2,3-Bis[(2-cyano­eth­yl)sulfan­yl]-1,4,5,8-tetra­thia­fulvalene-6,7-dicarbonitrile

Jiang, C.-P.; Li, B.; Yin, B.-Z.; Wu, L.-X.

doi:10.1107/S1600536810028473

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2079

https://doi.org/10.1107/S1600536810028473

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2,3-Bis[(2-cyanoethyl)sulfanyl]-1,4,5,8-tetrathiafulvalene-6,7-dicarbonitrile

Cui-Ping Jiang,^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 7 July 2010; accepted 16 July 2010; online 21 July 2010)

In the title compound, C₁₄H₈N₄S₆, the two five-membered rings lie in the same plane with an r.m.s. deviation of 0.0334 (5) Å. The crystal structure features intermolecular S⋯N interactions of 3.295 (4) Å.

Related literature

For background to the electrical properties of tetrathiafulvalene derivatives, see: Fabre (2000 ); Batail (2004 ). For the synthesis, see Chen et al. (2005 ). For a related structure, see: Hou et al. (2010 ).

Experimental

Crystal data

C₁₄H₈N₄S₆
M_r = 424.66
Triclinic, $[P \overline 1]$
a = 7.3055 (15) Å
b = 8.5193 (17) Å
c = 15.386 (3) Å
α = 82.52 (3)°
β = 76.97 (3)°
γ = 72.43 (3)°
V = 887.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 290 K
0.13 × 0.12 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.906, T_max = 0.920
8751 measured reflections
4020 independent reflections
3415 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.072
S = 1.09
4020 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.20 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/S1600536810028473/ng2799sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028473/ng2799Isup2.hkl

checkCIF report

Comment top

The derivants of tetrathiafulvalene (TTF), especially functionalized with hydroxyl or amine groups, have been studies extensively for their interesting electrical properties (Fabre, 2000; Batail, 2004). Herein, we report the crystal structure of the title compound.

The title compound, as shown in Fig. 1, all bond lengths and angles are normal and comparable with those reported for the related structure (Hou et al., 2010). In the crystal, the two five-membered rings lie in the same plane with an r.m.s. deviation of 0.0334 (5) Å. The intermolecular S···N interactions with the distance of 3.295 (4) Å link the molecules into one-dimensional chain along a+c dirction.

Related literature top

For background to the electrical properties of tetrathiafulvalene derivatives, see: Fabre (2000); Batail (2004). For the synthesis, see Chen et al. (2005). For a related structure, see: Hou et al. (2010).

Experimental top

The title compound was synthesized as described in the literature for the analogous compound 2,3-Bis(butylthio)-6,7-dicarbonitrile-1,4,5,8- tetrathiafulvalene (Chen et al., 2005). Single crystals and 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

For background to the electrical properties of tetrathiafulvalene derivatives, see: Fabre (2000); Batail (2004). For the synthesis, see Chen et al. (2005). For a related structure, see: Hou et al. (2010).

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. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

2-{4,5-bis[(cyanomethyl)sulfanyl]-1,3-dithiolan-2-ylidene}-1,3-dithiolane- 4,5-dicarbonitrile top

Crystal data top

C₁₄H₈N₄S₆	Z = 2
M_r = 424.66	F(000) = 432
Triclinic, P1	D_x = 1.589 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3055 (15) Å	Cell parameters from 7465 reflections
b = 8.5193 (17) Å	θ = 3.0–27.5°
c = 15.386 (3) Å	µ = 0.77 mm⁻¹
α = 82.52 (3)°	T = 290 K
β = 76.97 (3)°	Block, black
γ = 72.43 (3)°	0.13 × 0.12 × 0.11 mm
V = 887.4 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	4020 independent reflections
Radiation source: fine-focus sealed tube	3415 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.906, T_max = 0.920	k = −11→9
8751 measured reflections	l = −19→19

