6,12-Dihydro­dipyrido[1,2-a:1′,2′-d]pyrazinium bis­(perchlorate)

Nam-Ho Kim; Kwang Ha

doi:10.1107/S1600536809032528

. 2009 Aug 22;65(Pt 9):o2203. doi: 10.1107/S1600536809032528

6,12-Dihydrodipyrido[1,2-a:1′,2′-d]pyrazinium bis(perchlorate)

Nam-Ho Kim ^a, Kwang Ha ^a,^*

PMCID: PMC2969923 PMID: 21577605

Abstract

In the title compound, C₁₂H₁₂N₂ ²⁺·2ClO₄ ⁻, the dihedral angle between the two outer pyridine rings of the dication is 44.8 (1)°. In the crystal, weak intermolecular C—H⋯O hydrogen bonds occur.

Related literature

For the crystal structure of (C₁₂H₁₂N₂)Br₂, see: Bryce et al. (1985 ▶). For a MNDO (modified neglect of diatomic overlap) study of dipyridopyrazinium and related cations, see: Eaves et al. (1986 ▶).

Experimental

Crystal data

C₁₂H₁₂N₂ ²⁺·2ClO₄ ⁻
M _r = 383.14
Monoclinic,
a = 8.1632 (8) Å
b = 13.9396 (14) Å
c = 13.5903 (13) Å
β = 96.023 (2)°
V = 1537.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.22 × 0.16 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.646, T _max = 0.954
11269 measured reflections
3809 independent reflections
1871 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.163
S = 1.06
3809 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.48 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: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032528/om2266sup1.cif

e-65-o2203-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032528/om2266Isup2.hkl

e-65-o2203-Isup2.hkl^{(186.7KB, 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
C1—H1⋯O1	0.93	2.49	3.358 (6)	156
C2—H2⋯O1ⁱ	0.93	2.57	3.160 (5)	122
C4—H4⋯O6ⁱ	0.93	2.54	3.228 (5)	132
C6—H6B⋯O3ⁱⁱ	0.97	2.56	3.343 (5)	137
C7—H7⋯O6ⁱⁱⁱ	0.93	2.45	3.249 (5)	144
C9—H9⋯O7^iv	0.93	2.44	3.190 (5)	138

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

Acknowledgments

This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

supplementary crystallographic information

Comment

The asymmetric unit of the title compound, C₁₂H₁₂N₂²⁺.2ClO₄^-, consists of a 6,12-dihydrodipyrido[1,2-a:1',2'-d]pyrazinium dication and two perchlorate counter-anions (Fig. 1). In the dication, two pyridine rings are linked by two methylene groups and the bridgehead N atoms are disposed on the opposite side of the central six-membered ring which adopts an eclipsed boat conforamtion. The two methylene C atoms (C6 and C12) lie practically on the pyridine ring planes with the largest deviations 0.046 (6) Å (C6) and 0.023 (6) Å (C12) from the respective least-squares planes, and the dihedral angles between these planes is 44.8 (1)°. The geometry of the ClO₄^- anions is nearly tetrahedral with the O—Cl—O bond angles of 107.4 (2)°–112.5 (2)°, and the Cl—O bond distances are almost equal (1.416 (3)–1.426 (3) Å). The compound displays intermolecular C—H···O hydrogen bonds (Table 1 and Fig. 2). There may also be weak intermolecular π-π interactions between adjacent pyridine rings, with a shortest centroid-centroid distance of 5.057 (2) Å.

Experimental

Single crystals of the title compound were unexpectedly obtained as a byproduct of an attempted preparation of an Mn(II) complex by reacting 2-(chloromethyl)pyridine hydrochloride (0.99 g, 6.04 mmol), 1,6-diaminohexane (0.17 g, 1.46 mmol), NaOH (for adjustment of pH 7–8) and Mn(ClO₄)₂.6H₂O (0.37 g, 1.02 mmol) in EtOH (10 ml) and H₂O (5 ml) for 2 h at 60 °C. Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution of the orange reaction product.