1-(2-Bromo­ethyl)-1,4-diazo­niabicyclo­[2.2.2]octane bromide dihydrogen phosphate–phospho­ric acid (1/1)

Jing-Mei Xiao

doi:10.1107/S1600536810017071

. 2010 May 15;66(Pt 6):o1339. doi: 10.1107/S1600536810017071

1-(2-Bromoethyl)-1,4-diazoniabicyclo[2.2.2]octane bromide dihydrogen phosphate–phosphoric acid (1/1)

Jing-Mei Xiao ^a,^*

PMCID: PMC2979413 PMID: 21579428

Abstract

In the crystal structure of the title compound, C₈H₁₇BrN₂ ²⁺·Br⁻·H₂PO₄ ⁻·H₃PO₄, the cations, anions and phosphoric acid molecules are linked by O—H⋯O, N—H⋯O and O—H⋯Br hydrogen bonds into layers parallel to (101).

Related literature

For the dielectric properties of N-protonated compounds, see: Szafranski & Katrusiak (2008 ▶); Katrusiak & Szafranski (1999 ▶); Chen et al. (2008 ▶); Fu et al. (2009 ▶); Zhao et al. (2008 ▶).

Experimental

Crystal data

C₈H₁₇BrN₂ ²⁺·Br⁻·H₂PO₄ ⁻·H₃PO₄
M _r = 496.02
Monoclinic,
a = 12.963 (3) Å
b = 7.5959 (15) Å
c = 17.721 (4) Å
β = 92.00 (3)°
V = 1743.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 4.87 mm⁻¹
T = 293 K
0.3 × 0.25 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.240, T _max = 0.379
17431 measured reflections
3991 independent reflections
3097 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.147
S = 1.10
3991 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −1.30 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017071/rz2443sup1.cif

e-66-o1339-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017071/rz2443Isup2.hkl

e-66-o1339-Isup2.hkl^{(195.6KB, 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—H1C⋯O2	0.91	1.79	2.667 (6)	162
O1—H1D⋯O6	0.82	1.71	2.519 (5)	170
O4—H4C⋯O3ⁱ	0.82	1.80	2.560 (5)	155
O5—H5C⋯O3ⁱ	0.82	1.73	2.555 (5)	179
O7—H7C⋯O2ⁱⁱ	0.82	1.77	2.555 (5)	159
O8—H8D⋯Br1ⁱⁱⁱ	0.96	2.18	3.100 (4)	160

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

Acknowledgments

This work was supported by a start-up grant from Southeast University.

supplementary crystallographic information

Comment

The variable-temperature dielectric response, especially in relatively high frequency range, is very useful for searching phase transitions in which there is a dielectric anomaly at the transition temperature (Szafranski & Katrusiak, 2008; Katrusiak & Szafranski, 1999; Chen et al., 2008; Fu et al., 2009; Zhao et al., 2008). Unluckily, the title compound, whose crystal structure is reported herein, has no dielectric disuniformity from 93 K to 400 K (m.p. = 410-412 K).

The asymmetric unit of the title compound (Fig. 1) consists of a 1-(2-bromoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium dication, a bromide anion, a dihydrogenphosphate anion and a phosphoric acid molecule. In the crystal packing (Fig. 2), intermolecular N—H···O, O—H···O and O—H···Br hydrogen interactions (Table 1) link ions and molecules forming layers parallel to the (101) plane.

Experimental

To a solution of 1,4-diazabicyclo[2.2.2]octane (5.6 g, 0.05 mol) in chloroform (20 ml) 1,2-dibromoethane (0.048 mol) was added in one portion and the mixture was refluxed for 8 hour. On standing for about 16 hour at room temperature, colourless hygroscopic crystals of 4-diazabicyclo[2.2.2]octan-1-ium bromide were obtained. The crude product was collected and dissolved in 20 ml methanol, then 1 M H₃PO₄ was dropped slowly with stirring. The white precipitate formed (yield 80%) was filtered and dissolved in the H₂O. After a few weeks, colourless hygroscopic block crystals of the title compound were obtained on slow evaporation of the solvent.