Perhydro­benzimidazole-2-thione

Liu, Y.C.; Li, X.Y.

doi:10.1107/S1600536808043894

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o248

doi:10.1107/S1600536808043894

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Perhydrobenzimidazole-2-thione

YingChun Liu ^a ^* and XiaoYu Li ^a

^aDepartment of Biomedicine, Zhongshan Torch Polytechnic, Zhongshan 528436, Guangdong Province, People's Republic of China
^*Correspondence e-mail: chemliuyingchun@126.com

(Received 8 December 2008; accepted 24 December 2008; online 8 January 2009)

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 ). For useful applications of thiourea derivetives, see: Schroeder (2006 ); Amos et al. (2007 ).

Experimental

Crystal data

C₇H₁₂N₂S
M_r = 156.25
Monoclinic, P 2₁ /m
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 ) 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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.154
S = 1.03
934 reflections
91 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯S1Aⁱ	0.86	2.53	3.367 (11)	166
N1B—H1B⋯S1Bⁱⁱ	0.86	2.76	3.483 (11)	142
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (ii) -x+2, -y+1, -z+2.

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

Supporting information

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

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

checkCIF report

Comment top

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].

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

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

Perhydrobenzimidazole-2-thione top

Crystal data top

C₇H₁₂N₂S	F(000) = 168
M_r = 156.25	D_x = 1.211 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1728 reflections
a = 5.7459 (16) Å	θ = 2.3–24.6°
b = 8.543 (2) Å	µ = 0.31 mm⁻¹
c = 8.816 (2) Å	T = 293 K
β = 98.208 (4)°	Block, colourless
V = 428.3 (2) Å³	0.20 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	934 independent reflections
Radiation source: fine-focus sealed tube	740 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.931, T_max = 0.970	k = −9→10
4541 measured reflections	l = −11→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1091P)² + 0.0156P] where P = (F_o² + 2F_c²)/3
934 reflections	(Δ/σ)_max = 0.009
91 parameters	Δρ_max = 0.19 e Å⁻³
6 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₇H₁₂N₂S	V = 428.3 (2) Å³
M_r = 156.25	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 5.7459 (16) Å	µ = 0.31 mm⁻¹
b = 8.543 (2) Å	T = 293 K
c = 8.816 (2) Å	0.20 × 0.10 × 0.10 mm
β = 98.208 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	934 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	740 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.970	R_int = 0.019
4541 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	6 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
934 reflections	Δρ_min = −0.14 e Å⁻³
91 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C2	0.8296 (4)	0.2500	0.9716 (3)	0.0734 (7)
S1A	1.0495 (14)	0.2500	1.1194 (10)	0.0811 (15)	0.50
N1A	0.746 (3)	0.1176 (10)	0.9007 (16)	0.095 (4)	0.50
H1A	0.8101	0.0266	0.9121	0.113*	0.50
C3A	0.534 (2)	0.1541 (15)	0.8039 (15)	0.102 (4)	0.50
H3A	0.4166	0.1316	0.8715	0.122*	0.50
C4A	0.4237 (9)	0.0818 (6)	0.6596 (6)	0.0974 (14)	0.50
H4A1	0.3843	−0.0258	0.6803	0.117*	0.50
H4A2	0.5382	0.0796	0.5887	0.117*	0.50
C5A	0.2070 (17)	0.1621 (11)	0.5834 (11)	0.119 (6)	0.50
H5A1	0.0758	0.1270	0.6327	0.143*	0.50
H5A2	0.1779	0.1270	0.4777	0.143*	0.50
S1B	1.0773 (15)	0.2500	1.0974 (10)	0.088 (2)	0.50
N1B	0.697 (2)	0.3722 (7)	0.9103 (13)	0.0720 (19)	0.50
H1B	0.7108	0.4663	0.9453	0.086*	0.50
C3B	0.5339 (13)	0.3261 (13)	0.7810 (14)	0.0718 (18)	0.50
H3B	0.6275	0.3463	0.6985	0.086*	0.50
C4B	0.3201 (9)	0.4183 (6)	0.7250 (7)	0.0994 (15)	0.50
H4B1	0.3630	0.5236	0.6986	0.119*	0.50
H4B2	0.2188	0.4249	0.8039	0.119*	0.50
C5B	0.1951 (16)	0.3360 (13)	0.5860 (11)	0.121 (6)	0.50
H5B1	0.0328	0.3707	0.5709	0.146*	0.50
H5B2	0.2648	0.3707	0.4979	0.146*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0817 (15)	0.0481 (12)	0.0918 (16)	0.000	0.0170 (12)	0.000
S1A	0.094 (2)	0.0635 (17)	0.0790 (14)	0.000	−0.010 (3)	0.000
N1A	0.079 (6)	0.063 (4)	0.136 (6)	0.015 (2)	−0.001 (4)	−0.013 (3)
C3A	0.141 (8)	0.044 (3)	0.118 (7)	−0.013 (3)	0.008 (5)	0.009 (4)
C4A	0.096 (3)	0.074 (3)	0.119 (4)	0.003 (3)	0.000 (3)	−0.018 (3)
C5A	0.112 (7)	0.091 (8)	0.134 (8)	−0.016 (5)	−0.050 (5)	−0.018 (6)
S1B	0.105 (2)	0.0474 (14)	0.114 (4)	0.000	0.0191 (14)	0.000
N1B	0.077 (5)	0.0334 (19)	0.102 (3)	−0.008 (2)	0.002 (3)	−0.002 (2)
C3B	0.063 (3)	0.052 (3)	0.096 (3)	0.006 (2)	−0.003 (2)	−0.014 (3)
C4B	0.096 (4)	0.070 (3)	0.130 (4)	0.022 (3)	0.009 (3)	0.010 (3)
C5B	0.098 (7)	0.122 (11)	0.148 (9)	−0.009 (5)	0.030 (5)	−0.011 (6)

Geometric parameters (Å, º) top

C2—N1A	1.348 (6)	C5A—C5Aⁱ	1.502 (19)
C2—N1Aⁱ	1.348 (6)	C5A—H5A1	0.9700
C2—N1B	1.357 (5)	C5A—H5A2	0.9700
C2—N1Bⁱ	1.357 (5)	N1B—C3B	1.426 (7)
C2—S1B	1.675 (5)	N1B—H1B	0.8600
C2—S1A	1.680 (4)	C3B—C3Bⁱ	1.30 (2)
N1A—C3A	1.420 (8)	C3B—C4B	1.483 (7)
N1A—H1A	0.8600	C3B—H3B	0.9800
C3A—C4A	1.473 (8)	C4B—C5B	1.504 (7)
C3A—C3Aⁱ	1.64 (3)	C4B—H4B1	0.9700
C3A—H3A	0.9800	C4B—H4B2	0.9700
C4A—C5A	1.494 (7)	C5B—C5Bⁱ	1.47 (2)
C4A—H4A1	0.9700	C5B—H5B1	0.9700
C4A—H4A2	0.9700	C5B—H5B2	0.9700

N1A—C2—N1Aⁱ	114.2 (10)	C4A—C5A—C5Aⁱ	117.3 (4)
N1A—C2—N1B	108.6 (3)	C4A—C5A—H5A1	108.0
N1Aⁱ—C2—N1Bⁱ	108.6 (3)	C5Aⁱ—C5A—H5A1	108.0
N1B—C2—N1Bⁱ	100.6 (9)	C4A—C5A—H5A2	108.0
N1A—C2—S1B	121.3 (5)	C5Aⁱ—C5A—H5A2	108.0
N1Aⁱ—C2—S1B	121.3 (6)	H5A1—C5A—H5A2	107.2
N1B—C2—S1B	129.6 (4)	C2—N1B—C3B	111.9 (5)
N1Bⁱ—C2—S1B	129.6 (4)	C2—N1B—H1B	124.0
N1A—C2—S1A	122.6 (5)	C3B—N1B—H1B	124.0
N1Aⁱ—C2—S1A	122.6 (5)	C3Bⁱ—C3B—N1B	106.0 (4)
N1B—C2—S1A	128.7 (4)	C3Bⁱ—C3B—C4B	122.1 (5)
N1Bⁱ—C2—S1A	128.7 (4)	N1B—C3B—C4B	122.6 (11)
C2—N1A—C3A	108.2 (8)	C3Bⁱ—C3B—H3B	100.1
C2—N1A—H1A	125.9	N1B—C3B—H3B	100.1
C3A—N1A—H1A	125.9	C4B—C3B—H3B	100.1
N1A—C3A—C4A	130.7 (11)	C3B—C4B—C5B	107.4 (7)
N1A—C3A—C3Aⁱ	102.7 (5)	C3B—C4B—H4B1	110.2
C4A—C3A—C3Aⁱ	114.8 (6)	C5B—C4B—H4B1	110.2
N1A—C3A—H3A	101.3	C3B—C4B—H4B2	110.2
C4A—C3A—H3A	101.3	C5B—C4B—H4B2	110.2
C3Aⁱ—C3A—H3A	101.3	H4B1—C4B—H4B2	108.5
C3A—C4A—C5A	115.0 (7)	C5Bⁱ—C5B—C4B	117.9 (5)
C3A—C4A—H4A1	108.5	C5Bⁱ—C5B—H5B1	107.8
C5A—C4A—H4A1	108.5	C4B—C5B—H5B1	107.8
C3A—C4A—H4A2	108.5	C5Bⁱ—C5B—H5B2	107.8
C5A—C4A—H4A2	108.5	C4B—C5B—H5B2	107.8
H4A1—C4A—H4A2	107.5	H5B1—C5B—H5B2	107.2

N1Aⁱ—C2—N1A—C3A	−21 (2)	N1A—C2—N1B—C3B	−6.9 (9)
N1B—C2—N1A—C3A	−7.6 (10)	N1Aⁱ—C2—N1B—C3B	110 (5)
N1Bⁱ—C2—N1A—C3A	47 (3)	N1Bⁱ—C2—N1B—C3B	−18 (2)
S1B—C2—N1A—C3A	179.0 (10)	S1B—C2—N1B—C3B	165.7 (10)
S1A—C2—N1A—C3A	168.3 (11)	S1A—C2—N1B—C3B	177.5 (9)
C2—N1A—C3A—C4A	151.0 (13)	C2—N1B—C3B—C3Bⁱ	11.8 (14)
C2—N1A—C3A—C3Aⁱ	11.4 (13)	C2—N1B—C3B—C4B	159.0 (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—C5B	178.7 (11)
C3A—C4A—C5A—C5Aⁱ	40.4 (9)	C3B—C4B—C5B—C5Bⁱ	37.3 (8)

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
N1A—H1A···S1Aⁱⁱ	0.86	2.53	3.367 (11)	166
N1B—H1B···S1Bⁱⁱⁱ	0.86	2.76	3.483 (11)	142

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

Experimental details

Crystal data
Chemical formula	C₇H₁₂N₂S
M_r	156.25
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	5.7459 (16), 8.543 (2), 8.816 (2)
β (°)	98.208 (4)
V (Å³)	428.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.931, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	4541, 934, 740
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.154, 1.03
No. of reflections	934
No. of parameters	91
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S1Aⁱ	0.86	2.53	3.367 (11)	166
N1B—H1B···S1Bⁱⁱ	0.86	2.76	3.483 (11)	142

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

Acknowledgements

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

References

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