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

Dai, W.; Wang, W.-X.; Zhao, Y.-Y.; Zhao, H.

doi:10.1107/S1600536808012932

organic compounds

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Volume 64| Part 6| June 2008| Page o1017

doi:10.1107/S1600536808012932

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

Wei Dai,^a Wen-Xiang Wang,^a Yu-Yuan Zhao ^a and Hong Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 19 April 2008; accepted 1 May 2008; online 7 May 2008)

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 ); Howarth & Hanlon (2001 ); Kazak et al. (2006 ); Li et al. (1998 ); Íkizler & Sancak (1992 ).

Experimental

Crystal data

C₁₄H₉N₃
M_r = 219.24
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.118
S = 1.08
2581 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯N1	0.93	2.54	2.861 (2)	101
N2—H2A⋯N3ⁱ	0.910 (17)	2.14 (2)	3.033 (2)	169.1 (15)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

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

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

Crystal data top

C₁₄H₉N₃	F(000) = 456
M_r = 219.24	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2461 reflections
a = 7.2172 (10) Å	θ = 3.2–27.5°
b = 11.818 (2) Å	µ = 0.08 mm⁻¹
c = 12.719 (2) Å	T = 293 K
β = 92.057 (7)°	Prism, colourless
V = 1084.1 (3) Å³	0.35 × 0.15 × 0.10 mm
Z = 4

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2581 independent reflections
Radiation source: fine-focus sealed tube	2073 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.9°, θ_min = 2.4°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.911, T_max = 1.000	l = −16→16
11203 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.056P)² + 0.1336P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2581 reflections	Δρ_max = 0.16 e Å⁻³
159 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.115 (7)

Crystal data top

C₁₄H₉N₃	V = 1084.1 (3) Å³
M_r = 219.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2172 (10) Å	µ = 0.08 mm⁻¹
b = 11.818 (2) Å	T = 293 K
c = 12.719 (2) Å	0.35 × 0.15 × 0.10 mm
β = 92.057 (7)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2581 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2073 reflections with I > 2σ(I)
T_min = 0.911, T_max = 1.000	R_int = 0.037
11203 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.16 e Å⁻³
2581 reflections	Δρ_min = −0.17 e Å⁻³
159 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N2	0.23276 (15)	0.98417 (9)	−0.07818 (9)	0.0381 (3)
C8	0.14908 (17)	0.84634 (11)	0.06171 (10)	0.0367 (3)
N1	0.08189 (15)	0.82641 (9)	−0.12784 (8)	0.0404 (3)
C7	0.15245 (17)	0.88501 (10)	−0.04772 (10)	0.0360 (3)
N3	0.11261 (18)	0.68424 (11)	0.45407 (10)	0.0543 (3)
C11	0.13598 (18)	0.76582 (11)	0.26664 (10)	0.0389 (3)
C6	0.21340 (17)	0.98948 (10)	−0.18604 (10)	0.0363 (3)
C9	0.23427 (19)	0.90578 (12)	0.14485 (10)	0.0439 (3)
H9A	0.2963	0.9730	0.1315	0.053*
C1	0.11833 (17)	0.89042 (11)	−0.21590 (10)	0.0377 (3)
C5	0.2689 (2)	1.06900 (11)	−0.25904 (11)	0.0443 (3)
H5A	0.3300	1.1351	−0.2384	0.053*
C14	0.12508 (18)	0.72221 (12)	0.37201 (11)	0.0425 (3)
C13	0.05688 (19)	0.74595 (12)	0.08336 (11)	0.0432 (3)
H13A	−0.0015	0.7058	0.0287	0.052*
C12	0.05122 (19)	0.70550 (12)	0.18459 (11)	0.0436 (3)
H12A	−0.0093	0.6378	0.1980	0.052*
C10	0.2277 (2)	0.86617 (12)	0.24669 (11)	0.0459 (3)
H10A	0.2846	0.9066	0.3017	0.055*
C4	0.2292 (2)	1.04531 (13)	−0.36315 (11)	0.0496 (4)
H4A	0.2652	1.0964	−0.4142	0.060*
C3	0.1362 (2)	0.94670 (13)	−0.39450 (11)	0.0492 (4)
H3A	0.1134	0.9332	−0.4658	0.059*
C2	0.07759 (19)	0.86882 (12)	−0.32224 (10)	0.0451 (3)
H2B	0.0131	0.8041	−0.3435	0.054*
H2A	0.281 (2)	1.0377 (15)	−0.0336 (13)	0.058 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0439 (6)	0.0349 (6)	0.0354 (6)	0.0001 (4)	0.0010 (5)	−0.0012 (4)
C8	0.0358 (6)	0.0391 (7)	0.0352 (7)	0.0032 (5)	0.0033 (5)	0.0003 (5)
N1	0.0455 (6)	0.0407 (6)	0.0349 (6)	−0.0031 (5)	−0.0001 (4)	0.0003 (4)
C7	0.0377 (6)	0.0355 (6)	0.0350 (7)	0.0035 (5)	0.0025 (5)	0.0001 (5)
N3	0.0641 (8)	0.0563 (8)	0.0425 (7)	−0.0005 (6)	0.0002 (6)	0.0094 (6)
C11	0.0391 (7)	0.0420 (7)	0.0357 (7)	0.0050 (5)	0.0029 (5)	0.0042 (5)
C6	0.0382 (6)	0.0351 (7)	0.0357 (7)	0.0050 (5)	0.0020 (5)	0.0003 (5)
C9	0.0535 (8)	0.0389 (7)	0.0393 (8)	−0.0058 (6)	−0.0006 (6)	0.0025 (5)
C1	0.0394 (6)	0.0375 (7)	0.0360 (7)	0.0042 (5)	−0.0002 (5)	0.0023 (5)
C5	0.0502 (8)	0.0360 (7)	0.0468 (8)	0.0010 (6)	0.0028 (6)	0.0046 (6)
C14	0.0468 (8)	0.0425 (7)	0.0381 (7)	0.0035 (5)	0.0011 (6)	0.0026 (5)
C13	0.0463 (7)	0.0464 (8)	0.0369 (7)	−0.0059 (6)	0.0000 (5)	−0.0026 (6)
C12	0.0461 (7)	0.0434 (7)	0.0414 (7)	−0.0061 (6)	0.0034 (6)	0.0025 (6)
C10	0.0549 (8)	0.0448 (8)	0.0376 (7)	−0.0049 (6)	−0.0038 (6)	−0.0009 (6)
C4	0.0590 (9)	0.0472 (8)	0.0430 (8)	0.0079 (6)	0.0050 (6)	0.0122 (6)
C3	0.0611 (9)	0.0508 (8)	0.0354 (7)	0.0113 (7)	−0.0042 (6)	0.0050 (6)
C2	0.0519 (8)	0.0439 (7)	0.0390 (7)	0.0023 (6)	−0.0058 (6)	−0.0016 (6)

