13-[4,5-Bis(methyl­sulfan­yl)-1,3-dithiol-2-yl­idene]-6-oxa-3,9,12,14-tetra­thia­bicyclo­[9.3.0]tetra­dec-1(11)-ene

In the title mol­ecule, C₁₄H₁₈OS₈, one O atom, two S atoms and six C atoms form an 11-membered ring with a chair-like conformation; the planes of the two five-membered rings connected by a carbon–carbon double bond form a dihedral angle of 29.97 (11)°. In the crystal, pairs of weak inter­molecular C—H...S hydrogen bonds link two mol­ecules into inversion dimers.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.056
• wR factor = 0.170
• Data-to-parameter ratio = 21.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.31 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.71 Ratio
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S8     --  C14     ..       9.33 su

Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =       5.25
            Cell volume su given      =       3.00
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S8
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          6
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C7     -   C8     ...       1.39 Ang.
PLAT410_ALERT_2_C Short Intra H...H Contact  H8B    ..  H9B     ..       1.93 Ang.
PLAT152_ALERT_1_C The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B    ..  S2      ..       3.00 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         18
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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

---

S1. Comment

Tetrathiafulvalene (TTF) derivatives with a fused crown ether ring have received much attention as component molecules for cation sensors (Hansen et al., 1993). We are incorporated TTF with a sulfur hybrid crown ether to synthesize the title compound

The molecule structure of tiltle compound, (I), C₁₄H₁₈S₈O, as shown in Fig. 1, all bond lengths and angles are normal and comparable with the related structure (Hou et al., 2009). In the crystal, weak intermolecular C—H···S hydrogen bonds (Table 1) link the molecules into dimer.

Related literature

For background to crown ether-annulated 1,3-dithiol-2-thiones, see: Hansen et al. (1993). For the synthesis, see: Chen et al. (2005). For a related structure, see: Hou et al. (2009)

S2. Experimental

The title compound, (I), was prepared according to literature (Chen et al.,2005) and the single crystals suitable for X-ray diffraction were prepared by slow evaporation a mixture of dichloromethane and petroleum (60–90 °C) at room temperature.

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model with U_iso(H) = 1.2 or 1.5 U_eq(C).

Computing details

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

Fig. 1. The asymmetric of title compound, with the atom numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

13-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-6-oxa-3,9,12,14- tetrathiabicyclo[9.3.0]tetradec-1(11)-ene

