3-(Ammonio­methyl)­pyridinium bis­(perchlorate)

Imen Bayar; Riadh Kefi; Pedro Sidonio Pereira da Silva; Manuela Ramos Silva; Cherif Ben Nasr

doi:10.1107/S1600536813012038

. 2013 May 11;69(Pt 6):o843. doi: 10.1107/S1600536813012038

3-(Ammoniomethyl)pyridinium bis(perchlorate)

Imen Bayar ^a, Riadh Kefi ^a, Pedro Sidonio Pereira da Silva ^b, Manuela Ramos Silva ^b, Cherif Ben Nasr ^a,^*

PMCID: PMC3684928 PMID: 23795030

Abstract

In the title molecular salt, C₆H₁₀N₂ ²⁺·2ClO₄ ⁻, the Cl—O bond lengths [anion 1: 1.369 (3)–1.415 (3); anion 2: 1.420 (2)–1.441 (2) Å] and the O—Cl—O angles [anion 1: 105.4 (2)–111.8 (4); anion 2: 107.8 (1)–110.3 (1)°] indicate a slight distortion of the perchlorate anions from regular tetrahedral symmetry. In the crystal, the components are linked into columns along the a-axis direction via N—H⋯O and C—H⋯O hydrogen bonds, with stacks of the organic molecules being surrounded by stacks of perchlorate anions.

Related literature

For general background to perchlorate salts with organic cations, see: Czarnecki et al. (1994 ▶); Czupinski et al. (2002 ▶, 2006 ▶). For related structures, see: Kapplinger & Keutel (1999 ▶); Ye et al. (2002 ▶) graphic file with name e-69-0o843-scheme1.jpg

Experimental

Crystal data

C₆H₁₀N₂ ²⁺·2ClO₄ ⁻
M _r = 309.06
Monoclinic,
a = 5.1947 (1) Å
b = 12.1221 (3) Å
c = 18.2724 (5) Å
β = 98.067 (1)°
V = 1139.24 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 293 K
0.44 × 0.33 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.765, T _max = 0.875
26338 measured reflections
3509 independent reflections
3007 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.148
S = 1.06
3509 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(16KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012038/lr2104sup1.cif

e-69-0o843-sup1.cif^{(16KB, cif)}

Click here for additional data file.^{(168.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012038/lr2104Isup2.hkl

e-69-0o843-Isup2.hkl^{(168.6KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813012038/lr2104Isup3.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
N1—H1⋯O5	0.86	2.16	2.901 (3)	144
N1—H1⋯O7ⁱ	0.86	2.36	2.945 (3)	125
N2—H2A⋯O2ⁱⁱ	0.89	2.09	2.866 (3)	146
N2—H2A⋯O6ⁱⁱⁱ	0.89	2.54	3.166 (3)	128
N2—H2B⋯O6ⁱⁱ	0.89	2.10	2.925 (3)	155
N2—H2B⋯O3^iv	0.89	2.47	2.922 (4)	112
N2—H2C⋯O1^v	0.89	2.08	2.933 (3)	160
C5—H5⋯O1^vi	0.93	2.54	3.350 (4)	145
C6—H6A⋯O8^vii	0.97	2.50	3.137 (3)	123

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

Acknowledgments

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia. PSPS acknowledges support by the Fundação para a Ciência e a Tecnologia (FCT), under scholarship SFRH/BPD/84173/2012.

supplementary crystallographic information

Comment

Studies of perchlorate salts containing organic cations have had a great deal of attention in recent years, because of their ferroelectric and dielectric behaviour (Czupinski et al., 2002; Czupinski et al., 2006). It was shown that dynamics of pyridinium cations contributes mainly to the mecanism of solid-solid phase transition and leads ferroelectricity in these molecular-ionic crystals (Czarnecki et al., 1994) Here, we report the synthesis and the crystal structure of the title compound (I), (C₆H₁₀N₂)(ClO₄)₂.

The structure consists of one 3-ammoniomethylpyrinidinium dication and two perchlorate anions (Fig. 1). In the crystal, the three H atoms of the ammonium group are involved into N—H···Cl and N—H···O hydrogen bonds: N2—H2C···Cl1(v), N2—H2B···Cl2(ii), N2—H2C···O1(v), N2—H2A··· (O6vi, O2iv) and N2—H2B··· (O6iv, O3vii), the two laters are bifurcated (for the symmetry codes, see Table 1). These hydrogen bonds link the ionic units (NH₃⁺ and [ClO₄]^-) to form columns running along the a-axis direction (Fig.2) and situated at y = z = 1/2 (Fig.3). The organic groups are located between these columns via two kinds of hydrogen bonds: a bifurcated N—H···O and two C—H···O: N1—H1 (O5, O7viii), C6—H6A···O8(iii) and C5—H5···O1(vi) (Fig. 3, Table 1). No π-π stacking interactions between the organic rings or C—H··· π interactions towards them are observed. It is worth noting that the C—N—C angles of pyridine are very sensitive to protonation: a pyridinium cation always has an expanded angle of the C—N—C in comparison with the parent pydidine. The angle C(5)—N(1)—C(1) [123.4 (2)°] is consistent with the type of pyridinium cation. The hydrogen atom HN(1), which is deprived from its parent, attaches the nitrogen atom. As expected, the [ClO₄]^- anion has typical tetrahedral geometry where the Cl—O bond lengths and O—Cl—O angles are not equal to one another but vary with the environment around the O atoms. In the title compound, the Cl—O bond lengths vary from 1.369 (3) to 1.415 (3) Å for [Cl(1)O₄]^- anion and from 1.420 (2) to 1.440 (2) Å for [Cl(2)O₄]^- anion are comparable to that previuosly reported for the perchlorate anions (Kapplinger & Keutel, 1999). The O—Cl—O angles range from 105.4 (2) to 111.8 (4)° for the first anion and from 109.04 (15) to 110.33 (13)° for the second one. These values, which are characteristic of perchlorate anions (Ye et al., 2002), clearly indicate that the coordination geometry of the Cl(2) atom can be regarded as being a less distorted tetrahedron than the one of the Cl(1). However, for the Cl(2)O₄ tetrahedron, all the oxygen atoms are involved in hydrogen bonds, while only three oxygen atoms act as acceptors of hydrogen bonds for the [Cl(1)O₄] tetrahedron.

Experimental

3-ammoniomethylpyrinidinium (1 mmol, 0.108 g) was dissolved in a mixture of distilled water (10 ml) and perchloric acid (0.5 ml).The resultant solution was evaporated at room temperature. Crystals of the title compound, which remained stable under normal conditions of temperature and humidity, were isolated after several days and subjected to X-ray diffraction analysis (yield 64%).