2,3-Bis(ethyl­sulfan­yl)-1,4,5,8-tetra­thia­fulvalene-6,7-dicarbonitrile

Hou, R.; Li, D.

doi:10.1107/S1600536811028601

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2096

doi:10.1107/S1600536811028601

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2,3-Bis(ethylsulfanyl)-1,4,5,8-tetrathiafulvalene-6,7-dicarbonitrile

Rui-bin Hou ^a and Dong-feng Li ^a ^*

^aSchool of Chemistry and Life Science, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: lidongfeng@mail.ccut.edu.cn

(Received 1 July 2011; accepted 16 July 2011; online 23 July 2011)

In the title compound, C₁₂H₁₀N₂S₆, all non-H atoms, except for those in the ethyl groups, lie in the same non-crystallographic plane, with a r.m.s. deviation of 0.0366 (5) Å. In the crystal structure, molecules are linked through weak C—H⋯N hydrogen bonds between methyl and cyano groups, forming centrosymmetric dimers. The dimers are arranged along the a axis, due to intermolecular N⋯S [3.337 (4) Å] interactions.

Related literature

For synthetic uses of dicyano-substituted tetrathiafulvalene derivatives, see: Chen et al. (2007 ); Leng et al. (2010 ). For a related structure, see: Jiang et al. (2010 ). For the synthesis of the title compound, see: Chen et al. (2005 ).

Experimental

Crystal data

C₁₂H₁₀N₂S₆
M_r = 374.58
Triclinic, $[P \overline 1]$
a = 7.8357 (16) Å
b = 8.9777 (18) Å
c = 12.618 (3) Å
α = 76.48 (3)°
β = 77.59 (3)°
γ = 73.20 (3)°
V = 815.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.886, T_max = 0.907
8038 measured reflections
3689 independent reflections
3079 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.109
S = 1.15
3689 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10C⋯N2ⁱ	0.96	2.73	3.659 (4)	164
Symmetry code: (i) -x+2, -y+1, -z+2.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks Global, I. DOI: 10.1107/S1600536811028601/bh2367sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028601/bh2367Isup2.hkl

checkCIF report

Comment top

Dicyano-substituted tetrathiafulvalene derivatives (TTFs) are key precursors for the preparation of the TTF-annulated prophyrazines. We have recently synthesized the symmetrical (Chen et al., 2007) and the unsymmetrical TTF-annulated porphyrazines (Leng et al., 2010) using such precursors. In this paper, we report the crystal structure of the title compound.

In the title compound (Fig. 1), all bond lengths and angles are in the normal ranges and comparable with those observed in a closely related compound (Jiang et al., 2010). In the title compound, except for two ethyl groups, all atoms lie on the same plane. In the crystal, the molecules form dimers through weak intermolecular C—H···N hydrogen bonds (Table 1), and dimers are arranged along the a axis, due to N···S interactions.

Related literature top

For synthetic uses of dicyano-substituted tetrathiafulvalene derivatives, see: Chen et al. (2007); Leng et al. (2010). For a related structure, see: Jiang et al. (2010). For the synthesis of the title compound, see: Chen et al. (2005).

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 of a solution in a mixture of dichloromethane and petroleum ether, at room temperature.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The crystal structure of the title compound, with displacement ellipsoids for non-H atoms drawn at the 20% probability level.

2,3-Bis(ethylsulfanyl)-1,4,5,8-tetrathiafulvalene-6,7-dicarbonitrile top

Crystal data top

C₁₂H₁₀N₂S₆	Z = 2
M_r = 374.58	F(000) = 384
Triclinic, P1	D_x = 1.525 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8357 (16) Å	Cell parameters from 3994 reflections
b = 8.9777 (18) Å	θ = 3.2–27.5°
c = 12.618 (3) Å	µ = 0.83 mm⁻¹
α = 76.48 (3)°	T = 293 K
β = 77.59 (3)°	Block, black
γ = 73.20 (3)°	0.15 × 0.13 × 0.12 mm
V = 815.8 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3689 independent reflections
Radiation source: fine-focus sealed tube	3079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.886, T_max = 0.907	k = −11→10
8038 measured reflections	l = −16→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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0602P)² + 0.1175P] where P = (F_o² + 2F_c²)/3
3689 reflections	(Δ/σ)_max = 0.001
183 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³
0 constraints

Crystal data top

C₁₂H₁₀N₂S₆	γ = 73.20 (3)°
M_r = 374.58	V = 815.8 (3) Å³
Triclinic, P1	Z = 2
a = 7.8357 (16) Å	Mo Kα radiation
b = 8.9777 (18) Å	µ = 0.83 mm⁻¹
c = 12.618 (3) Å	T = 293 K
α = 76.48 (3)°	0.15 × 0.13 × 0.12 mm
β = 77.59 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3689 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3079 reflections with I > 2σ(I)
T_min = 0.886, T_max = 0.907	R_int = 0.022
8038 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.15	Δρ_max = 0.37 e Å⁻³
3689 reflections	Δρ_min = −0.42 e Å⁻³
183 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.3781 (3)	0.3004 (3)	1.17179 (18)	0.0471 (5)
C2	1.2353 (2)	0.2956 (2)	1.11964 (14)	0.0346 (4)
C3	1.0593 (2)	0.3581 (2)	1.15573 (14)	0.0325 (4)
C4	0.9973 (3)	0.4385 (2)	1.24706 (16)	0.0404 (4)
C5	1.0603 (2)	0.2358 (2)	0.99101 (14)	0.0312 (4)
C6	1.0078 (2)	0.1834 (2)	0.91471 (14)	0.0314 (4)
C7	0.8174 (3)	0.1324 (2)	0.78825 (14)	0.0362 (4)
C8	0.9902 (3)	0.0668 (2)	0.74847 (14)	0.0348 (4)
C9	1.2580 (3)	0.0150 (3)	0.56711 (17)	0.0514 (5)
H9A	1.3429	−0.0101	0.6183	0.062*
H9B	1.3115	−0.0489	0.5104	0.062*
C10	1.2308 (4)	0.1859 (3)	0.5143 (2)	0.0673 (7)
H10A	1.1425	0.2134	0.4662	0.101*
H10B	1.3430	0.2042	0.4725	0.101*
H10C	1.1895	0.2499	0.5705	0.101*
C11	0.5366 (3)	0.3331 (3)	0.6882 (2)	0.0658 (7)
H11A	0.4252	0.3457	0.6615	0.079*
H11B	0.5078	0.3900	0.7489	0.079*
C12	0.6628 (5)	0.4051 (4)	0.5971 (3)	0.1003 (13)
H12A	0.7769	0.3859	0.6210	0.150*
H12B	0.6122	0.5171	0.5789	0.150*
H12C	0.6801	0.3584	0.5333	0.150*
N1	1.4901 (3)	0.3032 (3)	1.21488 (19)	0.0733 (6)
N2	0.9451 (3)	0.5027 (2)	1.31940 (17)	0.0632 (5)
S1	1.28831 (6)	0.20402 (6)	1.00515 (4)	0.03914 (14)
S2	0.89965 (6)	0.33925 (6)	1.08715 (4)	0.03802 (14)
S3	0.77877 (6)	0.21620 (6)	0.90659 (4)	0.04141 (14)
S4	1.15711 (6)	0.07338 (6)	0.81983 (4)	0.03804 (14)
S5	0.62815 (7)	0.12625 (7)	0.73859 (4)	0.04650 (16)
S6	1.05259 (8)	−0.03845 (7)	0.64039 (4)	0.04750 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0377 (10)	0.0631 (13)	0.0461 (11)	−0.0110 (10)	−0.0063 (9)	−0.0232 (10)
C2	0.0360 (9)	0.0404 (9)	0.0320 (9)	−0.0122 (8)	−0.0083 (7)	−0.0094 (7)
C3	0.0369 (9)	0.0348 (9)	0.0290 (8)	−0.0107 (7)	−0.0058 (7)	−0.0090 (7)
C4	0.0420 (10)	0.0436 (10)	0.0369 (10)	−0.0073 (9)	−0.0071 (8)	−0.0136 (8)
C5	0.0324 (8)	0.0345 (9)	0.0288 (8)	−0.0090 (7)	−0.0058 (7)	−0.0081 (7)
C6	0.0341 (8)	0.0355 (9)	0.0274 (8)	−0.0107 (7)	−0.0068 (7)	−0.0070 (7)
C7	0.0404 (9)	0.0443 (10)	0.0301 (9)	−0.0177 (8)	−0.0111 (7)	−0.0050 (7)
C8	0.0434 (9)	0.0416 (9)	0.0255 (8)	−0.0183 (8)	−0.0084 (7)	−0.0060 (7)
C9	0.0471 (11)	0.0647 (14)	0.0430 (11)	−0.0095 (11)	0.0012 (9)	−0.0245 (10)
C10	0.0797 (18)	0.0730 (16)	0.0516 (14)	−0.0346 (14)	0.0086 (12)	−0.0144 (12)
C11	0.0585 (14)	0.0618 (15)	0.0846 (18)	−0.0060 (12)	−0.0410 (14)	−0.0121 (13)
C12	0.115 (3)	0.085 (2)	0.110 (3)	−0.050 (2)	−0.065 (2)	0.0395 (19)
N1	0.0473 (11)	0.1120 (18)	0.0767 (15)	−0.0167 (12)	−0.0174 (11)	−0.0453 (14)
N2	0.0704 (13)	0.0684 (13)	0.0527 (12)	−0.0068 (11)	−0.0075 (10)	−0.0303 (10)
S1	0.0314 (2)	0.0513 (3)	0.0399 (3)	−0.0088 (2)	−0.00407 (19)	−0.0216 (2)
S2	0.0303 (2)	0.0491 (3)	0.0386 (3)	−0.0089 (2)	−0.00466 (18)	−0.0176 (2)
S3	0.0336 (2)	0.0591 (3)	0.0365 (3)	−0.0109 (2)	−0.00710 (19)	−0.0180 (2)
S4	0.0348 (2)	0.0504 (3)	0.0336 (3)	−0.0103 (2)	−0.00648 (18)	−0.0162 (2)
S5	0.0454 (3)	0.0585 (3)	0.0465 (3)	−0.0236 (3)	−0.0173 (2)	−0.0084 (2)
S6	0.0633 (3)	0.0552 (3)	0.0346 (3)	−0.0267 (3)	−0.0028 (2)	−0.0185 (2)