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0391P)² + 0.0566P] where P = (F_o² + 2F_c²)/3
4020 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₈N₄S₆	γ = 72.43 (3)°
M_r = 424.66	V = 887.4 (3) Å³
Triclinic, P1	Z = 2
a = 7.3055 (15) Å	Mo Kα radiation
b = 8.5193 (17) Å	µ = 0.77 mm⁻¹
c = 15.386 (3) Å	T = 290 K
α = 82.52 (3)°	0.13 × 0.12 × 0.11 mm
β = 76.97 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	4020 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3415 reflections with I > 2σ(I)
T_min = 0.906, T_max = 0.920	R_int = 0.021
8751 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.09	Δρ_max = 0.35 e Å⁻³
4020 reflections	Δρ_min = −0.20 e Å⁻³
217 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.3844 (2)	0.29787 (18)	−0.14033 (10)	0.0352 (3)
C2	−0.2172 (2)	0.25475 (16)	−0.09903 (9)	0.0298 (3)
C3	−0.0448 (2)	0.14665 (16)	−0.13307 (9)	0.0292 (3)
C4	−0.0139 (2)	0.06331 (18)	−0.21181 (10)	0.0343 (3)
C5	0.01227 (19)	0.24707 (15)	0.00609 (9)	0.0275 (3)
C6	0.09080 (19)	0.27024 (15)	0.07290 (9)	0.0276 (3)
C7	0.3151 (2)	0.25405 (16)	0.18511 (9)	0.0292 (3)
C8	0.14603 (19)	0.36850 (16)	0.21550 (8)	0.0277 (3)
C9	0.4763 (2)	0.01342 (18)	0.30608 (10)	0.0420 (4)
H9A	0.4424	−0.0567	0.2711	0.050*
H9B	0.5960	−0.0498	0.3258	0.050*
C10	0.3135 (2)	0.05787 (19)	0.38801 (10)	0.0428 (4)
H10A	0.1927	0.1205	0.3690	0.051*
H10B	0.2928	−0.0424	0.4210	0.051*
C11	0.3623 (2)	0.1552 (2)	0.44647 (10)	0.0433 (4)
C12	−0.1478 (2)	0.56270 (19)	0.33796 (10)	0.0423 (4)
H12A	−0.1782	0.6517	0.3770	0.051*
H12B	−0.2004	0.6090	0.2847	0.051*
C13	−0.2516 (3)	0.4360 (2)	0.38520 (11)	0.0539 (4)
H13A	−0.3915	0.4887	0.3985	0.065*
H13B	−0.2281	0.3495	0.3454	0.065*
C14	−0.1865 (3)	0.3618 (2)	0.46835 (13)	0.0552 (4)
N1	−0.5150 (2)	0.33249 (19)	−0.17432 (10)	0.0528 (4)
N2	0.0141 (2)	−0.00538 (19)	−0.27451 (10)	0.0527 (4)
N3	0.4075 (2)	0.22886 (19)	0.49019 (10)	0.0591 (4)
N4	−0.1328 (3)	0.3044 (2)	0.53217 (12)	0.0805 (6)
S1	−0.23311 (5)	0.34738 (4)	−0.00256 (2)	0.03481 (10)
S2	0.14881 (5)	0.11197 (4)	−0.07788 (2)	0.03252 (10)
