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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1017.
Published online 2008 May 7. doi:  10.1107/S1600536808012932
PMCID: PMC2961444

4-(1H-Benzimidazol-2-yl)benzonitrile

Abstract

The mol­ecule of the title compound, C14H9N3, is essentially planar, the dihedral angle formed by the benzimidazole ring system with the benzene ring being 3.87 (3)°. In the crystal packing, mol­ecules are linked into zigzag chains running parallel to the b axis by inter­molecular N—H(...)N hydrogen-bond inter­actions.

Related literature

For related literature, see: Gallagher et al. (2001 [triangle]); Howarth & Hanlon (2001 [triangle]); Kazak et al. (2006 [triangle]); Li et al. (1998 [triangle]); Íkizler & Sancak (1992 [triangle]).

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Object name is e-64-o1017-scheme1.jpg

Experimental

Crystal data

  • C14H9N3
  • M r = 219.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1017-efi1.jpg
  • a = 7.2172 (10) Å
  • b = 11.818 (2) Å
  • c = 12.719 (2) Å
  • β = 92.057 (7)°
  • V = 1084.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 (2) K
  • 0.35 × 0.15 × 0.10 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.910, T max = 1.000 (expected range = 0.903–0.992)
  • 11203 measured reflections
  • 2581 independent reflections
  • 2073 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.118
  • S = 1.08
  • 2581 reflections
  • 159 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012932/rz2211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012932/rz2211Isup2.hkl

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

Acknowledgments

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

Benzimidazole systems continue to attract much attention in chemical synthesis, structural science and applied biological research (Li et al., 1998; Gallagher et al., 2001; Howarth & Hanlon, 2001; Kazak et al., 2006). Nitriles are parent compounds for the preparation of various functional organic materials having triazole, imidazole or thidiazole moieties (Íkizler & Sancak, 1992) and their derivatives have found many industrial applications. We report here the crystal structure of the title compound, 4-(1H-benzo[d]imidazol-2-yl) benzonitrile.

The structural analysis shows that in the title compound (Fig. 1) the benzimidazole ring system and the phenyl ring are nearly coplanar, the dihedral angle they form being 3.87 (3)°. In the imidazole ring, the C7δb N1 bond length of 1.3191 (16) Å conforms to the value for a double bond. The molecular conformation is stabilized by an intramolecular C—H..N hydrogen bond (Table 1). In the crystal structure, molecules are linked into zig-zag chains running parallel to the b axis by intermolecular N—H···N hydrogen bonding interactions involving the protonated N atom of the imidazole ring as H-donor and the N atom of the nitrile group as acceptor.

Experimental

4-Formylbenzonitrile (2 mmol), malononitrile (1 mmol) and benzene-1,2-diamine (1 mmol) were heated at 100°C with stirring for 5 min. The mixture was washed with dichloromethane(5 mL) and dried. A white solid was obtained after recrystallization from ethanol. 4-(1H-Benzo[d]imidazol-2-yl)benzonitrile (0.3 mmol) was placed in a thick-walled Pyrex tube. EtOH (0.3 mL) and H2O (0.3 mL) were then added, the tube was frozen with liquid N2, evacuated and flame-sealed. The tube was heated at 100°C for 2 days to give colourless crystals of the title compound.

Refinement

The H atom bound to the imidazole N atom was located in a difference Fourier synthesis and refined freely. All other H atoms were placed in calculated positions and refined using a riding model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C14H9N3F000 = 456
Mr = 219.24Dx = 1.343 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2461 reflections
a = 7.2172 (10) Åθ = 3.2–27.5º
b = 11.818 (2) ŵ = 0.08 mm1
c = 12.719 (2) ÅT = 293 (2) K
β = 92.057 (7)ºPrism, colourless
V = 1084.1 (3) Å30.35 × 0.15 × 0.10 mm
Z = 4

