Acta Cryst. (2008). E64, o1899 [ doi:10.1107/S1600536808028031 ]
In the title compound, C6H6N3+·NO3-, the packing is consolidatedby N-H
N and N-HO hydrogen bonds.
6-aminonicotinonitrile (3 mmol) was dissolved in the solution of ethanol (20 ml) and nitric acid (1 ml), and evaporated in the air affording colorless block crystals of this compound suitable for X-ray analysis.
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]](./wk2092fig1thm.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]](./wk2092fig2thm.gif)
| Fig. 2. The crystal packing of the title compound viewed along the a axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity. |
| C6H6N3+·NO3− | F(000) = 376 |
| Mr = 182.15 | Dx = 1.541 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1796 reflections |
| a = 4.6475 (9) Å | θ = 3.1–27.5° |
| b = 12.713 (3) Å | µ = 0.13 mm−1 |
| c = 13.417 (3) Å | T = 298 K |
| β = 97.91 (3)° | Block, colourless |
| V = 785.1 (3) Å3 | 0.25 × 0.15 × 0.15 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 1798 independent reflections |
| Radiation source: fine-focus sealed tube | 1163 reflections with I > 2σ(I) |
| graphite | Rint = 0.050 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −6→6 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −16→16 |
| Tmin = 0.975, Tmax = 0.981 | l = −17→17 |
| 8053 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)] = 0.053 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.127 | All H-atom parameters refined |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0514P)2 + 0.1542P] where P = (Fo2 + 2Fc2)/3 |
| 1798 reflections | (Δ/σ)max < 0.001 |
| 142 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C6H6N3+·NO3− | V = 785.1 (3) Å3 |
| Mr = 182.15 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 4.6475 (9) Å | µ = 0.13 mm−1 |
| b = 12.713 (3) Å | T = 298 K |
| c = 13.417 (3) Å | 0.25 × 0.15 × 0.15 mm |
| β = 97.91 (3)° |
| Rigaku Mercury2 diffractometer | 1798 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1163 reflections with I > 2σ(I) |
| Tmin = 0.975, Tmax = 0.981 | Rint = 0.050 |
| 8053 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.053 | All H-atom parameters refined |
| wR(F2) = 0.127 | Δρmax = 0.17 e Å−3 |
| S = 1.07 | Δρmin = −0.17 e Å−3 |
| 1798 reflections | Absolute structure: ? |
| 142 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| C2 | 0.7591 (5) | 0.86151 (17) | 0.31844 (17) | 0.0428 (5) | |
| N4 | 0.0550 (4) | 0.94943 (14) | 0.12683 (14) | 0.0456 (5) | |
| N2 | 0.4566 (4) | 0.71680 (19) | 0.25422 (16) | 0.0509 (5) | |
| O1 | −0.1866 (3) | 0.98288 (12) | 0.08728 (13) | 0.0604 (5) | |
| O2 | 0.2162 (4) | 1.00628 (14) | 0.18518 (14) | 0.0651 (5) | |
| O3 | 0.1266 (4) | 0.85819 (13) | 0.10891 (13) | 0.0610 (5) | |
| N1 | 0.8152 (4) | 0.69031 (15) | 0.38842 (14) | 0.0406 (4) | |
| C3 | 0.9809 (5) | 0.89511 (17) | 0.38692 (17) | 0.0435 (5) | |
| C5 | 1.0356 (4) | 0.72284 (18) | 0.45750 (17) | 0.0402 (5) | |
| C6 | 1.3541 (5) | 0.86115 (17) | 0.53382 (18) | 0.0476 (6) | |
| C1 | 0.6718 (4) | 0.75525 (16) | 0.31857 (15) | 0.0379 (5) | |
| C4 | 1.1235 (4) | 0.82498 (16) | 0.45893 (16) | 0.0388 (5) | |
| N3 | 1.5342 (5) | 0.89264 (16) | 0.59161 (18) | 0.0684 (7) | |
| H5 | 1.126 (4) | 0.6708 (16) | 0.5011 (15) | 0.036 (5)* | |
| H2A | 0.655 (4) | 0.9049 (16) | 0.2716 (15) | 0.033 (5)* | |
| H3 | 1.041 (4) | 0.9695 (19) | 0.3867 (16) | 0.051 (6)* | |
| H2B | 0.401 (5) | 0.650 (2) | 0.2641 (17) | 0.048 (7)* | |
| H1 | 0.764 (5) | 0.620 (2) | 0.389 (2) | 0.067 (8)* | |
| H2C | 0.370 (6) | 0.761 (3) | 0.216 (2) | 0.082 (10)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0473 (13) | 0.0351 (11) | 0.0432 (12) | 0.0020 (9) | −0.0043 (11) | 0.0098 (10) |
