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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o248.
Published online 2009 January 8. doi:  10.1107/S1600536808043894
PMCID: PMC2968239

Perhydro­benzimidazole-2-thione

Abstract

The studied crystal of the title compound, C7H12N2S, is a racemic mixture of two isomers, viz. S,S and R,R. The two isomers share the same position on a mirror plane in the space group P21/m; thus all atoms except one are disordered between two positions in a 1:1 ratio. Inter­molecular N—H(...)S hydrogen bonds link the mol­ecules into chains propagating in the [010] direction.

Related literature

For details of the synthesis, see: Allen et al. (1946 [triangle]). For useful applications of thio­urea derivetives, see: Schroeder (2006 [triangle]); Amos et al. (2007 [triangle]).

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Object name is e-65-0o248-scheme1.jpg

Experimental

Crystal data

  • C7H12N2S
  • M r = 156.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o248-efi1.jpg
  • a = 5.7459 (16) Å
  • b = 8.543 (2) Å
  • c = 8.816 (2) Å
  • β = 98.208 (4)°
  • V = 428.3 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.31 mm−1
  • T = 293 (2) K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.931, T max = 0.970
  • 4541 measured reflections
  • 934 independent reflections
  • 740 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.154
  • S = 1.03
  • 934 reflections
  • 91 parameters
  • 6 restraints
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043894/cv2499sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043894/cv2499Isup2.hkl

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

Acknowledgments

The authors are grateful to Zhongshan Torch Polytechnic for financial support.

supplementary crystallographic information

Comment

Thiourea and its derivatives are used in dyes, photographic film, elastomers, plastics, textiles, insecticides, preservatives, rodenticides and pharmaceuticals (Schroeder et al., 2006; Amos et al., 2007)

The title molecule consists of one thioimidazole five-membered ring and one six-membered ring which display chair conformation. The studied crystal is a racemic mixture of two isomers - (S,S) and (R,R), respectively - which share the same position on a mirror plane in space group P21/m, thus all atoms except one are disordered between two positions in a ratio 1:1. In the crystal, intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into chains propagating in direction [010].

Experimental

The title compound was prepared according to the reported method (Allen et al.,1946). Crystals of (I) suitable for X-ray data collection were obtained by slow evaporation of a CH2Cl2 and MeOH solution in a ratio of 4:1 at 293 K.

Refinement

All H atoms were geometrically positioned (C–H 0.97-0.98 Å, N–H 0.86 Å) and refined as riding, with Uiso(H) = 1.2 Ueq(C, N). The crystal structure was refined in two space groups - P21 and P21/m, respectively. In both groups the severe disorder has been observed with almost identical values of final R-factors, so the preference has been made for P21/m.

Figures

Fig. 1.
View (S,S)-isomer of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C7H12N2SF(000) = 168
Mr = 156.25Dx = 1.211 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 1728 reflections
a = 5.7459 (16) Åθ = 2.3–24.6°
b = 8.543 (2) ŵ = 0.31 mm1
c = 8.816 (2) ÅT = 293 K
β = 98.208 (4)°Block, colourless
V = 428.3 (2) Å30.20 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer934 independent reflections
Radiation source: fine-focus sealed tube740 reflections with I > 2σ(I)
graphiteRint = 0.019
[var phi] and ω scansθmax = 26.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −7→7
Tmin = 0.931, Tmax = 0.970k = −9→10
4541 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.1091P)2 + 0.0156P] where P = (Fo2 + 2Fc2)/3
934 reflections(Δ/σ)max = 0.009
91 parametersΔρmax = 0.19 e Å3
6 restraintsΔρmin = −0.14 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/UeqOcc. (<1)
C20.8296 (4)0.25000.9716 (3)0.0734 (7)
S1A1.0495 (14)0.25001.1194 (10)0.0811 (15)0.50
N1A0.746 (3)0.1176 (10)0.9007 (16)0.095 (4)0.50
H1A0.81010.02660.91210.113*0.50
C3A0.534 (2)0.1541 (15)0.8039 (15)0.102 (4)0.50
H3A0.41660.13160.87150.122*0.50
C4A0.4237 (9)0.0818 (6)0.6596 (6)0.0974 (14)0.50
H4A10.3843−0.02580.68030.117*0.50
H4A20.53820.07960.58870.117*0.50
C5A0.2070 (17)0.1621 (11)0.5834 (11)0.119 (6)0.50
H5A10.07580.12700.63270.143*0.50
H5A20.17790.12700.47770.143*0.50
S1B1.0773 (15)0.25001.0974 (10)0.088 (2)0.50
N1B0.697 (2)0.3722 (7)0.9103 (13)0.0720 (19)0.50
H1B0.71080.46630.94530.086*0.50
C3B0.5339 (13)0.3261 (13)0.7810 (14)0.0718 (18)0.50
H3B0.62750.34630.69850.086*0.50
C4B0.3201 (9)0.4183 (6)0.7250 (7)0.0994 (15)0.50
H4B10.36300.52360.69860.119*0.50
H4B20.21880.42490.80390.119*0.50
C5B0.1951 (16)0.3360 (13)0.5860 (11)0.121 (6)0.50
H5B10.03280.37070.57090.146*0.50
H5B20.26480.37070.49790.146*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C20.0817 (15)0.0481 (12)0.0918 (16)0.0000.0170 (12)0.000
S1A0.094 (2)0.0635 (17)0.0790 (14)0.000−0.010 (3)0.000
N1A0.079 (6)0.063 (4)0.136 (6)0.015 (2)−0.001 (4)−0.013 (3)
C3A0.141 (8)0.044 (3)0.118 (7)−0.013 (3)0.008 (5)0.009 (4)
C4A0.096 (3)0.074 (3)0.119 (4)0.003 (3)0.000 (3)−0.018 (3)
C5A0.112 (7)0.091 (8)0.134 (8)−0.016 (5)−0.050 (5)−0.018 (6)
S1B0.105 (2)0.0474 (14)0.114 (4)0.0000.0191 (14)0.000
N1B0.077 (5)0.0334 (19)0.102 (3)−0.008 (2)0.002 (3)−0.002 (2)
C3B0.063 (3)0.052 (3)0.096 (3)0.006 (2)−0.003 (2)−0.014 (3)
C4B0.096 (4)0.070 (3)0.130 (4)0.022 (3)0.009 (3)0.010 (3)
C5B0.098 (7)0.122 (11)0.148 (9)−0.009 (5)0.030 (5)−0.011 (6)

