supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

gk2361 scheme

Acta Cryst. (2011). E67, o1091    [ doi:10.1107/S1600536811012578 ]

1,3-Bis(prop-2-ynyl)-1H-1,3-benzimidazol-2(3H)-one

Y. Ouzidan, Y. Kandri Rodi, J. P. Jasinski, R. J. Butcher, J. A. Golen and L. El Ammari

Abstract top

In the title compound, C13H10N2O, the fused-ring system is essentially planar, the largest deviation from the mean plane being 0.015 (1) Å. The two propynyl groups are nearly perpendicular to the benzimidazole plane, making dihedral angles of 85 (3) and 80 (2) °, and point in opposite directions. There are two short intermolecular C-H...O contacts to the carbonyl O atom, one involving the acetylenic H atom and the other a H atom of the methylene group.

Comment top

Benzimidazoles are very useful intermediates/subunits for the development of molecules of pharmaceutical or biological interest. Benzimidazole and its derivatives are an important class of bioactive molecules in the field of drugs and pharmaceuticals.

Benzimidazole derivatives have found applications in diverse therapeutic areas including anti-ulcers, anti-hypertensives, anti-virals, anti-fungals, anti-cancers (Gravatt et al., 1994; Horton et al., 2003; Kim et al., 1996; Roth et al., 1997).

As a continuation of our research works devoted to the development benzimidazol-2-one derivatives (Ouzidan et al., 2011a,b), we report in this paper the synthesis of a new benzimidazol-2-one derivative prepared by action of propargyl bromide on 1H-benzimidazol-2(3H)-one in the presence of a catalytic quantity of tetra-n-butylammonium bromide under mild conditions to furnish the title compound (Scheme 1).

In the title compound (Fig. 1), the benzimidazole ring system is essentially planar with a maximum deviation of 0.015 (1) Å for C1 atom. The two propynyl chains are almost perpendicular to the benzimidazole mean plane but oriented one above and one below the plane. The molecular conformation is also characterized by the following torsion angles: C1-N1-C8-C9 = 93.5 (2) ° and C1-N2-C11-C12 = 105.9 (2) °. In the crystal structure, molecules are linked by weak intermolecular C—H···O no classic hydrogen bonds as shown in Fig. 2 and Table 2.

Related literature top

For applications of benzimidazole compounds, see: Gravatt et al. (1994); Horton et al. (2003); Kim et al. (1996); Roth et al. (1997); Ouzidan et al. (2011a,b).

Experimental top

To a mixture of 1H-benzimidazol-2(3H)-one (0.2 g, 1.5 mmol), potassium carbonate (0.45 g, 3.2 mmol), tetra-n-butylammonium bromide (0.1 g, 0.2 mmol) in DMF (15 ml) was added propargyl bromide (0.28 ml, 3.2 mmol). Stirring was continued at room temperature for 6 h. The salt was removed by filtration and the filtrate concentrated under reduced pressure. The product was purified by recrystallization from dichloromethane to give colourless crystals (m.p. 425 K).