| N4 | 0.0556 (12) | 0.0365 (10) | 0.0425 (10) | 0.0046 (9) | −0.0013 (9) | 0.0013 (9) |
| N2 | 0.0512 (12) | 0.0424 (12) | 0.0529 (12) | −0.0048 (10) | −0.0146 (10) | 0.0011 (10) |
| O1 | 0.0532 (10) | 0.0445 (9) | 0.0766 (12) | 0.0102 (8) | −0.0156 (9) | −0.0064 (8) |
| O2 | 0.0615 (11) | 0.0566 (11) | 0.0698 (11) | 0.0031 (8) | −0.0179 (9) | −0.0180 (9) |
| O3 | 0.0770 (12) | 0.0405 (9) | 0.0599 (11) | 0.0171 (8) | −0.0098 (9) | −0.0044 (8) |
| N1 | 0.0405 (10) | 0.0306 (10) | 0.0478 (11) | −0.0032 (8) | −0.0041 (8) | 0.0032 (8) |
| C3 | 0.0471 (13) | 0.0323 (12) | 0.0492 (13) | −0.0021 (10) | −0.0003 (11) | 0.0029 (10) |
| C5 | 0.0394 (11) | 0.0383 (12) | 0.0408 (12) | 0.0034 (9) | −0.0025 (10) | 0.0052 (10) |
| C6 | 0.0495 (14) | 0.0373 (12) | 0.0515 (14) | −0.0002 (10) | −0.0089 (12) | 0.0008 (10) |
| C1 | 0.0356 (11) | 0.0399 (12) | 0.0370 (11) | 0.0027 (9) | 0.0007 (9) | 0.0003 (9) |
| C4 | 0.0355 (11) | 0.0377 (12) | 0.0414 (11) | −0.0002 (9) | −0.0014 (9) | 0.0020 (10) |
| N3 | 0.0697 (14) | 0.0501 (13) | 0.0755 (16) | −0.0045 (11) | −0.0249 (13) | −0.0036 (11) |
| C2—C3 | 1.352 (3) | N1—C5 | 1.348 (3) |
| C2—C1 | 1.411 (3) | N1—C1 | 1.354 (3) |
| C2—H2A | 0.92 (2) | N1—H1 | 0.92 (3) |
| N4—O3 | 1.239 (2) | C3—C4 | 1.411 (3) |
| N4—O2 | 1.239 (2) | C3—H3 | 0.99 (2) |
| N4—O1 | 1.249 (2) | C5—C4 | 1.361 (3) |
| N2—C1 | 1.322 (3) | C5—H5 | 0.94 (2) |
| N2—H2B | 0.90 (2) | C6—N3 | 1.133 (3) |
| N2—H2C | 0.83 (3) | C6—C4 | 1.440 (3) |
| C3—C2—C1 | 119.6 (2) | C2—C3—H3 | 119.4 (13) |
| C3—C2—H2A | 123.7 (12) | C4—C3—H3 | 120.0 (13) |
| C1—C2—H2A | 116.7 (12) | N1—C5—C4 | 120.1 (2) |
| O3—N4—O2 | 120.89 (19) | N1—C5—H5 | 116.3 (12) |
| O3—N4—O1 | 119.08 (18) | C4—C5—H5 | 123.6 (12) |
| O2—N4—O1 | 120.00 (18) | N3—C6—C4 | 177.9 (2) |
| C1—N2—H2B | 117.2 (15) | N2—C1—N1 | 118.9 (2) |
| C1—N2—H2C | 115 (2) | N2—C1—C2 | 123.1 (2) |
| H2B—N2—H2C | 127 (3) | N1—C1—C2 | 118.07 (19) |
| C5—N1—C1 | 123.0 (2) | C5—C4—C3 | 118.77 (19) |
| C5—N1—H1 | 117.7 (16) | C5—C4—C6 | 120.53 (19) |
| C1—N1—H1 | 119.4 (17) | C3—C4—C6 | 120.69 (19) |
| C2—C3—C4 | 120.5 (2) | ||
| C1—C2—C3—C4 | −0.6 (3) | C3—C2—C1—N1 | 0.2 (3) |
| C1—N1—C5—C4 | −0.2 (3) | N1—C5—C4—C3 | −0.3 (3) |
| C5—N1—C1—N2 | −179.4 (2) | N1—C5—C4—C6 | 178.5 (2) |
| C5—N1—C1—C2 | 0.2 (3) | C2—C3—C4—C5 | 0.6 (3) |
| C3—C2—C1—N2 | 179.8 (2) | C2—C3—C4—C6 | −178.2 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2B···O2i | 0.90 (2) | 2.05 (3) | 2.941 (3) | 169 (2) |
| N1—H1···O1i | 0.92 (3) | 1.82 (3) | 2.733 (2) | 170 (2) |
| N1—H1···N4i | 0.92 (3) | 2.62 (3) | 3.505 (3) | 161 (2) |
| N2—H2C···O3 | 0.83 (3) | 2.10 (3) | 2.926 (3) | 174 (3) |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2B···O2i | 0.90 (2) | 2.05 (3) | 2.941 (3) | 169 (2) |
| N1—H1···O1i | 0.92 (3) | 1.82 (3) | 2.733 (2) | 170 (2) |
| N1—H1···N4i | 0.92 (3) | 2.62 (3) | 3.505 (3) | 161 (2) |
| N2—H2C···O3 | 0.83 (3) | 2.10 (3) | 2.926 (3) | 174 (3) |
| Symmetry codes: (i) −x+1/2, 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. igaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wen, X.-C. (2008). Acta Cryst. E64, o1461.
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; Wen 2008). We report here the crystal structure of the title compound.
In the title compound (Fig. 1), the N1 atom of the pyridine ring is protonated. The nitrile group and the pyridinium ring are essentially coplanar. The nitrile group C6≡N3 bond length of 1.133 (3)Å is within the normal range. Crystal cohesion is enforced by N—H···N and N—H···O hydrogen bonds (Table 1, Fig. 2).