Crystal data

C14H18OS8	Z = 2
Mr = 458.76	F(000) = 476
Triclinic, P1	Dx = 1.510 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4542 (17) Å	Cell parameters from 8201 reflections
b = 10.158 (2) Å	θ = 3.1–27.5°
c = 13.612 (3) Å	µ = 0.88 mm^−1
α = 105.00 (3)°	T = 291 K
β = 97.83 (3)°	Block, yellow
γ = 112.22 (3)°	0.14 × 0.12 × 0.12 mm
V = 1008.8 (3) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	4572 independent reflections
Radiation source: fine-focus sealed tube	3655 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
Tmin = 0.886, Tmax = 0.901	k = −11→13
9961 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0884P)^2 + 0.6622P] where P = (Fo^2 + 2Fc^2)/3
4572 reflections	(Δ/σ)max = 0.016
210 parameters	Δρmax = 1.09 e Å^−3
18 restraints	Δρmin = −0.64 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0932 (11)	0.6629 (10)	0.3460 (6)	0.147 (3)
H1A	0.1923	0.7484	0.3443	0.220*
H1B	0.0094	0.6954	0.3720	0.220*
H1C	0.0378	0.5904	0.2761	0.220*
C2	0.3190 (6)	0.5333 (5)	0.3702 (3)	0.0698 (11)
C3	0.4341 (5)	0.4102 (4)	0.2243 (3)	0.0507 (7)
C4	0.4512 (4)	0.3545 (3)	0.1275 (2)	0.0461 (7)
C5	0.3940 (4)	0.2608 (3)	−0.0741 (2)	0.0413 (6)
C6	0.2894 (5)	0.2050 (4)	−0.1861 (3)	0.0525 (8)
H6A	0.3691	0.2087	−0.2314	0.063*
H6B	0.2366	0.2724	−0.1949	0.063*
C7	0.2424 (8)	−0.0950 (6)	−0.2145 (6)	0.1025 (17)
H7A	0.3145	−0.0519	−0.1423	0.123*
H7B	0.1583	−0.1969	−0.2240	0.123*
C8	0.3534 (6)	−0.1067 (5)	−0.2800 (5)	0.0943 (17)
H8A	0.2905	−0.1288	−0.3517	0.113*
H8B	0.3794	−0.1915	−0.2786	0.113*
C9	0.6658 (6)	0.0075 (5)	−0.2091 (4)	0.0740 (12)
H9A	0.7526	0.0358	−0.2487	0.089*
H9B	0.6321	−0.0978	−0.2166	0.089*
C10	0.7491 (5)	0.1017 (4)	−0.0953 (3)	0.0649 (10)
H10A	0.8265	0.0635	−0.0660	0.078*
H10B	0.6563	0.0882	−0.0589	0.078*
C11	0.7040 (4)	0.3605 (4)	−0.0996 (3)	0.0469 (7)
H11A	0.7589	0.4682	−0.0874	0.056*
H11B	0.6438	0.3094	−0.1740	0.056*
C12	0.5700 (4)	0.3284 (3)	−0.0371 (2)	0.0407 (6)
C13	0.4928 (6)	0.6013 (4)	0.4070 (3)	0.0661 (10)
C14	0.7619 (13)	0.8815 (12)	0.4955 (7)	0.176 (4)
H14A	0.8239	0.8368	0.4545	0.264*
H14B	0.8442	0.9598	0.5587	0.264*
H14C	0.7053	0.9239	0.4552	0.264*
O1	0.5140 (4)	0.0229 (3)	−0.2531 (2)	0.0707 (7)
S1	0.1683 (2)	0.5780 (2)	0.43099 (13)	0.1162 (6)
S2	0.22953 (15)	0.37585 (11)	0.25246 (8)	0.0674 (3)
S3	0.26931 (11)	0.23691 (10)	0.01898 (7)	0.0513 (2)
S4	0.11564 (12)	0.01405 (12)	−0.22817 (9)	0.0704 (3)
S5	0.87487 (12)	0.30094 (10)	−0.06741 (8)	0.0602 (3)
S6	0.65644 (11)	0.38520 (10)	0.10015 (6)	0.0504 (2)
S7	0.61409 (14)	0.52278 (11)	0.33593 (7)	0.0619 (3)
S8	0.6096 (2)	0.74971 (15)	0.52682 (9)	0.1030 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.123 (4)	0.173 (5)	0.156 (5)	0.087 (4)	0.053 (4)	0.031 (4)
C2	0.087 (3)	0.059 (2)	0.060 (2)	0.022 (2)	0.044 (2)	0.0171 (18)
C3	0.062 (2)	0.0419 (16)	0.0491 (17)	0.0220 (15)	0.0185 (14)	0.0151 (13)
C4	0.0529 (18)	0.0395 (15)	0.0474 (16)	0.0223 (13)	0.0130 (13)	0.0134 (13)
C5	0.0474 (16)	0.0328 (13)	0.0428 (15)	0.0202 (12)	0.0075 (12)	0.0091 (11)
C6	0.0540 (19)	0.0458 (17)	0.0492 (17)	0.0240 (15)	−0.0016 (14)	0.0069 (14)
C7	0.090 (3)	0.068 (3)	0.143 (4)	0.032 (2)	0.033 (3)	0.029 (3)
C8	0.068 (3)	0.057 (2)	0.122 (4)	0.027 (2)	0.009 (3)	−0.017 (3)
C9	0.065 (2)	0.053 (2)	0.098 (3)	0.0339 (19)	0.016 (2)	0.005 (2)
C10	0.063 (2)	0.0484 (19)	0.089 (3)	0.0315 (18)	0.0179 (19)	0.0217 (19)
C11	0.0480 (17)	0.0389 (15)	0.0520 (17)	0.0195 (13)	0.0122 (13)	0.0119 (13)
C12	0.0467 (16)	0.0331 (13)	0.0423 (15)	0.0210 (12)	0.0087 (12)	0.0083 (11)
C13	0.089 (3)	0.0504 (19)	0.0500 (19)	0.019 (2)	0.0335 (19)	0.0126 (16)
C14	0.172 (5)	0.168 (5)	0.142 (5)	0.025 (4)	0.065 (4)	0.040 (4)
O1	0.0666 (17)	0.0519 (15)	0.090 (2)	0.0287 (13)	0.0162 (14)	0.0151 (14)
S1	0.1153 (12)	0.1136 (11)	0.1043 (11)	0.0336 (9)	0.0798 (10)	0.0109 (9)
S2	0.0694 (6)	0.0561 (5)	0.0642 (6)	0.0132 (5)	0.0322 (5)	0.0144 (4)
S3	0.0450 (4)	0.0472 (4)	0.0537 (5)	0.0173 (3)	0.0116 (3)	0.0093 (3)
S4	0.0446 (5)	0.0586 (6)	0.0766 (7)	0.0161 (4)	0.0007 (4)	−0.0092 (5)
S5	0.0433 (5)	0.0514 (5)	0.0791 (6)	0.0218 (4)	0.0133 (4)	0.0108 (4)
S6	0.0480 (4)	0.0542 (5)	0.0435 (4)	0.0262 (4)	0.0036 (3)	0.0059 (3)
S7	0.0723 (6)	0.0586 (5)	0.0457 (5)	0.0226 (5)	0.0151 (4)	0.0123 (4)
S8	0.1440 (13)	0.0685 (7)	0.0543 (6)	0.0108 (8)	0.0411 (7)	0.0005 (5)

Geometric parameters (Å, º)

C1—S1	1.794 (9)	C8—O1	1.405 (6)
C1—H1A	0.9600	C8—H8A	0.9700
C1—H1B	0.9600	C8—H8B	0.9700
C1—H1C	0.9600	C9—O1	1.421 (5)
C2—C13	1.319 (7)	C9—C10	1.495 (6)
C2—S1	1.744 (4)	C9—H9A	0.9700
C2—S2	1.768 (4)	C9—H9B	0.9700
C3—C4	1.344 (5)	C10—S5	1.798 (4)
C3—S2	1.747 (4)	C10—H10A	0.9700
C3—S7	1.756 (4)	C10—H10B	0.9700
C4—S3	1.747 (3)	C11—C12	1.498 (4)
C4—S6	1.753 (3)	C11—S5	1.809 (3)
C5—C12	1.335 (4)	C11—H11A	0.9700
C5—C6	1.496 (4)	C11—H11B	0.9700
C5—S3	1.762 (3)	C12—S6	1.763 (3)
C6—S4	1.814 (4)	C13—S8	1.752 (4)
C6—H6A	0.9700	C13—S7	1.765 (4)
C6—H6B	0.9700	C14—S8	1.665 (9)
C7—C8	1.397 (8)	C14—H14A	0.9600
C7—S4	1.833 (6)	C14—H14B	0.9600
C7—H7A	0.9700	C14—H14C	0.9600
C7—H7B	0.9700
S1—C1—H1A	109.5	C10—C9—H9A	108.9
S1—C1—H1B	109.5	O1—C9—H9B	108.9
H1A—C1—H1B	109.5	C10—C9—H9B	108.9
S1—C1—H1C	109.5	H9A—C9—H9B	107.7
H1A—C1—H1C	109.5	C9—C10—S5	116.1 (3)
H1B—C1—H1C	109.5	C9—C10—H10A	108.3
C13—C2—S1	125.9 (3)	S5—C10—H10A	108.3
C13—C2—S2	117.2 (3)	C9—C10—H10B	108.3
S1—C2—S2	116.8 (3)	S5—C10—H10B	108.3
C4—C3—S2	123.3 (3)	H10A—C10—H10B	107.4
C4—C3—S7	123.7 (3)	C12—C11—S5	113.4 (2)
S2—C3—S7	112.98 (18)	C12—C11—H11A	108.9
C3—C4—S3	122.6 (3)	S5—C11—H11A	108.9
C3—C4—S6	123.2 (3)	C12—C11—H11B	108.9
S3—C4—S6	114.08 (18)	S5—C11—H11B	108.9
C12—C5—C6	127.3 (3)	H11A—C11—H11B	107.7
C12—C5—S3	116.9 (2)	C5—C12—C11	127.1 (3)
C6—C5—S3	115.8 (2)	C5—C12—S6	117.2 (2)
C5—C6—S4	113.5 (3)	C11—C12—S6	115.7 (2)
C5—C6—H6A	108.9	C2—C13—S8	125.2 (3)
S4—C6—H6A	108.9	C2—C13—S7	116.7 (3)
C5—C6—H6B	108.9	S8—C13—S7	117.7 (3)
S4—C6—H6B	108.9	S8—C14—H14A	109.5
H6A—C6—H6B	107.7	S8—C14—H14B	109.5
C8—C7—S4	119.7 (5)	H14A—C14—H14B	109.5
C8—C7—H7A	107.4	S8—C14—H14C	109.5
S4—C7—H7A	107.4	H14A—C14—H14C	109.5
C8—C7—H7B	107.4	H14B—C14—H14C	109.5
S4—C7—H7B	107.4	C8—O1—C9	114.7 (4)
H7A—C7—H7B	106.9	C2—S1—C1	100.8 (3)
C7—C8—O1	114.6 (4)	C3—S2—C2	94.04 (19)
C7—C8—H8A	108.6	C4—S3—C5	94.20 (15)
O1—C8—H8A	108.6	C6—S4—C7	102.0 (2)
C7—C8—H8B	108.6	C10—S5—C11	102.29 (17)
O1—C8—H8B	108.6	C4—S6—C12	93.92 (15)
H8A—C8—H8B	107.6	C3—S7—C13	94.02 (19)
O1—C9—C10	113.4 (3)	C14—S8—C13	104.6 (3)
O1—C9—H9A	108.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···S2^i	0.97	3.00	3.793 (6)	140

Symmetry code: (i) −x, −y, −z.