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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 π–π stacking inter­actions [perpendicular distance 3.504 Å and centroid-to-centroid distance 4.080 Å], displaying a two-dimensional supra­molecular array.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037373/rt2008sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037373/rt2008Isup2.hkl
Contains datablock I

CCDC reference: 660197

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.052
  • wR factor = 0.135
  • Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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 ππ 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 ππ 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.

Structure description 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 ππ 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 ππ stacking interactions form a two dimensional supramolecular array.

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).

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. ORTEP-II (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 ππ 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
C14H12N2F(000) = 880
Mr = 208.26Dx = 1.262 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2911 reflections
a = 9.0763 (10) Åθ = 2.8–24.9°
b = 9.8053 (11) ŵ = 0.08 mm1
c = 24.628 (3) ÅT = 295 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)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1111
Tmin = 0.970, Tmax = 0.988k = 114
9605 measured reflectionsl = 3024
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0639P)2 + 0.6749P]
where P = (Fo2 + 2Fc2)/3
2133 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C14H12N2V = 2191.8 (4) Å3
Mr = 208.26Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.0763 (10) ŵ = 0.08 mm1
b = 9.8053 (11) ÅT = 295 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)] = 0.0520 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.10Δρmax = 0.21 e Å3
2133 reflectionsΔρmin = 0.18 e Å3
146 parameters
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)
C30.0747 (2)1.06679 (19)0.30950 (8)0.0477 (5)
H30.09771.15900.31200.057*
C40.1665 (2)0.9773 (2)0.28295 (8)0.0523 (5)
H40.25231.01000.26700.063*
C50.1337 (2)0.8385 (2)0.27942 (8)0.0494 (5)
H50.19800.78100.26100.059*
C60.00918 (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, º) 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—N10.80 (18)C3—C2—C7—C60.0 (3)
C2—N2—C1—C8177.07 (15)N2—C2—C7—C6178.71 (15)
C7—N1—C1—N20.53 (19)N2—C1—C8—C9150.60 (19)
C7—N1—C1—C8177.40 (14)N1—C1—C8—C927.1 (2)
C1—N2—C2—C3177.71 (18)N2—C1—C8—C1327.3 (3)
C1—N2—C2—C70.76 (18)N1—C1—C8—C13155.08 (17)
N2—C2—C3—C4177.59 (18)C13—C8—C9—C100.5 (3)
C7—C2—C3—C40.8 (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—C120.2 (3)
C4—C5—C6—C71.1 (3)C9—C10—C11—C14179.5 (2)
C1—N1—C7—C6177.98 (18)C10—C11—C12—C130.2 (3)
C1—N1—C7—C20.02 (18)C14—C11—C12—C13179.46 (19)
C5—C6—C7—N1176.77 (17)C11—C12—C13—C80.4 (3)
C5—C6—C7—C20.9 (3)C9—C8—C13—C120.5 (3)
C3—C2—C7—N1178.21 (15)C1—C8—C13—C12177.42 (16)
N2—C2—C7—N10.46 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.852.072.9151 (19)171
Symmetry code: (i) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC14H12N2
Mr208.26
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)295
a, b, c (Å)9.0763 (10), 9.8053 (11), 24.628 (3)
V3)2191.8 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.20 × 0.16
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.970, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
9605, 2133, 1850
Rint0.025
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.135, 1.10
No. of reflections2133
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.18

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) 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, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.852.072.9151 (19)170.8
Symmetry code: (i) x+1/2, y1/2, z.
 

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