organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Yamada, J. & Sugimoto, T. (2004). TTF Chemistry. Fundamentals and applications of Tetrathiafulvalene. Berlin: Springer.]). For the synthesis and properties of tetra­thio­fulvalene and its derivatives, see: Otsubo & Takimiya (2004[Otsubo, T. & Takimiya, K. (2004). Bull. Chem. Soc. Jpn, 77, 43-58.]); Krief (1986[Krief, A. (1986). Tetrahedron, 42, 1209-1252.]); Jia et al. (2007[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.]).

[Scheme 1]

Experimental

Crystal data
  • C7H6N2S3

  • Mr = 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.910, Tmax = 0.961

  • 4517 measured reflections

  • 1702 independent reflections

  • 1521 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms were located in a difference Fourier map and refined freely.

Structure description 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).

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
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] 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
C7H6N2S3F(000) = 440
Mr = 214.35Dx = 1.626 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2863 reflections
a = 5.7695 (9) Åθ = 3.1–27.3°
b = 7.6130 (11) ŵ = 0.79 mm1
c = 19.993 (3) ÅT = 291 K
β = 94.265 (2)°Block, yellow
V = 875.7 (2) Å30.35 × 0.10 × 0.05 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1702 independent reflections
Radiation source: sealed tube1521 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
phi and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 67
Tmin = 0.910, Tmax = 0.961k = 99
4517 measured reflectionsl = 2024
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H 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 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C7H6N2S3V = 875.7 (2) Å3
Mr = 214.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.7695 (9) ŵ = 0.79 mm1
b = 7.6130 (11) ÅT = 291 K
c = 19.993 (3) Å0.35 × 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)
Tmin = 0.910, Tmax = 0.961Rint = 0.029
4517 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.21 e Å3
1702 reflectionsΔρmin = 0.29 e Å3
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
xyzUiso*/Ueq
C10.5326 (4)0.8170 (3)0.39432 (11)0.0350 (5)
C20.3149 (4)0.8999 (3)0.37772 (11)0.0334 (4)
C30.2459 (4)0.9342 (3)0.31133 (11)0.0316 (4)
C40.3887 (3)0.8872 (3)0.26093 (10)0.0305 (4)
C50.6025 (4)0.8080 (3)0.27734 (10)0.0312 (4)
C60.6739 (4)0.7722 (3)0.34410 (11)0.0332 (4)
C70.5787 (4)0.8467 (3)0.14729 (11)0.0369 (5)
H30.097 (5)0.992 (3)0.3011 (12)0.038 (6)*
H60.820 (4)0.719 (3)0.3564 (12)0.040 (6)*
H1A0.724 (6)0.720 (4)0.4636 (16)0.073 (10)*
H2A0.490 (7)0.760 (4)0.4841 (17)0.066 (10)*
H3A0.250 (5)0.978 (4)0.4623 (15)0.058 (9)*
H4A0.060 (6)0.999 (4)0.4153 (15)0.057 (8)*
N10.6017 (4)0.7889 (3)0.46186 (11)0.0482 (5)
N20.1723 (4)0.9361 (3)0.42920 (11)0.0465 (5)
S10.32535 (10)0.93005 (7)0.17590 (3)0.03893 (19)
S20.76856 (9)0.76272 (7)0.20996 (3)0.03781 (19)
S30.63040 (13)0.84730 (10)0.06737 (3)0.0540 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0329 (11)0.0347 (10)0.0364 (11)0.0004 (8)0.0046 (8)0.0003 (8)
C20.0290 (10)0.0325 (10)0.0383 (11)0.0010 (8)0.0003 (8)0.0026 (8)
C30.0246 (10)0.0318 (10)0.0380 (11)0.0016 (8)0.0013 (8)0.0015 (8)
C40.0274 (10)0.0288 (9)0.0347 (10)0.0011 (8)0.0011 (8)0.0014 (8)
C50.0274 (10)0.0276 (9)0.0385 (11)0.0005 (8)0.0006 (8)0.0028 (8)
C60.0261 (10)0.0326 (10)0.0399 (11)0.0047 (8)0.0037 (8)0.0011 (8)
C70.0378 (12)0.0344 (11)0.0382 (12)0.0078 (9)0.0023 (9)0.0027 (8)
N10.0430 (13)0.0641 (13)0.0362 (11)0.0132 (11)0.0044 (9)0.0018 (10)
N20.0384 (11)0.0626 (14)0.0382 (11)0.0120 (10)0.0008 (9)0.0053 (10)
S10.0351 (3)0.0450 (3)0.0360 (3)0.0018 (2)0.0018 (2)0.0058 (2)
S20.0304 (3)0.0421 (3)0.0412 (3)0.0014 (2)0.0044 (2)0.0036 (2)
S30.0592 (4)0.0666 (4)0.0368 (4)0.0103 (3)0.0088 (3)0.0028 (3)
Geometric parameters (Å, º) top
C1—C61.382 (3)C5—S21.745 (2)
C1—N11.396 (3)C6—H60.95 (3)
C1—C21.423 (3)C7—S31.647 (2)
C2—C31.382 (3)C7—S21.725 (2)
C2—N21.392 (3)C7—S11.730 (2)
C3—C41.395 (3)N1—H1A0.88 (4)
C3—H30.97 (3)N1—H2A0.84 (4)
C4—C51.390 (3)N2—H3A0.83 (3)
C4—S11.743 (2)N2—H4A0.84 (3)
C5—C61.394 (3)
C6—C1—N1121.6 (2)C1—C6—C5119.9 (2)
C6—C1—C2119.9 (2)C1—C6—H6118.4 (14)
N1—C1—C2118.5 (2)C5—C6—H6121.7 (15)
C3—C2—N2121.9 (2)S3—C7—S2123.70 (14)
C3—C2—C1119.6 (2)S3—C7—S1122.57 (14)
N2—C2—C1118.4 (2)S2—C7—S1113.73 (13)
C2—C3—C4120.15 (19)C1—N1—H1A108 (2)
C2—C3—H3118.3 (14)C1—N1—H2A112 (2)
C4—C3—H3121.6 (14)H1A—N1—H2A118 (3)
C5—C4—C3120.12 (19)C2—N2—H3A110 (2)
C5—C4—S1115.43 (16)C2—N2—H4A111 (2)
C3—C4—S1124.37 (16)H3A—N2—H4A114 (3)
C4—C5—C6120.3 (2)C7—S1—C497.64 (10)
C4—C5—S2115.60 (16)C7—S2—C597.59 (10)
C6—C5—S2124.07 (16)
C6—C1—C2—C30.3 (3)N1—C1—C6—C5177.7 (2)
N1—C1—C2—C3178.0 (2)C2—C1—C6—C50.2 (3)
C6—C1—C2—N2177.2 (2)C4—C5—C6—C10.6 (3)
N1—C1—C2—N25.2 (3)S2—C5—C6—C1178.36 (16)
N2—C2—C3—C4176.5 (2)S3—C7—S1—C4180.00 (14)
C1—C2—C3—C40.2 (3)S2—C7—S1—C40.34 (13)
C2—C3—C4—C51.0 (3)C5—C4—S1—C70.28 (17)
C2—C3—C4—S1177.76 (16)C3—C4—S1—C7177.22 (18)
C3—C4—C5—C61.1 (3)S3—C7—S2—C5179.66 (14)
S1—C4—C5—C6178.20 (16)S1—C7—S2—C50.69 (13)
C3—C4—C5—S2177.88 (15)C4—C5—S2—C70.90 (17)
S1—C4—C5—S20.8 (2)C6—C5—S2—C7178.06 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2A···S3i0.84 (4)2.87 (4)3.711 (3)176 (3)
N2—H3A···N1ii0.83 (3)2.45 (3)3.226 (3)156 (3)
N2—H4A···S3iii0.84 (3)2.90 (3)3.588 (2)141 (3)
Symmetry codes: (i) x1/2, 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 formulaC7H6N2S3
Mr214.35
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)5.7695 (9), 7.6130 (11), 19.993 (3)
β (°) 94.265 (2)
V3)875.7 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.79
Crystal size (mm)0.35 × 0.10 × 0.05
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.910, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections
4517, 1702, 1521
Rint0.029
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.097, 1.00
No. of reflections1702
No. of parameters133
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.29

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2A···S3i0.84 (4)2.87 (4)3.711 (3)176 (3)
N2—H3A···N1ii0.83 (3)2.45 (3)3.226 (3)156 (3)
N2—H4A···S3iii0.84 (3)2.90 (3)3.588 (2)141 (3)
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x+1, y+2, z+1; (iii) x+1/2, y+1/2, z+1/2.
 

References

First citationBruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationJia, 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
First citationKrief, A. (1986). Tetrahedron, 42, 1209–1252.  CrossRef CAS Google Scholar
First citationOtsubo, T. & Takimiya, K. (2004). Bull. Chem. Soc. Jpn, 77, 43–58.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYamada, J. & Sugimoto, T. (2004). TTF Chemistry. Fundamentals and applications of Tetrathiafulvalene. Berlin: Springer.  Google Scholar

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ISSN: 2056-9890
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