	109.9	H7'1—C7'—H7'2	107.8
C4—C5—H5A	109.9

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₀O₃S₅
M_r	384.59
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	290
a, b, c (Å)	14.040 (3), 13.616 (3), 10.004 (2)
β (°)	110.89 (3)
V (Å³)	1786.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.13 × 0.13 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.920, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	8683, 2054, 1795
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.05
No. of reflections	2054
No. of parameters	116
No. of restraints	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.40

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.

References

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