3-Carb­oxy-2-(2-cyclo­propyl­amino-4-methyl­pyridinium-3-yl­amino)­pyridinium dinitrate dihydrate

Qiong Dong; Shouwen Jin; Kai Tong; Haidong He; YuanQi Yu

doi:10.1107/S1600536811040323

. 2011 Oct 8;67(Pt 11):o2864. doi: 10.1107/S1600536811040323

3-Carboxy-2-(2-cyclopropylamino-4-methylpyridinium-3-ylamino)pyridinium dinitrate dihydrate

Qiong Dong ^a, Shouwen Jin ^b,^*, Kai Tong ^a, Haidong He ^a, YuanQi Yu ^a

PMCID: PMC3247599 PMID: 22219904

Abstract

The two benzene rings in the cation of the title compound, C₁₅H₁₈N₄O₂ ²⁺·2NO₃ ⁻·2H₂O, are almost perpendicular [dihedral angle = 91.6 (2)°]. In the crystal, the components are linked by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000 ▶); Desiraju (2002 ▶); Liu et al. (2008 ▶); Biswas et al. (2009 ▶); Jin et al. (2010 ▶).

Experimental

Crystal data

C₁₅H₁₈N₄O₂ ²⁺·2NO₃ ⁻·2H₂O
M _r = 446.39
Orthorhombic,
a = 7.4463 (6) Å
b = 15.0032 (14) Å
c = 35.975 (2) Å
V = 4019.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.44 × 0.36 × 0.34 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.947, T _max = 0.958
18931 measured reflections
3540 independent reflections
1964 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.084
wR(F ²) = 0.295
S = 1.04
3540 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536811040323/jh2324sup1.cif

e-67-o2864-sup1.cif^{(21KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040323/jh2324Isup2.hkl

e-67-o2864-Isup2.hkl^{(173.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040323/jh2324Isup3.cml

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
O10—H10D⋯O8ⁱ	0.85	2.10	2.942 (8)	171
O10—H10C⋯O4ⁱⁱ	0.85	2.19	3.037 (7)	172
O9—H9D⋯O5ⁱⁱⁱ	0.85	2.55	3.089 (7)	123
O9—H9D⋯O4ⁱⁱⁱ	0.85	2.07	2.916 (6)	174
O9—H9C⋯O1^iv	0.85	1.96	2.809 (5)	173
O2—H2A⋯O9^v	0.82	1.73	2.535 (5)	168
N4—H4⋯O7^vi	0.86	1.94	2.787 (6)	166
N3—H3⋯O6	0.86	2.01	2.746 (6)	143
N2—H2⋯O3	0.86	1.98	2.810 (5)	163
N1—H1⋯O10	0.86	2.22	2.900 (6)	136
N1—H1⋯O1	0.86	2.05	2.697 (4)	131
C4—H4A⋯O5^vii	0.93	2.34	3.162 (7)	147
C6—H6⋯O3^iv	0.93	2.26	3.161 (6)	162
C11—H11⋯O8^vi	0.93	2.57	3.252 (8)	131
C15—H15A⋯O3ⁱⁱ	0.96	2.58	3.533 (7)	174

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

Acknowledgments

We gratefully acknowledge financial support by the Education Office Foundation of ZheJiang Province (project No. Y201017321) and the Innovation Project of ZheJiang A & F University.

supplementary crystallographic information

Comment

Intermolecular interactions are responsible for crystal packing and gaining an understanding of them allows us to comprehend collective properties and permits the design of new crystals with specific physical and chemical properties (Lam & Mak, 2000). Hydrogen bonding is one of the most important noncovalent interactions that determines and controls the assembly of molecules and ions (Desiraju, 2002, Liu et al., 2008, Biswas et al., 2009).

Organic salts based on hydrogen bonding are also a research field receiving great attention in recent years. As an extension of our study concentrating on hydrogen bonded assembly of organic acid and organic base (Jin et al., 2010), herein we report the crystal structure of 2-(2-(cyclopropylamino)-4-methylpyridinium-3-ylamino) nicotinic acid dinitrate dihydrate.

The crystal of the title compound of the formula C₁₅H₂₂N₆O₁₀ was obtained by recrystallization of 2-(2-(cyclopropylamino)-4-methylpyridin-3-ylamino) nicotinic acid from aqueous solution of HNO₃.

The asymmetric unit of the compound consists of one dication, two nitrate anions, and two free water molecules (Fig. 1), respectively.

The compound is an organic salt. At every cation there are bound two nitrate anions through the N—H···O hydrogen bond. And the two water molecules were connected with carbonyl and OH of the carboxyl group of the cation rspectively via the O—H···O hydrogen bond. Under these interactions the cation, the anions, and the water molecules form a pentacomponent adduct. Such kind of adducts were connected together by the N—H···O, O—H···O, O-pi, and CH₂—O interactions to form a one-dimensional chain running along the a axis direction. Two such chains were joined together via the CH—O, and CH₂—O interactions to form double chain structure (Fig. 2). The double chains were linked together via the water molecule that is bound with the carboxyl group to form two-dimensional sheet extending along the ac plane. The two-dimensional sheets further stacked along the b axis direction through the nitrate group to form three-dimensional layer network structure.

Experimental

A solution of 2-(2-(cyclopropylamino)-4-methylpyridin-3-ylamino) nicotinic acid (28.4 mg, 0.1 mmol) was dissolved in 5 ml of water and 1 ml of conc. HNO₃ under continuous stirring. The solution was stirred for about 1 h at room temperature, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days, colorless block crystals were isolated after slow evaporation of the solution in air at ambient temperature. The crystals were collected and dried in air to give the title compound.