Geometric parameters (Å, º) top

N2—C7	1.3696 (16)	C9—C10	1.3798 (19)
N2—C6	1.3754 (17)	C9—H9A	0.9300
N2—H2A	0.910 (17)	C1—C2	1.3972 (18)
C8—C13	1.3926 (19)	C5—C4	1.374 (2)
C8—C9	1.3940 (19)	C5—H5A	0.9300
C8—C7	1.4661 (17)	C13—C12	1.3756 (18)
N1—C7	1.3191 (16)	C13—H13A	0.9300
N1—C1	1.3846 (16)	C12—H12A	0.9300
N3—C14	1.1427 (17)	C10—H10A	0.9300
C11—C10	1.3861 (19)	C4—C3	1.396 (2)
C11—C12	1.3877 (19)	C4—H4A	0.9300
C11—C14	1.4407 (18)	C3—C2	1.378 (2)
C6—C5	1.3901 (18)	C3—H3A	0.9300
C6—C1	1.4025 (18)	C2—H2B	0.9300

C7—N2—C6	107.00 (11)	C4—C5—C6	116.80 (13)
C7—N2—H2A	125.0 (10)	C4—C5—H5A	121.6
C6—N2—H2A	127.8 (10)	C6—C5—H5A	121.6
C13—C8—C9	118.70 (12)	N3—C14—C11	177.40 (16)
C13—C8—C7	118.53 (12)	C12—C13—C8	120.77 (13)
C9—C8—C7	122.77 (12)	C12—C13—H13A	119.6
C7—N1—C1	105.01 (11)	C8—C13—H13A	119.6
N1—C7—N2	112.72 (11)	C13—C12—C11	119.89 (13)
N1—C7—C8	123.42 (12)	C13—C12—H12A	120.1
N2—C7—C8	123.84 (11)	C11—C12—H12A	120.1
C10—C11—C12	120.16 (12)	C11—C10—C9	119.67 (13)
C10—C11—C14	121.25 (12)	C11—C10—H10A	120.2
C12—C11—C14	118.59 (12)	C9—C10—H10A	120.2
N2—C6—C5	132.50 (12)	C5—C4—C3	121.81 (13)
N2—C6—C1	105.27 (11)	C5—C4—H4A	119.1
C5—C6—C1	122.23 (12)	C3—C4—H4A	119.1
C10—C9—C8	120.80 (13)	C2—C3—C4	121.54 (14)
C10—C9—H9A	119.6	C2—C3—H3A	119.2
C8—C9—H9A	119.6	C4—C3—H3A	119.2
N1—C1—C2	130.07 (12)	C3—C2—C1	117.69 (13)
N1—C1—C6	110.01 (11)	C3—C2—H2B	121.2
C2—C1—C6	119.91 (12)	C1—C2—H2B	121.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···N1	0.93	2.54	2.861 (2)	101
N2—H2A···N3ⁱ	0.910 (17)	2.14 (2)	3.033 (2)	169.1 (15)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉N₃
M_r	219.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.2172 (10), 11.818 (2), 12.719 (2)
β (°)	92.057 (7)
V (Å³)	1084.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.15 × 0.10

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.911, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11203, 2581, 2073
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.08
No. of reflections	2581
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: CrystalClear (Rigaku, 2005), 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
C13—H13A···N1	0.93	2.54	2.861 (2)	100.7
N2—H2A···N3ⁱ	0.910 (17)	2.14 (2)	3.033 (2)	169.1 (15)

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

Acknowledgements

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

References

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