2-[2-(1H-Imidazol-3-ium-5-yl)eth­yl]-3-(pyridin-2-yl)-2H-imidazo[1,5-a]pyridin-4-ium bis­(perchlorate)

Murat Türkyılmaz; Yakup Baran; Namık Özdemir

doi:10.1107/S1600536811015625

. 2011 Apr 29;67(Pt 5):o1282. doi: 10.1107/S1600536811015625

2-[2-(1H-Imidazol-3-ium-5-yl)ethyl]-3-(pyridin-2-yl)-2H-imidazo[1,5-a]pyridin-4-ium bis(perchlorate)

Murat Türkyılmaz ^a, Yakup Baran ^b, Namık Özdemir ^c,^*

PMCID: PMC3089310 PMID: 21754563

Abstract

In the title molecular salt, C₁₇H₁₇N₅ ⁺·2ClO₄ ⁻, the dihedral angles between the fused-ring system and the pendant five- and six-membered heterocyclic rings are 6.4 (2) and 41.29 (19)°, respectively. The O atoms of both perchlorate anions are disordered over two sets of sites with occupancy ratios of 0.614 (8):0.386 (8) and 0.591 (7):0.409 (7). An intramolecular C—H⋯N contact occurs in the cation. In the crystal, the components are linked by N—H⋯O and C—H⋯O hydrogen bonds and π–π stacking interactions [centroid–centroid separation = 3.642 (3) Å].

Related literature

For background to the biological properties of imidazopyridine compounds, see: Kaminski & Doweyko (1997 ▶); Sanfillipo et al. (1988 ▶); Lhassani et al. (1999 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₇H₁₇N₅ ²⁺·2ClO₄ ⁻
M _r = 490.26
Monoclinic,
a = 15.044 (6) Å
b = 11.303 (4) Å
c = 12.783 (5) Å
β = 108.009 (15)°
V = 2067.1 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 273 K
0.35 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
19199 measured reflections
4507 independent reflections
2540 reflections with I > 2σ(I)
R _int = 0.083

Refinement

R[F ² > 2σ(F ²)] = 0.074
wR(F ²) = 0.214
S = 1.07
4507 reflections
363 parameters
198 restraints
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004) ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015625/hb5862sup1.cif

e-67-o1282-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015625/hb5862Isup2.hkl

e-67-o1282-Isup2.hkl^{(216.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015625/hb5862Isup3.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
C13—H13A⋯N3	0.97	2.48	3.001 (6)	113
C16—H16⋯O1A	0.93	2.44	3.351 (8)	167
N4—H4N⋯O7A	0.86	1.97	2.807 (10)	165
N5—H5N⋯O4Aⁱ	0.86	2.18	2.927 (16)	145
C11—H11⋯O6Aⁱⁱ	0.93	2.46	3.224 (9)	139
C6—H6⋯O5Aⁱⁱⁱ	0.93	2.60	3.331 (17)	136
C5—H5⋯O6A^iv	0.93	2.43	3.139 (8)	133

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

Acknowledgments

Financial support received from the Scientific and Technological Research Council of Turkey research program 1001 grant for 104 T389 is gratefully acknowledged

supplementary crystallographic information

Comment

Imidazopyridine derivatives are of great importance because of their remarkable biological properties. For example, gastric antisecretory (Kaminski & Doweyko, 1997), local anesthetic (Sanfillipo et al., 1988) and antiviral (Lhassani et al., 1999) properties of imidazo[1,2-a]pyridine derivatives have been described.

The title salt comprises a double protonated 2-[2-(1H-imidazol-3-ium-5-yl)ethyl]-3-(pyridin-2-yl)-2H-imidazo [1,5-a]pyridin-4-ium cation and two perchlorate anion (Fig. 1). The interatomic distances and angles in the title salt show no anomalies.

The molecular structure of the title compound, (I), contains one intramolecular C—H···N contact leading to the formation of a six-membered ring with graph-set descriptor S(6) (Bernstein et al., 1995). In the crystal structure, intermolecular C—H···O and N—H···O type hydrogen bonds and π—π stacking interactions between the (N2/C2—C6) and (N3/C8—C12) pyridine rings interconnect the ions into a three-dimensional supramolecular structure (Table 1).

Experimental

Histamine-HCl (8 mmol, 1.18 g) was dissolved in argon saturated methanol and the solution was placed on a magnetic stirrer at room temperature. 2-Pyridinecarboxaldehyde (10 mmol, 1.08 g) was dissolved in argon saturated methanol and this solution was added to the histamine solution slowly. The final solution was left on a magnetic stirrer and temperature was raised to 333 K and the solution was left there for 24 h. Solvent volume was reduced and the solution was left for crystallization. After several days, brown blocks of (I) were separated, which were collected and dried.