2-Methyl­benzimidazolium nitrate

Ma, Q.; Duan, W.; Ma, Y.; Liu, X.; Qu, B.

doi:10.1107/S1600536810008615

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o814

doi:10.1107/S1600536810008615

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2-Methylbenzimidazolium nitrate

Qingshuang Ma,^a Wenzeng Duan,^a,^b Yudao Ma,^a ^* Xiao Liu ^a and Bo Qu ^a

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, and ^bDepartment of Chemistry and Environmental Science, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: ydma@sdu.edu.cn

(Received 15 January 2010; accepted 6 March 2010; online 13 March 2010)

In the title compound, C₈H₉N₂⁺·NO₃⁻, intermolecular N—H⋯O hydrogen bonds join the molecules into a chain extending along the b axis.

Related literature

For the applications of related benzimidazole compounds, see: Wright (1951 ); El-masry et al. (2000 ); Gümüş et al. (2003 ).

Experimental

Crystal data

C₈H₉N₂⁺·NO₃⁻
M_r = 195.18
Monoclinic, P 2₁ /c
a = 7.711 (4) Å
b = 15.127 (7) Å
c = 8.270 (4) Å
β = 99.398 (7)°
V = 951.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.18 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.981, T_max = 0.987
4774 measured reflections
1685 independent reflections
1319 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.135
S = 1.07
1685 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.03	2.855 (3)	162
N3—H3⋯O2ⁱⁱ	0.86	1.93	2.775 (2)	166
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008615/gk2255sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008615/gk2255Isup2.hkl

checkCIF report

Comment top

Benzimidazole and its derivatives have found practical applications in a number of fields (Wright, 1951). This ring system is present in numerous antiparasitic, antihelmintic and anti-inflammatory drugs (El-masry et al., 2000). The complexes of transition metals with benzimidazole and related ligands have been extensively studied as models of some important biological molecules (Gümüş et al., 2003). During our search to find new benzimidazole-metal complexes 2-methylbenzimidazole nitrate was unintentionally obtained.

Herein, we report the structure of the title compound, C₈H₉N₃O₃(Fig 1). The crystal structure showed that intermolecular N—H···O hydrogen bonds link the molecules into a 1D polymeric structure (Fig. 2).

Related literature top

For the applications of related benzimidazole compounds, see: Wright (1951); El-masry et al. (2000); Gümüş et al. (2003).

Experimental top

A mixture of o-phenylenediamine(1.08 g, 10 mmol) and anhydrous sodium acetate (2.46 g, 30 mmol) were dissolved in 100 mL 5% hydrochloric acid. After stirring for 2 h under reflux, the solution was cooled to room temperature. Then the solution was treated with ammonia solution to pH 9-10 and an orange precipitate was formed. The precipitate was filtred and washed with water. 2-methylbenzimidazolium chloride was gained in 27.32% yield. The compound 2-methylbenzimidazole nitrate was obtained in 35% yield when the 2-methylbenzimidazolium chloride (0.46 g, 2.73 mmol) was reacted with Cr(NO₃)₃.9H₂O (1.01 g, 2.54 mmol) in ethanol under reflux. The crystals suitable for X-ray diffraction analysis were obtained by recrystallization from ethanol.

Computing details top

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound showing 50% probability displacement.
	Fig. 2. The supramolecular chain of the title compound formed via N—H···O hydrogen bonds.

2-methylbenzimidazolium nitrate top

Crystal data top

C₈H₉N₂⁺·NO₃⁻	F(000) = 408
M_r = 195.18	D_x = 1.362 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2174 reflections
a = 7.711 (4) Å	θ = 2.5–25.5°
b = 15.127 (7) Å	µ = 0.11 mm⁻¹
c = 8.270 (4) Å	T = 298 K
β = 99.398 (7)°	Block, colorless
V = 951.7 (8) Å³	0.18 × 0.16 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1685 independent reflections
Radiation source: fine-focus sealed tube	1319 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.981, T_max = 0.987	k = −11→18
4774 measured reflections	l = −9→9

