organic compounds
1-(Prop-2-ynyl)-1H-benzimidazol-2(3H)-one
aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'immouzzer, BP 2202 Fès, Morocco, bLaboratoire de Chimie Organique Hétérocyclique URAC21, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, cInstitute of Nanomaterials and Nanotechnology, MASCIR, Rabat, Morocco, and dLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: ouazzani_chahid@yahoo.fr
The benzimidazolone part of the title molecule, C10H8N2O, is almost planar [r.m.s. deviation = 0.014 (1) Å] and the NCH2C≡CH group forms a dihedral angle of 67.95 (6)° with its best plane. In the crystal, molecules form inversion dimers via pairs of N—H⋯O hydrogen bonds. C—H⋯O interactions connect the dimers, forming a two-dimensional polymeric network parallel to (100).
Related literature
For pharmacological and biochemical properties of benzimidazole dirivatives, see: Gravatt et al. (1994); Horton et al. (2003); Kim et al. (1996); Roth et al. (1997). For similar structures, see: Ouzidan, Kandri Rodi, Butcheret al. (2011); Ouzidan, Kandri Rodi, Fronczek et al. (2011); Ouzidan, Kandri Rodi, Jasinski et al. (2011); Belaziz et al. (2012).
Experimental
Crystal data
|
Data collection
|
Refinement
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S160053681205088X/gk2546sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681205088X/gk2546Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681205088X/gk2546Isup3.cml
To 1H-benzo[d]imidazol-2(3H)-one (0.2 g, 1.5 mmol), potassium carbonate (0.41 g, 3 mmol) and tetra-n-butylammonium bromide (0.05 g, 0.15 mmol) in DMF (15 ml) was added propargyl bromide (0.16 ml, 1.8 mmol). Stirring was continued at room temperature for 6 h. The salt was removed by filtration and the filtrate concentrated under reduced pressure. The residue was separated by
on a column of silica gel with ethyl acetate/petroleum ether (1/2) as Colourless crystals were isolated when the solvent was allowed to evaporate (m.p. 399 K).All H atoms could be located in a difference Fourier map. However, they were placed in calculated positions with N—H = 0.86 Å, C—H = 0.93 Å (aromatic), and C—H = 0.97 Å (methylene) and refined as riding on their parent atoms with Uiso(H) = 1.2 Ueq (C, N).
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 work devoted to the development of substituted benzimidazol-2-one derivatives (Ouzidan, Kandri Rodi, Butcher et al., 2011; Ouzidan, Kandri Rodi, Fronczek et al., 2011; Belaziz et al. 2012), we reported in this paper the synthesis of benzimidazol-2-one derivative by action of propargyl bromide with 1H-benzo[d]imidazol-2(3H)-one in the presence of a catalytic quantity of tetra-n-butylammonium bromide under mild conditions to furnish two compounds: di-substituted (Ouzidan, Kandri Rodi, Jasinski et al., 2011) and mono-substituted (Scheme 1).
The two fused five- and six-membered rings building the molecule of the title compound, C10H8N2O, are approximately planar, the largest deviation from the mean plane being 0.014 (2) Å at C1 (Fig.1). The C1–N2–C8–C9 torsion angle along the bond between the benzimidazolone and the prop-2-ynyl groups is -109.99 (12)°. In the crystal, the molecules form centrosymmetric cyclic dimers via a pair of N1–H1···O1 hydrogen-bonds (Fig.2 and Table2). In addition, intermolecular C10–H10···O1 interaction beteen the acetylenic H atom and the carbonyl O atom connects the dimers into (100) layers.
For pharmacological and biochemical properties of benzimidazole dirivatives, see: Gravatt et al. (1994); Horton et al. (2003); Kim et al. (1996); Roth et al. (1997). For similar structures, see: Ouzidan, Kandri Rodi, Butcher et al. (2011); Ouzidan, Kandri Rodi, Fronczek et al. (2011); Ouzidan, Kandri Rodi, Jasinski et al. (2011); Belaziz et al. (2012).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C10H8N2O | F(000) = 360 |
Mr = 172.18 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/c | Melting point: 399 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 4.5553 (6) Å | Cell parameters from 2080 reflections |
b = 18.001 (3) Å | θ = 3.0–27.9° |
c = 10.7488 (13) Å | µ = 0.09 mm−1 |
β = 93.645 (8)° | T = 296 K |
V = 879.6 (2) Å3 | Block, colourless |
Z = 4 | 0.41 × 0.32 × 0.15 mm |
Bruker X8 APEXII diffractometer | 1753 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 27.9°, θmin = 3.0° |
φ and ω scans | h = −5→5 |
10826 measured reflections | k = −23→23 |
2080 independent reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.1197P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2080 reflections | Δρmax = 0.16 e Å−3 |
119 parameters | Δρmin = −0.16 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: 0.018 (4) |
C10H8N2O | V = 879.6 (2) Å3 |
Mr = 172.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.5553 (6) Å | µ = 0.09 mm−1 |
b = 18.001 (3) Å | T = 296 K |
c = 10.7488 (13) Å | 0.41 × 0.32 × 0.15 mm |
β = 93.645 (8)° |
Bruker X8 APEXII diffractometer | 1753 reflections with I > 2σ(I) |
10826 measured reflections | Rint = 0.020 |
2080 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.16 e Å−3 |
2080 reflections | Δρmin = −0.16 e Å−3 |
119 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.43254 (19) | 0.40104 (4) | 0.43888 (7) | 0.0527 (2) | |
N1 | 0.25564 (19) | 0.46700 (5) | 0.60486 (8) | 0.0425 (2) | |
H1 | 0.3557 | 0.5125 | 0.5955 | 0.051* | |
N2 | 0.0986 (2) | 0.35310 (5) | 0.57304 (8) | 0.0436 (2) | |
C1 | 0.2795 (2) | 0.40708 (5) | 0.52935 (9) | 0.0412 (2) | |
C2 | 0.0662 (2) | 0.45135 (6) | 0.69742 (9) | 0.0412 (2) | |
C3 | −0.0238 (3) | 0.49315 (7) | 0.79538 (11) | 0.0523 (3) | |
H3 | 0.0420 | 0.5416 | 0.8087 | 0.063* | |
C4 | −0.2163 (3) | 0.46000 (9) | 0.87330 (12) | 0.0623 (4) | |
H4 | −0.2806 | 0.4868 | 0.9403 | 0.075* | |
C5 | −0.3150 (3) | 0.38814 (9) | 0.85397 (12) | 0.0625 (4) | |
H5 | −0.4446 | 0.3677 | 0.9080 | 0.075* | |
C6 | −0.2248 (3) | 0.34587 (7) | 0.75573 (11) | 0.0543 (3) | |
H6 | −0.2904 | 0.2974 | 0.7427 | 0.065* | |
C7 | −0.0329 (2) | 0.37902 (6) | 0.67788 (9) | 0.0421 (3) | |
C8 | 0.0605 (3) | 0.27990 (6) | 0.51808 (11) | 0.0539 (3) | |
H8A | 0.1497 | 0.2789 | 0.4385 | 0.065* | |
H8B | −0.1478 | 0.2697 | 0.5029 | 0.065* | |
C9 | 0.1941 (3) | 0.22211 (6) | 0.59936 (12) | 0.0553 (3) | |
C10 | 0.2989 (4) | 0.17785 (7) | 0.66881 (15) | 0.0737 (4) | |
H10 | 0.3795 | 0.1424 | 0.7281 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0709 (5) | 0.0453 (4) | 0.0429 (4) | −0.0091 (4) | 0.0121 (4) | −0.0023 (3) |
N1 | 0.0500 (5) | 0.0341 (4) | 0.0435 (5) | −0.0036 (3) | 0.0030 (4) | 0.0009 (3) |
N2 | 0.0516 (5) | 0.0355 (4) | 0.0434 (5) | −0.0065 (4) | 0.0002 (4) | 0.0010 (3) |
C1 | 0.0490 (6) | 0.0359 (5) | 0.0381 (5) | −0.0023 (4) | −0.0020 (4) | 0.0038 (4) |
C2 | 0.0389 (5) | 0.0424 (5) | 0.0415 (5) | 0.0029 (4) | −0.0029 (4) | 0.0030 (4) |
C3 | 0.0491 (6) | 0.0549 (7) | 0.0525 (6) | 0.0059 (5) | 0.0004 (5) | −0.0075 (5) |
C4 | 0.0502 (7) | 0.0862 (10) | 0.0506 (7) | 0.0099 (6) | 0.0061 (5) | −0.0070 (6) |
C5 | 0.0464 (6) | 0.0881 (10) | 0.0536 (7) | −0.0025 (6) | 0.0081 (5) | 0.0120 (6) |
C6 | 0.0478 (6) | 0.0594 (7) | 0.0555 (7) | −0.0086 (5) | 0.0009 (5) | 0.0114 (5) |
C7 | 0.0401 (5) | 0.0444 (6) | 0.0411 (5) | −0.0010 (4) | −0.0038 (4) | 0.0049 (4) |
C8 | 0.0690 (8) | 0.0412 (6) | 0.0505 (6) | −0.0135 (5) | −0.0032 (5) | −0.0032 (5) |
C9 | 0.0709 (8) | 0.0365 (6) | 0.0590 (7) | −0.0124 (5) | 0.0083 (6) | −0.0038 (5) |
C10 | 0.0977 (11) | 0.0425 (7) | 0.0799 (10) | −0.0040 (7) | −0.0020 (8) | 0.0087 (6) |
N1—C1 | 1.3583 (13) | C8—H8A | 0.9700 |
N1—C2 | 1.3869 (13) | C8—H8B | 0.9700 |
N1—H1 | 0.9458 | C9—C10 | 1.1725 (19) |
N2—C1 | 1.3760 (13) | C3—C4 | 1.3856 (18) |
N2—C7 | 1.3900 (14) | C3—H3 | 0.9300 |
N2—C8 | 1.4500 (13) | C6—C5 | 1.3848 (19) |
C2—C3 | 1.3775 (15) | C6—H6 | 0.9300 |
C2—C7 | 1.3894 (15) | C5—C4 | 1.381 (2) |
O1—C1 | 1.2367 (13) | C5—H5 | 0.9300 |
C7—C6 | 1.3835 (15) | C4—H4 | 0.9300 |
C8—C9 | 1.4657 (17) | C10—H10 | 0.9580 |
C1—N1—C2 | 110.15 (9) | N2—C8—H8B | 109.3 |
C1—N1—H1 | 124.5 | C9—C8—H8B | 109.3 |
C2—N1—H1 | 125.3 | H8A—C8—H8B | 108.0 |
C1—N2—C7 | 109.75 (9) | C10—C9—C8 | 177.04 (14) |
C1—N2—C8 | 124.15 (9) | C2—C3—C4 | 117.20 (12) |
C7—N2—C8 | 126.08 (9) | C2—C3—H3 | 121.4 |
C3—C2—N1 | 131.78 (10) | C4—C3—H3 | 121.4 |
C3—C2—C7 | 121.20 (10) | C7—C6—C5 | 116.98 (12) |
N1—C2—C7 | 107.02 (9) | C7—C6—H6 | 121.5 |
C6—C7—C2 | 121.62 (10) | C5—C6—H6 | 121.5 |
C6—C7—N2 | 131.84 (10) | C4—C5—C6 | 121.32 (12) |
C2—C7—N2 | 106.54 (9) | C4—C5—H5 | 119.3 |
O1—C1—N1 | 127.61 (9) | C6—C5—H5 | 119.3 |
O1—C1—N2 | 125.87 (9) | C5—C4—C3 | 121.67 (12) |
N1—C1—N2 | 106.52 (9) | C5—C4—H4 | 119.2 |
N2—C8—C9 | 111.58 (9) | C3—C4—H4 | 119.2 |
N2—C8—H8A | 109.3 | C9—C10—H10 | 177.7 |
C9—C8—H8A | 109.3 | ||
C1—N1—C2—C3 | 178.95 (11) | C8—N2—C1—O1 | −0.04 (17) |
C1—N1—C2—C7 | −0.44 (11) | C7—N2—C1—N1 | −1.39 (11) |
C3—C2—C7—C6 | −0.13 (16) | C8—N2—C1—N1 | −179.94 (9) |
N1—C2—C7—C6 | 179.33 (9) | C1—N2—C8—C9 | 109.99 (12) |
C3—C2—C7—N2 | −179.88 (9) | C7—N2—C8—C9 | −68.32 (15) |
N1—C2—C7—N2 | −0.42 (11) | N1—C2—C3—C4 | −179.25 (10) |
C1—N2—C7—C6 | −178.59 (11) | C7—C2—C3—C4 | 0.07 (16) |
C8—N2—C7—C6 | −0.07 (18) | C2—C7—C6—C5 | 0.22 (16) |
C1—N2—C7—C2 | 1.13 (11) | N2—C7—C6—C5 | 179.90 (11) |
C8—N2—C7—C2 | 179.65 (10) | C7—C6—C5—C4 | −0.25 (18) |
C2—N1—C1—O1 | −178.79 (10) | C6—C5—C4—C3 | 0.2 (2) |
C2—N1—C1—N2 | 1.12 (11) | C2—C3—C4—C5 | −0.10 (18) |
C7—N2—C1—O1 | 178.52 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.95 | 1.88 | 2.8226 (12) | 174 |
C10—H10···O1ii | 0.96 | 2.39 | 3.2541 (17) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H8N2O |
Mr | 172.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 4.5553 (6), 18.001 (3), 10.7488 (13) |
β (°) | 93.645 (8) |
V (Å3) | 879.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.41 × 0.32 × 0.15 |
Data collection | |
Diffractometer | Bruker X8 APEXII |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10826, 2080, 1753 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.101, 1.05 |
No. of reflections | 2080 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.16 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.95 | 1.88 | 2.8226 (12) | 174 |
C10—H10···O1ii | 0.96 | 2.39 | 3.2541 (17) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
References
Belaziz, D., Kandri Rodi, Y., Ouazzani Chahdi, F., Essassi, E. M., Saadi, M. & El Ammari, L. (2012). Acta Cryst. E68, o3212. CSD CrossRef IUCr Journals Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gravatt, G. L., Baguley, B. C., Wilson, W. R. & Denny, W. A. (1994). J. Med. Chem. 37, 4338–4345. CrossRef CAS PubMed Web of Science Google Scholar
Horton, D. A., Bourne, G. T. & Smythe, M. L. (2003). Chem. Rev. 103, 893–930. Web of Science CrossRef PubMed CAS Google Scholar
Kim, J. S., Gatto, B., Yu, C., Liu, A., Liu, L. F. & La Voie, E. J. (1996). J. Med. Chem. 39, 992–998. CrossRef CAS PubMed Web of Science Google Scholar
Ouzidan, Y., Kandri Rodi, Y., Butcher, R. J., Essassi, E. M. & El Ammari, L. (2011). Acta Cryst. E67, o283. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ouzidan, Y., Kandri Rodi, Y., Fronczek, F. R., Venkatraman, R., El Ammari, L. & Essassi, E. M. (2011). Acta Cryst. E67, o362–o363. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ouzidan, Y., Kandri Rodi, Y., Jasinski, J. P., Butcher, R. J., Golen, J. A. & El Ammari, L. (2011). Acta Cryst. E67, o1091. CSD CrossRef IUCr Journals Google Scholar
Roth, T., Morningstar, M. L., Boyer, P. L., Hughes, S. H., Buckheit, R. W. & Michejda, C. J. (1997). J. Med. Chem. 40, 4199–4207. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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 work devoted to the development of substituted benzimidazol-2-one derivatives (Ouzidan, Kandri Rodi, Butcher et al., 2011; Ouzidan, Kandri Rodi, Fronczek et al., 2011; Belaziz et al. 2012), we reported in this paper the synthesis of benzimidazol-2-one derivative by action of propargyl bromide with 1H-benzo[d]imidazol-2(3H)-one in the presence of a catalytic quantity of tetra-n-butylammonium bromide under mild conditions to furnish two compounds: di-substituted (Ouzidan, Kandri Rodi, Jasinski et al., 2011) and mono-substituted (Scheme 1).
The two fused five- and six-membered rings building the molecule of the title compound, C10H8N2O, are approximately planar, the largest deviation from the mean plane being 0.014 (2) Å at C1 (Fig.1). The C1–N2–C8–C9 torsion angle along the bond between the benzimidazolone and the prop-2-ynyl groups is -109.99 (12)°. In the crystal, the molecules form centrosymmetric cyclic dimers via a pair of N1–H1···O1 hydrogen-bonds (Fig.2 and Table2). In addition, intermolecular C10–H10···O1 interaction beteen the acetylenic H atom and the carbonyl O atom connects the dimers into (100) layers.