4-(4-Pyridylamino)pyridinium perchlorate

Gregory A Farnum; Robert L LaDuca

doi:10.1107/S1600536809003353

. 2009 Jan 31;65(Pt 2):o423. doi: 10.1107/S1600536809003353

4-(4-Pyridylamino)pyridinium perchlorate

Gregory A Farnum ^a, Robert L LaDuca ^a,^*

PMCID: PMC2968340 PMID: 21582011

Abstract

In the title salt, C₁₀H₁₀N₃ ⁺·ClO₄ ⁻, the 4-(4-pyridylamino)pyridinium cations are linked into chains via N—H⋯N hydrogen bonding and into layers by C—H⋯π interactions [C⋯Cg = 3.3875 (19) Å]. Perchlorate ions are anchored to the layer motifs by N—H⋯O hydrogen bonding. The perchlorate anion was found to be disordered about a Cl—O axis, with two sites, each of equal occupancy, being resolved for the three remaining O atoms.

Related literature

For divalent metal adipate coordination polymers incorporating 4,4′-dipyridylamine as a ligand, see: Montney et al. (2007 ▶).

Experimental

Crystal data

C₁₀H₁₀N₃ ⁺·ClO₄ ⁻
M _r = 271.66
Monoclinic,
a = 7.6254 (10) Å
b = 15.991 (2) Å
c = 9.8358 (13) Å
β = 101.913 (1)°
V = 1173.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 173 (2) K
0.36 × 0.24 × 0.18 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.907, T _max = 0.941
12615 measured reflections
2728 independent reflections
2165 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 1.03
2728 reflections
196 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2007 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003353/tk2362sup1.cif

e-65-0o423-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003353/tk2362Isup2.hkl

e-65-0o423-Isup2.hkl^{(134KB, 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—H1N⋯N3ⁱ	0.85 (2)	2.04 (2)	2.839 (2)	157 (2)
N2—H2N⋯O3Aⁱⁱ	0.85 (2)	2.17 (2)	2.873 (8)	140.2 (18)
N2—H2N⋯O4ⁱⁱ	0.85 (2)	2.27 (2)	3.098 (5)	166.1 (19)

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

Acknowledgments

The authors gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

supplementary crystallographic information

Comment

The dipodal tethering ligand 4,4'-dipyridylamine (dpa) has proven beneficial for the construction of divalent metal adipate coordination polymers with novel topologies (Montney et al., 2007). In an attempt to probe the effect of alkyl group substitution on coordination polymer structure by using methyladipate, colourless crystals of the title salt (I) were obtained.

The asymmetric unit of (I) comprises a Hdpa⁺ cation and a perchlorate ion, with three of its O atoms disordered equally over two positions (Fig. 1). The Hdpa⁺ cations aggregate into supramolecular chains, aligned along [201] by means of N—H···N hydrogen bonding interactions between protonated and unprotonated pyridyl rings, Table 1. These chains are organized into layers (Fig. 2), oriented parallel to the ac-plane, and connected by C—H···π interactions between pyridyl rings in neighbouring Hdpa⁺ cations [C1—H1···Cg(N2,C6–C10)ⁱ = 2.82 Å, C1···Cgⁱ = 3.3875 (19) Å with angle at H1 = 119° for i = -1+x, y, z]. Supramolecular interactions are optimized by the 33.77 (8)° torsion angle between the pyridyl rings. Perchlorate anions are anchored to the layer motifs by N—H···O hydrogen bonding; the layers stack along the b-direction (Fig. 3)

Experimental

All chemicals were obtained commercially. Cadmium perchlorate hydrate (20 mg, 0.064 mmol) and methyladipic acid (10 mg, 0.064 mmol) were dissolved in water (1.5 ml) in a glass vial. A 0.75 ml aliquot of a 1:1 water:ethanol mixture was carefully layered onto the aqueous solution, followed by an ethanolic solution (1.5 ml) of 4,4'-dipyridylamine (22 mg, 0.12 mmol). Colourless blocks of the title salt formed after 2 weeks.