S3	−0.04110 (5)	0.40991 (4)	0.15451 (2)	0.03209 (10)
S4	0.33230 (5)	0.16723 (4)	0.08462 (2)	0.03296 (10)
S5	0.11523 (6)	0.48537 (4)	0.30581 (2)	0.03523 (10)
S6	0.52255 (5)	0.19092 (5)	0.23438 (2)	0.03667 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0287 (7)	0.0404 (7)	0.0378 (8)	−0.0074 (6)	−0.0108 (6)	−0.0051 (6)
C2	0.0279 (7)	0.0340 (7)	0.0304 (7)	−0.0099 (5)	−0.0106 (5)	−0.0011 (5)
C3	0.0290 (7)	0.0339 (7)	0.0276 (7)	−0.0101 (5)	−0.0094 (5)	−0.0024 (5)
C4	0.0298 (7)	0.0405 (7)	0.0339 (8)	−0.0080 (6)	−0.0107 (6)	−0.0040 (6)
C5	0.0256 (6)	0.0296 (6)	0.0279 (6)	−0.0058 (5)	−0.0082 (5)	−0.0033 (5)
C6	0.0266 (7)	0.0298 (6)	0.0265 (6)	−0.0061 (5)	−0.0071 (5)	−0.0036 (5)
C7	0.0284 (7)	0.0358 (7)	0.0247 (6)	−0.0073 (5)	−0.0090 (5)	−0.0039 (5)
C8	0.0299 (7)	0.0316 (7)	0.0232 (6)	−0.0087 (5)	−0.0079 (5)	−0.0026 (5)
C9	0.0485 (9)	0.0365 (8)	0.0406 (8)	−0.0009 (6)	−0.0209 (7)	−0.0058 (6)
C10	0.0468 (9)	0.0429 (8)	0.0410 (8)	−0.0129 (7)	−0.0177 (7)	0.0061 (7)
C11	0.0442 (9)	0.0469 (9)	0.0318 (8)	−0.0025 (7)	−0.0095 (7)	0.0002 (7)
C12	0.0417 (9)	0.0431 (8)	0.0338 (8)	0.0021 (6)	−0.0044 (6)	−0.0126 (6)
C13	0.0451 (10)	0.0769 (12)	0.0416 (9)	−0.0216 (9)	0.0003 (8)	−0.0158 (8)
C14	0.0595 (12)	0.0595 (11)	0.0473 (10)	−0.0259 (9)	0.0031 (9)	−0.0079 (9)
N1	0.0366 (8)	0.0634 (9)	0.0596 (9)	−0.0057 (6)	−0.0221 (7)	−0.0064 (7)
N2	0.0516 (9)	0.0652 (9)	0.0444 (8)	−0.0106 (7)	−0.0157 (7)	−0.0181 (7)
N3	0.0653 (11)	0.0632 (9)	0.0453 (8)	−0.0030 (8)	−0.0172 (8)	−0.0165 (7)
N4	0.1064 (17)	0.0812 (13)	0.0587 (11)	−0.0397 (12)	−0.0161 (11)	0.0099 (10)
S1	0.02631 (18)	0.0407 (2)	0.0367 (2)	−0.00195 (14)	−0.01004 (15)	−0.01111 (15)
S2	0.02509 (18)	0.03996 (19)	0.03258 (19)	−0.00337 (14)	−0.00934 (14)	−0.01026 (15)
S3	0.02685 (18)	0.03621 (19)	0.03086 (18)	−0.00055 (13)	−0.00891 (14)	−0.00827 (14)
S4	0.02534 (18)	0.0421 (2)	0.02945 (18)	−0.00093 (14)	−0.00827 (14)	−0.01089 (14)
S5	0.0400 (2)	0.03828 (19)	0.02918 (18)	−0.01030 (15)	−0.00711 (15)	−0.00961 (14)
S6	0.02798 (19)	0.0510 (2)	0.03197 (19)	−0.00714 (15)	−0.01181 (15)	−0.00518 (16)

