Methyl 2,3-(3,6,9-trioxaundecane-1,11-diyldithio)-1,4,5,8-tetra-thia-fulvalene-6-carboxyl-ate.

In the title mol-ecule, C(16)H(20)O(5)S(6), the two five-membered rings form a dihedral angle of 4.7 (3)°. The crystal packing exhibits weak inter-molecular C-H⋯O hydrogen bonds, which link the mol-ecules into chains propagating in [10], and π-π inter-actions, indicated by the short distances [3.756 (5) Å] between the centroids of five-membered rings from mol-ecules related by translation along the b axis.

Related literature

For background to tetra­thia­fulvalene derivatives, see Hansen et al. (1992 ▶); Trippé et al. (2002 ▶). For details of the synthesis, see Liu et al. (2000 ▶).

Experimental

Crystal data

C16H20O5S6

M = 484.68

Monoclinic,

a = 22.604 (5) Å

b = 5.2048 (10) Å

c = 17.801 (4) Å

β = 90.65 (3)°

V = 2094.1 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.68 mm−1

T = 291 K

0.20 × 0.13 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.876, T max = 0.923

9505 measured reflections

4254 independent reflections

3370 reflections with I > 2σ(I)

R int = 0.101

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.172

S = 0.96

4254 reflections

245 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.46 e Å−3

Absolute structure: Flack (1983 ▶), 1855 Friedel pairs

Flack parameter: −0.12 (12)

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013154/cv2536sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013154/cv2536Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H20O5S6	F(000) = 1008
Mr = 484.68	Dx = 1.537 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 7343 reflections
a = 22.604 (5) Å	θ = 3.4–27.1°
b = 5.2048 (10) Å	µ = 0.68 mm−1
c = 17.801 (4) Å	T = 291 K
β = 90.65 (3)°	Block, red
V = 2094.1 (7) Å3	0.20 × 0.13 × 0.12 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	4254 independent reflections
Radiation source: fine-focus sealed tube	3370 reflections with I > 2σ(I)
graphite	Rint = 0.101
ω scans	θmax = 27.5°, θmin = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −28→28
Tmin = 0.876, Tmax = 0.923	k = −6→6
9505 measured reflections	l = −23→23

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)] = 0.060	H-atom parameters constrained
wR(F2) = 0.172	w = 1/[σ2(Fo2) + (0.0878P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96	(Δ/σ)max = 0.001
4254 reflections	Δρmax = 0.49 e Å−3
245 parameters	Δρmin = −0.45 e Å−3
2 restraints	Absolute structure: Flack (1983), 1855 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.12 (12)

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.

	x	y	z	Uiso*/Ueq
C1	0.4826 (4)	1.8931 (13)	0.5758 (4)	0.0638 (17)
H1A	0.4419	1.8858	0.5598	0.096*
H1B	0.5076	1.8546	0.5340	0.096*
H1C	0.4915	2.0622	0.5942	0.096*
C2	0.4534 (3)	1.7154 (11)	0.6912 (3)	0.0426 (12)
C3	0.4679 (2)	1.5069 (10)	0.7458 (3)	0.0388 (11)
C4	0.4324 (2)	1.4479 (11)	0.8031 (3)	0.0413 (11)
H4	0.3979	1.5404	0.8115	0.050*
C5	0.5199 (2)	1.1345 (9)	0.8157 (3)	0.0368 (10)
C6	0.5581 (2)	0.9558 (10)	0.8382 (3)	0.0392 (11)
C7	0.6165 (2)	0.6004 (9)	0.9111 (3)	0.0361 (10)
C8	0.6520 (2)	0.6615 (10)	0.8524 (3)	0.0405 (11)
C9	0.7699 (3)	0.7676 (12)	0.8282 (3)	0.0507 (13)
H9A	0.8086	0.7011	0.8154	0.061*
H9B	0.7580	0.8888	0.7895	0.061*
C10	0.7740 (3)	0.9042 (10)	0.9022 (3)	0.0438 (12)
H10A	0.7372	0.9930	0.9122	0.053*
H10B	0.7813	0.7818	0.9423	0.053*
C11	0.8288 (3)	1.2375 (11)	0.9635 (4)	0.0546 (15)
H11A	0.7901	1.2783	0.9834	0.066*
H11B	0.8474	1.3978	0.9492	0.066*
C12	0.8653 (3)	1.1139 (13)	1.0241 (4)	0.0609 (16)
H12A	0.9037	1.0707	1.0039	0.073*
H12B	0.8715	1.2373	1.0643	0.073*
C13	0.7993 (3)	0.9435 (13)	1.1131 (4)	0.0578 (15)
H13A	0.7692	1.0616	1.0949	0.069*
H13B	0.8202	1.0245	1.1547	0.069*
C14	0.7710 (3)	0.7016 (13)	1.1390 (4)	0.0606 (16)
H14A	0.8020	0.5776	1.1497	0.073*
H14B	0.7511	0.7368	1.1858	0.073*
C15	0.6760 (3)	0.7176 (13)	1.0822 (3)	0.0577 (16)
H15A	0.6784	0.8429	1.0420	0.069*
H15B	0.6677	0.8086	1.1284	0.069*
C16	0.6266 (3)	0.5309 (13)	1.0653 (3)	0.0519 (14)
H16A	0.5894	0.6240	1.0649	0.062*
H16B	0.6250	0.4058	1.1056	0.062*
O1	0.49274 (19)	1.7087 (8)	0.6344 (2)	0.0524 (10)
O2	0.4141 (2)	1.8633 (9)	0.6967 (2)	0.0571 (11)
O3	0.82120 (18)	1.0828 (8)	0.8984 (2)	0.0526 (10)
O4	0.8395 (2)	0.8877 (8)	1.0548 (2)	0.0560 (10)
O5	0.7302 (2)	0.5875 (8)	1.0894 (2)	0.0587 (11)
S1	0.53276 (5)	1.3254 (3)	0.73569 (7)	0.0415 (3)
S2	0.45240 (6)	1.1969 (3)	0.86052 (7)	0.0456 (3)
S3	0.62439 (6)	0.8944 (3)	0.78907 (7)	0.0453 (3)
S4	0.54731 (6)	0.7502 (3)	0.91476 (7)	0.0417 (3)
S5	0.71732 (7)	0.5055 (3)	0.83051 (8)	0.0492 (4)
S6	0.63337 (7)	0.3600 (3)	0.97634 (7)	0.0486 (4)

