1-Methyl-1H-benzimidazole-2(3H)-thione

Khan, H.; Badshah, A.; Shaheen, F.; Gieck, C.; Qureshi, R.A.

doi:10.1107/S1600536808015043

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1141

doi:10.1107/S1600536808015043

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1-Methyl-1H-benzimidazole-2(3H)-thione

Hizbullah Khan,^a Amin Badshah,^a ^* Farkhanda Shaheen,^a Christine Gieck ^b and Rizwana Aleem Qureshi ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, ^bDISTA, Universita del Piemonte Orientale, Alessandria I-15100, Italy, and ^cDepartment of Plant Sciences, Faculty of Biological Sciences, Quaid-I-Azam University, Islamabad 45320, Pakistan
^*Correspondence e-mail: aminbadshah@yahoo.com

(Received 21 April 2008; accepted 18 May 2008; online 24 May 2008)

The title compound, C₈H₈N₂S, was prepared by the condensation of N-methyl-1,2-phenylenediamine and carbon disulfide. The crystal structure is stabilized by a C—H⋯π interaction between a benzene H atom and the benzene ring of a neighbouring molecule, and by intermolecular N—H⋯S interactions.

Related literature

For related literature, see: Baily et al. (1996 ); Koch (2001 ); Namgun et al. (2001 ); Schuster et al. (1990 ); Patel & Chedekel (1984 ).

Experimental

Crystal data

C₈H₈N₂S
M_r = 164.22
Monoclinic, P 2₁ /n
a = 9.997 (4) Å
b = 5.8140 (7) Å
c = 13.703 (4) Å
β = 94.05 (3)°
V = 794.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 (2) K
0.20 × 0.10 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction; 2004 $[Oxford Diffraction (2004). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ; Clark & Reid, 1995 ) T_min = 0.929, T_max = 0.967
7237 measured reflections
962 independent reflections
855 reflections with I > 2σ(I)
R_int = 0.023
θ_max = 23.1°

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.09
962 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Sⁱ	0.86	2.57	3.408 (2)	166
C3—H3⋯Cgⁱⁱ	0.93	2.74	3.464 (3)	136
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ . Cg is the centroid of the C2–C7 ring.

Data collection: CrysAlis CCD (Oxford Diffraction, 2004 $[Oxford Diffraction (2004). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2004 $[Oxford Diffraction (2004). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015043/lx2055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015043/lx2055Isup2.hkl

checkCIF report

Comment top

N,N'- disubstituted and N-substituted thiourea derivatives are the major building blocks of organic macromolecular compounds. Thiourea derivatives such as benzothiazoles have been isolated by bromination of arylthioureas (Patil & Chedekel, 1984) and by condensation of 2-aminothiazole (Baily et al., 1996), by cyclization of N-(2-hydroxyethyl-N-methylthioureas and 2-methyl-aminothiazole (Namgun et al., 2001). Aliphatic and acylthioureas have a wide range of application due to their coordination behavior towards transition metals (Schuster et al., 1990). N,N-dialkyl-N-arylthioureas have been used for the extraction of metals such as nickel, palladium and platinum (Koch, 2001). Here we report the crystal structure of the title compound, 1-methyl-2H-benzimidazole-2-thione (Fig. 1).

The benzimidazole unit is essentially planar, with a mean deviation of 0.023 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by a C—H···π interaction between a benzene H atom and the benzene ring of neighbouring molecules, with a C3—H3···Cgⁱ separation of 2.735 (3) Å (Fig. 2 and Table 1; Cg is the C2-C7 benzene ring, symmetry code as in Fig. 2). Additionally, intermolecular N—H···S interactions in the structure were observed (Fig. 2 and Table 1; symmetry code as in Fig. 2).

Related literature top

For related literature, see: Baily et al. (1996); Koch (2001); Namgun et al. (2001); Schuster et al. (1990); Patel & Chedekel (1984). Cg is the centroid of the C2–C7 ring

For related literature, see: Patel & Chedekel (1984).

Experimental top

Compound (I) was synthesized by the addition of carbondisulfide (0.79 ml, 13.02 mmol) to N-methyl-1,2-phenylenediamine (0.744 ml, 6.55 mmol) in methanol (20 ml). The resulting mixture was stirred for 24 h, at 0°C temperature, giving a clear light yellow solution. The solution was evaporated under reduced pressure to give a light yellow solid, which was recrystallized in methanol/peteroleum ether (9:1) to afford compound (I) (yield : 76%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2004); data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. C—H···π and N—H···S interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (i) -x+1/2, y-1/2, -z+3/2; (ii) -x+3/2, y+1/2, -z+3/2; (iii) -x+3/2, y-1/2, -z+3/2; (iv) -x+1/2, y+1/2, -z+3/2.]

1-Methyl-1H-benzimidazole-2(3H)-thione top

Crystal data top

C₈H₈N₂S	F(000) = 344
M_r = 164.22	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 402 K
Hall symbol: -P_2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.997 (4) Å	Cell parameters from 5701 reflections
b = 5.8140 (7) Å	θ = 3.7–23.1°
c = 13.703 (4) Å	µ = 0.34 mm⁻¹
β = 94.05 (3)°	T = 293 K
V = 794.5 (4) Å³	Block, colourless
Z = 4	0.20 × 0.10 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	962 independent reflections
Radiation source: Enhance (Mo) X-ray Source	855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 10.0 pixels mm^-1	θ_max = 23.1°, θ_min = 3.8°
ω scans	h = −10→11
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction; 2004; Clark & Reid, 1995)	k = −6→6
T_min = 0.929, T_max = 0.967	l = −14→14
7237 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0353P)² + 0.4983P] where P = (F_o² + 2F_c²)/3
962 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₈N₂S	V = 794.5 (4) Å³
M_r = 164.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.997 (4) Å	µ = 0.34 mm⁻¹
b = 5.8140 (7) Å	T = 293 K
c = 13.703 (4) Å	0.20 × 0.10 × 0.02 mm
β = 94.05 (3)°

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	962 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction; 2004; Clark & Reid, 1995)	855 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.967	R_int = 0.023
7237 measured reflections	θ_max = 23.1°

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.09	Δρ_max = 0.21 e Å⁻³
962 reflections	Δρ_min = −0.19 e Å⁻³
101 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
S	0.73449 (6)	0.62833 (10)	0.62836 (4)	0.0475 (3)
N1	0.52959 (17)	0.3736 (3)	0.69273 (12)	0.0345 (5)
N2	0.57646 (17)	0.6789 (3)	0.78071 (12)	0.0380 (5)
H2	0.6119	0.8071	0.8004	0.046*
C1	0.6119 (2)	0.5599 (4)	0.70145 (15)	0.0359 (6)
C2	0.4462 (2)	0.3690 (3)	0.77058 (15)	0.0323 (5)
C3	0.3528 (2)	0.2095 (4)	0.79703 (16)	0.0399 (6)
H3	0.3342	0.0773	0.7603	0.048*
C4	0.2882 (2)	0.2566 (4)	0.88107 (17)	0.0461 (6)
H4	0.2255	0.1524	0.9017	0.055*
C5	0.3145 (2)	0.4548 (4)	0.93499 (17)	0.0466 (6)
H5	0.2684	0.4812	0.9906	0.056*
C6	0.4079 (2)	0.6150 (4)	0.90824 (16)	0.0412 (6)
H6	0.4246	0.7492	0.9440	0.049*
C7	0.4752 (2)	0.5656 (4)	0.82572 (15)	0.0330 (5)
C8	0.5331 (3)	0.1997 (4)	0.61682 (17)	0.0518 (7)
H8A	0.5508	0.2717	0.5560	0.078*
H8B	0.4482	0.1221	0.6098	0.078*
H8C	0.6026	0.0904	0.6345	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0446 (4)	0.0454 (4)	0.0547 (4)	0.0026 (3)	0.0184 (3)	0.0102 (3)
N1	0.0345 (10)	0.0313 (10)	0.0384 (10)	0.0019 (8)	0.0071 (8)	−0.0027 (8)
N2	0.0379 (11)	0.0323 (10)	0.0443 (11)	−0.0042 (8)	0.0064 (9)	−0.0040 (9)
C1	0.0350 (12)	0.0332 (12)	0.0396 (13)	0.0068 (11)	0.0026 (10)	0.0050 (10)
C2	0.0283 (11)	0.0339 (13)	0.0348 (12)	0.0062 (10)	0.0024 (9)	0.0023 (10)
C3	0.0365 (12)	0.0356 (13)	0.0478 (14)	−0.0024 (11)	0.0043 (11)	−0.0016 (11)
C4	0.0380 (13)	0.0483 (16)	0.0529 (15)	−0.0053 (11)	0.0094 (12)	0.0080 (13)
C5	0.0425 (13)	0.0601 (16)	0.0383 (13)	0.0015 (13)	0.0104 (11)	0.0021 (12)
C6	0.0423 (13)	0.0431 (14)	0.0380 (13)	0.0040 (11)	0.0017 (10)	−0.0060 (11)
C7	0.0302 (12)	0.0330 (12)	0.0358 (12)	0.0021 (10)	0.0019 (10)	0.0020 (10)
C8	0.0536 (15)	0.0493 (15)	0.0542 (15)	−0.0015 (13)	0.0150 (12)	−0.0150 (13)

Geometric parameters (Å, º) top

S—C1	1.684 (2)	C3—H3	0.9300
N1—C1	1.361 (3)	C4—C5	1.384 (3)
N1—C2	1.400 (3)	C4—H4	0.9300
N1—C8	1.453 (3)	C5—C6	1.386 (3)
N2—C1	1.356 (3)	C5—H5	0.9300
N2—C7	1.389 (3)	C6—C7	1.386 (3)
N2—H2	0.8600	C6—H6	0.9300
C2—C3	1.383 (3)	C8—H8A	0.9600
C2—C7	1.389 (3)	C8—H8B	0.9600
C3—C4	1.387 (3)	C8—H8C	0.9600

C1—N1—C2	109.71 (17)	C3—C4—H4	119.2
C1—N1—C8	124.88 (18)	C4—C5—C6	121.6 (2)
C2—N1—C8	125.34 (18)	C4—C5—H5	119.2
C1—N2—C7	110.71 (18)	C6—C5—H5	119.2
C1—N2—H2	124.6	C7—C6—C5	116.8 (2)
C7—N2—H2	124.6	C7—C6—H6	121.6
N2—C1—N1	106.62 (18)	C5—C6—H6	121.6
N2—C1—S	126.72 (18)	C6—C7—N2	132.5 (2)
N1—C1—S	126.65 (17)	C6—C7—C2	121.3 (2)
C3—C2—C7	121.86 (19)	N2—C7—C2	106.21 (17)
C3—C2—N1	131.46 (19)	N1—C8—H8A	109.5
C7—C2—N1	106.66 (17)	N1—C8—H8B	109.5
C2—C3—C4	116.6 (2)	H8A—C8—H8B	109.5
C2—C3—H3	121.7	N1—C8—H8C	109.5
C4—C3—H3	121.7	H8A—C8—H8C	109.5
C5—C4—C3	121.7 (2)	H8B—C8—H8C	109.5
C5—C4—H4	119.2

C7—N2—C1—N1	2.4 (2)	C2—C3—C4—C5	0.9 (3)
C7—N2—C1—S	−177.28 (16)	C3—C4—C5—C6	−0.7 (4)
C2—N1—C1—N2	−3.2 (2)	C4—C5—C6—C7	−1.0 (3)
C8—N1—C1—N2	179.79 (19)	C5—C6—C7—N2	−177.1 (2)
C2—N1—C1—S	176.50 (15)	C5—C6—C7—C2	2.4 (3)
C8—N1—C1—S	−0.5 (3)	C1—N2—C7—C6	178.9 (2)
C1—N1—C2—C3	−175.6 (2)	C1—N2—C7—C2	−0.7 (2)
C8—N1—C2—C3	1.4 (3)	C3—C2—C7—C6	−2.3 (3)
C1—N1—C2—C7	2.8 (2)	N1—C2—C7—C6	179.11 (19)
C8—N1—C2—C7	179.79 (19)	C3—C2—C7—N2	177.32 (19)
C7—C2—C3—C4	0.6 (3)	N1—C2—C7—N2	−1.2 (2)
N1—C2—C3—C4	178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Sⁱ	0.86	2.57	3.408 (2)	166
C3—H3···Cgⁱⁱ	0.93	2.74	3.464 (3)	136

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₈N₂S
M_r	164.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.997 (4), 5.8140 (7), 13.703 (4)
β (°)	94.05 (3)
V (Å³)	794.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.10 × 0.02

Data collection
Diffractometer	Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction; 2004; Clark & Reid, 1995)
T_min, T_max	0.929, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	7237, 962, 855
R_int	0.023
θ_max (°)	23.1
(sin θ/λ)_max (Å⁻¹)	0.552

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.078, 1.09
No. of reflections	962
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Sⁱ	0.86	2.57	3.408 (2)	166.3
C3—H3···Cgⁱⁱ	0.93	2.74	3.464 (3)	136

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

The authors acknowledge the Higher Education Commission, Pakistan, for financial support.

References

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