Geometric parameters (Å, °)

C2—N1A1.348 (6)C5A—C5Ai1.502 (19)
C2—N1Ai1.348 (6)C5A—H5A10.9700
C2—N1B1.357 (5)C5A—H5A20.9700
C2—N1Bi1.357 (5)N1B—C3B1.426 (7)
C2—S1B1.675 (5)N1B—H1B0.8600
C2—S1A1.680 (4)C3B—C3Bi1.30 (2)
N1A—C3A1.420 (8)C3B—C4B1.483 (7)
N1A—H1A0.8600C3B—H3B0.9800
C3A—C4A1.473 (8)C4B—C5B1.504 (7)
C3A—C3Ai1.64 (3)C4B—H4B10.9700
C3A—H3A0.9800C4B—H4B20.9700
C4A—C5A1.494 (7)C5B—C5Bi1.47 (2)
C4A—H4A10.9700C5B—H5B10.9700
C4A—H4A20.9700C5B—H5B20.9700
N1A—C2—N1Ai114.2 (10)C4A—C5A—C5Ai117.3 (4)
N1A—C2—N1B108.6 (3)C4A—C5A—H5A1108.0
N1Ai—C2—N1Bi108.6 (3)C5Ai—C5A—H5A1108.0
N1B—C2—N1Bi100.6 (9)C4A—C5A—H5A2108.0
N1A—C2—S1B121.3 (5)C5Ai—C5A—H5A2108.0
N1Ai—C2—S1B121.3 (6)H5A1—C5A—H5A2107.2
N1B—C2—S1B129.6 (4)C2—N1B—C3B111.9 (5)
N1Bi—C2—S1B129.6 (4)C2—N1B—H1B124.0
N1A—C2—S1A122.6 (5)C3B—N1B—H1B124.0
N1Ai—C2—S1A122.6 (5)C3Bi—C3B—N1B106.0 (4)
N1B—C2—S1A128.7 (4)C3Bi—C3B—C4B122.1 (5)
N1Bi—C2—S1A128.7 (4)N1B—C3B—C4B122.6 (11)
C2—N1A—C3A108.2 (8)C3Bi—C3B—H3B100.1
C2—N1A—H1A125.9N1B—C3B—H3B100.1
C3A—N1A—H1A125.9C4B—C3B—H3B100.1
N1A—C3A—C4A130.7 (11)C3B—C4B—C5B107.4 (7)
N1A—C3A—C3Ai102.7 (5)C3B—C4B—H4B1110.2
C4A—C3A—C3Ai114.8 (6)C5B—C4B—H4B1110.2
N1A—C3A—H3A101.3C3B—C4B—H4B2110.2
C4A—C3A—H3A101.3C5B—C4B—H4B2110.2
C3Ai—C3A—H3A101.3H4B1—C4B—H4B2108.5
C3A—C4A—C5A115.0 (7)C5Bi—C5B—C4B117.9 (5)
C3A—C4A—H4A1108.5C5Bi—C5B—H5B1107.8
C5A—C4A—H4A1108.5C4B—C5B—H5B1107.8
C3A—C4A—H4A2108.5C5Bi—C5B—H5B2107.8
C5A—C4A—H4A2108.5C4B—C5B—H5B2107.8
H4A1—C4A—H4A2107.5H5B1—C5B—H5B2107.2
N1Ai—C2—N1A—C3A−21 (2)N1A—C2—N1B—C3B−6.9 (9)
N1B—C2—N1A—C3A−7.6 (10)N1Ai—C2—N1B—C3B110 (5)
N1Bi—C2—N1A—C3A47 (3)N1Bi—C2—N1B—C3B−18 (2)
S1B—C2—N1A—C3A179.0 (10)S1B—C2—N1B—C3B165.7 (10)
S1A—C2—N1A—C3A168.3 (11)S1A—C2—N1B—C3B177.5 (9)
C2—N1A—C3A—C4A151.0 (13)C2—N1B—C3B—C3Bi11.8 (14)
C2—N1A—C3A—C3Ai11.4 (13)C2—N1B—C3B—C4B159.0 (10)
N1A—C3A—C4A—C5A−175.2 (15)C3Bi—C3B—C4B—C5B−39.2 (8)
C3Ai—C3A—C4A—C5A−39.3 (9)N1B—C3B—C4B—C5B178.7 (11)
C3A—C4A—C5A—C5Ai40.4 (9)C3B—C4B—C5B—C5Bi37.3 (8)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1A—H1A···S1Aii0.862.533.367 (11)166
N1B—H1B···S1Biii0.862.763.483 (11)142

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2499).

References

  • Allen, C. F. H., Edens, C. O. & VanAllan, J. (1946). Org. Synth.26, 34–35.
  • Amos, F. F., Morin, S. A., Streifer, J. A., Hamers, R. J. & Jin, S. (2007). J. Am. Chem. Soc 129, 14296–14302. [PubMed]
  • Bruker (1997). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Schroeder, D. C. (1995). Chem. Rev.55, 181–228.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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