	U11	U22	U33	U12	U13	U23
C1	0.081 (5)	0.063 (4)	0.047 (3)	−0.001 (4)	0.006 (3)	0.016 (3)
C2	0.043 (3)	0.044 (3)	0.040 (3)	−0.004 (2)	−0.003 (2)	−0.004 (2)
C3	0.031 (3)	0.049 (3)	0.036 (3)	0.000 (2)	0.0000 (19)	0.000 (2)
C4	0.028 (3)	0.050 (3)	0.046 (3)	−0.001 (2)	0.005 (2)	−0.005 (2)
C5	0.032 (3)	0.042 (2)	0.037 (3)	−0.002 (2)	0.0045 (19)	−0.0003 (19)
C6	0.044 (3)	0.038 (2)	0.035 (2)	−0.013 (2)	0.005 (2)	−0.0006 (18)
C7	0.038 (3)	0.033 (2)	0.038 (2)	−0.005 (2)	0.002 (2)	−0.0025 (18)
C8	0.045 (3)	0.038 (2)	0.038 (3)	−0.006 (2)	0.006 (2)	−0.0047 (19)
C9	0.046 (3)	0.064 (3)	0.042 (3)	0.000 (3)	0.014 (2)	0.004 (2)
C10	0.039 (3)	0.044 (3)	0.049 (3)	−0.002 (2)	0.011 (2)	0.003 (2)
C11	0.048 (3)	0.043 (3)	0.074 (4)	−0.003 (3)	0.021 (3)	−0.001 (3)
C12	0.049 (4)	0.062 (4)	0.072 (4)	−0.008 (3)	0.008 (3)	0.001 (3)
C13	0.058 (4)	0.063 (4)	0.053 (3)	−0.005 (3)	0.007 (3)	−0.009 (3)
C14	0.065 (4)	0.070 (4)	0.047 (3)	−0.009 (3)	−0.003 (3)	0.007 (3)
C15	0.071 (4)	0.061 (3)	0.042 (3)	0.011 (3)	0.006 (3)	−0.006 (3)
C16	0.048 (3)	0.071 (4)	0.038 (3)	0.003 (3)	0.018 (2)	0.006 (2)
O1	0.050 (2)	0.060 (2)	0.048 (2)	0.014 (2)	0.0091 (18)	0.0153 (18)
O2	0.050 (2)	0.064 (2)	0.058 (3)	0.024 (2)	0.0010 (19)	0.0008 (19)
O3	0.043 (2)	0.058 (2)	0.057 (2)	−0.007 (2)	0.0155 (18)	0.0001 (18)
O4	0.061 (3)	0.052 (2)	0.054 (2)	0.006 (2)	0.0100 (19)	0.0062 (17)
O5	0.056 (3)	0.062 (2)	0.058 (3)	−0.001 (2)	0.001 (2)	−0.0022 (19)
S1	0.0371 (7)	0.0476 (7)	0.0400 (6)	0.0027 (6)	0.0104 (5)	0.0065 (5)
S2	0.0393 (7)	0.0540 (7)	0.0439 (7)	−0.0046 (6)	0.0138 (5)	0.0040 (6)
S3	0.0413 (7)	0.0513 (7)	0.0436 (7)	0.0017 (6)	0.0109 (5)	0.0095 (5)
S4	0.0392 (7)	0.0459 (7)	0.0403 (6)	−0.0028 (5)	0.0083 (5)	0.0052 (5)
S5	0.0482 (8)	0.0440 (7)	0.0557 (9)	0.0045 (6)	0.0117 (6)	−0.0058 (6)
S6	0.0592 (9)	0.0414 (7)	0.0452 (7)	−0.0013 (6)	0.0026 (6)	0.0061 (5)

