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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1926.
Published online 2009 July 18. doi:  10.1107/S1600536809027342
PMCID: PMC2977465

2-Amino-6-nitro-1H-benzoimidazol-3-ium chloride

Abstract

In the cation of the title compound, C7H7N4O2 +·Cl, the benzimidazole ring system is planar with a maximum deviation of −0.019 (3) Å. In the crystal structure, C—H(...)Cl, N—H(...)Cl, and N—H(...)Cl inter­actions link the mol­ecules into a two-dimensional network. π–π contacts between benzimidazole rings [centroid–centroid distances = 3.928 (1) and 3.587 (1) Å] may further stabilize the structure.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1926-scheme1.jpg

Experimental

Crystal data

  • C7H7N4O2 +·Cl
  • M r = 214.62
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1926-efi1.jpg
  • a = 13.969 (3) Å
  • b = 7.8064 (19) Å
  • c = 16.490 (4) Å
  • β = 91.303 (3)°
  • V = 1797.7 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.40 mm−1
  • T = 291 K
  • 0.12 × 0.12 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.953, T max = 0.961
  • 4345 measured reflections
  • 1580 independent reflections
  • 1242 reflections with I > 2σ(I)
  • R int = 0.041
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.096
  • S = 1.02
  • 1580 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027342/hk2728sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027342/hk2728Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Some derivatives of 2-aminobenzimidazolium are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/N2/C1-C3) and B (C2-C7) are, of course, planar and they are oriented at a dihedral angle of 1.70 (3)°. The benzimidazole ring system is planar with a maximum deviation of -0.019 (3) Å for atom C5. Atoms O1, N3 and N4 are 0.064 (3), -0.044 (3) and -0.094 (3) Å away from the plane of the benzimidazole ring system, respectively.

In the crystal structure, intramolecular C-H···Cl and N-H···Cl and intermolecular N-H···Cl interactions (Table 1) link the molecules into a two dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the benzimidazole rings, Cg1—Cg2i and Cg2—Cg2ii [symmetry codes: (i) 1/2 - x, 3/2 - y, -z, (ii) -x, 1 - y, -z, where Cg1 and Cg2 are centroids of the rings A (N1/N2/C1-C3) and B (C2-C7), respectively] may further stabilize the structure, with centroid-centroid distances of 3.928 (1) and 3.587 (1) Å, respectively.

