4,6,7,9,10,12,13,15-Octa­hydro-2H-1,3-dithiolo[4,5-i][1,4,7,12]dioxadithia­cyclo­tetra­decine-2-thione

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

doi:10.1107/S1600536809029468

organic compounds

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4,6,7,9,10,12,13,15-Octahydro-2H-1,3-dithiolo[4,5-i][1,4,7,12]dioxadithiacyclotetradecine-2-thione

Rui-Bin Hou,^a Bao Li,^b Tie Chen,^a 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 21 July 2009; accepted 24 July 2009; online 31 July 2009)

In the title molecule, C₁₁H₁₆O₂S₅, the two S atoms from the macrocycle are situated on opposite sides of the mean plane of the five-membered ring, deviating from it by 1.288 (3) and 1.728 (3) Å. In the crystal, weak intermolecular C—H⋯S and C—H⋯O hydrogen bonds link the molecules into layers parallel to (100). The crystal studied was a racemic twin.

Related literature

For crown ether annulated 1,3-dithiol-2-thiones, see: Hansen et al. (1992 ); Trippé et al. (2002 ). For details of the synthesis, see: Chen et al. (2005 ). For a related structure, see: Hou et al. (2009 )

Experimental

Crystal data

C₁₁H₁₆O₂S₅
M_r = 340.54
Monoclinic, P 2₁
a = 8.9201 (18) Å
b = 8.5317 (17) Å
c = 10.128 (2) Å
β = 97.00 (3)°
V = 765.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 291 K
0.13 × 0.12 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.909, T_max = 0.922
7527 measured reflections
3221 independent reflections
3100 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.06
3221 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ); 1359 Friedel pairs
Flack parameter: 0.42 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯S1ⁱ	0.97	2.86	3.695 (3)	145
C10—H10A⋯O2ⁱⁱ	0.97	2.51	3.317 (3)	140
Symmetry codes: (i) x-1, y, z-1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

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/S1600536809029468/cv2592sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029468/cv2592Isup2.hkl

checkCIF report

Comment top

In the context of redox-responsive ligands, TTF is an ideal redox-active unit in view of its unique π-electron donating properties. Attachment of ligands such as crown ethers to TTF in many cases results in the electrochemical tunable ligands (Trippé et al., 2002). Crowned 1,3-dithiole-2-thiones, important precursors to TTF derivatives, have also attracted attention (Hansen et al., 1992). In this paper, we report the crystal structure of the title compound.

In the title compound (Fig. 1), all bond lengths and angles are normal and comparable with those reported for the related structure (Hou et al., 2009). In the crystal, weak intermolecular C—H···S and C—H···O hydrogen bonds (Table 1) link the molecules into layers parallel to (a+c)b plane.

Related literature top

For crown ether annulated 1,3-dithiol-2-thiones, see: Hansen et al. (1992); Trippé et al. (2002). 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) and single crystals suitable for X-ray diffraction were prepared by slow evaporation a mixture of dichloromthane and petroleum (60–90 °C) 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 the title compound showing the atomic numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

4,6,7,9,10,12,13,15-Octahydro-2H-1,3- dithiolo[4,5-i][1,4,7,12]dioxadithiacyclotetradecine-2-thione top

Crystal data top

C₁₁H₁₆O₂S₅	F(000) = 356
M_r = 340.54	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7211 reflections
a = 8.9201 (18) Å	θ = 3.1–27.5°
b = 8.5317 (17) Å	µ = 0.75 mm⁻¹
c = 10.128 (2) Å	T = 291 K
β = 97.00 (3)°	Block, yellow
V = 765.0 (3) Å³	0.13 × 0.12 × 0.11 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	3221 independent reflections
Radiation source: fine-focus sealed tube	3100 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.909, T_max = 0.922	k = −11→10
7527 measured reflections	l = −13→11