C1—O1	1.434 (7)	C10—O3	1.418 (7)
C1—H1A	0.9600	C10—H10A	0.9700
C1—H1B	0.9600	C10—H10B	0.9700
C1—H1C	0.9600	C11—O3	1.420 (7)
C2—O2	1.182 (7)	C11—C12	1.496 (10)
C2—O1	1.354 (7)	C11—H11A	0.9700
C2—C3	1.491 (7)	C11—H11B	0.9700
C3—C4	1.342 (7)	C12—O4	1.425 (8)
C3—S1	1.754 (5)	C12—H12A	0.9700
C4—S2	1.716 (6)	C12—H12B	0.9700
C4—H4	0.9300	C13—O4	1.418 (7)
C5—C6	1.328 (7)	C13—C14	1.487 (9)
C5—S2	1.761 (5)	C13—H13A	0.9700
C5—S1	1.763 (5)	C13—H13B	0.9700
C6—S4	1.752 (5)	C14—O5	1.403 (8)
C6—S3	1.772 (6)	C14—H14A	0.9700
C7—C8	1.362 (7)	C14—H14B	0.9700
C7—S6	1.747 (5)	C15—O5	1.404 (8)
C7—S4	1.749 (6)	C15—C16	1.507 (10)
C8—S5	1.733 (6)	C15—H15A	0.9700
C8—S3	1.765 (6)	C15—H15B	0.9700
C9—C10	1.498 (8)	C16—S6	1.824 (6)
C9—S5	1.811 (6)	C16—H16A	0.9700
C9—H9A	0.9700	C16—H16B	0.9700
C9—H9B	0.9700
O1—C1—H1A	109.5	C12—C11—H11B	108.8
O1—C1—H1B	109.5	H11A—C11—H11B	107.7
H1A—C1—H1B	109.5	O4—C12—C11	114.1 (5)
O1—C1—H1C	109.5	O4—C12—H12A	108.7
H1A—C1—H1C	109.5	C11—C12—H12A	108.7
H1B—C1—H1C	109.5	O4—C12—H12B	108.7
O2—C2—O1	125.4 (5)	C11—C12—H12B	108.7
O2—C2—C3	125.5 (6)	H12A—C12—H12B	107.6
O1—C2—C3	109.1 (5)	O4—C13—C14	109.6 (5)
C4—C3—C2	122.2 (5)	O4—C13—H13A	109.8
C4—C3—S1	117.6 (4)	C14—C13—H13A	109.8
C2—C3—S1	120.2 (4)	O4—C13—H13B	109.8
C3—C4—S2	118.1 (4)	C14—C13—H13B	109.8
C3—C4—H4	121.0	H13A—C13—H13B	108.2
S2—C4—H4	121.0	O5—C14—C13	116.4 (5)
C6—C5—S2	123.8 (4)	O5—C14—H14A	108.2
C6—C5—S1	121.7 (4)	C13—C14—H14A	108.2
S2—C5—S1	114.4 (3)	O5—C14—H14B	108.2
C5—C6—S4	124.5 (4)	C13—C14—H14B	108.2
C5—C6—S3	121.9 (4)	H14A—C14—H14B	107.3
S4—C6—S3	113.6 (3)	O5—C15—C16	110.5 (5)
C8—C7—S6	123.4 (4)	O5—C15—H15A	109.5
C8—C7—S4	117.4 (4)	C16—C15—H15A	109.5
S6—C7—S4	118.9 (3)	O5—C15—H15B	109.5
C7—C8—S5	125.0 (4)	C16—C15—H15B	109.5
C7—C8—S3	116.3 (4)	H15A—C15—H15B	108.1
S5—C8—S3	118.3 (3)	C15—C16—S6	114.7 (4)
C10—C9—S5	111.8 (4)	C15—C16—H16A	108.6
C10—C9—H9A	109.3	S6—C16—H16A	108.6
S5—C9—H9A	109.3	C15—C16—H16B	108.6
C10—C9—H9B	109.3	S6—C16—H16B	108.6
S5—C9—H9B	109.3	H16A—C16—H16B	107.6
H9A—C9—H9B	107.9	C2—O1—C1	115.2 (5)
O3—C10—C9	107.9 (4)	C10—O3—C11	114.6 (4)
O3—C10—H10A	110.1	C13—O4—C12	112.3 (5)
C9—C10—H10A	110.1	C14—O5—C15	114.9 (5)
O3—C10—H10B	110.1	C3—S1—C5	94.3 (2)
C9—C10—H10B	110.1	C4—S2—C5	95.4 (2)
H10A—C10—H10B	108.4	C8—S3—C6	95.9 (3)
O3—C11—C12	113.9 (5)	C7—S4—C6	96.3 (3)
O3—C11—H11A	108.8	C8—S5—C9	102.3 (3)
C12—C11—H11A	108.8	C7—S6—C16	102.0 (3)
O3—C11—H11B	108.8

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3i	0.93	2.35	3.127 (7)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3i	0.93	2.35	3.127 (7)	141

Symmetry code: (i) .