2-(3,4,5-Trimethoxy­phen­yl)-1H-benzimidazole

Khalaji, A.D.; Jian, F.; Xiao, H.; Harrison, W.T.A.

doi:10.1107/S1600536808014189

organic compounds

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Volume 64| Part 6| June 2008| Page o1093

doi:10.1107/S1600536808014189

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2-(3,4,5-Trimethoxyphenyl)-1H-benzimidazole

Aliakbar Dehno Khalaji,^a Fangfang Jian,^b Hailian Xiao ^b and William T. A. Harrison ^c ^*

^aDepartment of Science, Gorgan University of Agricultrual Sciences and Natural Resources, Gorgan 49189-43464, Iran, ^bNew Materials and Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China, and ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 29 April 2008; accepted 12 May 2008; online 17 May 2008)

In the title compound, C₁₆H₁₆N₂O₃, the dihedral angle between the mean planes of the aromatic ring systems is 30.90 (15)°. In the crystal structure, the molecules form [010] chains by way of N—H⋯N hydrogen bonds.

Related literature

For a related structure, see: Rashid et al. (2007 ). For background, see: Gupta et al. (2004 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₃
M_r = 284.31
Orthorhombic, P b c a
a = 8.2270 (16) Å
b = 9.5750 (19) Å
c = 37.375 (7) Å
V = 2944.2 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Enraf-Nonius CAD-4 diffractometer
Absorption correction: none
5421 measured reflections
2733 independent reflections
960 reflections with I > 2σ(I)
R_int = 0.085
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.143
S = 0.94
2733 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.07	2.918 (4)	169
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014189/bt2706sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014189/bt2706Isup2.hkl

checkCIF report

Comment top

The title compound, (I), (Fig. 1), complements substituted imidazoles with biological properties (Gupta et al., 2004). The dihedral angle between the N1/N2/C10—C16 and C4—C9 aromatic ring planes in (I) is 30.90 (15)°. This twisting may help to relieve steric strain between H1a and H5a (H1a···H5a = 2.32 Å) and a number of related 2-phenyl-1H-benzimidazoles show a similar dihedral angle between the adjacent ring planes (Rashid et al., 2007). Atoms C1, C2 and C3 in (I) are displaced from the mean plane of the C4—C9 ring by 1.010 (5) Å, 0.115 (5)Å and 0.257 (4) Å, respectively. Otherwise, the geometry of (I) may be regarded as normal (Allen et al., 1987).

In the crystal of (I), an N—H···N hydrogen bond (Table 1) links the molecules into chains propagating in [010] (Fig. 2). There are no aromatic π-π stacking interactions in (I) as the closest centroid-centroid separation of aromatic rings is greater than 5.11 Å, which contrasts with the situation in 2-(4-fluorophenyl)-1H-benzimidazole (Rashid et al., 2007) in which both N—H···N and π-π stacking help to establish the packing.

Related literature top

For a related structure, see: Rashid et al. (2007). For background, see: Gupta et al. (2004). For reference structural data, see: Allen et al. (1987).

Experimental top

1,2-Phenylenediamine (2 mmol, 216 mg) and 3,4,5-trimethoxybenzaldehyde (2 mmol, 392 mg) were dissolved in methanol (25 ml) at 323 K. The mixture was stirred for 30 min to give a colourless solution. After the solution had been allowed to stand in air for 3 d, colourless blocks of (I) formed, in about 74% yield, on slow evaporation of the solvent at room temperature.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. Fragment of a [010] hydrogen bonded chain of molecules in the crystal of (I). Symmetry code: (i) 3/2 - x, y - 1/2, z.

2-(3,4,5-Trimethoxyphenyl)-1H-benzimidazole top

Crystal data top

C₁₆H₁₆N₂O₃	F(000) = 1200
M_r = 284.31	D_x = 1.283 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.2270 (16) Å	θ = 4–14°
b = 9.5750 (19) Å	µ = 0.09 mm⁻¹
c = 37.375 (7) Å	T = 295 K
V = 2944.2 (10) Å³	Block, colourless
Z = 8	0.25 × 0.20 × 0.18 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.085
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 1.1°
Graphite monochromator	h = −9→0
ω scans	k = −11→0
5421 measured reflections	l = −44→44
2733 independent reflections	3 standard reflections every 100 reflections
960 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0483P)²] where P = (F_o² + 2F_c²)/3
2733 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₃	V = 2944.2 (10) Å³
M_r = 284.31	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.2270 (16) Å	µ = 0.09 mm⁻¹
b = 9.5750 (19) Å	T = 295 K
c = 37.375 (7) Å	0.25 × 0.20 × 0.18 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.085
5421 measured reflections	3 standard reflections every 100 reflections
2733 independent reflections	intensity decay: none
960 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.94	Δρ_max = 0.21 e Å⁻³
2733 reflections	Δρ_min = −0.20 e Å⁻³
190 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	1.2012 (3)	0.2286 (3)	0.03723 (7)	0.0646 (9)
O2	0.9428 (3)	0.3940 (3)	0.03507 (7)	0.0591 (9)
O3	1.2638 (3)	0.0641 (3)	0.09566 (8)	0.0609 (8)
N1	0.7160 (3)	0.0683 (3)	0.16552 (8)	0.0387 (8)
H1A	0.7705	−0.0074	0.1623	0.046*
N2	0.6374 (3)	0.2921 (3)	0.15868 (8)	0.0406 (8)
C1	1.3578 (5)	0.2888 (6)	0.04310 (12)	0.0800 (15)
H1B	1.4197	0.2852	0.0213	0.120*
H1C	1.4134	0.2375	0.0615	0.120*
H1D	1.3455	0.3843	0.0505	0.120*
C2	0.8079 (6)	0.4863 (5)	0.03285 (12)	0.0772 (15)
H2B	0.8153	0.5402	0.0112	0.116*
H2C	0.8083	0.5479	0.0531	0.116*
H2D	0.7089	0.4332	0.0327	0.116*
C3	1.3004 (5)	−0.0119 (5)	0.12749 (11)	0.0772 (15)
H3A	1.4032	−0.0581	0.1248	0.116*
H3B	1.2171	−0.0801	0.1317	0.116*
H3C	1.3055	0.0513	0.1474	0.116*
C4	1.1200 (5)	0.1366 (4)	0.09509 (12)	0.0446 (11)
C5	1.0041 (5)	0.1274 (4)	0.12166 (11)	0.0429 (10)
H5A	1.0203	0.0672	0.1409	0.052*
C6	0.8635 (4)	0.2074 (4)	0.11992 (10)	0.0368 (9)
C7	0.8382 (4)	0.2994 (4)	0.09110 (10)	0.0397 (10)
H7A	0.7448	0.3540	0.0901	0.048*
C8	0.9539 (5)	0.3074 (4)	0.06435 (11)	0.0422 (10)
C9	1.0951 (4)	0.2256 (4)	0.06576 (10)	0.0446 (11)
C10	0.7391 (5)	0.1932 (4)	0.14767 (9)	0.0374 (9)
C11	0.5910 (4)	0.0866 (4)	0.18929 (10)	0.0338 (9)
C12	0.5161 (5)	−0.0025 (4)	0.21332 (10)	0.0453 (11)
H12A	0.5493	−0.0948	0.2158	0.054*
C13	0.3906 (5)	0.0513 (4)	0.23340 (11)	0.0532 (11)
H13A	0.3387	−0.0055	0.2500	0.064*
C14	0.3390 (5)	0.1916 (5)	0.22919 (12)	0.0541 (11)
H14A	0.2522	0.2242	0.2428	0.065*
C15	0.4139 (4)	0.2808 (4)	0.20549 (10)	0.0508 (11)
H15A	0.3801	0.3730	0.2031	0.061*
C16	0.5427 (4)	0.2280 (4)	0.18510 (10)	0.0359 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0561 (19)	0.085 (2)	0.0526 (18)	−0.0022 (18)	0.0156 (16)	−0.0106 (18)
O2	0.061 (2)	0.068 (2)	0.048 (2)	0.0042 (18)	0.0086 (16)	0.0139 (18)
O3	0.0506 (18)	0.0599 (19)	0.072 (2)	0.0141 (17)	0.0108 (18)	0.0009 (18)
N1	0.0409 (19)	0.0233 (17)	0.052 (2)	0.0028 (16)	0.0007 (18)	0.0074 (17)
N2	0.044 (2)	0.0254 (17)	0.052 (2)	−0.0002 (18)	0.0067 (17)	−0.0009 (19)
C1	0.059 (3)	0.100 (4)	0.081 (3)	−0.011 (3)	0.019 (3)	−0.009 (3)
C2	0.085 (4)	0.074 (3)	0.073 (4)	0.019 (3)	0.007 (3)	0.029 (3)
C3	0.067 (3)	0.096 (4)	0.069 (3)	0.034 (3)	−0.013 (3)	−0.004 (3)
C4	0.034 (2)	0.042 (3)	0.057 (3)	0.004 (2)	0.004 (2)	−0.008 (2)
C5	0.042 (2)	0.031 (2)	0.056 (3)	−0.001 (2)	0.005 (2)	0.002 (2)
C6	0.038 (2)	0.030 (2)	0.042 (2)	−0.002 (2)	0.005 (2)	−0.001 (2)
C7	0.036 (2)	0.032 (2)	0.051 (3)	0.000 (2)	0.002 (2)	−0.003 (2)
C8	0.045 (3)	0.042 (2)	0.040 (2)	−0.003 (2)	−0.001 (2)	−0.003 (2)
C9	0.041 (3)	0.053 (3)	0.040 (2)	−0.006 (2)	0.007 (2)	−0.004 (2)
C10	0.038 (2)	0.027 (2)	0.047 (2)	−0.003 (2)	−0.006 (2)	0.003 (2)
C11	0.033 (2)	0.030 (2)	0.038 (2)	−0.0061 (18)	0.005 (2)	−0.003 (2)
C12	0.047 (3)	0.034 (2)	0.054 (3)	−0.007 (2)	−0.002 (2)	0.006 (2)
C13	0.054 (3)	0.053 (3)	0.053 (3)	−0.010 (2)	0.005 (2)	0.010 (3)
C14	0.050 (3)	0.051 (3)	0.062 (3)	−0.002 (3)	0.017 (2)	−0.005 (3)
C15	0.052 (3)	0.037 (3)	0.064 (3)	0.008 (2)	0.012 (2)	−0.004 (2)
C16	0.040 (2)	0.023 (2)	0.044 (2)	−0.0011 (19)	0.001 (2)	−0.001 (2)

Geometric parameters (Å, º) top

C9—O1	1.379 (4)	C4—C5	1.379 (5)
C1—O1	1.428 (5)	C4—C9	1.403 (5)
C8—O2	1.377 (4)	C5—C6	1.389 (5)
C2—O2	1.422 (4)	C5—H5A	0.9300
C4—O3	1.372 (4)	C6—C7	1.407 (5)
C3—O3	1.427 (4)	C6—C10	1.464 (5)
N1—C11	1.371 (4)	C7—C8	1.383 (5)
N1—C10	1.383 (4)	C7—H7A	0.9300
N1—H1A	0.8600	C8—C9	1.401 (5)
N2—C10	1.329 (4)	C11—C12	1.383 (5)
N2—C16	1.400 (4)	C11—C16	1.419 (5)
C1—H1B	0.9600	C12—C13	1.376 (5)
C1—H1C	0.9600	C12—H12A	0.9300
C1—H1D	0.9600	C13—C14	1.418 (5)
C2—H2B	0.9600	C13—H13A	0.9300
C2—H2C	0.9600	C14—C15	1.376 (5)
C2—H2D	0.9600	C14—H14A	0.9300
C3—H3A	0.9600	C15—C16	1.400 (5)
C3—H3B	0.9600	C15—H15A	0.9300
C3—H3C	0.9600

C9—O1—C1	117.4 (3)	C5—C6—C10	119.9 (4)
C8—O2—C2	118.2 (3)	C7—C6—C10	119.8 (3)
C4—O3—C3	116.9 (3)	C8—C7—C6	119.1 (4)
C11—N1—C10	107.7 (3)	C8—C7—H7A	120.5
C11—N1—H1A	126.1	C6—C7—H7A	120.5
C10—N1—H1A	126.1	O2—C8—C7	124.2 (4)
C10—N2—C16	104.8 (3)	O2—C8—C9	114.9 (4)
O1—C1—H1B	109.5	C7—C8—C9	120.8 (4)
O1—C1—H1C	109.5	O1—C9—C8	118.9 (4)
H1B—C1—H1C	109.5	O1—C9—C4	121.6 (4)
O1—C1—H1D	109.5	C8—C9—C4	119.3 (4)
H1B—C1—H1D	109.5	N2—C10—N1	112.4 (3)
H1C—C1—H1D	109.5	N2—C10—C6	126.4 (3)
O2—C2—H2B	109.5	N1—C10—C6	121.2 (3)
O2—C2—H2C	109.5	N1—C11—C12	132.5 (4)
H2B—C2—H2C	109.5	N1—C11—C16	105.1 (3)
O2—C2—H2D	109.5	C12—C11—C16	122.4 (4)
H2B—C2—H2D	109.5	C13—C12—C11	117.2 (4)
H2C—C2—H2D	109.5	C13—C12—H12A	121.4
O3—C3—H3A	109.5	C11—C12—H12A	121.4
O3—C3—H3B	109.5	C12—C13—C14	121.3 (4)
H3A—C3—H3B	109.5	C12—C13—H13A	119.4
O3—C3—H3C	109.5	C14—C13—H13A	119.4
H3A—C3—H3C	109.5	C15—C14—C13	121.7 (4)
H3B—C3—H3C	109.5	C15—C14—H14A	119.2
O3—C4—C5	123.5 (4)	C13—C14—H14A	119.2
O3—C4—C9	116.4 (4)	C14—C15—C16	117.7 (4)
C5—C4—C9	120.0 (4)	C14—C15—H15A	121.1
C4—C5—C6	120.4 (4)	C16—C15—H15A	121.1
C4—C5—H5A	119.8	N2—C16—C15	130.3 (3)
C6—C5—H5A	119.8	N2—C16—C11	109.9 (3)
C5—C6—C7	120.3 (3)	C15—C16—C11	119.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.07	2.918 (4)	169

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₃
M_r	284.31
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	8.2270 (16), 9.5750 (19), 37.375 (7)
V (Å³)	2944.2 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5421, 2733, 960
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.143, 0.94
No. of reflections	2733
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.07	2.918 (4)	169

Symmetry code: (i) −x+3/2, y−1/2, z.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gupta, P., Hameed, S. & Jain, R. (2004). Eur. J. Med. Chem. 39, 805–814. Web of Science CrossRef PubMed CAS Google Scholar
Rashid, N., Tahir, M. K., Kanwal, S., Yusof, N. M. & Yamin, B. M. (2007). Acta Cryst. E63, o1402–o1403. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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