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0681P)² + 0.208P] where P = (F_o² + 2F_c²)/3
1685 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₉N₂⁺·NO₃⁻	V = 951.7 (8) Å³
M_r = 195.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.711 (4) Å	µ = 0.11 mm⁻¹
b = 15.127 (7) Å	T = 298 K
c = 8.270 (4) Å	0.18 × 0.16 × 0.12 mm
β = 99.398 (7)°

Data collection top

Bruker SMART APEX diffractometer	1685 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1319 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.987	R_int = 0.027
4774 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.07	Δρ_max = 0.22 e Å⁻³
1685 reflections	Δρ_min = −0.21 e Å⁻³
128 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.3641 (2)	0.06287 (10)	0.78462 (18)	0.0735 (5)
O2	0.33057 (19)	0.15524 (9)	0.97555 (17)	0.0643 (4)
O3	0.2248 (3)	0.02349 (11)	0.9773 (2)	0.0915 (6)
N1	0.3063 (2)	0.07987 (10)	0.9136 (2)	0.0538 (4)
N2	0.6679 (2)	0.12445 (11)	0.25067 (19)	0.0600 (5)
H2	0.6828	0.0687	0.2374	0.072*
N3	0.5577 (2)	0.24731 (11)	0.31726 (19)	0.0576 (5)
H3	0.4889	0.2842	0.3542	0.069*
C1	0.3941 (3)	0.11166 (15)	0.3743 (3)	0.0727 (6)
H1A	0.3921	0.0516	0.3368	0.109*
H1B	0.2839	0.1395	0.3331	0.109*
H1C	0.4132	0.1126	0.4920	0.109*
C2	0.5376 (3)	0.15990 (13)	0.3145 (2)	0.0569 (5)
C3	0.7769 (3)	0.19049 (13)	0.2083 (2)	0.0561 (5)
C4	0.7057 (3)	0.26993 (13)	0.2519 (2)	0.0542 (5)
C5	0.7834 (3)	0.35057 (14)	0.2303 (3)	0.0677 (6)
H5	0.7356	0.4035	0.2595	0.081*
C6	0.9355 (3)	0.34816 (19)	0.1630 (3)	0.0805 (7)
H6	0.9920	0.4009	0.1463	0.097*
C7	1.0070 (3)	0.2684 (2)	0.1191 (3)	0.0802 (7)
H7	1.1095	0.2695	0.0734	0.096*
C8	0.9302 (3)	0.18829 (18)	0.1416 (3)	0.0715 (7)
H8	0.9787	0.1353	0.1134	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1006 (12)	0.0560 (9)	0.0718 (10)	0.0061 (8)	0.0370 (9)	−0.0048 (7)
O2	0.0865 (10)	0.0434 (8)	0.0651 (9)	−0.0085 (7)	0.0188 (7)	−0.0067 (6)
O3	0.1307 (16)	0.0554 (10)	0.0990 (13)	−0.0287 (10)	0.0499 (12)	0.0017 (8)
N1	0.0628 (10)	0.0406 (9)	0.0590 (10)	0.0020 (7)	0.0127 (8)	0.0042 (7)
N2	0.0735 (11)	0.0464 (9)	0.0564 (10)	0.0153 (8)	−0.0006 (8)	−0.0086 (7)
N3	0.0710 (11)	0.0476 (10)	0.0521 (9)	0.0150 (8)	0.0038 (8)	−0.0094 (7)
C1	0.0902 (16)	0.0612 (14)	0.0673 (13)	0.0017 (12)	0.0145 (12)	−0.0006 (11)
C2	0.0728 (13)	0.0487 (12)	0.0462 (10)	0.0126 (10)	0.0004 (9)	−0.0052 (8)
C3	0.0621 (12)	0.0575 (12)	0.0440 (10)	0.0131 (10)	−0.0051 (8)	−0.0086 (9)
C4	0.0619 (11)	0.0536 (11)	0.0433 (10)	0.0096 (9)	−0.0024 (8)	−0.0058 (8)
C5	0.0810 (15)	0.0539 (13)	0.0631 (13)	0.0037 (11)	−0.0033 (11)	−0.0019 (10)
C6	0.0806 (16)	0.0842 (18)	0.0716 (15)	−0.0133 (14)	−0.0030 (12)	0.0061 (13)
C7	0.0679 (14)	0.105 (2)	0.0662 (14)	0.0061 (14)	0.0070 (11)	−0.0032 (14)
C8	0.0685 (14)	0.0831 (17)	0.0593 (13)	0.0169 (13)	−0.0007 (11)	−0.0124 (11)

Geometric parameters (Å, º) top

O1—N1	1.248 (2)	C1—H1C	0.9600
O2—N1	1.252 (2)	C3—C8	1.384 (3)
O3—N1	1.228 (2)	C3—C4	1.393 (3)
N2—C2	1.322 (3)	C4—C5	1.383 (3)
N2—C3	1.387 (3)	C5—C6	1.378 (4)
N2—H2	0.8600	C5—H5	0.9300
N3—C2	1.331 (3)	C6—C7	1.399 (4)
N3—C4	1.383 (3)	C6—H6	0.9300
N3—H3	0.8600	C7—C8	1.374 (4)
C1—C2	1.476 (3)	C7—H7	0.9300
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600

O3—N1—O1	120.19 (17)	C8—C3—N2	132.5 (2)
O3—N1—O2	120.66 (17)	C8—C3—C4	121.5 (2)
O1—N1—O2	119.14 (16)	N2—C3—C4	105.96 (18)
C2—N2—C3	109.90 (17)	C5—C4—N3	132.13 (19)
C2—N2—H2	125.1	C5—C4—C3	122.0 (2)
C3—N2—H2	125.1	N3—C4—C3	105.85 (18)
C2—N3—C4	109.90 (16)	C6—C5—C4	116.3 (2)
C2—N3—H3	125.1	C6—C5—H5	121.8
C4—N3—H3	125.1	C4—C5—H5	121.8
C2—C1—H1A	109.5	C5—C6—C7	121.7 (2)
C2—C1—H1B	109.5	C5—C6—H6	119.2
H1A—C1—H1B	109.5	C7—C6—H6	119.2
C2—C1—H1C	109.5	C8—C7—C6	121.9 (2)
H1A—C1—H1C	109.5	C8—C7—H7	119.1
H1B—C1—H1C	109.5	C6—C7—H7	119.1
N2—C2—N3	108.40 (19)	C7—C8—C3	116.6 (2)
N2—C2—C1	126.37 (19)	C7—C8—H8	121.7
N3—C2—C1	125.23 (19)	C3—C8—H8	121.7

C3—N2—C2—N3	−0.6 (2)	C8—C3—C4—N3	−178.53 (17)
C3—N2—C2—C1	179.86 (19)	N2—C3—C4—N3	−0.24 (19)
C4—N3—C2—N2	0.4 (2)	N3—C4—C5—C6	178.52 (19)
C4—N3—C2—C1	179.99 (19)	C3—C4—C5—C6	0.0 (3)
C2—N2—C3—C8	178.5 (2)	C4—C5—C6—C7	0.0 (3)
C2—N2—C3—C4	0.5 (2)	C5—C6—C7—C8	−0.4 (4)
C2—N3—C4—C5	−178.8 (2)	C6—C7—C8—C3	0.7 (3)
C2—N3—C4—C3	−0.1 (2)	N2—C3—C8—C7	−178.4 (2)
C8—C3—C4—C5	0.3 (3)	C4—C3—C8—C7	−0.7 (3)
N2—C3—C4—C5	178.59 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.03	2.855 (3)	162
N3—H3···O2ⁱⁱ	0.86	1.93	2.775 (2)	166

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₂⁺·NO₃⁻
M_r	195.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.711 (4), 15.127 (7), 8.270 (4)
β (°)	99.398 (7)
V (Å³)	951.7 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.981, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	4774, 1685, 1319
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.135, 1.07
No. of reflections	1685
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), 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
N2—H2···O1ⁱ	0.86	2.03	2.855 (3)	162
N3—H3···O2ⁱⁱ	0.86	1.93	2.775 (2)	166

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

Acknowledgements

Financial support from the National Natural Science Foundation of China (grant Nos. 20441004, 20671059) and the Department of Science and Technology of Shandong Province is gratefully acknowledged.

References

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El-masry, A. H., Fahmy, H. H. & Ali Abdelwahed, S. H. (2000). Molecules, 5, 1429–1438. CAS Google Scholar
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