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

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

doi:10.1107/S1600536811012578

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1091

doi:10.1107/S1600536811012578

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

Younes Ouzidan,^a Youssef Kandri Rodi,^a ^* Jerry P. Jasinski,^b Raymond J. Butcher,^c James A. Golen ^b and Lahcen El Ammari ^d

^aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202 Fès, Morocco, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^dLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: kandri_rodi@yahoo.fr

(Received 28 March 2011; accepted 4 April 2011; online 13 April 2011)

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.

Related literature

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

Crystal data

C₁₃H₁₀N₂O
M_r = 210.23
Monoclinic, P 2₁ /c
a = 7.7398 (4) Å
b = 17.1869 (9) Å
c = 8.4856 (5) Å
β = 101.459 (6)°
V = 1106.28 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 170 K
0.42 × 0.41 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur E Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.966, T_max = 0.984
5295 measured reflections
2631 independent reflections
2244 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.104
S = 1.05
2631 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.99	2.42	3.3096 (15)	149
C13—H13⋯O1ⁱⁱ	0.95	2.34	3.2252 (17)	156
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012578/gk2361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012578/gk2361Isup2.hkl

checkCIF report

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).

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

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
	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

C₁₃H₁₀N₂O	F(000) = 440
M_r = 210.23	D_x = 1.262 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3141 reflections
a = 7.7398 (4) Å	θ = 3.4–32.2°
b = 17.1869 (9) Å	µ = 0.08 mm⁻¹
c = 8.4856 (5) Å	T = 170 K
β = 101.459 (6)°	Block, colorless
V = 1106.28 (10) Å³	0.42 × 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 Source	2244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Detector resolution: 16.1500 pixels mm^-1	θ_max = 27.9°, θ_min = 3.4°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −20→22
T_min = 0.966, T_max = 0.984	l = −11→4
5295 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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0447P)² + 0.2172P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2631 reflections	Δρ_max = 0.19 e Å⁻³
146 parameters	Δρ_min = −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: 0.042 (4)

Crystal data top

C₁₃H₁₀N₂O	V = 1106.28 (10) Å³
M_r = 210.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7398 (4) Å	µ = 0.08 mm⁻¹
b = 17.1869 (9) Å	T = 170 K
c = 8.4856 (5) Å	0.42 × 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)
T_min = 0.966, T_max = 0.984	R_int = 0.014
5295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
2631 reflections	Δρ_min = −0.16 e Å⁻³
146 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
O1	0.19931 (12)	0.56190 (5)	0.15005 (11)	0.0468 (2)
N1	0.13961 (12)	0.46462 (5)	0.32281 (11)	0.0338 (2)
N2	0.29126 (12)	0.56670 (5)	0.42832 (12)	0.0356 (2)
C1	0.20862 (14)	0.53446 (6)	0.28398 (14)	0.0346 (3)
C2	0.18290 (13)	0.45232 (6)	0.48810 (13)	0.0319 (2)
C3	0.14722 (15)	0.39128 (7)	0.58201 (15)	0.0400 (3)
H3A	0.0826	0.3470	0.5362	0.048*
C4	0.21003 (18)	0.39733 (9)	0.74692 (16)	0.0493 (3)
H4A	0.1871	0.3565	0.8153	0.059*
C5	0.30518 (18)	0.46160 (9)	0.81362 (16)	0.0524 (4)
H5A	0.3463	0.4638	0.9267	0.063*
C6	0.34172 (16)	0.52287 (8)	0.71876 (15)	0.0447 (3)
H6A	0.4073	0.5669	0.7646	0.054*
C7	0.27878 (14)	0.51721 (6)	0.55512 (14)	0.0337 (3)
C8	0.06303 (16)	0.40760 (7)	0.20295 (15)	0.0398 (3)
H8A	0.0159	0.4343	0.1000	0.048*
H8B	−0.0362	0.3810	0.2383	0.048*
C9	0.19408 (17)	0.34996 (7)	0.17828 (16)	0.0438 (3)
C10	0.3035 (2)	0.30587 (10)	0.1615 (2)	0.0748 (5)
H10	0.3927	0.2699	0.1479	0.090*
C11	0.39412 (16)	0.63759 (7)	0.43751 (18)	0.0443 (3)
H11A	0.4208	0.6484	0.3302	0.053*
H11B	0.5076	0.6293	0.5131	0.053*
C12	0.30770 (17)	0.70582 (7)	0.48968 (16)	0.0454 (3)
C13	0.2472 (2)	0.76260 (9)	0.5312 (2)	0.0678 (5)
H13	0.1980	0.8088	0.5649	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0561 (5)	0.0414 (5)	0.0426 (5)	0.0004 (4)	0.0090 (4)	0.0060 (4)
N1	0.0375 (5)	0.0275 (4)	0.0351 (5)	0.0017 (4)	0.0043 (4)	−0.0037 (4)
N2	0.0349 (5)	0.0290 (5)	0.0430 (5)	−0.0006 (4)	0.0080 (4)	−0.0051 (4)
C1	0.0339 (5)	0.0297 (5)	0.0405 (6)	0.0054 (4)	0.0079 (5)	−0.0013 (4)
C2	0.0276 (5)	0.0317 (5)	0.0363 (6)	0.0059 (4)	0.0060 (4)	−0.0026 (4)
C3	0.0359 (6)	0.0374 (6)	0.0481 (7)	0.0031 (5)	0.0118 (5)	0.0028 (5)
C4	0.0470 (7)	0.0577 (8)	0.0457 (7)	0.0070 (6)	0.0150 (6)	0.0114 (6)
C5	0.0489 (7)	0.0727 (9)	0.0351 (6)	0.0086 (7)	0.0068 (5)	0.0004 (6)
C6	0.0367 (6)	0.0538 (7)	0.0419 (7)	0.0025 (5)	0.0034 (5)	−0.0114 (6)
C7	0.0278 (5)	0.0348 (5)	0.0390 (6)	0.0055 (4)	0.0077 (4)	−0.0044 (4)
C8	0.0396 (6)	0.0349 (6)	0.0413 (6)	−0.0008 (5)	−0.0003 (5)	−0.0066 (5)
C9	0.0525 (7)	0.0328 (6)	0.0440 (7)	−0.0025 (5)	0.0043 (6)	−0.0082 (5)
C10	0.0733 (11)	0.0515 (9)	0.0976 (14)	0.0171 (8)	0.0124 (10)	−0.0250 (9)
C11	0.0358 (6)	0.0355 (6)	0.0628 (8)	−0.0057 (5)	0.0128 (6)	−0.0079 (6)
C12	0.0447 (7)	0.0340 (6)	0.0536 (8)	−0.0026 (5)	0.0002 (6)	−0.0054 (5)
C13	0.0771 (11)	0.0436 (8)	0.0749 (11)	0.0136 (7)	−0.0038 (9)	−0.0170 (7)

Geometric parameters (Å, º) top

O1—C1	1.2194 (14)	C5—H5A	0.9500
N1—C1	1.3800 (14)	C6—C7	1.3806 (17)
N1—C2	1.3919 (14)	C6—H6A	0.9500
N1—C8	1.4515 (14)	C8—C9	1.4622 (17)
N2—C1	1.3802 (15)	C8—H8A	0.9900
N2—C7	1.3899 (15)	C8—H8B	0.9900
N2—C11	1.4491 (14)	C9—C10	1.166 (2)
C2—C3	1.3782 (16)	C10—H10	0.9500
C2—C7	1.3965 (15)	C11—C12	1.4615 (17)
C3—C4	1.3911 (19)	C11—H11A	0.9900
C3—H3A	0.9500	C11—H11B	0.9900
C4—C5	1.385 (2)	C12—C13	1.1665 (19)
C4—H4A	0.9500	C13—H13	0.9500
C5—C6	1.388 (2)

C1—N1—C2	110.22 (9)	C7—C6—H6A	121.4
C1—N1—C8	122.92 (10)	C5—C6—H6A	121.4
C2—N1—C8	125.91 (9)	C6—C7—N2	132.11 (11)
C1—N2—C7	110.49 (9)	C6—C7—C2	121.24 (11)
C1—N2—C11	122.56 (10)	N2—C7—C2	106.65 (10)
C7—N2—C11	126.50 (10)	N1—C8—C9	111.07 (10)
O1—C1—N1	127.23 (11)	N1—C8—H8A	109.4
O1—C1—N2	127.08 (11)	C9—C8—H8A	109.4
N1—C1—N2	105.69 (10)	N1—C8—H8B	109.4
C3—C2—N1	131.49 (11)	C9—C8—H8B	109.4
C3—C2—C7	121.59 (11)	H8A—C8—H8B	108.0
N1—C2—C7	106.92 (9)	C10—C9—C8	177.43 (15)
C2—C3—C4	117.04 (12)	C9—C10—H10	180.0
C2—C3—H3A	121.5	N2—C11—C12	114.29 (10)
C4—C3—H3A	121.5	N2—C11—H11A	108.7
C5—C4—C3	121.47 (12)	C12—C11—H11A	108.7
C5—C4—H4A	119.3	N2—C11—H11B	108.7
C3—C4—H4A	119.3	C12—C11—H11B	108.7
C4—C5—C6	121.41 (13)	H11A—C11—H11B	107.6
C4—C5—H5A	119.3	C13—C12—C11	176.21 (15)
C6—C5—H5A	119.3	C12—C13—H13	180.0
C7—C6—C5	117.25 (12)

C2—N1—C1—O1	177.95 (11)	C4—C5—C6—C7	0.21 (19)
C8—N1—C1—O1	8.50 (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—C6	178.83 (11)
C7—N2—C1—O1	−178.10 (11)	C11—N2—C7—C6	6.44 (19)
C11—N2—C1—O1	−5.36 (18)	C1—N2—C7—C2	−0.87 (12)
C7—N2—C1—N1	1.61 (12)	C11—N2—C7—C2	−173.26 (10)
C11—N2—C1—N1	174.35 (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—N2	179.66 (10)
C1—N1—C2—C7	1.26 (11)	N1—C2—C7—N2	−0.23 (11)
C8—N1—C2—C7	170.33 (10)	C1—N1—C8—C9	93.46 (13)
N1—C2—C3—C4	−179.74 (11)	C2—N1—C8—C9	−74.31 (14)
C7—C2—C3—C4	0.40 (16)	C1—N2—C11—C12	105.88 (13)
C2—C3—C4—C5	−0.42 (18)	C7—N2—C11—C12	−82.58 (15)
C3—C4—C5—C6	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.99	2.42	3.3096 (15)	149
C13—H13···O1ⁱⁱ	0.95	2.34	3.2252 (17)	156

Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀N₂O
M_r	210.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	7.7398 (4), 17.1869 (9), 8.4856 (5)
β (°)	101.459 (6)
V (Å³)	1106.28 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.41 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur E Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.966, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	5295, 2631, 2244
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.104, 1.05
No. of reflections	2631
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), 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
C8—H8A···O1ⁱ	0.99	2.42	3.3096 (15)	149
C13—H13···O1ⁱⁱ	0.95	2.34	3.2252 (17)	156

Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.

Acknowledgements

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

References

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