6,7-Bis(methyl­sulfan­yl)-2,3-[(3,6,9-trioxaundecane-1,11-di­yl)bis­(sulfanediylmethyl­ene)]-1,4,5,8-tetra­thia­fulvalene

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

doi:10.1107/S160053681001192X

6,7-Bis(methylsulfanyl)-2,3-[(3,6,9-trioxaundecane-1,11-diyl)bis(sulfanediylmethylene)]-1,4,5,8-tetrathiafulvalene

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

In the title compound, C₁₈H₂₆O₃S₈, the two five-membered rings exhibit envelope conformations. The two S atoms in the 17-membered macrocycle deviate from the plane of the fused five-membered ring by 1.429 (3) and -1.434 (3) Å in opposite directions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681001192X/cv2706sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681001192X/cv2706Isup2.hkl Contains datablock I

CCDC reference: 777957

checkCIF report

Key indicators

Single-crystal X-ray study
T = 290 K
Mean (C-C) = 0.005 Å
R factor = 0.045
wR factor = 0.125
Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S8
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          8
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         12
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         55

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Dithiacrown ether annulated tetrathiafulvalenes (TTF) have been received great attention as sensor molecules for various metal cations (Otsubo & Ogura, 1985; Moore et al., 2000). These sensors can recognize selectively the various metal cations to signal electrochemical information. We fused TTF unit with a extended dithiacrown ether to synthesize the title compound, (I). Herewith we report its crystal structure.

In (I) (Fig. 1), all bond lengths and angles are normal and comparable to those observed in the related structure (Hou et al., 2009). Two five-membered rings have an envelope conformation. Two S atoms in the 17-membered macrocycle deviate from the plane of the fused five-membered ring in opposite directions at 1.429 (3) and -1.434 (3) Å, respectively. The mean planes of two five-membered rings form a dihedral angle of 29.84 (10) °.

Related literature top

For background to dithiacrown ether annulated tetrathiafulvalenes, see: Otsubo & Ogura (1985); 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 evaporation a mixture of dichloromethane and petroleum (60-90 °C) at room temperature.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 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 and 30% probability displacement ellipsoids.

6,7-Bis(methylsulfanyl)-2,3-[(3,6,9-trioxaundecane-1,11- diyl)bis(sulfanediylmethylene)]-1,4,5,8-tetrathiafulvalene top

Crystal data top

C₁₈H₂₆O₃S₈	Z = 2
M_r = 546.87	F(000) = 572
Triclinic, P1	D_x = 1.482 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.715 (5) Å	Cell parameters from 8201 reflections
b = 11.585 (7) Å	θ = 3.1–27.5°
c = 12.548 (5) Å	µ = 0.75 mm⁻¹
α = 98.37 (2)°	T = 290 K
β = 112.112 (18)°	Block, yellow
γ = 103.94 (2)°	0.13 × 0.11 × 0.11 mm
V = 1225.3 (11) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	5535 independent reflections
Radiation source: fine-focus sealed tube	4519 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→11
T_min = 0.909, T_max = 0.922	k = −14→15
12067 measured reflections	l = −15→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0606P)² + 0.6546P] where P = (F_o² + 2F_c²)/3
5535 reflections	(Δ/σ)_max = 0.004
264 parameters	Δρ_max = 1.19 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