Experimental

For the preparation of the title compound, a suspension of 4-nitro-o-phenylenediamine (1.4 g, 9.1 mmol) in a solution of BrCN (0.97 g, 9.2 mmol) in water (30 ml) was refluxed for 7 h, and then cooled and neutralized with NH4OH (25%) to pH = 11. The formed precipitate was filtered, washed with water and dried to give the title compound, as a yellow solid (yield; 1.5 g, 92%). Crystals suitable for X-ray analysis were obtained after 3 d by slow evaporation of the mother liquid at room temperature.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH and NH2) and C-H = 0.93 Å for aromatic H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C7H7N4O2+·ClF(000) = 880
Mr = 214.62Dx = 1.586 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 13.969 (3) Åθ = 2.1–25.3°
b = 7.8064 (19) ŵ = 0.40 mm1
c = 16.490 (4) ÅT = 291 K
β = 91.303 (3)°Block, yellow
V = 1797.7 (7) Å30.12 × 0.12 × 0.10 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer1242 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
graphiteθmax = 25.0°, θmin = 2.5°
ω/2θ scansh = −16→16
Absorption correction: ψ scan (North et al., 1968)k = −9→9
Tmin = 0.953, Tmax = 0.961l = −19→13
4345 measured reflections3 standard reflections every 120 min
1580 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0429P)2 + 0.969P] where P = (Fo2 + 2Fc2)/3
1580 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.19 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.40318 (4)0.59647 (8)0.67245 (4)0.0535 (2)
O10.38248 (13)0.6546 (3)0.39469 (12)0.0718 (6)
O20.42766 (13)0.8483 (3)0.31128 (11)0.0743 (6)
N10.61668 (12)0.7489 (2)0.63485 (10)0.0424 (5)
H1A0.58350.68400.66560.051*
N20.72946 (12)0.9189 (2)0.59344 (10)0.0403 (4)
H2A0.78050.98040.59340.048*
N30.73958 (14)0.8248 (3)0.72889 (12)0.0552 (6)
H3A0.79160.88120.73800.066*
H3B0.71500.76490.76690.066*
N40.43847 (13)0.7660 (3)0.37360 (12)0.0491 (5)
C10.69763 (15)0.8301 (3)0.65691 (13)0.0392 (5)
C20.59515 (14)0.7865 (3)0.55416 (12)0.0363 (5)
C30.66716 (14)0.8960 (3)0.52782 (13)0.0361 (5)
C40.66616 (16)0.9615 (3)0.44987 (13)0.0420 (5)
H40.71471.03320.43230.050*
C50.59021 (16)0.9163 (3)0.39925 (13)0.0432 (5)
H50.58590.95900.34660.052*
C60.52047 (15)0.8067 (3)0.42752 (13)0.0392 (5)
C70.52051 (15)0.7385 (3)0.50434 (13)0.0401 (5)
H70.47280.66440.52130.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0422 (4)0.0708 (4)0.0475 (4)−0.0144 (3)0.0034 (3)−0.0083 (3)
O10.0580 (12)0.0805 (13)0.0762 (13)−0.0252 (10)−0.0151 (10)0.0019 (11)
O20.0612 (12)0.1070 (16)0.0539 (12)−0.0053 (11)−0.0168 (9)0.0130 (11)
N10.0447 (11)0.0431 (11)0.0393 (11)−0.0091 (9)0.0011 (8)0.0035 (8)
N20.0328 (10)0.0461 (11)0.0419 (10)−0.0076 (8)−0.0012 (8)0.0000 (8)
N30.0523 (13)0.0663 (14)0.0466 (12)−0.0117 (10)−0.0096 (10)0.0075 (10)
N40.0387 (11)0.0593 (13)0.0491 (12)0.0016 (10)−0.0039 (9)−0.0090 (10)
C10.0351 (11)0.0413 (12)0.0411 (13)0.0005 (9)−0.0013 (9)−0.0016 (10)
C20.0357 (11)0.0366 (11)0.0367 (12)0.0003 (9)0.0019 (9)−0.0012 (9)
C30.0311 (11)0.0368 (11)0.0405 (12)0.0005 (9)0.0022 (9)−0.0035 (9)
C40.0372 (12)0.0445 (13)0.0446 (13)−0.0050 (10)0.0064 (10)0.0019 (10)
C50.0430 (13)0.0479 (13)0.0387 (12)0.0007 (10)0.0026 (10)0.0006 (10)
C60.0364 (12)0.0420 (12)0.0391 (12)0.0023 (9)−0.0021 (9)−0.0063 (10)
C70.0362 (12)0.0393 (12)0.0448 (13)−0.0059 (9)0.0039 (10)−0.0051 (10)

Geometric parameters (Å, °)

N1—H1A0.8600C2—C71.365 (3)
N2—H2A0.8600C3—N21.385 (3)
N3—H3A0.8600C3—C41.383 (3)
N3—H3B0.8600C4—C51.381 (3)
N4—O11.225 (3)C4—H40.9300
N4—O21.219 (2)C5—C61.385 (3)
C1—N11.340 (3)C5—H50.9300
C1—N21.340 (3)C6—C71.374 (3)
C1—N31.312 (3)C6—N41.469 (3)
C2—N11.389 (3)C7—H70.9300
C2—C31.397 (3)
C1—N1—C2108.84 (17)C7—C2—C3121.8 (2)
C1—N1—H1A125.6N2—C3—C2106.28 (18)
C2—N1—H1A125.6C4—C3—N2132.2 (2)
C1—N2—C3109.26 (17)C4—C3—C2121.6 (2)
C1—N2—H2A125.4C3—C4—H4121.4
C3—N2—H2A125.4C5—C4—C3117.3 (2)
C1—N3—H3A120.0C5—C4—H4121.4
C1—N3—H3B120.0C4—C5—C6119.4 (2)
H3A—N3—H3B120.0C4—C5—H5120.3
O1—N4—C6118.4 (2)C6—C5—H5120.3
O2—N4—O1123.1 (2)C5—C6—N4118.3 (2)
O2—N4—C6118.5 (2)C7—C6—N4117.27 (19)
N2—C1—N1109.02 (18)C7—C6—C5124.3 (2)
N3—C1—N1126.0 (2)C2—C7—C6115.6 (2)
N3—C1—N2125.0 (2)C2—C7—H7122.2
N1—C2—C3106.60 (18)C6—C7—H7122.2
C7—C2—N1131.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7···Cl10.932.753.436 (2)132
N1—H1A···Cl10.862.613.2830 (19)135
N1—H1A···Cl1i0.862.763.4102 (19)134
N3—H3A···Cl1ii0.862.553.269 (2)142
N2—H2A···Cl1ii0.862.313.0601 (19)145

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2728).

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.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography