5,6-Diamino-1,3-benzodithiole-2-thione

Wang, F.-M.

doi:10.1107/S1600536810046532

organic compounds

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Volume 66| Part 12| December 2010| Page o3184

https://doi.org/10.1107/S1600536810046532

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5,6-Diamino-1,3-benzodithiole-2-thione

Fang-Ming Wang ^a ^*

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: wangfmzj@yahoo.com.cn

(Received 30 October 2010; accepted 10 November 2010; online 13 November 2010)

The molecule of the title compound, C₇H₆N₂S₃, is almost planar, the dihedral angle between the benzene plane and the 1,3-dithiole-2-thione plane being 2.21 (6)°. In the crystal, molecules are linked by intermolecular N—H⋯S and N—H⋯N hydrogen bonds into a three-dimensional network. The crystal packing also exhibits weak intermolecular S⋯S interactions [3.5681 (9) Å].

Related literature

For background to tetrathiofulvalene and its derivatives, see: Yamada & Sugimoto (2004 ). For the synthesis and properties of tetrathiofulvalene and its derivatives, see: Otsubo & Takimiya (2004 ); Krief (1986 ); Jia et al. (2007 ).

Experimental

Crystal data

C₇H₆N₂S₃
M_r = 214.35
Monoclinic, P 2₁ /n
a = 5.7695 (9) Å
b = 7.6130 (11) Å
c = 19.993 (3) Å
β = 94.265 (2)°
V = 875.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 291 K
0.35 × 0.10 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.910, T_max = 0.961
4517 measured reflections
1702 independent reflections
1521 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.097
S = 1.00
1702 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2A⋯S3ⁱ	0.84 (4)	2.87 (4)	3.711 (3)	176 (3)
N2—H3A⋯N1ⁱⁱ	0.83 (3)	2.45 (3)	3.226 (3)	156 (3)
N2—H4A⋯S3ⁱⁱⁱ	0.84 (3)	2.90 (3)	3.588 (2)	141 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046532/rz2516sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046532/rz2516Isup2.hkl

checkCIF report

Comment top

Tetrathiofulvalene (TTF) and its derivatives are successfully used as versatile building blocks for charge-transfer salts, giving rise to organic conductors and superconductors because of their unique π-donor properties (Yamada & Sugimoto, 2004). Extensive reviews on the synthesis and properties of TTF and its derivatives have been published (Otsubo & Takimiya, 2004; Krief, 1986). 1,3-Dithiole-2-thiones are a key intermediates in TTF synthesis routes (Jia et al., 2007). The synthesis and crystal structure of the title compound is reported herein.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the benzene plane and the 1,3-dithiole-2-thione plane is 2.21 (6)°. The moleculess are linked by the intermolecular N–H···S and N–H···N hydrogen bonds (Table 1) and S···S weak interactions (3.5681 (9) Å) into a three-dimensional network (Fig. 2).

Related literature top

For background to tetrathiofulvalene and its derivatives, see: Yamada & Sugimoto (2004). For the synthesis and properties of tetrathiofulvalene and its derivatives, see: Otsubo & Takimiya (2004); Krief (1986); Jia et al. (2007).

Experimental top

1,2-Diaminobenzene-4,5-bis(thiocyanate) (10 mmol) was added to a degassed solution of Na₂S.9H₂O (33 mmol) in water (100 mL), and the mixture was heated to 70 °C for an hour to produce a clear brownish solution. The mixture was cooled to 50 °C, and CS₂ (1.4 ml, 23.2 mmol) was slowly added dropwise. The mixture was stirred for two hours at 50 °C and for further three hours at room temperature. The precipitate was filtered off, washed with water, and air-dried. The crude product was purified by flash column chromatography to give the title compound as a yellow powder (yield 50%). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution at room temperature for two weeks.

Structure description top

For background to tetrathiofulvalene and its derivatives, see: Yamada & Sugimoto (2004). For the synthesis and properties of tetrathiofulvalene and its derivatives, see: Otsubo & Takimiya (2004); Krief (1986); Jia et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound viewed along the a axis. Intermolecular hydrogen bonds are shown as dashed lines.

5,6-Diamino-1,3-benzodithiole-2-thione top

Crystal data top

C₇H₆N₂S₃	F(000) = 440
M_r = 214.35	D_x = 1.626 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2863 reflections
a = 5.7695 (9) Å	θ = 3.1–27.3°
b = 7.6130 (11) Å	µ = 0.79 mm⁻¹
c = 19.993 (3) Å	T = 291 K
β = 94.265 (2)°	Block, yellow
V = 875.7 (2) Å³	0.35 × 0.10 × 0.05 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1702 independent reflections
Radiation source: sealed tube	1521 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
phi and ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→7
T_min = 0.910, T_max = 0.961	k = −9→9
4517 measured reflections	l = −20→24

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0558P)² + 0.4807P] where P = (F_o² + 2F_c²)/3
1702 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₆N₂S₃	V = 875.7 (2) Å³
M_r = 214.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.7695 (9) Å	µ = 0.79 mm⁻¹
b = 7.6130 (11) Å	T = 291 K
c = 19.993 (3) Å	0.35 × 0.10 × 0.05 mm
β = 94.265 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1702 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1521 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.961	R_int = 0.029
4517 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.21 e Å⁻³
1702 reflections	Δρ_min = −0.29 e Å⁻³
133 parameters

Special details top

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	0.5326 (4)	0.8170 (3)	0.39432 (11)	0.0350 (5)
C2	0.3149 (4)	0.8999 (3)	0.37772 (11)	0.0334 (4)
C3	0.2459 (4)	0.9342 (3)	0.31133 (11)	0.0316 (4)
C4	0.3887 (3)	0.8872 (3)	0.26093 (10)	0.0305 (4)
C5	0.6025 (4)	0.8080 (3)	0.27734 (10)	0.0312 (4)
C6	0.6739 (4)	0.7722 (3)	0.34410 (11)	0.0332 (4)
C7	0.5787 (4)	0.8467 (3)	0.14729 (11)	0.0369 (5)
H3	0.097 (5)	0.992 (3)	0.3011 (12)	0.038 (6)*
H6	0.820 (4)	0.719 (3)	0.3564 (12)	0.040 (6)*
H1A	0.724 (6)	0.720 (4)	0.4636 (16)	0.073 (10)*
H2A	0.490 (7)	0.760 (4)	0.4841 (17)	0.066 (10)*
H3A	0.250 (5)	0.978 (4)	0.4623 (15)	0.058 (9)*
H4A	0.060 (6)	0.999 (4)	0.4153 (15)	0.057 (8)*
N1	0.6017 (4)	0.7889 (3)	0.46186 (11)	0.0482 (5)
N2	0.1723 (4)	0.9361 (3)	0.42920 (11)	0.0465 (5)
S1	0.32535 (10)	0.93005 (7)	0.17590 (3)	0.03893 (19)
S2	0.76856 (9)	0.76272 (7)	0.20996 (3)	0.03781 (19)
S3	0.63040 (13)	0.84730 (10)	0.06737 (3)	0.0540 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0329 (11)	0.0347 (10)	0.0364 (11)	0.0004 (8)	−0.0046 (8)	0.0003 (8)
C2	0.0290 (10)	0.0325 (10)	0.0383 (11)	0.0010 (8)	0.0003 (8)	−0.0026 (8)
C3	0.0246 (10)	0.0318 (10)	0.0380 (11)	0.0016 (8)	−0.0013 (8)	−0.0015 (8)
C4	0.0274 (10)	0.0288 (9)	0.0347 (10)	−0.0011 (8)	−0.0011 (8)	0.0014 (8)
C5	0.0274 (10)	0.0276 (9)	0.0385 (11)	−0.0005 (8)	0.0006 (8)	−0.0028 (8)
C6	0.0261 (10)	0.0326 (10)	0.0399 (11)	0.0047 (8)	−0.0037 (8)	0.0011 (8)
C7	0.0378 (12)	0.0344 (11)	0.0382 (12)	−0.0078 (9)	0.0023 (9)	−0.0027 (8)
N1	0.0430 (13)	0.0641 (13)	0.0362 (11)	0.0132 (11)	−0.0044 (9)	0.0018 (10)
N2	0.0384 (11)	0.0626 (14)	0.0382 (11)	0.0120 (10)	0.0008 (9)	−0.0053 (10)
S1	0.0351 (3)	0.0450 (3)	0.0360 (3)	0.0018 (2)	−0.0018 (2)	0.0058 (2)
S2	0.0304 (3)	0.0421 (3)	0.0412 (3)	0.0014 (2)	0.0044 (2)	−0.0036 (2)
S3	0.0592 (4)	0.0666 (4)	0.0368 (4)	−0.0103 (3)	0.0088 (3)	−0.0028 (3)

Geometric parameters (Å, º) top

C1—C6	1.382 (3)	C5—S2	1.745 (2)
C1—N1	1.396 (3)	C6—H6	0.95 (3)
C1—C2	1.423 (3)	C7—S3	1.647 (2)
C2—C3	1.382 (3)	C7—S2	1.725 (2)
C2—N2	1.392 (3)	C7—S1	1.730 (2)
C3—C4	1.395 (3)	N1—H1A	0.88 (4)
C3—H3	0.97 (3)	N1—H2A	0.84 (4)
C4—C5	1.390 (3)	N2—H3A	0.83 (3)
C4—S1	1.743 (2)	N2—H4A	0.84 (3)
C5—C6	1.394 (3)

C6—C1—N1	121.6 (2)	C1—C6—C5	119.9 (2)
C6—C1—C2	119.9 (2)	C1—C6—H6	118.4 (14)
N1—C1—C2	118.5 (2)	C5—C6—H6	121.7 (15)
C3—C2—N2	121.9 (2)	S3—C7—S2	123.70 (14)
C3—C2—C1	119.6 (2)	S3—C7—S1	122.57 (14)
N2—C2—C1	118.4 (2)	S2—C7—S1	113.73 (13)
C2—C3—C4	120.15 (19)	C1—N1—H1A	108 (2)
C2—C3—H3	118.3 (14)	C1—N1—H2A	112 (2)
C4—C3—H3	121.6 (14)	H1A—N1—H2A	118 (3)
C5—C4—C3	120.12 (19)	C2—N2—H3A	110 (2)
C5—C4—S1	115.43 (16)	C2—N2—H4A	111 (2)
C3—C4—S1	124.37 (16)	H3A—N2—H4A	114 (3)
C4—C5—C6	120.3 (2)	C7—S1—C4	97.64 (10)
C4—C5—S2	115.60 (16)	C7—S2—C5	97.59 (10)
C6—C5—S2	124.07 (16)

C6—C1—C2—C3	0.3 (3)	N1—C1—C6—C5	−177.7 (2)
N1—C1—C2—C3	178.0 (2)	C2—C1—C6—C5	−0.2 (3)
C6—C1—C2—N2	177.2 (2)	C4—C5—C6—C1	−0.6 (3)
N1—C1—C2—N2	−5.2 (3)	S2—C5—C6—C1	178.36 (16)
N2—C2—C3—C4	−176.5 (2)	S3—C7—S1—C4	180.00 (14)
C1—C2—C3—C4	0.2 (3)	S2—C7—S1—C4	0.34 (13)
C2—C3—C4—C5	−1.0 (3)	C5—C4—S1—C7	0.28 (17)
C2—C3—C4—S1	−177.76 (16)	C3—C4—S1—C7	177.22 (18)
C3—C4—C5—C6	1.1 (3)	S3—C7—S2—C5	179.66 (14)
S1—C4—C5—C6	178.20 (16)	S1—C7—S2—C5	−0.69 (13)
C3—C4—C5—S2	−177.88 (15)	C4—C5—S2—C7	0.90 (17)
S1—C4—C5—S2	−0.8 (2)	C6—C5—S2—C7	−178.06 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2A···S3ⁱ	0.84 (4)	2.87 (4)	3.711 (3)	176 (3)
N2—H3A···N1ⁱⁱ	0.83 (3)	2.45 (3)	3.226 (3)	156 (3)
N2—H4A···S3ⁱⁱⁱ	0.84 (3)	2.90 (3)	3.588 (2)	141 (3)

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₆N₂S₃
M_r	214.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	5.7695 (9), 7.6130 (11), 19.993 (3)
β (°)	94.265 (2)
V (Å³)	875.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.35 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.910, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	4517, 1702, 1521
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.097, 1.00
No. of reflections	1702
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.29

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2A···S3ⁱ	0.84 (4)	2.87 (4)	3.711 (3)	176 (3)
N2—H3A···N1ⁱⁱ	0.83 (3)	2.45 (3)	3.226 (3)	156 (3)
N2—H4A···S3ⁱⁱⁱ	0.84 (3)	2.90 (3)	3.588 (2)	141 (3)

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, y+1/2, −z+1/2.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jia, C., Liu, S.-X., Tanner, C., Leiggener, C., Neels, A., Sanguinet, L., Levillain, E., Leutwyler, S., Hauser, A. & Decurtins, S. (2007). Chem. Eur. J. 13, 3804–3812. Web of Science CSD CrossRef PubMed CAS Google Scholar
Krief, A. (1986). Tetrahedron, 42, 1209–1252. CrossRef CAS Google Scholar
Otsubo, T. & Takimiya, K. (2004). Bull. Chem. Soc. Jpn, 77, 43–58. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yamada, J. & Sugimoto, T. (2004). TTF Chemistry. Fundamentals and applications of Tetrathiafulvalene. Berlin: Springer. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3184

https://doi.org/10.1107/S1600536810046532

Open

access