C₁₈H₂₆O₃S₈	γ = 103.94 (2)°
M_r = 546.87	V = 1225.3 (11) Å³
Triclinic, P1	Z = 2
a = 9.715 (5) Å	Mo Kα radiation
b = 11.585 (7) Å	µ = 0.75 mm⁻¹
c = 12.548 (5) Å	T = 290 K
α = 98.37 (2)°	0.13 × 0.11 × 0.11 mm
β = 112.112 (18)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5535 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4519 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.922	R_int = 0.021
12067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.09	Δρ_max = 1.19 e Å⁻³
5535 reflections	Δρ_min = −0.84 e Å⁻³
264 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
C1	0.8329 (4)	0.2619 (3)	−0.0795 (3)	0.0673 (8)
H1A	0.9100	0.3281	−0.0122	0.101*
H1B	0.8797	0.2016	−0.0963	0.101*
H1C	0.7472	0.2243	−0.0620	0.101*
C2	0.6741 (3)	0.4211 (2)	−0.1600 (2)	0.0461 (6)
C3	0.6468 (3)	0.6002 (2)	−0.0284 (2)	0.0378 (5)
C4	0.6879 (3)	0.7034 (2)	0.0568 (2)	0.0375 (5)
C5	0.8608 (3)	0.9048 (2)	0.2248 (2)	0.0377 (5)
C6	1.0049 (3)	0.9939 (2)	0.3263 (2)	0.0453 (6)
H6A	1.0222	0.9641	0.3970	0.054*
H6B	0.9875	1.0724	0.3417	0.054*
C7	1.1338 (4)	1.0744 (4)	0.1696 (3)	0.0672 (9)
H7A	1.1946	1.0522	0.1287	0.081*
H7B	1.0238	1.0324	0.1167	0.081*
C8	1.1631 (4)	1.2111 (4)	0.1912 (4)	0.0809 (11)
H8A	1.2668	1.2551	0.2548	0.097*
H8B	1.1577	1.2362	0.1197	0.097*
C9	1.0704 (4)	1.3669 (3)	0.2552 (3)	0.0717 (9)
H9A	1.0745	1.4025	0.1906	0.086*
H9B	1.1688	1.4080	0.3253	0.086*
C10	0.9373 (4)	1.3834 (3)	0.2801 (3)	0.0631 (8)
H10A	0.9445	1.4696	0.2948	0.076*
H10B	0.8383	1.3365	0.2124	0.076*
C11	0.8268 (4)	1.3533 (3)	0.4170 (3)	0.0631 (8)
H11A	0.7245	1.3175	0.3497	0.076*
H11B	0.8427	1.4396	0.4478	0.076*
C12	0.8366 (4)	1.2872 (3)	0.5112 (3)	0.0684 (9)
H12A	0.9438	1.3157	0.5724	0.082*
H12B	0.7701	1.3060	0.5479	0.082*
C13	0.6293 (4)	1.0953 (3)	0.4346 (3)	0.0646 (8)
H13A	0.5700	1.1524	0.4205	0.077*
H13B	0.6215	1.0642	0.5006	0.077*
C14	0.5624 (4)	0.9902 (3)	0.3249 (3)	0.0579 (7)
H14A	0.4659	0.9349	0.3191	0.070*
H14B	0.6358	0.9445	0.3335	0.070*
C15	0.7020 (3)	1.0495 (2)	0.1709 (2)	0.0424 (5)
H15A	0.6948	1.0792	0.1011	0.051*
H15B	0.7895	1.1095	0.2398	0.051*
C16	0.7328 (3)	0.9291 (2)	0.1574 (2)	0.0369 (5)
C17	0.5549 (3)	0.4512 (3)	−0.2335 (2)	0.0542 (7)
C18	0.2899 (5)	0.2958 (4)	−0.4241 (4)	0.0993 (14)
H18A	0.3042	0.2321	−0.3839	0.149*
H18B	0.2354	0.2598	−0.5086	0.149*
H18C	0.2296	0.3380	−0.3983	0.149*
O1	1.0472 (3)	1.2390 (2)	0.2231 (2)	0.0649 (6)
O2	0.9459 (2)	1.3412 (2)	0.38150 (17)	0.0585 (5)
O3	0.7891 (2)	1.1573 (2)	0.46389 (19)	0.0605 (5)
S1	0.76152 (11)	0.32107 (7)	−0.20652 (7)	0.0659 (2)
S2	0.75246 (8)	0.49614 (6)	−0.00808 (5)	0.04786 (17)
S3	0.85994 (8)	0.75086 (6)	0.19036 (5)	0.04658 (17)
S4	1.18116 (8)	1.01831 (8)	0.30089 (7)	0.0583 (2)
S5	0.52206 (8)	1.03736 (6)	0.18849 (6)	0.04905 (17)
S6	0.57706 (7)	0.80320 (6)	0.04603 (6)	0.04656 (17)
S7	0.48777 (8)	0.55840 (7)	−0.16902 (6)	0.05239 (18)
S8	0.47241 (13)	0.40014 (12)	−0.39012 (7)	0.0970 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.070 (2)	0.0609 (19)	0.077 (2)	0.0254 (16)	0.0397 (18)	0.0044 (16)
C2	0.0520 (15)	0.0406 (13)	0.0391 (12)	−0.0002 (11)	0.0261 (11)	−0.0012 (10)
C3	0.0382 (12)	0.0360 (12)	0.0364 (11)	0.0085 (9)	0.0153 (9)	0.0096 (9)
C4	0.0378 (12)	0.0352 (11)	0.0389 (11)	0.0118 (9)	0.0159 (9)	0.0096 (9)
C5	0.0369 (12)	0.0373 (12)	0.0380 (11)	0.0115 (9)	0.0178 (10)	0.0038 (9)
C6	0.0406 (13)	0.0497 (14)	0.0390 (12)	0.0129 (11)	0.0150 (10)	0.0013 (10)
C7	0.0522 (17)	0.100 (3)	0.0579 (17)	0.0260 (17)	0.0347 (15)	0.0127 (17)
C8	0.059 (2)	0.110 (3)	0.091 (3)	0.019 (2)	0.0487 (19)	0.045 (2)
C9	0.078 (2)	0.0544 (18)	0.069 (2)	−0.0044 (16)	0.0316 (17)	0.0209 (15)
C10	0.081 (2)	0.0383 (14)	0.0566 (16)	0.0106 (14)	0.0199 (15)	0.0147 (12)
C11	0.0613 (19)	0.0534 (17)	0.0645 (18)	0.0204 (15)	0.0203 (15)	0.0021 (14)
C12	0.064 (2)	0.081 (2)	0.0460 (15)	0.0117 (17)	0.0222 (14)	−0.0003 (14)
C13	0.0501 (16)	0.091 (2)	0.0611 (18)	0.0179 (16)	0.0329 (14)	0.0263 (17)
C14	0.0535 (17)	0.0573 (17)	0.078 (2)	0.0194 (14)	0.0388 (15)	0.0305 (15)
C15	0.0411 (13)	0.0337 (12)	0.0526 (14)	0.0112 (10)	0.0212 (11)	0.0106 (10)
C16	0.0335 (11)	0.0338 (11)	0.0437 (12)	0.0084 (9)	0.0193 (10)	0.0076 (9)
C17	0.0500 (15)	0.0618 (17)	0.0353 (12)	−0.0017 (13)	0.0199 (12)	−0.0028 (11)
C18	0.090 (3)	0.098 (3)	0.070 (2)	0.000 (2)	0.016 (2)	0.008 (2)
O1	0.0606 (13)	0.0569 (12)	0.0870 (15)	0.0080 (10)	0.0468 (12)	0.0237 (11)
O2	0.0605 (12)	0.0613 (12)	0.0532 (11)	0.0206 (10)	0.0208 (10)	0.0212 (9)
O3	0.0486 (11)	0.0760 (14)	0.0617 (12)	0.0191 (10)	0.0265 (10)	0.0257 (11)
S1	0.0891 (6)	0.0546 (4)	0.0623 (4)	0.0167 (4)	0.0508 (4)	−0.0005 (3)
S2	0.0601 (4)	0.0414 (3)	0.0366 (3)	0.0208 (3)	0.0156 (3)	0.0012 (2)
S3	0.0475 (4)	0.0435 (3)	0.0412 (3)	0.0221 (3)	0.0095 (3)	0.0030 (2)
S4	0.0325 (3)	0.0715 (5)	0.0582 (4)	0.0171 (3)	0.0114 (3)	0.0018 (3)
S5	0.0395 (3)	0.0518 (4)	0.0557 (4)	0.0219 (3)	0.0173 (3)	0.0103 (3)
S6	0.0351 (3)	0.0367 (3)	0.0556 (4)	0.0113 (2)	0.0094 (3)	0.0050 (3)
S7	0.0433 (4)	0.0610 (4)	0.0404 (3)	0.0105 (3)	0.0102 (3)	0.0091 (3)
S8	0.0877 (7)	0.1331 (10)	0.0378 (4)	−0.0061 (6)	0.0267 (4)	−0.0001 (5)

Geometric parameters (Å, º) top

C1—S1	1.790 (4)	C10—O2	1.408 (3)
C1—H1A	0.9600	C10—H10A	0.9700
C1—H1B	0.9600	C10—H10B	0.9700
C1—H1C	0.9600	C11—O2	1.415 (4)
C2—C17	1.341 (4)	C11—C12	1.485 (5)
C2—S1	1.748 (3)	C11—H11A	0.9700
C2—S2	1.753 (3)	C11—H11B	0.9700
C3—C4	1.345 (3)	C12—O3	1.425 (4)
C3—S2	1.750 (3)	C12—H12A	0.9700
C3—S7	1.753 (2)	C12—H12B	0.9700
C4—S6	1.746 (2)	C13—O3	1.420 (4)
C4—S3	1.756 (2)	C13—C14	1.503 (5)
C5—C16	1.337 (3)	C13—H13A	0.9700
C5—C6	1.492 (3)	C13—H13B	0.9700
C5—S3	1.770 (3)	C14—S5	1.803 (3)
C6—S4	1.821 (3)	C14—H14A	0.9700
C6—H6A	0.9700	C14—H14B	0.9700
C6—H6B	0.9700	C15—C16	1.496 (3)
C7—C8	1.504 (5)	C15—S5	1.818 (3)
C7—S4	1.798 (4)	C15—H15A	0.9700
C7—H7A	0.9700	C15—H15B	0.9700
C7—H7B	0.9700	C16—S6	1.767 (3)
C8—O1	1.419 (4)	C17—S8	1.761 (3)
C8—H8A	0.9700	C17—S7	1.765 (3)
C8—H8B	0.9700	C18—S8	1.742 (5)
C9—O1	1.416 (4)	C18—H18A	0.9600
C9—C10	1.487 (5)	C18—H18B	0.9600
C9—H9A	0.9700	C18—H18C	0.9600
C9—H9B	0.9700

S1—C1—H1A	109.5	O2—C11—H11B	110.3
S1—C1—H1B	109.5	C12—C11—H11B	110.3
H1A—C1—H1B	109.5	H11A—C11—H11B	108.6
S1—C1—H1C	109.5	O3—C12—C11	111.5 (2)
H1A—C1—H1C	109.5	O3—C12—H12A	109.3
H1B—C1—H1C	109.5	C11—C12—H12A	109.3
C17—C2—S1	124.5 (2)	O3—C12—H12B	109.3
C17—C2—S2	116.3 (2)	C11—C12—H12B	109.3
S1—C2—S2	119.01 (17)	H12A—C12—H12B	108.0
C4—C3—S2	121.99 (19)	O3—C13—C14	109.6 (2)
C4—C3—S7	124.10 (19)	O3—C13—H13A	109.7
S2—C3—S7	113.89 (13)	C14—C13—H13A	109.7
C3—C4—S6	123.71 (19)	O3—C13—H13B	109.7
C3—C4—S3	122.82 (19)	C14—C13—H13B	109.7
S6—C4—S3	113.46 (13)	H13A—C13—H13B	108.2
C16—C5—C6	126.9 (2)	C13—C14—S5	114.0 (2)
C16—C5—S3	116.77 (18)	C13—C14—H14A	108.8
C6—C5—S3	116.37 (18)	S5—C14—H14A	108.8
C5—C6—S4	114.01 (17)	C13—C14—H14B	108.8
C5—C6—H6A	108.7	S5—C14—H14B	108.8
S4—C6—H6A	108.7	H14A—C14—H14B	107.7
C5—C6—H6B	108.7	C16—C15—S5	112.39 (16)
S4—C6—H6B	108.7	C16—C15—H15A	109.1
H6A—C6—H6B	107.6	S5—C15—H15A	109.1
C8—C7—S4	115.4 (2)	C16—C15—H15B	109.1
C8—C7—H7A	108.4	S5—C15—H15B	109.1
S4—C7—H7A	108.4	H15A—C15—H15B	107.9
C8—C7—H7B	108.4	C5—C16—C15	127.2 (2)
S4—C7—H7B	108.4	C5—C16—S6	116.68 (18)
H7A—C7—H7B	107.5	C15—C16—S6	115.94 (18)
O1—C8—C7	108.5 (3)	C2—C17—S8	124.0 (2)
O1—C8—H8A	110.0	C2—C17—S7	117.57 (19)
C7—C8—H8A	110.0	S8—C17—S7	118.18 (19)
O1—C8—H8B	110.0	S8—C18—H18A	109.5
C7—C8—H8B	110.0	S8—C18—H18B	109.5
H8A—C8—H8B	108.4	H18A—C18—H18B	109.5
O1—C9—C10	108.2 (2)	S8—C18—H18C	109.5
O1—C9—H9A	110.1	H18A—C18—H18C	109.5
C10—C9—H9A	110.1	H18B—C18—H18C	109.5
O1—C9—H9B	110.1	C9—O1—C8	113.5 (3)
C10—C9—H9B	110.1	C10—O2—C11	114.0 (2)
H9A—C9—H9B	108.4	C13—O3—C12	113.9 (3)
O2—C10—C9	107.8 (3)	C2—S1—C1	101.77 (14)
O2—C10—H10A	110.2	C3—S2—C2	95.28 (13)
C9—C10—H10A	110.2	C4—S3—C5	94.67 (11)
O2—C10—H10B	110.2	C7—S4—C6	103.95 (13)
C9—C10—H10B	110.2	C14—S5—C15	102.32 (13)
H10A—C10—H10B	108.5	C4—S6—C16	94.86 (12)
O2—C11—C12	107.1 (3)	C3—S7—C17	94.12 (13)
O2—C11—H11A	110.3	C18—S8—C17	102.48 (18)
C12—C11—H11A	110.3

Experimental details

Crystal data
Chemical formula	C₁₈H₂₆O₃S₈
M_r	546.87
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	9.715 (5), 11.585 (7), 12.548 (5)
α, β, γ (°)	98.37 (2), 112.112 (18), 103.94 (2)
V (Å³)	1225.3 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.13 × 0.11 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID
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	12067, 5535, 4519
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.125, 1.09
No. of reflections	5535
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.84

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

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		Medline
		CIF
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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

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6,7-Bis(methyl­sulfan­yl)-2,3-[(3,6,9-trioxaundecane-1,11-di­yl)bis­(sulfanediylmethyl­ene)]-1,4,5,8-tetra­thia­fulvalene

Supporting information

Key indicators

checkCIF/PLATON results

6,7-Bis(methylsulfanyl)-2,3-[(3,6,9-trioxaundecane-1,11-diyl)bis(sulfanediylmethylene)]-1,4,5,8-tetrathiafulvalene