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer2581 independent reflections
Radiation source: fine-focus sealed tube2073 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
Detector resolution: 13.6612 pixels mm-1θmax = 27.9º
T = 293(2) Kθmin = 2.4º
CCD_Profile_fitting scansh = −9→9
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −15→15
Tmin = 0.911, Tmax = 1.000l = −16→16
11203 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.046  w = 1/[σ2(Fo2) + (0.056P)2 + 0.1336P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.118(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.16 e Å3
2581 reflectionsΔρmin = −0.17 e Å3
159 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.115 (7)
Secondary atom site location: difference Fourier map

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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*/Ueq
N20.23276 (15)0.98417 (9)−0.07818 (9)0.0381 (3)
C80.14908 (17)0.84634 (11)0.06171 (10)0.0367 (3)
N10.08189 (15)0.82641 (9)−0.12784 (8)0.0404 (3)
C70.15245 (17)0.88501 (10)−0.04772 (10)0.0360 (3)
N30.11261 (18)0.68424 (11)0.45407 (10)0.0543 (3)
C110.13598 (18)0.76582 (11)0.26664 (10)0.0389 (3)
C60.21340 (17)0.98948 (10)−0.18604 (10)0.0363 (3)
C90.23427 (19)0.90578 (12)0.14485 (10)0.0439 (3)
H9A0.29630.97300.13150.053*
C10.11833 (17)0.89042 (11)−0.21590 (10)0.0377 (3)
C50.2689 (2)1.06900 (11)−0.25904 (11)0.0443 (3)
H5A0.33001.1351−0.23840.053*
C140.12508 (18)0.72221 (12)0.37201 (11)0.0425 (3)
C130.05688 (19)0.74595 (12)0.08336 (11)0.0432 (3)
H13A−0.00150.70580.02870.052*
C120.05122 (19)0.70550 (12)0.18459 (11)0.0436 (3)
H12A−0.00930.63780.19800.052*
C100.2277 (2)0.86617 (12)0.24669 (11)0.0459 (3)
H10A0.28460.90660.30170.055*
C40.2292 (2)1.04531 (13)−0.36315 (11)0.0496 (4)
H4A0.26521.0964−0.41420.060*
C30.1362 (2)0.94670 (13)−0.39450 (11)0.0492 (4)
H3A0.11340.9332−0.46580.059*
C20.07759 (19)0.86882 (12)−0.32224 (10)0.0451 (3)
H2B0.01310.8041−0.34350.054*
H2A0.281 (2)1.0377 (15)−0.0336 (13)0.058 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0439 (6)0.0349 (6)0.0354 (6)0.0001 (4)0.0010 (5)−0.0012 (4)
C80.0358 (6)0.0391 (7)0.0352 (7)0.0032 (5)0.0033 (5)0.0003 (5)
N10.0455 (6)0.0407 (6)0.0349 (6)−0.0031 (5)−0.0001 (4)0.0003 (4)
C70.0377 (6)0.0355 (6)0.0350 (7)0.0035 (5)0.0025 (5)0.0001 (5)
N30.0641 (8)0.0563 (8)0.0425 (7)−0.0005 (6)0.0002 (6)0.0094 (6)
C110.0391 (7)0.0420 (7)0.0357 (7)0.0050 (5)0.0029 (5)0.0042 (5)
C60.0382 (6)0.0351 (7)0.0357 (7)0.0050 (5)0.0020 (5)0.0003 (5)
C90.0535 (8)0.0389 (7)0.0393 (8)−0.0058 (6)−0.0006 (6)0.0025 (5)
C10.0394 (6)0.0375 (7)0.0360 (7)0.0042 (5)−0.0002 (5)0.0023 (5)
C50.0502 (8)0.0360 (7)0.0468 (8)0.0010 (6)0.0028 (6)0.0046 (6)
C140.0468 (8)0.0425 (7)0.0381 (7)0.0035 (5)0.0011 (6)0.0026 (5)
C130.0463 (7)0.0464 (8)0.0369 (7)−0.0059 (6)0.0000 (5)−0.0026 (6)
C120.0461 (7)0.0434 (7)0.0414 (7)−0.0061 (6)0.0034 (6)0.0025 (6)
C100.0549 (8)0.0448 (8)0.0376 (7)−0.0049 (6)−0.0038 (6)−0.0009 (6)
C40.0590 (9)0.0472 (8)0.0430 (8)0.0079 (6)0.0050 (6)0.0122 (6)
C30.0611 (9)0.0508 (8)0.0354 (7)0.0113 (7)−0.0042 (6)0.0050 (6)
C20.0519 (8)0.0439 (7)0.0390 (7)0.0023 (6)−0.0058 (6)−0.0016 (6)