Refinement top

H atoms were located in a difference map and treated as riding with C—H = 0.95 Å or 0.99 Å with Uiso(H) = 1.2 Ueq (C).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
[Figure 2] Fig. 2. Partial packing view showing the C—H···O interactions (dashed lines).
1,3-Bis(prop-2-ynyl)-1H-1,3-benzimidazol-2(3H)-one top
Crystal data top
C13H10N2OF(000) = 440
Mr = 210.23Dx = 1.262 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3141 reflections
a = 7.7398 (4) Åθ = 3.4–32.2°
b = 17.1869 (9) ŵ = 0.08 mm−1
c = 8.4856 (5) ÅT = 170 K
β = 101.459 (6)°Block, colorless
V = 1106.28 (10) Å30.42 × 0.41 × 0.20 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur E Gemini
diffractometer		2631 independent reflections
Radiation source: Enhance (Mo) X-ray Source2244 reflections with I > 2σ(I)
graphiteRint = 0.014
Detector resolution: 16.1500 pixels mm-1θmax = 27.9°, θmin = 3.4°
ω scansh = −10→10
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −20→22
Tmin = 0.966, Tmax = 0.984l = −11→4
5295 measured reflections
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)] = 0.040H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0447P)2 + 0.2172P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2631 reflectionsΔρmax = 0.19 e Å−3
146 parametersΔρmin = −0.16 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.042 (4)
Crystal data top
C13H10N2OV = 1106.28 (10) Å3
Mr = 210.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7398 (4) ŵ = 0.08 mm−1
b = 17.1869 (9) ÅT = 170 K
c = 8.4856 (5) Å0.42 × 0.41 × 0.20 mm
β = 101.459 (6)°
Data collection top
Oxford Diffraction Xcalibur E Gemini
diffractometer		2631 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		2244 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.984Rint = 0.014
5295 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.19 e Å−3
S = 1.05Δρmin = −0.16 e Å−3
2631 reflectionsAbsolute structure: ?
146 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O10.19931 (12)0.56190 (5)0.15005 (11)0.0468 (2)
N10.13961 (12)0.46462 (5)0.32281 (11)0.0338 (2)
N20.29126 (12)0.56670 (5)0.42832 (12)0.0356 (2)
C10.20862 (14)0.53446 (6)0.28398 (14)0.0346 (3)
C20.18290 (13)0.45232 (6)0.48810 (13)0.0319 (2)
C30.14722 (15)0.39128 (7)0.58201 (15)0.0400 (3)
H3A0.08260.34700.53620.048*
C40.21003 (18)0.39733 (9)0.74692 (16)0.0493 (3)
H4A0.18710.35650.81530.059*
C50.30518 (18)0.46160 (9)0.81362 (16)0.0524 (4)
H5A0.34630.46380.92670.063*
C60.34172 (16)0.52287 (8)0.71876 (15)0.0447 (3)
H6A0.40730.56690.76460.054*
C70.27878 (14)0.51721 (6)0.55512 (14)0.0337 (3)
C80.06303 (16)0.40760 (7)0.20295 (15)0.0398 (3)
H8A0.01590.43430.10000.048*
H8B−0.03620.38100.23830.048*
C90.19408 (17)0.34996 (7)0.17828 (16)0.0438 (3)
C100.3035 (2)0.30587 (10)0.1615 (2)0.0748 (5)
H100.39270.26990.14790.090*
C110.39412 (16)0.63759 (7)0.43751 (18)0.0443 (3)
H11A0.42080.64840.33020.053*
H11B0.50760.62930.51310.053*
C120.30770 (17)0.70582 (7)0.48968 (16)0.0454 (3)
C130.2472 (2)0.76260 (9)0.5312 (2)0.0678 (5)
H130.19800.80880.56490.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0561 (5)0.0414 (5)0.0426 (5)0.0004 (4)0.0090 (4)0.0060 (4)
N10.0375 (5)0.0275 (4)0.0351 (5)0.0017 (4)0.0043 (4)−0.0037 (4)
N20.0349 (5)0.0290 (5)0.0430 (5)−0.0006 (4)0.0080 (4)−0.0051 (4)
C10.0339 (5)0.0297 (5)0.0405 (6)0.0054 (4)0.0079 (5)−0.0013 (4)
C20.0276 (5)0.0317 (5)0.0363 (6)0.0059 (4)0.0060 (4)−0.0026 (4)
C30.0359 (6)0.0374 (6)0.0481 (7)0.0031 (5)0.0118 (5)0.0028 (5)
C40.0470 (7)0.0577 (8)0.0457 (7)0.0070 (6)0.0150 (6)0.0114 (6)
C50.0489 (7)0.0727 (9)0.0351 (6)0.0086 (7)0.0068 (5)0.0004 (6)