Refinement top

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0508P)² + 0.1939P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3221 reflections	Δρ_max = 0.58 e Å⁻³
164 parameters	Δρ_min = −0.22 e Å⁻³
1 restraint	Absolute structure: Flack (1983); 1359 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.42 (9)

Crystal data top

C₁₁H₁₆O₂S₅	V = 765.0 (3) Å³
M_r = 340.54	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.9201 (18) Å	µ = 0.75 mm⁻¹
b = 8.5317 (17) Å	T = 291 K
c = 10.128 (2) Å	0.13 × 0.12 × 0.11 mm
β = 97.00 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3221 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3100 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.922	R_int = 0.028
7527 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.58 e Å⁻³
S = 1.06	Δρ_min = −0.22 e Å⁻³
3221 reflections	Absolute structure: Flack (1983); 1359 Friedel pairs
164 parameters	Absolute structure parameter: 0.42 (9)
1 restraint

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.

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	0.9104 (3)	0.5403 (4)	1.0514 (2)	0.0344 (5)
C2	0.6930 (2)	0.4126 (3)	0.8914 (2)	0.0264 (5)
C3	0.5748 (3)	0.2952 (3)	0.8447 (2)	0.0342 (5)
H3A	0.6206	0.1920	0.8492	0.041*
H3B	0.5391	0.3164	0.7521	0.041*
C4	0.3178 (3)	0.4733 (4)	0.8901 (3)	0.0406 (6)
H4A	0.2524	0.4990	0.9568	0.049*
H4B	0.3929	0.5556	0.8915	0.049*
C5	0.2242 (3)	0.4741 (4)	0.7555 (3)	0.0445 (7)
H5A	0.1638	0.3795	0.7439	0.053*
H5B	0.1566	0.5637	0.7482	0.053*
C6	0.2480 (3)	0.4848 (4)	0.5262 (3)	0.0426 (6)
H6A	0.1704	0.5650	0.5179	0.051*
H6B	0.2005	0.3842	0.5047	0.051*
C7	0.3637 (3)	0.5190 (4)	0.4329 (3)	0.0418 (6)
H7A	0.3150	0.5253	0.3421	0.050*
H7B	0.4128	0.6185	0.4558	0.050*
C8	0.5855 (3)	0.4162 (4)	0.3590 (3)	0.0427 (7)
H8A	0.5382	0.4495	0.2722	0.051*
H8B	0.6331	0.3156	0.3480	0.051*
C9	0.7060 (3)	0.5337 (4)	0.4090 (3)	0.0470 (7)
H9A	0.6589	0.6351	0.4175	0.056*
H9B	0.7765	0.5438	0.3438	0.056*
C10	0.6889 (3)	0.5696 (4)	0.6801 (2)	0.0381 (6)
H10A	0.6885	0.6826	0.6690	0.046*
H10B	0.5861	0.5322	0.6586	0.046*
C11	0.7448 (2)	0.5293 (3)	0.8207 (2)	0.0290 (5)
O1	0.3233 (2)	0.4825 (3)	0.65686 (18)	0.0432 (5)
O2	0.4715 (2)	0.3969 (2)	0.44464 (17)	0.0385 (4)
S1	1.03598 (9)	0.58767 (12)	1.17933 (8)	0.0558 (2)
S2	0.78149 (7)	0.39272 (8)	1.05411 (6)	0.03282 (15)
S3	0.41352 (8)	0.29178 (9)	0.93755 (8)	0.04456 (18)
S4	0.80970 (8)	0.48036 (12)	0.56811 (7)	0.0539 (2)
S5	0.89230 (7)	0.64009 (8)	0.90156 (7)	0.03733 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0240 (11)	0.0456 (15)	0.0325 (11)	0.0034 (10)	−0.0003 (9)	−0.0064 (11)
C2	0.0195 (10)	0.0336 (13)	0.0252 (10)	0.0033 (8)	−0.0005 (8)	−0.0022 (9)
C3	0.0310 (12)	0.0346 (13)	0.0356 (12)	0.0012 (10)	−0.0020 (9)	−0.0022 (11)
C4	0.0330 (13)	0.0503 (17)	0.0400 (13)	0.0006 (12)	0.0105 (10)	−0.0063 (12)
C5	0.0259 (12)	0.0616 (19)	0.0473 (15)	0.0072 (12)	0.0094 (11)	0.0041 (14)
C6	0.0275 (13)	0.0597 (19)	0.0388 (13)	0.0049 (12)	−0.0030 (10)	0.0054 (13)
C7	0.0369 (14)	0.0520 (17)	0.0346 (12)	0.0011 (12)	−0.0028 (11)	0.0071 (12)
C8	0.0417 (15)	0.0582 (19)	0.0283 (11)	−0.0032 (13)	0.0048 (10)	0.0000 (12)
C9	0.0413 (15)	0.069 (2)	0.0313 (12)	−0.0104 (14)	0.0065 (11)	0.0044 (13)
C10	0.0318 (13)	0.0507 (16)	0.0315 (12)	0.0060 (11)	0.0028 (10)	0.0054 (11)
C11	0.0184 (10)	0.0390 (13)	0.0292 (11)	0.0012 (9)	0.0020 (8)	−0.0002 (10)
O1	0.0233 (8)	0.0716 (14)	0.0349 (9)	0.0071 (9)	0.0045 (7)	0.0047 (9)
O2	0.0346 (10)	0.0433 (11)	0.0377 (9)	−0.0016 (8)	0.0049 (7)	0.0018 (9)
S1	0.0336 (4)	0.0887 (7)	0.0416 (4)	−0.0110 (4)	−0.0092 (3)	−0.0101 (4)
S2	0.0298 (3)	0.0407 (3)	0.0267 (3)	−0.0002 (2)	−0.0015 (2)	0.0031 (2)
S3	0.0319 (3)	0.0508 (4)	0.0507 (4)	−0.0110 (3)	0.0041 (3)	0.0134 (3)
S4	0.0314 (3)	0.0975 (7)	0.0325 (3)	0.0086 (4)	0.0027 (3)	−0.0032 (4)
S5	0.0254 (3)	0.0466 (4)	0.0399 (3)	−0.0089 (3)	0.0031 (2)	0.0025 (3)

Geometric parameters (Å, º) top

C1—S1	1.656 (3)	C6—H6A	0.9700
C1—S2	1.708 (3)	C6—H6B	0.9700
C1—S5	1.730 (3)	C7—O2	1.413 (4)
C2—C11	1.341 (4)	C7—H7A	0.9700
C2—C3	1.489 (3)	C7—H7B	0.9700
C2—S2	1.747 (2)	C8—O2	1.424 (3)
C3—S3	1.812 (3)	C8—C9	1.511 (4)
C3—H3A	0.9700	C8—H8A	0.9700
C3—H3B	0.9700	C8—H8B	0.9700
C4—C5	1.510 (4)	C9—S4	1.815 (3)
C4—S3	1.805 (3)	C9—H9A	0.9700
C4—H4A	0.9700	C9—H9B	0.9700
C4—H4B	0.9700	C10—C11	1.490 (3)
C5—O1	1.414 (3)	C10—S4	1.824 (3)
C5—H5A	0.9700	C10—H10A	0.9700
C5—H5B	0.9700	C10—H10B	0.9700
C6—O1	1.409 (3)	C11—S5	1.741 (2)
C6—C7	1.510 (4)

S1—C1—S2	124.03 (17)	C6—C7—H7A	110.0
S1—C1—S5	123.24 (18)	O2—C7—H7B	110.0
S2—C1—S5	112.70 (14)	C6—C7—H7B	110.0
C11—C2—C3	127.4 (2)	H7A—C7—H7B	108.4
C11—C2—S2	115.48 (18)	O2—C8—C9	113.8 (2)
C3—C2—S2	117.08 (18)	O2—C8—H8A	108.8
C2—C3—S3	114.98 (18)	C9—C8—H8A	108.8
C2—C3—H3A	108.5	O2—C8—H8B	108.8
S3—C3—H3A	108.5	C9—C8—H8B	108.8
C2—C3—H3B	108.5	H8A—C8—H8B	107.7
S3—C3—H3B	108.5	C8—C9—S4	113.3 (2)
H3A—C3—H3B	107.5	C8—C9—H9A	108.9
C5—C4—S3	115.9 (2)	S4—C9—H9A	108.9
C5—C4—H4A	108.3	C8—C9—H9B	108.9
S3—C4—H4A	108.3	S4—C9—H9B	108.9
C5—C4—H4B	108.3	H9A—C9—H9B	107.7
S3—C4—H4B	108.3	C11—C10—S4	110.08 (18)
H4A—C4—H4B	107.4	C11—C10—H10A	109.6
O1—C5—C4	108.3 (2)	S4—C10—H10A	109.6
O1—C5—H5A	110.0	C11—C10—H10B	109.6
C4—C5—H5A	110.0	S4—C10—H10B	109.6
O1—C5—H5B	110.0	H10A—C10—H10B	108.2
C4—C5—H5B	110.0	C2—C11—C10	125.7 (2)
H5A—C5—H5B	108.4	C2—C11—S5	116.22 (18)
O1—C6—C7	107.8 (2)	C10—C11—S5	118.0 (2)
O1—C6—H6A	110.1	C6—O1—C5	113.3 (2)
C7—C6—H6A	110.1	C7—O2—C8	113.1 (2)
O1—C6—H6B	110.1	C1—S2—C2	98.09 (12)
C7—C6—H6B	110.1	C4—S3—C3	103.16 (13)
H6A—C6—H6B	108.5	C9—S4—C10	99.88 (14)
O2—C7—C6	108.3 (2)	C1—S5—C11	97.47 (13)
O2—C7—H7A	110.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···S1ⁱ	0.97	2.86	3.695 (3)	145
C10—H10A···O2ⁱⁱ	0.97	2.51	3.317 (3)	140

Symmetry codes: (i) x−1, y, z−1; (ii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆O₂S₅
M_r	340.54
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	291
a, b, c (Å)	8.9201 (18), 8.5317 (17), 10.128 (2)
β (°)	97.00 (3)
V (Å³)	765.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.13 × 0.12 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.909, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	7527, 3221, 3100
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.06
No. of reflections	3221
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.22
Absolute structure	Flack (1983); 1359 Friedel pairs
Absolute structure parameter	0.42 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···S1ⁱ	0.97	2.86	3.695 (3)	144.5
C10—H10A···O2ⁱⁱ	0.97	2.51	3.317 (3)	140.4

Symmetry codes: (i) x−1, y, z−1; (ii) −x+1, y+1/2, −z+1.

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

Chen, T., Liu, W. J., Cong, Z. Q. & Yin, B. Z. (2005). Chin. J. Org. Chem. 25, 570–575. CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hansen, T. K., Jφrgensen, T., Stein, P. C. & Becher, J. (1992). J. Org. Chem. 57, 6403–6409. CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hou, R., Li, B., Yin, B. & Wu, L. (2009). Acta Cryst. E65, o1057. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Trippé, G., Levillain, E., Le Derf, F., Gorgues, A., Sallé, M., Jeppesen, J. O., Nielsen, K. & Becher, J. (2002). Org. Lett. 4, 2461–2464. Web of Science PubMed Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4,6,7,9,10,12,13,15-Octa­hydro-2H-1,3-di­thiolo[4,5-i][1,4,7,12]dioxadi­thia­cyclo­tetra­decine-2-thione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,6,7,9,10,12,13,15-Octahydro-2H-1,3-dithiolo[4,5-i][1,4,7,12]dioxadithiacyclotetradecine-2-thione