Geometric parameters (Å, º) top

C1—N1	1.136 (3)	C8—S4	1.7606 (18)
C1—C2	1.430 (3)	C9—C10	1.496 (3)
C2—C3	1.352 (3)	C9—S6	1.810 (2)
C2—S1	1.7423 (19)	C9—H9A	0.9700
C3—C4	1.425 (2)	C9—H9B	0.9700
C3—S2	1.7314 (18)	C10—H10A	0.9600
C4—N2	1.132 (3)	C10—H10B	0.9600
C5—C6	1.346 (2)	C10—H10C	0.9600
C5—S2	1.7646 (19)	C11—C12	1.500 (4)
C5—S1	1.7673 (18)	C11—S5	1.800 (3)
C6—S4	1.7495 (19)	C11—H11A	0.9700
C6—S3	1.7543 (18)	C11—H11B	0.9700
C7—C8	1.348 (3)	C12—H12A	0.9600
C7—S5	1.7483 (18)	C12—H12B	0.9600
C7—S3	1.7569 (19)	C12—H12C	0.9600
C8—S6	1.7439 (19)

N1—C1—C2	178.9 (3)	H9A—C9—H9B	107.7
C3—C2—C1	122.92 (17)	C9—C10—H10A	109.5
C3—C2—S1	117.99 (14)	C9—C10—H10B	109.5
C1—C2—S1	119.09 (15)	H10A—C10—H10B	109.5
C2—C3—C4	123.81 (17)	C9—C10—H10C	109.5
C2—C3—S2	118.14 (13)	H10A—C10—H10C	109.5
C4—C3—S2	118.05 (14)	H10B—C10—H10C	109.5
N2—C4—C3	178.8 (2)	C12—C11—S5	113.3 (2)
C6—C5—S2	120.78 (14)	C12—C11—H11A	108.9
C6—C5—S1	123.79 (15)	S5—C11—H11A	108.9
S2—C5—S1	115.42 (10)	C12—C11—H11B	108.9
C5—C6—S4	123.86 (14)	S5—C11—H11B	108.9
C5—C6—S3	121.49 (15)	H11A—C11—H11B	107.7
S4—C6—S3	114.62 (10)	C11—C12—H12A	109.5
C8—C7—S5	125.25 (15)	C11—C12—H12B	109.5
C8—C7—S3	117.19 (14)	H12A—C12—H12B	109.5
S5—C7—S3	117.34 (11)	C11—C12—H12C	109.5
C7—C8—S6	123.52 (14)	H12A—C12—H12C	109.5
C7—C8—S4	116.94 (14)	H12B—C12—H12C	109.5
S6—C8—S4	119.23 (11)	C2—S1—C5	94.04 (9)
C10—C9—S6	113.94 (17)	C3—S2—C5	94.40 (8)
C10—C9—H9A	108.8	C6—S3—C7	95.39 (9)
S6—C9—H9A	108.8	C6—S4—C8	95.48 (9)
C10—C9—H9B	108.8	C7—S5—C11	101.18 (10)
S6—C9—H9B	108.8	C8—S6—C9	102.91 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···N2ⁱ	0.96	2.73	3.659 (4)	164

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂S₆
M_r	374.58
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.8357 (16), 8.9777 (18), 12.618 (3)
α, β, γ (°)	76.48 (3), 77.59 (3), 73.20 (3)
V (Å³)	815.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.15 × 0.13 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.886, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	8038, 3689, 3079
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.109, 1.15
No. of reflections	3689
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.42

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···N2ⁱ	0.96	2.73	3.659 (4)	164.0

Symmetry code: (i) −x+2, −y+1, −z+2.

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 21062022).

References

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