Acta Cryst. (2009). E65, o2396 [ doi:10.1107/S1600536809034941 ]
In the cation of the title compound, C7H7N2+·Br-, all non-H atoms are essentially coplanar [r.m.s. deviation = 0.010 (5) Å]. The compound is isomorphous with the chloride analogue. In the crystal, the cations and anions are connected by N-H
Br hydrogen bonds.
The commercial 3-aminobenzonitrile (3 mmol, 0.55 g) and HBr (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.
All H atoms attached to C and N atoms were positioned geometrically and treated as riding, with C-H = 0.93 Å, N-H = 0.89 Å and Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(N). A rotating-group model was used for the -NH3 group.
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bx2236fig1thm.gif)
| Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./bx2236fig2thm.gif)
| Fig. 2. The crystal packing of the title compound, viewed along the a axis showing the N—H···Br interactions (dotted line) in the title compound. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity. |
| C7H7N2+·Br− | Z = 2 |
| Mr = 199.06 | F(000) = 196 |
| Triclinic, P1 | Dx = 1.732 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 4.6396 (9) Å | Cell parameters from 1378 reflections |
| b = 6.1757 (12) Å | θ = 3.0–27.5° |
| c = 13.542 (3) Å | µ = 5.31 mm−1 |
| α = 93.07 (3)° | T = 298 K |
| β = 96.22 (3)° | Block, colourless |
| γ = 97.33 (3)° | 0.40 × 0.05 × 0.05 mm |
| V = 381.68 (13) Å3 |
| Rigaku Mercury2 diffractometer | 1716 independent reflections |
| Radiation source: fine-focus sealed tube | 1378 reflections with I > 2σ(I) |
| graphite | Rint = 0.063 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
| CCD profile fitting scans | h = −6→5 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −8→8 |
| Tmin = 0.90, Tmax = 1.00 | l = −17→17 |
| 3777 measured reflections |
| 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.134 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.053P)2 + 0.0394P] where P = (Fo2 + 2Fc2)/3 |
| 1716 reflections | (Δ/σ)max < 0.001 |
| 92 parameters | Δρmax = 0.71 e Å−3 |
| 0 restraints | Δρmin = −0.75 e Å−3 |
| C7H7N2+·Br− | γ = 97.33 (3)° |
| Mr = 199.06 | V = 381.68 (13) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 4.6396 (9) Å | Mo Kα radiation |
| b = 6.1757 (12) Å | µ = 5.31 mm−1 |
| c = 13.542 (3) Å | T = 298 K |
| α = 93.07 (3)° | 0.40 × 0.05 × 0.05 mm |
| β = 96.22 (3)° |
| Rigaku Mercury2 diffractometer | 1716 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1378 reflections with I > 2σ(I) |
| Tmin = 0.90, Tmax = 1.00 | Rint = 0.063 |
| 3777 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.134 | Δρmax = 0.71 e Å−3 |
| S = 1.10 | Δρmin = −0.75 e Å−3 |
| 1716 reflections | Absolute structure: ? |
| 92 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| N2 | 0.6256 (9) | 0.2461 (6) | 0.6051 (3) | 0.0419 (10) | |
| H2A | 0.7437 | 0.1446 | 0.5990 | 0.063* | |
| H2B | 0.7175 | 0.3755 | 0.5927 | 0.063* | |
| H2C | 0.4653 | 0.2118 | 0.5619 | 0.063* | |
| N1 | −0.0113 (11) | 0.7158 (8) | 0.8871 (4) | 0.0575 (13) | |
| C4 | 0.5438 (10) | 0.2565 (7) | 0.7064 (4) | 0.0339 (10) | |
| C3 | 0.3783 (10) | 0.4177 (7) | 0.7330 (3) | 0.0349 (10) | |
| H3 | 0.3215 | 0.5166 | 0.6877 | 0.042* | |
| C2 | 0.3001 (10) | 0.4273 (7) | 0.8286 (4) | 0.0350 (10) | |
| C5 | 0.6331 (11) | 0.1113 (7) | 0.7719 (4) | 0.0389 (11) | |
| H5 | 0.7446 | 0.0048 | 0.7527 | 0.047* | |
| C7 | 0.3878 (12) | 0.2814 (8) | 0.8962 (4) | 0.0429 (12) | |
| H7 | 0.3345 | 0.2889 | 0.9604 | 0.051* | |
| C6 | 0.5540 (12) | 0.1259 (8) | 0.8677 (4) | 0.0473 (13) | |
| H6 | 0.6146 | 0.0287 | 0.9132 | 0.057* | |
| C1 | 0.1216 (11) | 0.5910 (8) | 0.8593 (4) | 0.0422 (12) | |
| Br1 | 0.09268 (11) | 0.23870 (7) | 0.42210 (4) | 0.0448 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N2 | 0.053 (3) | 0.044 (2) | 0.032 (2) | 0.0176 (19) | 0.0038 (19) | 0.0003 (18) |
| N1 | 0.058 (3) | 0.052 (3) | 0.067 (3) | 0.020 (2) | 0.016 (3) | −0.004 (2) |
| C4 | 0.040 (3) | 0.028 (2) | 0.033 (3) | 0.0073 (18) | 0.004 (2) | −0.0017 (18) |
| C3 | 0.039 (3) | 0.033 (2) | 0.032 (3) | 0.010 (2) | 0.000 (2) | 0.0010 (19) |
| C2 | 0.030 (2) | 0.034 (2) | 0.041 (3) | 0.0057 (18) | 0.005 (2) | −0.002 (2) |
| C5 | 0.049 (3) | 0.034 (2) | 0.037 (3) | 0.018 (2) | 0.007 (2) | −0.001 (2) |
| C7 | 0.056 (3) | 0.039 (3) | 0.035 (3) | 0.011 (2) | 0.010 (2) | 0.000 (2) |
| C6 | 0.062 (4) | 0.040 (3) | 0.045 (3) | 0.015 (2) | 0.010 (3) | 0.014 (2) |
| C1 | 0.045 (3) | 0.040 (3) | 0.044 (3) | 0.012 (2) | 0.011 (2) | 0.000 (2) |
| Br1 | 0.0573 (4) | 0.0399 (3) | 0.0423 (4) | 0.0214 (2) | 0.0112 (3) | 0.0037 (2) |
| N2—C4 | 1.463 (6) | C3—H3 | 0.9300 |
| N2—H2A | 0.8900 | C2—C7 | 1.384 (7) |
| N2—H2B | 0.8900 | C2—C1 | 1.457 (6) |
| N2—H2C | 0.8900 | C5—C6 | 1.388 (7) |
| N1—C1 | 1.121 (6) | C5—H5 | 0.9300 |
| C4—C5 | 1.365 (6) | C7—C6 | 1.371 (7) |
| C4—C3 | 1.388 (6) | C7—H7 | 0.9300 |
| C3—C2 | 1.383 (7) | C6—H6 | 0.9300 |
| C4—N2—H2A | 109.5 | C3—C2—C1 | 120.2 (4) |
| C4—N2—H2B | 109.5 | C7—C2—C1 | 119.1 (5) |
| H2A—N2—H2B | 109.5 | C4—C5—C6 | 118.6 (4) |
| C4—N2—H2C | 109.5 | C4—C5—H5 | 120.7 |
| H2A—N2—H2C | 109.5 | C6—C5—H5 | 120.7 |
| H2B—N2—H2C | 109.5 | C6—C7—C2 | 119.4 (5) |
| C5—C4—C3 | 122.0 (4) | C6—C7—H7 | 120.3 |
| C5—C4—N2 | 119.8 (4) | C2—C7—H7 | 120.3 |
| C3—C4—N2 | 118.2 (4) | C7—C6—C5 | 121.0 (5) |
| C2—C3—C4 | 118.2 (4) | C7—C6—H6 | 119.5 |
| C2—C3—H3 | 120.9 | C5—C6—H6 | 119.5 |
| C4—C3—H3 | 120.9 | N1—C1—C2 | 177.0 (6) |
| C3—C2—C7 | 120.7 (4) | ||
| C5—C4—C3—C2 | −0.9 (7) | N2—C4—C5—C6 | 179.6 (5) |
| N2—C4—C3—C2 | 179.8 (4) | C3—C2—C7—C6 | 0.0 (7) |
| C4—C3—C2—C7 | 0.7 (7) | C1—C2—C7—C6 | 179.5 (5) |
| C4—C3—C2—C1 | −178.8 (4) | C2—C7—C6—C5 | −0.6 (8) |
| C3—C4—C5—C6 | 0.3 (7) | C4—C5—C6—C7 | 0.5 (8) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Br1i | 0.89 | 2.59 | 3.434 (4) | 159 |
| N2—H2B···Br1ii | 0.89 | 2.46 | 3.337 (4) | 169 |
| N2—H2C···Br1 | 0.89 | 2.45 | 3.299 (4) | 160 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Br1i | 0.89 | 2.59 | 3.434 (4) | 159 |
| N2—H2B···Br1ii | 0.89 | 2.46 | 3.337 (4) | 169 |
| N2—H2C···Br1 | 0.89 | 2.45 | 3.299 (4) | 160 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.
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The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu et al., 2007; Chen et al., 2001; Fu & Xiong (2008); Xie et al., 2003; Zhao et al.,2004; Xiong et al., 1999). Nitrile derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks. (Wang et al. 2002; Fu et al., 2008). We report here the crystal structure of the title compound, which is isomorphous with the chloride analogue (Wen, 2008). In the cation all non-H atoms are essentially coplanar [r.m.s. deviation 0.010 (5) Å]. In the crystal structure, the organic cations and bromide ions are connected by N—H···Br hydrogen bonds along b axis, (Table 1), (Fig. 2).