supplementary materials
4-Amino-3-ammoniopyridinium dichloride
The anions and cations of the title compound, C5H9N32+·2Cl-, are connected by two chloride-bridged three-centered N-H
Cl hydrogen bonds into a three-dimensional network. The aromatic rings are not involved in stacking interactions.
3,4-diaminopyridine (0.01 mmol) and HCl (0.02 mmol) in 10 ml ethanol. Suitable
crystals for X-ray analysis, were grown by allowing the solution to slowly
evaporate for 15 days, and were subsequently filtered off, washed with
methanol and dried under air.
H atoms were constrained to idealized positions and refined using a riding
model, with C—H distances of 0.93 Å [Uiso(H) =
1.2Ueq(C)], and NH distances of 0.86 Å for NH2
[Uiso(H) = 1.2Ueq(N)]
and 0.89 Å for NH3 [Uiso(H) = 1.5Ueq(N)].
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).
4-Amino-3-ammoniopyridinium dichloride
top
Crystal data top
| C5H9N32+·2Cl− | F(000) = 376 |
| Mr = 182.05 | Dx = 1.493 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2439 reflections |
| a = 8.362 (2) Å | θ = 3.1–28.2° |
| b = 7.3218 (19) Å | µ = 0.73 mm−1 |
| c = 13.239 (3) Å | T = 296 K |
| β = 92.065 (4)° | Block, colorless |
| V = 810.0 (4) Å3 | 0.41 × 0.31 × 0.07 mm |
| Z = 4 | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1494 independent reflections |
| Radiation source: fine-focus sealed tube | 1345 reflections with I > 2σ(I) |
| graphite | Rint = 0.014 |
| φ and ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Bruker, 1997) | h = −10→9 |
| Tmin = 0.734, Tmax = 0.948 | k = −6→8 |
| 3949 measured reflections | l = −16→15 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.068 | H-atom parameters constrained |
| S = 1.14 | w = 1/[σ2(Fo2) + (0.0285P)2 + 0.2927P]
where P = (Fo2 + 2Fc2)/3 |
| 1494 reflections | (Δ/σ)max = 0.001 |
| 92 parameters | Δρmax = 0.24 e Å−3 |
| 0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
| C5H9N32+·2Cl− | V = 810.0 (4) Å3 |
| Mr = 182.05 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.362 (2) Å | µ = 0.73 mm−1 |
| b = 7.3218 (19) Å | T = 296 K |
| c = 13.239 (3) Å | 0.41 × 0.31 × 0.07 mm |
| β = 92.065 (4)° | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1494 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 1997) | 1345 reflections with I > 2σ(I) |
| Tmin = 0.734, Tmax = 0.948 | Rint = 0.014 |
| 3949 measured reflections | θmax = 25.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
| wR(F2) = 0.068 | Δρmax = 0.24 e Å−3 |
| S = 1.14 | Δρmin = −0.24 e Å−3 |
| 1494 reflections | Absolute structure: ? |
| 92 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Cl1 | 0.05806 (5) | 0.10977 (6) | 0.30663 (3) | 0.03884 (15) | |
| Cl2 | 0.51526 (5) | 0.00029 (6) | 0.35359 (3) | 0.03603 (14) | |
| N1 | 0.26647 (16) | 0.68257 (19) | 0.30328 (10) | 0.0320 (3) | |
| H1A | 0.3291 | 0.6281 | 0.2594 | 0.048* | |
| H1B | 0.3026 | 0.7949 | 0.3160 | 0.048* | |
| H1C | 0.1670 | 0.6887 | 0.2772 | 0.048* | |
| N2 | 0.11914 (19) | 0.8105 (2) | 0.48188 (12) | 0.0439 (4) | |
| H2A | 0.1182 | 0.8773 | 0.4284 | 0.053* | |
| H2B | 0.0737 | 0.8485 | 0.5352 | 0.053* | |
| N3 | 0.33856 (18) | 0.3102 (2) | 0.48536 (11) | 0.0376 (4) | |
| H3 | 0.3861 | 0.2061 | 0.4869 | 0.045* | |
| C1 | 0.3383 (2) | 0.4103 (2) | 0.40010 (13) | 0.0329 (4) | |
| H1 | 0.3866 | 0.3649 | 0.3431 | 0.039* | |
| C2 | 0.26762 (18) | 0.5778 (2) | 0.39701 (12) | 0.0271 (3) | |
| C3 | 0.19067 (19) | 0.6488 (2) | 0.48205 (12) | 0.0296 (4) | |
| C4 | 0.1921 (2) | 0.5357 (2) | 0.56891 (13) | 0.0366 (4) | |
| H4 | 0.1422 | 0.5751 | 0.6267 | 0.044* | |
| C5 | 0.2655 (2) | 0.3703 (2) | 0.56862 (14) | 0.0391 (4) | |
| H5 | 0.2656 | 0.2976 | 0.6262 | 0.047* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0414 (3) | 0.0428 (3) | 0.0324 (2) | 0.00951 (19) | 0.00267 (18) | −0.00166 (18) |
| Cl2 | 0.0410 (3) | 0.0298 (2) | 0.0379 (2) | 0.00388 (17) | 0.01080 (18) | 0.00231 (17) |
| N1 | 0.0335 (7) | 0.0344 (8) | 0.0283 (7) | 0.0006 (6) | 0.0044 (6) | −0.0002 (6) |
| N2 | 0.0617 (10) | 0.0360 (8) | 0.0348 (8) | 0.0202 (8) | 0.0147 (7) | 0.0032 (7) |
| N3 | 0.0403 (8) | 0.0265 (7) | 0.0462 (9) | 0.0089 (6) | 0.0023 (7) | 0.0007 (6) |
| C1 | 0.0319 (9) | 0.0323 (9) | 0.0346 (9) | 0.0018 (7) | 0.0031 (7) | −0.0054 (7) |
| C2 | 0.0260 (8) | 0.0283 (8) | 0.0270 (8) | −0.0013 (6) | 0.0012 (6) | −0.0008 (6) |
| C3 | 0.0309 (8) | 0.0274 (8) | 0.0306 (8) | 0.0029 (7) | 0.0017 (7) | −0.0016 (7) |
| C4 | 0.0434 (10) | 0.0377 (10) | 0.0291 (9) | 0.0069 (8) | 0.0069 (7) | 0.0021 (7) |
| C5 | 0.0459 (10) | 0.0366 (10) | 0.0349 (10) | 0.0038 (8) | 0.0013 (8) | 0.0077 (8) |
Geometric parameters (Å, °) top
| N1—C2 | 1.458 (2) | N3—H3 | 0.8600 |
| N1—H1A | 0.8900 | C1—C2 | 1.361 (2) |
| N1—H1B | 0.8900 | C1—H1 | 0.9300 |
| N1—H1C | 0.8900 | C2—C3 | 1.416 (2) |
| N2—C3 | 1.326 (2) | C3—C4 | 1.417 (2) |
| N2—H2A | 0.8600 | C4—C5 | 1.358 (3) |
| N2—H2B | 0.8600 | C4—H4 | 0.9300 |
| N3—C1 | 1.346 (2) | C5—H5 | 0.9300 |
| N3—C5 | 1.353 (2) | | |
| | | |
| C2—N1—H1A | 109.5 | C2—C1—H1 | 119.9 |
| C2—N1—H1B | 109.5 | C1—C2—C3 | 121.06 (15) |
| H1A—N1—H1B | 109.5 | C1—C2—N1 | 119.26 (14) |
| C2—N1—H1C | 109.5 | C3—C2—N1 | 119.65 (14) |
| H1A—N1—H1C | 109.5 | N2—C3—C2 | 122.95 (15) |
| H1B—N1—H1C | 109.5 | N2—C3—C4 | 120.92 (15) |
| C3—N2—H2A | 120.0 | C2—C3—C4 | 116.12 (15) |
| C3—N2—H2B | 120.0 | C5—C4—C3 | 120.64 (16) |
| H2A—N2—H2B | 120.0 | C5—C4—H4 | 119.7 |
| C1—N3—C5 | 121.29 (15) | C3—C4—H4 | 119.7 |
| C1—N3—H3 | 119.4 | N3—C5—C4 | 120.64 (16) |
| C5—N3—H3 | 119.4 | N3—C5—H5 | 119.7 |
| N3—C1—C2 | 120.23 (16) | C4—C5—H5 | 119.7 |
| N3—C1—H1 | 119.9 | | |
| | | |
| C5—N3—C1—C2 | 1.9 (3) | N1—C2—C3—C4 | 177.72 (15) |
| N3—C1—C2—C3 | −1.2 (2) | N2—C3—C4—C5 | 179.99 (18) |
| N3—C1—C2—N1 | −178.99 (14) | C2—C3—C4—C5 | 0.7 (3) |
| C1—C2—C3—N2 | −179.35 (16) | C1—N3—C5—C4 | −1.2 (3) |
| N1—C2—C3—N2 | −1.6 (2) | C3—C4—C5—N3 | −0.1 (3) |
| C1—C2—C3—C4 | −0.1 (2) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl2i | 0.89 | 2.22 | 3.1142 (15) | 178 |
| N1—H1B···Cl2ii | 0.89 | 2.37 | 3.1754 (16) | 151 |
| N1—H1C···Cl1iii | 0.89 | 2.23 | 3.0790 (16) | 160 |
| N2—H2A···Cl1ii | 0.86 | 2.39 | 3.2188 (17) | 163 |
| N2—H2B···Cl1iv | 0.86 | 2.42 | 3.2672 (17) | 168 |
| N3—H3···Cl2 | 0.86 | 2.59 | 3.2499 (16) | 135 |
| N3—H3···Cl2v | 0.86 | 2.70 | 3.3198 (16) | 130 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl2i | 0.89 | 2.22 | 3.1142 (15) | 178 |
| N1—H1B···Cl2ii | 0.89 | 2.37 | 3.1754 (16) | 151 |
| N1—H1C···Cl1iii | 0.89 | 2.23 | 3.0790 (16) | 160 |
| N2—H2A···Cl1ii | 0.86 | 2.39 | 3.2188 (17) | 163 |
| N2—H2B···Cl1iv | 0.86 | 2.42 | 3.2672 (17) | 168 |
| N3—H3···Cl2 | 0.86 | 2.59 | 3.2499 (16) | 135 |
| N3—H3···Cl2v | 0.86 | 2.70 | 3.3198 (16) | 130 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
The authors thank Luo Yang Normal University for supporting this work.
Iyere, P. A., Boadi, W. Y., Atwood, D. & Parkin, S. (2003). Acta Cryst. B59, 664–669.
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.
Jones, P. G., Vancea, F. & Herbst-Irmer, R. (2002). Acta Cryst. C58, o665–o668.
Kochel, A. (2005). Acta Cryst. E61, o926–o927.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sørensen, G. O., Mahler, L. & Rastrup-Andersen, N. (1974). J. Mol. Struct. 20, 119–126.
Sykora, R. E. & Cioffi, E. A. (2007). Acta Cryst. E63, o3148–o3149.
![[Figure 1]](./si2142fig1thm.gif)
![[Figure 2]](./si2142fig2thm.gif)
The title compound is a salt containing a diprotonated 3,4-diaminopyridine cation and two Cl- anions (Fig. 1). The C1—N3—C5 bond angle is wider than that in pyridine (116.94 (3)°; Sørensen et al., 1974) which indicates that the pyridine ring N atom is protonated (Table 1). Also, the 4-amino N atom is protonated. The projection of the crystal packing along the b axis is shown in Fig. 2. The Cl- anions and the 3,4-diaminopyridinium cations in the title compound are bonded by two chlorine-bridged, three-centered N—H···Cl hydrogen bonds into a three-dimensional network (Fig. 2, Table 2). Example structures of related compounds with two- and three-centered N—H···Cl hydrogen bonds are discussed by Iyere et al. (2003); Jones et al. (2002); Kochel (2005) and Sykora & Cioffi (2007).