3-(Piperidin-1-ium-1-yl)-6-azoniaspiro­[5.5]undecane dibromide monohydrate

Jorge Gonzalez; Roberto Atilano-Coral; Ana Lilia Peraza-Campos; David Ortegón-Reyna; Eleuterio Álvarez

doi:10.1107/S1600536811008713

. 2011 May 7;67(Pt 6):o1308–o1309. doi: 10.1107/S1600536811008713

3-(Piperidin-1-ium-1-yl)-6-azoniaspiro[5.5]undecane dibromide monohydrate

Jorge Gonzalez ^a, Roberto Atilano-Coral ^a, Ana Lilia Peraza-Campos ^a, David Ortegón-Reyna ^a, Eleuterio Álvarez ^b,^*

PMCID: PMC3120340 PMID: 21754710

Abstract

The title compound, C₁₅H₃₀N₂ ²⁺·2Br⁻·H₂O, was synthesized by reaction of 4-piperidinopiperidine with dibromopentane. The dication is built up from three linked piperidine rings, two of which have one quaternary N atom in common (azoniaspiro), whereas the third is N—C bonded to the azoniaspiro system and protonated on the N atom (piperidinium). All three piperidine rings adopt chair conformations. The crystal structure features O—H⋯Br and N—H⋯Br hydrogen bonds.

Related literature

For applications of spiro compounds, see: Camblor et al. (2001 ▶); Jiang et al. (1998 ▶); Kolocouris et al. (2007 ▶); Pinto et al. (1992 ▶); Salbeck et al. (2002 ▶). For related structures, see: Clemente (2003 ▶); Day et al. (2005 ▶); Estienne et al. (1984 ▶); Huber (1969 ▶); Monkowius et al. (2004 ▶); Rosen & Guarino (1991 ▶). For the synthesis, see: Tchoubar & Verrier (1960 ▶).

Experimental

Crystal data

C₁₅H₃₀N₂ ²⁺·2Br⁻·H₂O
M _r = 416.25
Monoclinic,
a = 6.5491 (2) Å
b = 23.3325 (9) Å
c = 12.2715 (5) Å
β = 102.141 (1)°
V = 1833.23 (12) Å³
Z = 4
Mo Kα radiation
μ = 4.42 mm⁻¹
T = 173 K
0.34 × 0.32 × 0.30 mm

Data collection

Bruker–Nonius X8 Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.245, T _max = 0.271
28905 measured reflections
5130 independent reflections
4273 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.068
S = 1.03
5130 reflections
190 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008713/qk2002sup1.cif

e-67-o1308-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008713/qk2002Isup2.hkl

e-67-o1308-Isup2.hkl^{(251.2KB, 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
N2—H1N2⋯Br1	0.90	2.36 (1)	3.2425 (11)	168 (2)
O1—H1O1⋯Br2	0.90	2.48 (1)	3.3664 (8)	168 (1)
O1—H2O1⋯Br2ⁱ	0.90	2.54 (1)	3.3528 (7)	151 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Junta de Andalucía (project P09-FQM-4826), CSIC (PIF08–017–1) and the Fondo Mixto CONACyT - Gobierno del Estado de Colima, is gratefully acknowledged by the authors.

supplementary crystallographic information

Comment

In the past few years, spiro compounds having cyclic structures fused at a central nitrogen atom have received great attention due to their potential applications in medicine (Kolocouris et al., 2007; Monkowius et al., 2004; Pinto et al., 1992; Rosen and Guarino, 1991), catalysis (Jiang et al., 1998), optical materials (Salbeck et al., 2002) and zeolitic solids synthesis (Camblor et al., 2001). The title compound was synthesized by reaction of 4-piperidinopiperidine with dibromopentane (Tchoubar and Verrier, 1960).

The structure of the title compound is shown in Fig. 1, and the geometrical parameters are given in the Supplementary Information and the archived CIF. The compound crystallized in the centrosymmetric space group P2₁/c with one dicationic molecule, two bromide anions and one water molecule in the asymmetric unit. The bond lengths and angles in the dicationic molecule are similar to those observed in some azoniaspiro analogues (Clemente, 2003; Day et al., 2005; Estienne et al., 1984; Huber, 1969). In all these compounds quaternary nitrogen centers appear with a very slightly distorted tetrahedral configuration.

One of the two bromide anions, Br1, is N—H···Br hydrogen bonded to a dicationic molecule and embedded in a double layer of the organocations parallel to (010) showing a number of weak C—H···Br interactions with them (Fig. 1). The second bromide, Br2, and the water molecule form infinite hydrogen bonded chains parallel to [001]. These chains are arranged in layers parallel to (010), which are inserted between the double layers of the organocations and Br1 (Fig. 2).

Experimental

The title compound (I) was synthesized by reaction of 4-piperidinopiperidine with dibromopentane. 3.0 g of 4-piperidinopiperidine (0.0178 mol) and 4.09 g of 1,5-dibromopentane (0.0178 mol) were dissolved in 170 ml of ethanol. The mixture was heated under reflux for 48 h. After that, the reaction mixture was cooled at 5 °C for 48 h. The precipitate thus formed was recovered by filtration, washed with fresh ethanol and dried at 80°C overnight (yield 70%) and then recrystallyzed from absolute ethanol. Crystals suitable for single-crystal X-Ray diffraction analysis were isolated and data collection was performed in order to determine the molecular structure of (I). The melting point, 336–337 °C (accompanied by thermal decomposition: bubbles were observed to develop during melting), was determined in a Barnstead 1201D Electrothermal MEL-TEMP apparatus.

NMR spectra were recorded on a Jeol 500 MHz spectrometer with D₂O as solvent. Chemical shifts were expressed in p.p.m. relative to TMS (tetramethylsilane) as internal standard. Signals associated with different hydrogen and carbon atoms (Fig.1) where identified by means of COSY, DEPT and HETCOR experiments.¹H NMR (500 MHz, D₂O): δ 3.95 and 3.32 (d, and m, 2H_1ax-eq, 2H_5ax-eq), 3.61 (m, 1H₃), 3.54 (t, 2H₁₁, 2H₁₅), 3.42 (t, 2H₆, 2H₁₀), 2.30 (m, 2H₂, 2H₄), 1.95 (m, 2H₉, 2H₇), 1.85 (m, 2H₁₂, 2H₁₄, 2H₈), 1.73 (m, 2H₁₃). ¹³C NMR (500 MHz, D₂O): δ 65.1 (C₆, C₁₀), 59.9 (C₃), 57.1 (C₁, C₅), 54.5 (C₁₁, C₁₅), 23.0 (C₁₂, C₁₄), 20.9 (C₁₃), 20.3 (C₂, C₄), 19.3 (C₇, C₉), 18.9 (C₈).