Geometric parameters (Å, º) top

C1—N1	1.1341 (19)	C9—C10	1.524 (2)
C1—C2	1.4316 (19)	C9—S6	1.8232 (17)
C2—C3	1.355 (2)	C9—H9A	0.9700
C2—S1	1.7352 (15)	C9—H9B	0.9700
C3—C4	1.424 (2)	C10—C11	1.464 (2)
C3—S2	1.7417 (14)	C10—H10A	0.9700
C4—N2	1.1404 (19)	C10—H10B	0.9700
C5—C6	1.3462 (19)	C11—N3	1.136 (2)
C5—S2	1.7611 (15)	C12—C13	1.520 (2)
C5—S1	1.7648 (14)	C12—S5	1.8066 (17)
C6—S3	1.7527 (15)	C12—H12A	0.9700
C6—S4	1.7558 (14)	C12—H12B	0.9700
C7—C8	1.351 (2)	C13—C14	1.465 (3)
C7—S6	1.7553 (14)	C13—H13A	0.9700
C7—S4	1.7628 (14)	C13—H13B	0.9700
C8—S5	1.7483 (14)	C14—N4	1.136 (2)
C8—S3	1.7536 (14)

N1—C1—C2	178.90 (18)	C11—C10—C9	111.21 (14)
C3—C2—C1	122.75 (13)	C11—C10—H10A	109.4
C3—C2—S1	118.32 (11)	C9—C10—H10A	109.4
C1—C2—S1	118.92 (11)	C11—C10—H10B	109.4
C2—C3—C4	123.46 (13)	C9—C10—H10B	109.4
C2—C3—S2	117.65 (11)	H10A—C10—H10B	108.0
C4—C3—S2	118.88 (10)	N3—C11—C10	177.38 (19)
N2—C4—C3	178.71 (16)	C13—C12—S5	115.32 (11)
C6—C5—S2	121.71 (11)	C13—C12—H12A	108.4
C6—C5—S1	122.52 (11)	S5—C12—H12A	108.4
S2—C5—S1	115.77 (8)	C13—C12—H12B	108.4
C5—C6—S3	122.05 (11)	S5—C12—H12B	108.4
C5—C6—S4	123.27 (11)	H12A—C12—H12B	107.5
S3—C6—S4	114.67 (8)	C14—C13—C12	112.75 (15)
C8—C7—S6	125.66 (11)	C14—C13—H13A	109.0
C8—C7—S4	117.08 (10)	C12—C13—H13A	109.0
S6—C7—S4	117.20 (8)	C14—C13—H13B	109.0
C7—C8—S5	123.02 (11)	C12—C13—H13B	109.0
C7—C8—S3	117.09 (10)	H13A—C13—H13B	107.8
S5—C8—S3	119.69 (8)	N4—C14—C13	178.8 (2)
C10—C9—S6	114.19 (10)	C2—S1—C5	94.05 (7)
C10—C9—H9A	108.7	C3—S2—C5	94.21 (7)
S6—C9—H9A	108.7	C6—S3—C8	95.71 (7)
C10—C9—H9B	108.7	C6—S4—C7	95.29 (7)
S6—C9—H9B	108.7	C8—S5—C12	102.98 (7)
H9A—C9—H9B	107.6	C7—S6—C9	100.68 (7)

N1—C1—C2—C3	−50 (9)	C1—C2—S1—C5	−178.05 (12)
N1—C1—C2—S1	129 (9)	C6—C5—S1—C2	−179.46 (12)
C1—C2—C3—C4	−1.2 (2)	S2—C5—S1—C2	−0.12 (8)
S1—C2—C3—C4	−179.88 (11)	C2—C3—S2—C5	0.78 (12)
C1—C2—C3—S2	177.64 (11)	C4—C3—S2—C5	179.67 (11)
S1—C2—C3—S2	−1.04 (16)	C6—C5—S2—C3	179.05 (12)
C2—C3—C4—N2	−168 (8)	S1—C5—S2—C3	−0.29 (9)
S2—C3—C4—N2	14 (8)	C5—C6—S3—C8	178.64 (12)
S2—C5—C6—S3	177.67 (7)	S4—C6—S3—C8	−2.39 (9)
S1—C5—C6—S3	−3.04 (18)	C7—C8—S3—C6	−0.40 (12)
S2—C5—C6—S4	−1.21 (18)	S5—C8—S3—C6	174.61 (8)
S1—C5—C6—S4	178.08 (7)	C5—C6—S4—C7	−177.40 (12)
S6—C7—C8—S5	5.36 (19)	S3—C6—S4—C7	3.65 (9)
S4—C7—C8—S5	−171.73 (7)	C8—C7—S4—C6	−4.05 (12)
S6—C7—C8—S3	−179.81 (8)	S6—C7—S4—C6	178.61 (8)
S4—C7—C8—S3	3.10 (16)	C7—C8—S5—C12	−162.25 (12)
S6—C9—C10—C11	−62.05 (14)	S3—C8—S5—C12	23.05 (10)
C9—C10—C11—N3	−17 (4)	C13—C12—S5—C8	73.13 (13)
S5—C12—C13—C14	59.88 (18)	C8—C7—S6—C9	93.08 (14)
C12—C13—C14—N4	−35 (11)	S4—C7—S6—C9	−89.84 (9)
C3—C2—S1—C5	0.68 (12)	C10—C9—S6—C7	−72.76 (12)

Experimental details

Crystal data
Chemical formula	C₁₄H₈N₄S₆
M_r	424.66
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	7.3055 (15), 8.5193 (17), 15.386 (3)
α, β, γ (°)	82.52 (3), 76.97 (3), 72.43 (3)
V (Å³)	887.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.13 × 0.12 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.906, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	8751, 4020, 3415
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.072, 1.09
No. of reflections	4020
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.20

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 Programme of Higher Education (grant No. 2006184001) and the Open Project of the State Key Laboratory of Supramolecular Structure and Materials, Jilin University.

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