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Acta Cryst. (2007). E63, o3688    [ doi:10.1107/S1600536807037373 ]

2-(4-Methylphenyl)-1H-benzimidazole

W.-J. Shi and C.-X. Ruan

Abstract top

In the title compound, C14H12N2, the benzimidazole and tolyl groups are not coplanar, exibiting a dihedral angle of 27.5 (3)°. The structure is held intact through N-H...N hydrogen bonds and [pi]-[pi] stacking interactions [perpendicular distance 3.504 Å and centroid-to-centroid distance 4.080 Å], displaying a two-dimensional supramolecular array.

Comment top

2-Substituted benzimidazoles have attracted considerable interest as intermediates in the development of molecules of pharmaceutical interest. Benzimidazole derivatives exhibit significant activity against several viruses such as HIV, herpes (HSV-1), RNA, influenza, and human cytomegalovirus (HCMV) (Tamm, 1957; Tamm & Seghal, 1978; Roth et al., 1997; Migawa et al., 1998; Porcari et al., 1998). The objective of this study therefore was to synthesize and elucidate the crystal structure of a new benzimidazole compound.

A view of the molecule of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1. The dihedral angle between the benzimidazole and tolyl portions of the title compound, (I), is 27.5 °. The molecules are linked into a linear chain through N—H···N hydrogen bonds interactions (N2···H1 2.072 Å, N1—H1···N2 170.8 °), as shown in Fig. 2. There exist π–π stacking interactions in adjacent linear chains, adjacent tolyl rings are exactly parallel, the perpendicular spacing of the rings is 3.504 Å, and the ring centroid-to-centroid distance is 4.080 Å. These π–π stacking interactions form a two dimensional supramolecular array.

Related literature top

For related literature, see: Johnson (1976); Ma et al. (2006); Migawa et al. (1998); Porcari et al. (1998); Roth et al. (1997); Tamm (1957); Tamm & Seghal (1978).

Experimental top

The title compound was synthesized according to the reported procedure (Ma et al., 2006). o-Phenylenediamine (10 mmol) and p-Tolualdehyde (10 mmol) were mixed in DMF (30 ml) thoroughly, followed by the addition of KHSO4 (3.4 mmol), heating and stirring for one hour. When the reaction was finished, the solution was cooled to room temperature. The reaction mixture was added dropwise with vigorous stirring into a mixture of Na2CO3 (3.4 mmol) and H2O (250 ml). The precipitate was collected by filtration, and recrystalized from ethanol to form the brown block crystals of the title compound. Yield: 416.5 mg (20%).

Refinement top

The H atoms were placed in calculated positions (aromatic C—H 0.93 Å and methyl C—H 0.96 Å; U 1.2UeqC) and were included in the refinement in the riding model approximation. The nitrogen-bound H atom was located and refined with an N—H distance restraint of 0.85 Å.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound, with displacement ellipsoids drawn at the 30% probability level, and H atoms given as spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of title compound, showing the extended two-dimensional structure linked by N—H····N hydrogen interactions and π–π stacking interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level, and H atoms given as spheres of arbitrary radii.
2-(4-Methylphenyl)-1H-benzimidazole top
Crystal data top
C14H12N2F000 = 880
Mr = 208.26Dx = 1.262 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2911 reflections
a = 9.0763 (10) Åθ = 2.8–24.9º
b = 9.8053 (11) ŵ = 0.08 mm−1
c = 24.628 (3) ÅT = 295 (2) K
V = 2191.8 (4) Å3Block, brown
Z = 80.40 × 0.20 × 0.16 mm
Data collection top
Bruker APEX area-detector
diffractometer		2133 independent reflections
Radiation source: fine-focus sealed tube1850 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 295(2) Kθmax = 26.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.970, Tmax = 0.988k = −11→4
9605 measured reflectionsl = −30→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.135  w = 1/[σ2(Fo2) + (0.0639P)2 + 0.6749P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2133 reflectionsΔρmax = 0.21 e Å−3
146 parametersΔρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C14H12N2V = 2191.8 (4) Å3
Mr = 208.26Z = 8
Orthorhombic, PbcaMo Kα
a = 9.0763 (10) ŵ = 0.08 mm−1
b = 9.8053 (11) ÅT = 295 (2) K
c = 24.628 (3) Å0.40 × 0.20 × 0.16 mm
Data collection top
Bruker APEX area-detector
diffractometer		2133 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1850 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.988Rint = 0.025
9605 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052146 parameters
wR(F2) = 0.135H-atom parameters constrained
S = 1.10Δρmax = 0.21 e Å−3
2133 reflectionsΔρmin = −0.18 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.21900 (15)0.85838 (14)0.35353 (6)0.0377 (4)
N20.16814 (14)1.08050 (14)0.35983 (6)0.0386 (4)
C10.26414 (18)0.98288 (16)0.37105 (6)0.0352 (4)
C20.05379 (17)1.01519 (17)0.33254 (7)0.0363 (4)
C3−0.0747 (2)1.06679 (19)0.30950 (8)0.0477 (5)
H3−0.09771.15900.31200.057*
C4−0.1665 (2)0.9773 (2)0.28295 (8)0.0523 (5)
H4−0.25231.01000.26700.063*
C5−0.1337 (2)0.8385 (2)0.27942 (8)0.0494 (5)
H5−0.19800.78100.26100.059*
C6−0.00918 (19)0.78515 (18)0.30242 (7)0.0445 (4)
H60.01180.69240.30060.053*
C70.08437 (17)0.87557 (17)0.32862 (7)0.0349 (4)
C80.40695 (17)1.00359 (17)0.39761 (7)0.0369 (4)
C90.5242 (2)0.9178 (2)0.38676 (8)0.0514 (5)
H90.51110.84410.36350.062*
C100.6605 (2)0.9398 (2)0.40998 (9)0.0557 (5)
H100.73780.88100.40190.067*
C110.68392 (19)1.0476 (2)0.44493 (8)0.0478 (5)
C120.5668 (2)1.1330 (2)0.45579 (8)0.0497 (5)
H120.58031.20650.47910.060*
C130.42976 (19)1.11181 (18)0.43277 (7)0.0429 (4)
H130.35241.17060.44090.052*
C140.8329 (2)1.0698 (3)0.47036 (11)0.0714 (7)
H14A0.82841.04750.50830.107*
H14B0.86121.16350.46620.107*
H14C0.90421.01240.45280.107*
H10.25950.78090.35770.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0392 (8)0.0252 (7)0.0488 (8)0.0010 (6)−0.0021 (6)−0.0011 (6)
N20.0376 (7)0.0267 (7)0.0513 (8)−0.0004 (5)−0.0035 (6)−0.0013 (6)
C10.0384 (8)0.0263 (8)0.0410 (9)−0.0015 (6)0.0025 (7)−0.0005 (7)
C20.0364 (8)0.0285 (9)0.0440 (9)−0.0025 (6)0.0002 (7)0.0011 (7)
C30.0463 (10)0.0342 (10)0.0625 (12)0.0031 (7)−0.0092 (9)0.0020 (9)
C40.0447 (10)0.0510 (12)0.0610 (12)−0.0014 (8)−0.0150 (9)0.0056 (10)
C50.0501 (10)0.0454 (11)0.0528 (11)−0.0134 (8)−0.0090 (8)−0.0005 (9)
C60.0501 (10)0.0315 (9)0.0518 (10)−0.0063 (7)−0.0021 (8)−0.0016 (8)
C70.0365 (8)0.0282 (9)0.0399 (9)−0.0025 (6)0.0026 (7)0.0019 (7)
C80.0382 (8)0.0295 (9)0.0430 (9)−0.0020 (7)−0.0007 (7)0.0021 (7)
C90.0449 (10)0.0441 (11)0.0651 (12)0.0054 (8)−0.0048 (9)−0.0164 (9)
C100.0394 (10)0.0581 (13)0.0697 (13)0.0092 (8)−0.0020 (9)−0.0072 (11)
C110.0430 (10)0.0499 (12)0.0506 (11)−0.0057 (8)−0.0054 (8)0.0060 (9)
C120.0532 (11)0.0434 (11)0.0525 (11)−0.0043 (8)−0.0098 (9)−0.0067 (9)
C130.0439 (9)0.0347 (10)0.0502 (10)0.0030 (7)−0.0031 (8)−0.0036 (8)
C140.0489 (12)0.0831 (18)0.0821 (16)−0.0062 (11)−0.0174 (11)0.0000 (14)
Geometric parameters (Å, °) top
N1—C11.358 (2)C6—H60.9300
N1—C71.378 (2)C8—C91.383 (2)
N1—H10.8500C8—C131.385 (2)
N2—C11.323 (2)C9—C101.379 (3)
N2—C21.392 (2)C9—H90.9300
C1—C81.466 (2)C10—C111.380 (3)
C2—C31.392 (2)C10—H100.9300
C2—C71.400 (2)C11—C121.379 (3)
C3—C41.375 (3)C11—C141.506 (3)
C3—H30.9300C12—C131.382 (2)
C4—C51.396 (3)C12—H120.9300
C4—H40.9300C13—H130.9300
C5—C61.368 (3)C14—H14A0.9600
C5—H50.9300C14—H14B0.9600
C6—C71.387 (2)C14—H14C0.9600
C1—N1—C7107.41 (13)C9—C8—C13118.16 (16)
C1—N1—H1129.3C9—C8—C1120.67 (15)
C7—N1—H1123.2C13—C8—C1121.14 (15)
C1—N2—C2105.01 (13)C10—C9—C8120.97 (18)
N2—C1—N1112.65 (14)C10—C9—H9119.5
N2—C1—C8125.11 (14)C8—C9—H9119.5
N1—C1—C8122.21 (14)C9—C10—C11121.14 (18)
C3—C2—N2130.84 (16)C9—C10—H10119.4
C3—C2—C7119.56 (15)C11—C10—H10119.4
N2—C2—C7109.59 (14)C12—C11—C10117.83 (17)
C4—C3—C2118.00 (17)C12—C11—C14121.60 (19)
C4—C3—H3121.0C10—C11—C14120.57 (19)
C2—C3—H3121.0C11—C12—C13121.52 (18)
C3—C4—C5121.50 (17)C11—C12—H12119.2
C3—C4—H4119.3C13—C12—H12119.2
C5—C4—H4119.3C12—C13—C8120.39 (16)
C6—C5—C4121.55 (17)C12—C13—H13119.8
C6—C5—H5119.2C8—C13—H13119.8
C4—C5—H5119.2C11—C14—H14A109.5
C5—C6—C7116.98 (17)C11—C14—H14B109.5
C5—C6—H6121.5H14A—C14—H14B109.5
C7—C6—H6121.5C11—C14—H14C109.5
N1—C7—C6132.22 (15)H14A—C14—H14C109.5
N1—C7—C2105.35 (14)H14B—C14—H14C109.5
C6—C7—C2122.40 (15)
C2—N2—C1—N1−0.80 (18)C3—C2—C7—C60.0 (3)
C2—N2—C1—C8177.07 (15)N2—C2—C7—C6−178.71 (15)
C7—N1—C1—N20.53 (19)N2—C1—C8—C9−150.60 (19)
C7—N1—C1—C8−177.40 (14)N1—C1—C8—C927.1 (2)
C1—N2—C2—C3−177.71 (18)N2—C1—C8—C1327.3 (3)
C1—N2—C2—C70.76 (18)N1—C1—C8—C13−155.08 (17)
N2—C2—C3—C4177.59 (18)C13—C8—C9—C10−0.5 (3)
C7—C2—C3—C4−0.8 (3)C1—C8—C9—C10177.46 (18)
C2—C3—C4—C50.6 (3)C8—C9—C10—C110.3 (3)
C3—C4—C5—C60.3 (3)C9—C10—C11—C12−0.2 (3)
C4—C5—C6—C7−1.1 (3)C9—C10—C11—C14179.5 (2)
C1—N1—C7—C6177.98 (18)C10—C11—C12—C130.2 (3)
C1—N1—C7—C2−0.02 (18)C14—C11—C12—C13−179.46 (19)
C5—C6—C7—N1−176.77 (17)C11—C12—C13—C8−0.4 (3)
C5—C6—C7—C20.9 (3)C9—C8—C13—C120.5 (3)
C3—C2—C7—N1178.21 (15)C1—C8—C13—C12−177.42 (16)
N2—C2—C7—N1−0.46 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.852.072.9151 (19)171
Symmetry codes: (i) −x+1/2, y−1/2, z.
Selected geometric parameters (Å, °) top
N1—C11.358 (2)C1—C81.466 (2)
N1—C71.378 (2)C2—C31.392 (2)
N2—C11.323 (2)C2—C71.400 (2)
N2—C21.392 (2)C11—C141.506 (3)
C1—N1—C7107.41 (13)C3—C2—C7119.56 (15)
C1—N2—C2105.01 (13)N2—C2—C7109.59 (14)
N2—C1—N1112.65 (14)N1—C7—C6132.22 (15)
N2—C1—C8125.11 (14)N1—C7—C2105.35 (14)
N1—C1—C8122.21 (14)C9—C8—C13118.16 (16)
C3—C2—N2130.84 (16)C12—C11—C10117.83 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.852.072.9151 (19)171
Symmetry codes: (i) −x+1/2, y−1/2, z.
Acknowledgements top

The authors thank Jiangxi Science and Technology Normal University for supporting this study.

references
References top

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