Geometric parameters (Å, °)

N2—C71.3696 (16)C9—C101.3798 (19)
N2—C61.3754 (17)C9—H9A0.9300
N2—H2A0.910 (17)C1—C21.3972 (18)
C8—C131.3926 (19)C5—C41.374 (2)
C8—C91.3940 (19)C5—H5A0.9300
C8—C71.4661 (17)C13—C121.3756 (18)
N1—C71.3191 (16)C13—H13A0.9300
N1—C11.3846 (16)C12—H12A0.9300
N3—C141.1427 (17)C10—H10A0.9300
C11—C101.3861 (19)C4—C31.396 (2)
C11—C121.3877 (19)C4—H4A0.9300
C11—C141.4407 (18)C3—C21.378 (2)
C6—C51.3901 (18)C3—H3A0.9300
C6—C11.4025 (18)C2—H2B0.9300
C7—N2—C6107.00 (11)C4—C5—C6116.80 (13)
C7—N2—H2A125.0 (10)C4—C5—H5A121.6
C6—N2—H2A127.8 (10)C6—C5—H5A121.6
C13—C8—C9118.70 (12)N3—C14—C11177.40 (16)
C13—C8—C7118.53 (12)C12—C13—C8120.77 (13)
C9—C8—C7122.77 (12)C12—C13—H13A119.6
C7—N1—C1105.01 (11)C8—C13—H13A119.6
N1—C7—N2112.72 (11)C13—C12—C11119.89 (13)
N1—C7—C8123.42 (12)C13—C12—H12A120.1
N2—C7—C8123.84 (11)C11—C12—H12A120.1
C10—C11—C12120.16 (12)C11—C10—C9119.67 (13)
C10—C11—C14121.25 (12)C11—C10—H10A120.2
C12—C11—C14118.59 (12)C9—C10—H10A120.2
N2—C6—C5132.50 (12)C5—C4—C3121.81 (13)
N2—C6—C1105.27 (11)C5—C4—H4A119.1
C5—C6—C1122.23 (12)C3—C4—H4A119.1
C10—C9—C8120.80 (13)C2—C3—C4121.54 (14)
C10—C9—H9A119.6C2—C3—H3A119.2
C8—C9—H9A119.6C4—C3—H3A119.2
N1—C1—C2130.07 (12)C3—C2—C1117.69 (13)
N1—C1—C6110.01 (11)C3—C2—H2B121.2
C2—C1—C6119.91 (12)C1—C2—H2B121.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13A···N10.932.542.861 (2)101
N2—H2A···N3i0.910 (17)2.14 (2)3.033 (2)169.1 (15)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2211).

References

  • Gallagher, J. F., Hanlon, K. & Howarth, J. (2001). Acta Cryst. C57, 1410–1414. [PubMed]
  • Howarth, J. & Hanlon, K. (2001). Tetrahedron Lett.42, 271–274.
  • Íkizler, A. A. & Sancak, K. (1992). Monatsh. Chem.123, 257–263.
  • Kazak, C., Yilmaz, V. T., Goker, H. & Kus, C. (2006). Cryst. Res. Technol.5, 528–532.
  • Li, P., Scowen, I. J., Davies, J. E. & Halcrow, M. A. (1998). J. Chem. Soc. Dalton Trans. pp. 3791–3799.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography