5-Nitro-1-n-octyl-1H-benzimidazol-2(3H)-one

Ouzidan, Y.; Kandri Rodi, Y.; Saffon, N.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536811003503

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o558

doi:10.1107/S1600536811003503

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5-Nitro-1-n-octyl-1H-benzimidazol-2(3H)-one

Younes Ouzidan,^a Y. Kandri Rodi,^a Natalie Saffon,^b El Mokhtar Essassi ^c and Seik Weng Ng ^d ^*

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fés, Morocco, ^bService Commun Rayons-X FR2599, Université Paul Sabatier Bâtiment 2R1, 118 route de Narbonne, Toulouse, France, ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 20 January 2011; accepted 26 January 2011; online 5 February 2011)

The benzimidazolone part of the molecule of the title compound, C₁₅H₂₁N₃O₃, is almost planar (r.m.s. deviation = 0.007 Å) with its mean plane aligned at a dihedral angle of 10.4 (3)° with respect to the mean plane of the nitro substituent. In the crystal, two molecules are disposed about a center of inversion, generating an N—H⋯O hydrogen-bonded cyclic dimer with R₂²(8) graph-set motif.

Related literature

For the crystal structure of 1-isopropenyl-1H-benzimidazol-2(3H)-one, see: Saber et al. (2010 ). For graph-set notation, see: Etter (1990 ).

Experimental

Crystal data

C₁₅H₂₁N₃O₃
M_r = 291.35
Triclinic, $[P \overline 1]$
a = 4.9997 (3) Å
b = 11.4942 (6) Å
c = 13.8739 (7) Å
α = 74.214 (3)°
β = 79.637 (4)°
γ = 84.108 (4)°
V = 753.50 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.22 × 0.12 × 0.06 mm

Data collection

Bruker APEXII diffractometer
10215 measured reflections
3084 independent reflections
1538 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.144
S = 0.95
3084 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 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
N2—H1⋯O1ⁱ	0.93 (3)	1.84 (3)	2.755 (3)	169 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003503/zs2090sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003503/zs2090Isup2.hkl

checkCIF report

Comment top

Tetraalkylammonium halides are used as phase-transfer catalyst in the synthesis of alkyl-substituted benzimidazolones. A previous study reported the 1-isopropenyl derivative; the amino –NH unit forms a hydrogen bond to the inversion-related molecule to generate a hydrogen-bonded dimer (Saber et al., 2010). The present compound (Scheme I) features a long n-octyl chain that adopts an extended zigzag conformation (Fig. 1). The benzimidazolone part of the C₁₅H₂₁N₃O₃ molecule is planar (r.m.s. deviation 0.007 Å) and its mean plane is aligned at 10.4 (3) ° with respect to the mean plane of the nitro substituent. Two molecules are disposed about a center of inversion to generate a hydrogen-bonded cyclic dimer, whose hydrogen-bonding motif is described by the R₂²(8) graph set (Etter, 1990).

Related literature top

For the crystal structure of 1-isopropenyl-1H-benzimidazol-2(3H)-one, see: Saber et al. (2010). For graph-set notation, see: Etter (1990).

Experimental top

To 5-nitro-1H-benzoimidazol-2(3H)-one (0.2 g, 1.1 mmol), potassium carbonate (0.30 g, 2.2 mmol) and tetra-n-butylammonium bromide (0.07 g, 0.2 mmol) in DMF (15 ml) was added 1-bromo-n-octane (0.38 ml, 2.2 mmol). Stirring was continued at room temperature for 6 h. The salt was removed by filtration and the filtrate concentrated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate/hexane (1/2) as eluent. The compound was recrystallized from diethyl ether to give colorless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of two molecules of C₁₅H₂₁N₃O₃ disposed about a center of inversion: drawn at the 50% probability level.

5-Nitro-1-n-octyl-1H-benzimidazol-2(3H)-one top

Crystal data top

C₁₅H₂₁N₃O₃	Z = 2
M_r = 291.35	F(000) = 312
Triclinic, P1	D_x = 1.284 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9997 (3) Å	Cell parameters from 926 reflections
b = 11.4942 (6) Å	θ = 2.1–26.5°
c = 13.8739 (7) Å	µ = 0.09 mm⁻¹
α = 74.214 (3)°	T = 295 K
β = 79.637 (4)°	Block, colorless
γ = 84.108 (4)°	0.22 × 0.12 × 0.06 mm
V = 753.50 (7) Å³

Data collection top

Bruker APEXII diffractometer	1538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.080
Graphite monochromator	θ_max = 26.5°, θ_min = 2.1°
ϕ and ω scans	h = −5→6
10215 measured reflections	k = −14→14
3084 independent reflections	l = −17→17

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0609P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max = 0.001
3084 reflections	Δρ_max = 0.21 e Å⁻³
195 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: 0.016 (4)

Crystal data top

C₁₅H₂₁N₃O₃	γ = 84.108 (4)°
M_r = 291.35	V = 753.50 (7) Å³
Triclinic, P1	Z = 2
a = 4.9997 (3) Å	Mo Kα radiation
b = 11.4942 (6) Å	µ = 0.09 mm⁻¹
c = 13.8739 (7) Å	T = 295 K
α = 74.214 (3)°	0.22 × 0.12 × 0.06 mm
β = 79.637 (4)°

Data collection top

Bruker APEXII diffractometer	1538 reflections with I > 2σ(I)
10215 measured reflections	R_int = 0.080
3084 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.21 e Å⁻³
3084 reflections	Δρ_min = −0.17 e Å⁻³
195 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.6268 (4)	0.47630 (17)	0.37325 (14)	0.0426 (5)
O2	−0.5372 (4)	0.15689 (19)	0.72705 (15)	0.0534 (6)
O3	−0.5678 (4)	0.02018 (19)	0.64945 (15)	0.0534 (6)
N1	0.3626 (4)	0.32787 (19)	0.35991 (16)	0.0325 (6)
N2	0.2757 (5)	0.3907 (2)	0.50001 (18)	0.0351 (6)
N3	−0.4666 (5)	0.1112 (2)	0.65519 (18)	0.0407 (6)
C1	0.1487 (5)	0.2628 (2)	0.42194 (19)	0.0299 (6)
C2	0.0021 (5)	0.1746 (2)	0.4085 (2)	0.0341 (7)
H2	0.0387	0.1491	0.3491	0.041*
C3	−0.2003 (5)	0.1257 (2)	0.48628 (19)	0.0336 (7)
H3	−0.3034	0.0660	0.4800	0.040*
C4	−0.2502 (5)	0.1658 (2)	0.57430 (19)	0.0324 (6)
C5	−0.1062 (5)	0.2549 (2)	0.58994 (19)	0.0339 (7)
H5	−0.1433	0.2802	0.6494	0.041*
C6	0.0937 (5)	0.3025 (2)	0.51182 (19)	0.0316 (7)
C7	0.4414 (6)	0.4067 (3)	0.4080 (2)	0.0364 (7)
C8	0.4867 (6)	0.3212 (3)	0.25805 (19)	0.0399 (7)
H8A	0.5128	0.2370	0.2563	0.048*
H8B	0.6644	0.3549	0.2417	0.048*
C9	0.3124 (6)	0.3898 (2)	0.17815 (19)	0.0381 (7)
H9A	0.4130	0.3908	0.1113	0.046*
H9B	0.1488	0.3469	0.1872	0.046*
C10	0.2313 (6)	0.5199 (2)	0.1835 (2)	0.0407 (7)
H10A	0.1183	0.5181	0.2484	0.049*
H10B	0.3947	0.5602	0.1806	0.049*
C11	0.0788 (6)	0.5937 (3)	0.0999 (2)	0.0429 (8)
H11A	−0.0721	0.5490	0.0964	0.051*
H11B	0.1997	0.6062	0.0354	0.051*
C12	−0.0298 (6)	0.7161 (3)	0.1179 (2)	0.0491 (8)
H12A	0.1215	0.7581	0.1248	0.059*
H12B	−0.1543	0.7024	0.1816	0.059*
C13	−0.1770 (6)	0.7985 (3)	0.0349 (2)	0.0507 (9)
H13A	−0.3121	0.7528	0.0213	0.061*
H13B	−0.2729	0.8647	0.0601	0.061*
C14	0.0045 (6)	0.8505 (3)	−0.0629 (2)	0.0509 (8)
H14A	0.0916	0.7847	−0.0908	0.061*
H14B	0.1463	0.8924	−0.0492	0.061*
C15	−0.1477 (7)	0.9384 (3)	−0.1419 (2)	0.0608 (10)
H15A	−0.0220	0.9683	−0.2027	0.091*
H15B	−0.2301	1.0050	−0.1156	0.091*
H15C	−0.2864	0.8972	−0.1568	0.091*
H1	0.296 (6)	0.428 (3)	0.549 (2)	0.059 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0398 (12)	0.0451 (12)	0.0468 (12)	−0.0145 (11)	−0.0018 (10)	−0.0170 (10)
O2	0.0546 (14)	0.0572 (14)	0.0491 (13)	−0.0085 (12)	0.0087 (11)	−0.0240 (11)
O3	0.0546 (14)	0.0502 (14)	0.0571 (14)	−0.0244 (12)	0.0059 (11)	−0.0184 (11)
N1	0.0301 (13)	0.0333 (13)	0.0366 (13)	−0.0044 (11)	−0.0056 (11)	−0.0123 (10)
N2	0.0323 (13)	0.0398 (14)	0.0369 (14)	−0.0067 (11)	−0.0038 (11)	−0.0153 (11)
N3	0.0350 (14)	0.0398 (15)	0.0446 (15)	−0.0036 (12)	−0.0038 (12)	−0.0074 (12)
C1	0.0253 (15)	0.0291 (15)	0.0350 (15)	−0.0002 (13)	−0.0035 (12)	−0.0089 (12)
C2	0.0343 (16)	0.0342 (16)	0.0353 (15)	0.0021 (13)	−0.0053 (13)	−0.0129 (12)
C3	0.0337 (16)	0.0302 (15)	0.0402 (16)	−0.0038 (13)	−0.0076 (13)	−0.0127 (13)
C4	0.0276 (15)	0.0311 (15)	0.0357 (15)	−0.0002 (13)	−0.0033 (12)	−0.0058 (12)
C5	0.0327 (16)	0.0371 (16)	0.0327 (15)	0.0001 (14)	−0.0044 (13)	−0.0119 (13)
C6	0.0306 (15)	0.0303 (15)	0.0371 (16)	0.0002 (13)	−0.0102 (13)	−0.0115 (12)
C7	0.0348 (17)	0.0355 (16)	0.0426 (17)	−0.0001 (14)	−0.0136 (14)	−0.0123 (14)
C8	0.0335 (16)	0.0457 (18)	0.0409 (17)	−0.0014 (14)	−0.0004 (13)	−0.0159 (14)
C9	0.0344 (16)	0.0467 (18)	0.0353 (16)	−0.0033 (14)	0.0021 (13)	−0.0186 (13)
C10	0.0399 (17)	0.0428 (17)	0.0394 (16)	−0.0041 (14)	−0.0029 (14)	−0.0121 (13)
C11	0.0412 (17)	0.0477 (18)	0.0393 (16)	−0.0004 (15)	−0.0021 (14)	−0.0142 (14)
C12	0.055 (2)	0.0479 (19)	0.0447 (18)	0.0084 (16)	−0.0101 (15)	−0.0150 (15)
C13	0.051 (2)	0.051 (2)	0.0470 (18)	0.0069 (16)	−0.0025 (16)	−0.0134 (15)
C14	0.0452 (19)	0.054 (2)	0.0514 (19)	−0.0034 (16)	−0.0071 (16)	−0.0098 (16)
C15	0.063 (2)	0.061 (2)	0.053 (2)	−0.0012 (19)	−0.0071 (18)	−0.0094 (17)

Geometric parameters (Å, º) top

O1—C7	1.230 (3)	C9—C10	1.526 (4)
O2—N3	1.231 (3)	C9—H9A	0.9700
O3—N3	1.235 (3)	C9—H9B	0.9700
N1—C7	1.385 (3)	C10—C11	1.515 (4)
N1—C1	1.388 (3)	C10—H10A	0.9700
N1—C8	1.457 (3)	C10—H10B	0.9700
N2—C7	1.368 (3)	C11—C12	1.524 (4)
N2—C6	1.389 (3)	C11—H11A	0.9700
N2—H1	0.93 (3)	C11—H11B	0.9700
N3—C4	1.464 (3)	C12—C13	1.527 (4)
C1—C2	1.380 (4)	C12—H12A	0.9700
C1—C6	1.414 (3)	C12—H12B	0.9700
C2—C3	1.378 (4)	C13—C14	1.500 (4)
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.392 (4)	C13—H13B	0.9700
C3—H3	0.9300	C14—C15	1.529 (4)
C4—C5	1.394 (4)	C14—H14A	0.9700
C5—C6	1.369 (4)	C14—H14B	0.9700
C5—H5	0.9300	C15—H15A	0.9600
C8—C9	1.530 (3)	C15—H15B	0.9600
C8—H8A	0.9700	C15—H15C	0.9600
C8—H8B	0.9700

C7—N1—C1	109.6 (2)	C10—C9—H9B	108.9
C7—N1—C8	123.1 (2)	C8—C9—H9B	108.9
C1—N1—C8	127.3 (2)	H9A—C9—H9B	107.8
C7—N2—C6	110.3 (2)	C11—C10—C9	114.5 (2)
C7—N2—H1	123.8 (19)	C11—C10—H10A	108.6
C6—N2—H1	125.6 (19)	C9—C10—H10A	108.6
O2—N3—O3	122.7 (2)	C11—C10—H10B	108.6
O2—N3—C4	118.5 (3)	C9—C10—H10B	108.6
O3—N3—C4	118.8 (2)	H10A—C10—H10B	107.6
C2—C1—N1	131.6 (2)	C10—C11—C12	111.7 (2)
C2—C1—C6	121.5 (2)	C10—C11—H11A	109.3
N1—C1—C6	106.8 (2)	C12—C11—H11A	109.3
C3—C2—C1	117.6 (3)	C10—C11—H11B	109.3
C3—C2—H2	121.2	C12—C11—H11B	109.3
C1—C2—H2	121.2	H11A—C11—H11B	107.9
C2—C3—C4	119.8 (3)	C11—C12—C13	115.1 (2)
C2—C3—H3	120.1	C11—C12—H12A	108.5
C4—C3—H3	120.1	C13—C12—H12A	108.5
C3—C4—C5	123.8 (3)	C11—C12—H12B	108.5
C3—C4—N3	118.1 (3)	C13—C12—H12B	108.5
C5—C4—N3	118.0 (2)	H12A—C12—H12B	107.5
C6—C5—C4	115.4 (2)	C14—C13—C12	114.8 (2)
C6—C5—H5	122.3	C14—C13—H13A	108.6
C4—C5—H5	122.3	C12—C13—H13A	108.6
C5—C6—N2	131.8 (3)	C14—C13—H13B	108.6
C5—C6—C1	121.7 (3)	C12—C13—H13B	108.6
N2—C6—C1	106.5 (2)	H13A—C13—H13B	107.6
O1—C7—N2	127.7 (3)	C13—C14—C15	113.2 (2)
O1—C7—N1	125.5 (3)	C13—C14—H14A	108.9
N2—C7—N1	106.8 (3)	C15—C14—H14A	108.9
N1—C8—C9	112.1 (2)	C13—C14—H14B	108.9
N1—C8—H8A	109.2	C15—C14—H14B	108.9
C9—C8—H8A	109.2	H14A—C14—H14B	107.8
N1—C8—H8B	109.2	C14—C15—H15A	109.5
C9—C8—H8B	109.2	C14—C15—H15B	109.5
H8A—C8—H8B	107.9	H15A—C15—H15B	109.5
C10—C9—C8	113.2 (2)	C14—C15—H15C	109.5
C10—C9—H9A	108.9	H15A—C15—H15C	109.5
C8—C9—H9A	108.9	H15B—C15—H15C	109.5

C7—N1—C1—C2	−179.8 (3)	C2—C1—C6—C5	0.4 (4)
C8—N1—C1—C2	2.2 (4)	N1—C1—C6—C5	−179.3 (2)
C7—N1—C1—C6	−0.2 (3)	C2—C1—C6—N2	−179.9 (2)
C8—N1—C1—C6	−178.2 (2)	N1—C1—C6—N2	0.5 (3)
N1—C1—C2—C3	179.3 (2)	C6—N2—C7—O1	−179.2 (3)
C6—C1—C2—C3	−0.3 (3)	C6—N2—C7—N1	0.4 (3)
C1—C2—C3—C4	0.0 (4)	C1—N1—C7—O1	179.5 (2)
C2—C3—C4—C5	0.1 (4)	C8—N1—C7—O1	−2.4 (4)
C2—C3—C4—N3	−179.8 (2)	C1—N1—C7—N2	−0.1 (3)
O2—N3—C4—C3	−170.3 (2)	C8—N1—C7—N2	177.9 (2)
O3—N3—C4—C3	10.9 (3)	C7—N1—C8—C9	−100.3 (3)
O2—N3—C4—C5	9.7 (3)	C1—N1—C8—C9	77.4 (3)
O3—N3—C4—C5	−169.1 (2)	N1—C8—C9—C10	52.0 (3)
C3—C4—C5—C6	0.0 (4)	C8—C9—C10—C11	175.1 (2)
N3—C4—C5—C6	179.9 (2)	C9—C10—C11—C12	172.1 (3)
C4—C5—C6—N2	−179.9 (2)	C10—C11—C12—C13	177.7 (3)
C4—C5—C6—C1	−0.2 (3)	C11—C12—C13—C14	−71.2 (4)
C7—N2—C6—C5	179.2 (3)	C12—C13—C14—C15	−176.5 (3)
C7—N2—C6—C1	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.93 (3)	1.84 (3)	2.755 (3)	169 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₂₁N₃O₃
M_r	291.35
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	4.9997 (3), 11.4942 (6), 13.8739 (7)
α, β, γ (°)	74.214 (3), 79.637 (4), 84.108 (4)
V (Å³)	753.50 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10215, 3084, 1538
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.144, 0.95
No. of reflections	3084
No. of parameters	195
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.93 (3)	1.84 (3)	2.755 (3)	169 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank Université Sidi Mohamed Ben Abdallah, Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

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