C60.0367 (6)0.0538 (7)0.0419 (7)0.0025 (5)0.0034 (5)−0.0114 (6)
C70.0278 (5)0.0348 (5)0.0390 (6)0.0055 (4)0.0077 (4)−0.0044 (4)
C80.0396 (6)0.0349 (6)0.0413 (6)−0.0008 (5)−0.0003 (5)−0.0066 (5)
C90.0525 (7)0.0328 (6)0.0440 (7)−0.0025 (5)0.0043 (6)−0.0082 (5)
C100.0733 (11)0.0515 (9)0.0976 (14)0.0171 (8)0.0124 (10)−0.0250 (9)
C110.0358 (6)0.0355 (6)0.0628 (8)−0.0057 (5)0.0128 (6)−0.0079 (6)
C120.0447 (7)0.0340 (6)0.0536 (8)−0.0026 (5)0.0002 (6)−0.0054 (5)
C130.0771 (11)0.0436 (8)0.0749 (11)0.0136 (7)−0.0038 (9)−0.0170 (7)
Geometric parameters (Å, °) top
O1—C11.2194 (14)C5—H5A0.9500
N1—C11.3800 (14)C6—C71.3806 (17)
N1—C21.3919 (14)C6—H6A0.9500
N1—C81.4515 (14)C8—C91.4622 (17)
N2—C11.3802 (15)C8—H8A0.9900
N2—C71.3899 (15)C8—H8B0.9900
N2—C111.4491 (14)C9—C101.166 (2)
C2—C31.3782 (16)C10—H100.9500
C2—C71.3965 (15)C11—C121.4615 (17)
C3—C41.3911 (19)C11—H11A0.9900
C3—H3A0.9500C11—H11B0.9900
C4—C51.385 (2)C12—C131.1665 (19)
C4—H4A0.9500C13—H130.9500
C5—C61.388 (2)
C1—N1—C2110.22 (9)C7—C6—H6A121.4
C1—N1—C8122.92 (10)C5—C6—H6A121.4
C2—N1—C8125.91 (9)C6—C7—N2132.11 (11)
C1—N2—C7110.49 (9)C6—C7—C2121.24 (11)
C1—N2—C11122.56 (10)N2—C7—C2106.65 (10)
C7—N2—C11126.50 (10)N1—C8—C9111.07 (10)
O1—C1—N1127.23 (11)N1—C8—H8A109.4
O1—C1—N2127.08 (11)C9—C8—H8A109.4
N1—C1—N2105.69 (10)N1—C8—H8B109.4
C3—C2—N1131.49 (11)C9—C8—H8B109.4
C3—C2—C7121.59 (11)H8A—C8—H8B108.0
N1—C2—C7106.92 (9)C10—C9—C8177.43 (15)
C2—C3—C4117.04 (12)C9—C10—H10180.0
C2—C3—H3A121.5N2—C11—C12114.29 (10)
C4—C3—H3A121.5N2—C11—H11A108.7
C5—C4—C3121.47 (12)C12—C11—H11A108.7
C5—C4—H4A119.3N2—C11—H11B108.7
C3—C4—H4A119.3C12—C11—H11B108.7
C4—C5—C6121.41 (13)H11A—C11—H11B107.6
C4—C5—H5A119.3C13—C12—C11176.21 (15)
C6—C5—H5A119.3C12—C13—H13180.0
C7—C6—C5117.25 (12)
C2—N1—C1—O1177.95 (11)C4—C5—C6—C70.21 (19)
C8—N1—C1—O18.50 (18)C5—C6—C7—N2−179.89 (11)
C2—N1—C1—N2−1.76 (11)C5—C6—C7—C2−0.23 (17)
C8—N1—C1—N2−171.22 (9)C1—N2—C7—C6178.83 (11)
C7—N2—C1—O1−178.10 (11)C11—N2—C7—C66.44 (19)
C11—N2—C1—O1−5.36 (18)C1—N2—C7—C2−0.87 (12)
C7—N2—C1—N11.61 (12)C11—N2—C7—C2−173.26 (10)
C11—N2—C1—N1174.35 (9)C3—C2—C7—C6−0.08 (16)
C1—N1—C2—C3−178.62 (11)N1—C2—C7—C6−179.97 (10)
C8—N1—C2—C3−9.55 (18)C3—C2—C7—N2179.66 (10)
C1—N1—C2—C71.26 (11)N1—C2—C7—N2−0.23 (11)
C8—N1—C2—C7170.33 (10)C1—N1—C8—C993.46 (13)
N1—C2—C3—C4−179.74 (11)C2—N1—C8—C9−74.31 (14)
C7—C2—C3—C40.40 (16)C1—N2—C11—C12105.88 (13)
C2—C3—C4—C5−0.42 (18)C7—N2—C11—C12−82.58 (15)
C3—C4—C5—C60.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.992.423.3096 (15)149
C13—H13···O1ii0.952.343.2252 (17)156
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.992.423.3096 (15)149
C13—H13···O1ii0.952.343.2252 (17)156
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.
Acknowledgements top

JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

references
References top

Gravatt, G. L., Baguley, B. C., Wilson, W. R. & Denny, W. A. (1994). J. Med. Chem. 37, 4338–4345.

Horton, D. A., Bourne, G. T. & Smythe, M. L. (2003). Chem. Rev. 103, 893–930.

Kim, J. S., Gatto, B., Yu, C., Liu, A., Liu, L. F. & La Voie, E. J. (1996). J. Med. Chem. 39, 992–998.

Ouzidan, Y., Kandri Rodi, Y., Fronczek, F. R., Venkatraman, R., El Ammari, L. & Essassi, E. M. (2011a). Acta Cryst. E67, o283.

Ouzidan, Y., Kandri Rodi, Y., Fronczek, F. R., Venkatraman, R., Essassi, E. M. & El Ammari, L. (2011b). Acta Cryst. E67, o362–o363.

Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.

Roth, T., Morningstar, M. L., Boyer, P. L., Hughes, S. H., Buckheit, R. W. & Michejda, C. J. (1997). J. Med. Chem. 40, 4199–4207.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.