1H-Benzimidazole-2(3H)-thione

Wang, D.-C.; Mi, S.; Xu, W.; Jiang, L.; Huang, X.-M.

doi:10.1107/S1600536809008058

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o756

doi:10.1107/S1600536809008058

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1H-Benzimidazole-2(3H)-thione

De-Cai Wang,^a ^* Shan Mi,^a Wei Xu,^a Liang Jiang ^a and Xin-Ming Huang ^b

^aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dcwang@njut.edu.cn

(Received 27 February 2009; accepted 5 March 2009; online 14 March 2009)

The asymmetric unit of the title compound, C₇H₆N₂S, contains one half-molecule; the C and S atoms of the C=S group lie on a crystallographic mirror plane. In the crystal structure, intermolecular N—H⋯S hydrogen bonds link the molecules.

Related literature

For a related structure, see: Mavrova et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₆N₂S
M_r = 150.21
Monoclinic, P 2₁ /m
a = 4.915 (1) Å
b = 8.5590 (17) Å
c = 8.2920 (17) Å
β = 91.76 (3)°
V = 348.66 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.896, T_max = 0.963
903 measured reflections
813 independent reflections
647 reflections with I > 2σ(I)
R_int = 0.044
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.152
S = 1.00
813 reflections
45 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯Sⁱ	0.86	2.57	3.3798 (19)	158
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+2]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008058/hk2638sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008058/hk2638Isup2.hkl

checkCIF report

Comment top

It is a kind of secondary age inhibitor, and could reinforce the effect combined with DNP AP and other nonpolluting age inhibitors. It disperses easily in rubber, and the color does not change under sun exposure. Its pollution capacity is limited. 2-Mercaptobenzimidiazole is a new kind of anti-leprosy drugs, and its toxicity is lower than sulphone drugs. It should not be used in the patients to which can not be given sulphone drugs. We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains one-half molecule, in which a mirror plane passes through S and C4 atoms. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal structure, intermolecular N-H···S hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For a related structure, see: Mavrova et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title comppund, 1,2-diaminobenzene (0.019 mol) and water (3 ml) were added to a solution of sodium hydroxide (0.022 mol) in ethanol (20 ml) and carbon disulfide (0.022 mol). The mixture was heated under reflux for 3 h. Charcoal was added cautiously and removed by filtration after the mixture has been refluxed for 10 min more. The filtrate was heated to 377 K and quenched with warm water (377 K, 20 ml), and then acetic acid (9 ml) was added by stirring. The product was separated and after cooling in refrigerator for 3 h the crystallization was completed (Mavrova et al., 2007). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution after two weeks.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

1H-Benzimidazole-2(3H)-thione top

Crystal data top

C₇H₆N₂S	F(000) = 156
M_r = 150.21	D_x = 1.431 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 25 reflections
a = 4.915 (1) Å	θ = 10–14°
b = 8.5590 (17) Å	µ = 0.38 mm⁻¹
c = 8.2920 (17) Å	T = 294 K
β = 91.76 (3)°	Block, colorless
V = 348.66 (12) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	647 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 27.0°, θ_min = 2.5°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.896, T_max = 0.963	l = −10→10
903 measured reflections	3 standard reflections every 120 min
813 independent reflections	intensity decay: 1%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.059P] where P = (F_o² + 2F_c²)/3
813 reflections	(Δ/σ)_max < 0.001
45 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₆N₂S	V = 348.66 (12) Å³
M_r = 150.21	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 4.915 (1) Å	µ = 0.38 mm⁻¹
b = 8.5590 (17) Å	T = 294 K
c = 8.2920 (17) Å	0.30 × 0.20 × 0.10 mm
β = 91.76 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	647 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.044
T_min = 0.896, T_max = 0.963	3 standard reflections every 120 min
903 measured reflections	intensity decay: 1%
813 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	Δρ_max = 0.37 e Å⁻³
813 reflections	Δρ_min = −0.26 e Å⁻³
45 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
S	0.06322 (19)	0.2500	0.88609 (10)	0.0510 (3)
N	−0.2841 (4)	0.1239 (2)	1.1022 (2)	0.0465 (5)
H0A	−0.2505	0.0281	1.0783	0.056*
C1	−0.7826 (5)	0.1687 (4)	1.4250 (3)	0.0644 (7)
H1A	−0.8914	0.1154	1.4964	0.077*
C2	−0.6229 (5)	0.0844 (3)	1.3201 (3)	0.0561 (7)
H2A	−0.6243	−0.0242	1.3195	0.067*
C3	−0.4611 (4)	0.1684 (3)	1.2162 (3)	0.0437 (5)
C4	−0.1646 (7)	0.2500	1.0292 (4)	0.047

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0671 (6)	0.0270 (5)	0.0588 (6)	0.000	0.0015 (4)	0.000
N	0.0585 (11)	0.0227 (9)	0.0578 (12)	−0.0010 (8)	−0.0061 (9)	0.0009 (8)
C1	0.0621 (14)	0.0558 (17)	0.0755 (18)	−0.0084 (13)	0.0082 (13)	0.0065 (14)
C2	0.0681 (15)	0.0359 (13)	0.0640 (16)	−0.0047 (12)	−0.0032 (13)	0.0047 (11)
C3	0.0484 (11)	0.0302 (12)	0.0519 (13)	0.0009 (9)	−0.0094 (9)	−0.0003 (9)
C4	0.057	0.029	0.054	0.000	−0.019	0.000

Geometric parameters (Å, º) top

S—C4	1.656 (4)	C1—H1A	0.9300
N—C3	1.359 (3)	C2—C3	1.390 (3)
N—C4	1.378 (3)	C2—H2A	0.9300
N—H0A	0.8600	C3—C3ⁱ	1.398 (4)
C1—C2	1.391 (4)	C4—Nⁱ	1.378 (3)
C1—C1ⁱ	1.391 (6)

C3—N—C4	112.1 (2)	C1—C2—H2A	121.2
C3—N—H0A	123.9	N—C3—C2	132.6 (2)
C4—N—H0A	123.9	N—C3—C3ⁱ	106.27 (12)
C2—C1—C1ⁱ	121.24 (16)	C2—C3—C3ⁱ	121.11 (15)
C2—C1—H1A	119.4	N—C4—Nⁱ	103.2 (3)
C1ⁱ—C1—H1A	119.4	N—C4—S	128.40 (15)
C3—C2—C1	117.6 (2)	Nⁱ—C4—S	128.40 (15)
C3—C2—H2A	121.2

C1ⁱ—C1—C2—C3	0.6 (3)	C1—C2—C3—C3ⁱ	−0.6 (3)
C4—N—C3—C2	−179.1 (2)	C3—N—C4—Nⁱ	−1.5 (3)
C4—N—C3—C3ⁱ	1.0 (2)	C3—N—C4—S	179.5 (2)
C1—C2—C3—N	179.5 (2)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Sⁱⁱ	0.86	2.57	3.3798 (19)	158

Symmetry code: (ii) −x, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₇H₆N₂S
M_r	150.21
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	294
a, b, c (Å)	4.915 (1), 8.5590 (17), 8.2920 (17)
β (°)	91.76 (3)
V (Å³)	348.66 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.896, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	903, 813, 647
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.152, 1.00
No. of reflections	813
No. of parameters	45
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Sⁱ	0.86	2.57	3.3798 (19)	158.00

Symmetry code: (i) −x, y−1/2, −z+2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Mavrova, A. Ts., Denkova, P., Tsenov, Y. A., Anichina, K. K. & Vutchev, D. I. (2007). Bioorg. Med. Chem. 15, 6291–6297. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar