Acta Cryst. (2008). E64, o1461 [ doi:10.1107/S1600536808020783 ]
In the crystal structure of the title compound, C6H6N3+·Cl-, cohesion is maintained by cation-anion N-H
Cl and cation-cation N-HN hydrogen bonds, which link the ions into a three-dimensional network.
6-Aminonicotinonitrile-1-ium chloride (3 mmol) was dissolved in ethanol (20 ml) and evaporated in the air affording colourless block-shaped crystals suitable for X-ray analysis.
All H atoms were fixed geometrically and treated as riding, with C–H = 0.93 Å, N–H =0.86 Å, and with Uiso(H) =1.2Ueq(C, N).
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/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).
![[Figure 1]](./rz2232fig1thm.gif)
| Fig. 1. A view of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. |
![[Figure 2]](./rz2232fig2thm.gif)
| Fig. 2. Partial crystal packing of the title compound viewed along the a axis showing H bonding pattern as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. |
| C6H6N3+·Cl– | F000 = 320 |
| Mr = 155.59 | Dx = 1.440 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1250 reflections |
| a = 4.0937 (8) Å | θ = 2.3–24.4º |
| b = 11.856 (2) Å | µ = 0.45 mm−1 |
| c = 14.842 (3) Å | T = 298 (2) K |
| β = 94.95 (3)º | Block, colourless |
| V = 717.7 (2) Å3 | 0.18 × 0.15 × 0.15 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 1652 independent reflections |
| Radiation source: fine-focus sealed tube | 1252 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.044 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5º |
| T = 298(2) K | θmin = 3.3º |
| ω scans | h = −5→5 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −15→15 |
| Tmin = 0.922, Tmax = 0.935 | l = −19→19 |
| 7307 measured reflections |
| 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)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.2213P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 1652 reflections | Δρmax = 0.21 e Å−3 |
| 91 parameters | Δρmin = −0.23 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C6H6N3+·Cl– | V = 717.7 (2) Å3 |
| Mr = 155.59 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 4.0937 (8) Å | µ = 0.45 mm−1 |
| b = 11.856 (2) Å | T = 298 (2) K |
| c = 14.842 (3) Å | 0.18 × 0.15 × 0.15 mm |
| β = 94.95 (3)º |
| Rigaku Mercury2 diffractometer | 1652 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1252 reflections with I > 2σ(I) |
| Tmin = 0.922, Tmax = 0.935 | Rint = 0.044 |
| 7307 measured reflections |
| R[F2 > 2σ(F2)] = 0.045 | 91 parameters |
| wR(F2) = 0.102 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.21 e Å−3 |
| 1652 reflections | Δρmin = −0.23 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.44244 (14) | 0.60704 (5) | 0.17252 (4) | 0.0459 (2) | |
| N2 | 0.0652 (4) | 0.69979 (14) | 0.32749 (11) | 0.0377 (4) | |
| H2A | 0.1041 | 0.6650 | 0.2787 | 0.045* | |
| C2 | −0.0884 (5) | 0.64335 (18) | 0.39019 (14) | 0.0385 (5) | |
| H2B | −0.1506 | 0.5687 | 0.3801 | 0.046* | |
| N3 | 0.3183 (5) | 0.85595 (16) | 0.27271 (13) | 0.0507 (5) | |
| H3A | 0.3567 | 0.8175 | 0.2256 | 0.061* | |
| H3B | 0.3816 | 0.9250 | 0.2777 | 0.061* | |
| C3 | −0.1527 (5) | 0.69550 (17) | 0.46837 (13) | 0.0352 (5) | |
| C1 | −0.3034 (6) | 0.63422 (18) | 0.53757 (15) | 0.0442 (5) | |
| C6 | 0.1619 (5) | 0.80885 (17) | 0.33739 (13) | 0.0355 (5) | |
| C4 | −0.0595 (5) | 0.81008 (17) | 0.48174 (14) | 0.0398 (5) | |
| H4A | −0.1029 | 0.8471 | 0.5346 | 0.048* | |
| N1 | −0.4184 (6) | 0.58515 (18) | 0.59282 (14) | 0.0626 (6) | |
| C5 | 0.0921 (5) | 0.86506 (17) | 0.41756 (15) | 0.0414 (5) | |
| H5A | 0.1510 | 0.9403 | 0.4261 | 0.050* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0522 (3) | 0.0472 (3) | 0.0398 (3) | 0.0063 (3) | 0.0124 (2) | −0.0055 (2) |
| N2 | 0.0471 (10) | 0.0364 (9) | 0.0305 (9) | −0.0004 (8) | 0.0091 (7) | −0.0073 (7) |
| C2 | 0.0442 (12) | 0.0344 (11) | 0.0376 (11) | −0.0020 (9) | 0.0082 (9) | −0.0007 (9) |
| N3 | 0.0672 (13) | 0.0442 (11) | 0.0435 (11) | −0.0080 (10) | 0.0207 (10) | −0.0001 (9) |
| C3 | 0.0370 (11) | 0.0378 (11) | 0.0313 (10) | 0.0033 (9) | 0.0063 (8) | 0.0016 (8) |
| C1 | 0.0523 (13) | 0.0414 (12) | 0.0400 (12) | 0.0027 (10) | 0.0101 (10) | −0.0022 (10) |
| C6 | 0.0370 (11) | 0.0366 (11) | 0.0332 (10) | 0.0022 (9) | 0.0054 (9) | 0.0028 (8) |
| C4 | 0.0486 (12) | 0.0384 (11) | 0.0334 (11) | 0.0036 (10) | 0.0104 (9) | −0.0066 (9) |
| N1 | 0.0862 (16) | 0.0547 (13) | 0.0514 (12) | −0.0085 (11) | 0.0316 (12) | 0.0009 (10) |
| C5 | 0.0530 (13) | 0.0306 (11) | 0.0419 (12) | −0.0015 (9) | 0.0106 (10) | −0.0060 (9) |
| N2—C2 | 1.345 (2) | C3—C4 | 1.420 (3) |
| N2—C6 | 1.356 (3) | C3—C1 | 1.440 (3) |
| N2—H2A | 0.8600 | C1—N1 | 1.140 (3) |
| C2—C3 | 1.360 (3) | C6—C5 | 1.414 (3) |
| C2—H2B | 0.9300 | C4—C5 | 1.349 (3) |
| N3—C6 | 1.323 (3) | C4—H4A | 0.9300 |
| N3—H3A | 0.8600 | C5—H5A | 0.9300 |
| N3—H3B | 0.8600 | ||
| C2—N2—C6 | 123.26 (17) | C4—C3—C1 | 120.62 (18) |
| C2—N2—H2A | 118.4 | N1—C1—C3 | 179.0 (3) |
| C6—N2—H2A | 118.4 | N3—C6—N2 | 118.60 (18) |
| N2—C2—C3 | 120.02 (19) | N3—C6—C5 | 123.9 (2) |
| N2—C2—H2B | 120.0 | N2—C6—C5 | 117.53 (18) |
| C3—C2—H2B | 120.0 | C5—C4—C3 | 119.85 (18) |
| C6—N3—H3A | 120.0 | C5—C4—H4A | 120.1 |
| C6—N3—H3B | 120.0 | C3—C4—H4A | 120.1 |
| H3A—N3—H3B | 120.0 | C4—C5—C6 | 120.34 (19) |
| C2—C3—C4 | 118.98 (18) | C4—C5—H5A | 119.8 |
| C2—C3—C1 | 120.37 (19) | C6—C5—H5A | 119.8 |
| C6—N2—C2—C3 | −0.3 (3) | C2—C3—C4—C5 | −0.4 (3) |
| N2—C2—C3—C4 | 0.9 (3) | C1—C3—C4—C5 | 177.6 (2) |
| N2—C2—C3—C1 | −177.1 (2) | C3—C4—C5—C6 | −0.7 (3) |
| C2—N2—C6—N3 | 178.4 (2) | N3—C6—C5—C4 | −177.9 (2) |
| C2—N2—C6—C5 | −0.8 (3) | N2—C6—C5—C4 | 1.2 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Cl1 | 0.86 | 2.29 | 3.0818 (18) | 153 |
| N3—H3A···Cl1 | 0.86 | 2.65 | 3.363 (2) | 141 |
| N3—H3A···N1i | 0.86 | 2.53 | 3.046 (3) | 120 |
| N3—H3B···Cl1ii | 0.86 | 2.37 | 3.216 (2) | 167 |
| Symmetry codes: (i) x+1, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Cl1 | 0.86 | 2.29 | 3.0818 (18) | 153 |
| N3—H3A···Cl1 | 0.86 | 2.65 | 3.363 (2) | 141 |
| N3—H3A···N1i | 0.86 | 2.53 | 3.046 (3) | 120 |
| N3—H3B···Cl1ii | 0.86 | 2.37 | 3.216 (2) | 167 |
| Symmetry codes: (i) x+1, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.
Austria, C., Zhang, J. & Valle, H. (2007). Inorg. Chem. 46, 6283–6290.
Ismayilov, R. H., Wang, W. Z. & Lee, G. H. (2007). Dalton Trans. pp. 2898–2907.
Manzur, J., Vega, A. & Garcia, A. M. (2007). Eur. J. Inorg. Chem. 35, 5500–5510.
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
In the past five years, we have focused on the chemistry of amine derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Manzur et al. 2007; Ismayilov et al. 2007; Austria et al. 2007). Herein the crystal structure of the title compound, 6-aminonicotinonitrile-1-ium chloride, is reported.
In the title compound (Fig.1), the N2 atom of the pyridine ring is protonated. The nitrile group and the pyridine ring are nearly coplanar, as indicated by the dihedral angle of 86.71 (14)° formed by the C≡N vector with the normal to the pyridine plane. Crystal cohesion is enforced by cation-anion N—H···Cl and cation-cation N—H···N hydrogen bonds (Table 1, Fig. 2) linking molecules into a three-dimensional network.