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

The mol-ecule of the title compound, C(7)H(6)N(2)S(3), 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, mol-ecules are linked by inter-molecular N-H⋯S and N-H⋯N hydrogen bonds into a three-dimensional network. The crystal packing also exhibits weak inter-molecular S⋯S inter-actions [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 = 214.35

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.097

S = 1.00

1702 reflections

133 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.29 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046532/rz2516Isup2.hkl

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

C7H6N2S3	F(000) = 440
Mr = 214.35	Dx = 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

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

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(Fo2) + (0.0558P)2 + 0.4807P] where P = (Fo2 + 2Fc2)/3
1702 reflections	(Δ/σ)max < 0.001
133 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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	0.5326 (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)

	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)

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)

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)

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) ; (ii) ; (iii) .