2-Amino-3-methyl­pyridinium 2-amino-5-methyl­pyridinium sulfate monohydrate

Jiang Gong; Gang Chen; Shi-Feng Ni; Yong-Yao Zhang; Hai-Bin Wang

doi:10.1107/S1600536809049241

. 2009 Nov 21;65(Pt 12):o3183. doi: 10.1107/S1600536809049241

2-Amino-3-methylpyridinium 2-amino-5-methylpyridinium sulfate monohydrate

Jiang Gong ^a,^b, Gang Chen ^c, Shi-Feng Ni ^b, Yong-Yao Zhang ^c, Hai-Bin Wang ^d,^*

PMCID: PMC2972034 PMID: 21578895

Abstract

The asymmetric unit of the title compound, 2C₆H₉N₂ ⁺·SO₄ ²⁻·H₂O, contains two isomeric protonated aminomethylpyridine cations, a sulfate anion and a solvent water molecule. The cations are in the iminium tautomeric form. In the crystal structure, intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds link the components into a three-dimensional network. Additional stabilization is provided by weak π–π stacking interactions, with centroid–centroid distances of 3.758 (2) and 3.774 (1) Å.

Related literature

For related structures, see: Nahringbauer & Kvick (1977 ▶); Espenbetov et al. (1985 ▶); Jin et al. (2000 ▶, 2001 ▶, 2005 ▶); Luque et al. (1997 ▶). For studies on the tautomeric forms of 2-aminopyridine systems, see: Inuzuka & Fujimoto (1986 ▶, 1990 ▶); Ishikawa et al. (2002 ▶). graphic file with name e-65-o3183-scheme1.jpg

Experimental

Crystal data

2C₆H₉N₂ ⁺·SO₄ ²⁻·H₂O
M _r = 332.39
Monoclinic,
a = 8.4071 (7) Å
b = 20.7654 (17) Å
c = 9.3369 (8) Å
β = 103.983 (1)°
V = 1581.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.908, T _max = 0.923
8087 measured reflections
2780 independent reflections
2492 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.129
S = 1.06
2780 reflections
207 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049241/lh2943sup1.cif

e-65-o3183-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049241/lh2943Isup2.hkl

e-65-o3183-Isup2.hkl^{(133.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.82	2.657 (2)	164
N2—H2A⋯O2	0.86	2.14	2.991 (3)	170
N3—H3⋯O3	0.86	1.93	2.781 (3)	173
N4—H4A⋯O1	0.86	2.02	2.826 (3)	156
N4—H4B⋯O5	0.86	2.07	2.857 (3)	152
C5—H5⋯O5	0.93	2.41	3.334 (3)	171
O5—H5B⋯O2ⁱ	0.82 (3)	2.03 (3)	2.833 (3)	167 (3)
O5—H5A⋯O3ⁱⁱ	0.80 (2)	2.10 (4)	2.845 (3)	157 (3)
C2—H2⋯O1ⁱⁱⁱ	0.93	2.41	3.334 (3)	176
N2—H2B⋯O4ⁱⁱⁱ	0.86	1.99	2.835 (3)	168
C11—H11⋯O3^iv	0.93	2.56	3.317 (3)	138

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We are grateful for the financial support of the Natural Science Foundation of Tibet (2009-10-12) and the Natural Science Foundation of the Key Laboratory of Resource Biology and Biotechnology in Western China (Northwest University), Ministry of Education (2009-11-12).

supplementary crystallographic information

Comment

We are not aware of any articles which report crystal structures containing different two pyridininium cations and a sulfate cation. We present the crystal structure of the title compound, (I), herein.

The asymmetric unit of the title compound (I) is shown in Fig. 1. Protonation of atom N1 of the 2-amino-5-methyl-pyridine and N3 of 2-amino-3-methyl-pyridine cation results in a widening of the C1—N1—C5 and C7—N3—C11 angles. These values can be compared to those of 117.5 (3)° in neutral 2-amino-5-methyl-pyridine (Nahringbauer & Kvick, 1977) and 118.0 (2)° in neutral 2-amino-3-methyl-pyridine (Espenbetov et al., 1985). The C1-C5/N1 ring and C7-C11/N3 pyridinium rings are both essentially planar, with a maximum deviation from the mean plane of the rings of 0.024 (3)Å for atom N2 and 0.007 (3)Å for atom C9. The geometries of the two pyridinium rings are similar to those observed in other 2-aminopyridine structures (Luque et al., 1997; Jin et al., 2000,2001,2005) that are in the iminium tautomeric form (Inuzuka & Fujimoto, 1986,1990; Ishikawa et al., 2002).

In the crystal structure, intermolecular O-H···O, N-H···O and weak C-H···O hydrogen bonds link the components of the structure into a three-dimensional network (Fig. 2). Additional stabilization is provided by weak π–π stacking interactions with centroid to centroid distances of 3.758 (2) and 3.774 (1)Å.

Experimental

2-Amino-3-methyl-pyridine, 2-amino-5-methyl-pyridine and sulfuric acid were mixed in molar ratio 1:1:1 and dissolved in sufficient water. The solution was stirred and heated until a clear solution resulted. Colourless crystals of (I) were formed by gradual evaporation of excess water over a period of one week at 293 K.