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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1339.
Published online 2010 May 15. doi:  10.1107/S1600536810017071
PMCID: PMC2979413

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

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 [triangle]); Katrusiak & Szafranski (1999 [triangle]); Chen et al. (2008 [triangle]); Fu et al. (2009 [triangle]); Zhao et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1339-scheme1.jpg

Experimental

Crystal data

  • C8H17BrN2 2+·Br·H2PO4 ·H3PO4
  • M r = 496.02
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1339-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 1.03 e Å−3
  • Δρmin = −1.30 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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.

Refinement

All the H atoms were calculated geometrically and refined using a riding model, with N—H = 0.90 Å, C—H = 0.97 Å, O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Crystal data

C8H17BrN22+·Br·H2PO4·H3PO4F(000) = 992
Mr = 496.02Dx = 1.889 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7671 reflections
a = 12.963 (3) Åθ = 3.4–27.5°
b = 7.5959 (15) ŵ = 4.87 mm1
c = 17.721 (4) ÅT = 293 K
β = 92.00 (3)°Prism, colourless
V = 1743.9 (7) Å30.3 × 0.25 × 0.2 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer3097 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.072
graphiteθmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.240, Tmax = 0.379l = −23→22
17431 measured reflections1814 standard reflections
3991 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.10w = 1/[σ2(Fo2) + (0.0703P)2 + 1.8668P] where P = (Fo2 + 2Fc2)/3
3991 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 1.03 e Å3
0 restraintsΔρmin = −1.29 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.8045 (5)0.7487 (8)0.5147 (3)0.0471 (14)
H1A0.82210.64580.54500.057*
H1B0.82400.85270.54360.057*
C20.8627 (4)0.7443 (7)0.4414 (3)0.0352 (11)
H2A0.90450.84960.43740.042*
H2B0.90830.64310.44130.042*
C30.6645 (5)0.9084 (8)0.4485 (3)0.0458 (14)
H3A0.68511.01540.47480.055*
H3B0.59050.91260.43870.055*
C40.7193 (4)0.8955 (6)0.3750 (2)0.0283 (10)
H4A0.76100.99990.36810.034*
H4B0.66900.88870.33330.034*
C50.6608 (5)0.5869 (8)0.4562 (3)0.0491 (15)
H5A0.58750.58940.44340.059*
H5B0.67480.48580.48850.059*
C60.7217 (4)0.5720 (6)0.3848 (3)0.0323 (11)
H6A0.76540.46840.38770.039*
H6B0.67450.55910.34150.039*
C70.8408 (4)0.7146 (7)0.3008 (3)0.0378 (12)
H7A0.88070.60650.30190.045*
H7B0.78880.70470.26030.045*
C80.9111 (5)0.8654 (8)0.2840 (3)0.0492 (14)
H8A0.96380.87780.32380.059*
H8B0.87220.97430.28030.059*
N10.6916 (4)0.7512 (5)0.4966 (2)0.0344 (10)
H1C0.65700.75800.54040.041*
N20.7874 (3)0.7339 (5)0.3752 (2)0.0262 (8)
O10.4055 (3)0.7844 (4)0.65616 (19)0.0342 (8)
H1D0.37130.75030.69140.051*
O20.5835 (3)0.8397 (4)0.6163 (2)0.0407 (9)
O30.5392 (3)0.5469 (4)0.6708 (2)0.0401 (9)
O40.5490 (3)0.8038 (5)0.7549 (2)0.0438 (9)
H4C0.51000.88350.76670.066*
O50.2784 (3)0.9370 (5)0.8525 (3)0.0589 (11)
H5C0.33710.97070.84480.088*
O60.2824 (3)0.6928 (6)0.7558 (2)0.0578 (12)
O70.3544 (4)0.6584 (6)0.8901 (2)0.0622 (12)
H7C0.36390.55480.87940.093*
O80.1613 (4)0.6852 (7)0.8600 (2)0.0734 (15)
H8D0.15110.72970.90990.110*
Br10.11078 (4)0.73719 (7)0.02823 (3)0.03808 (18)
Br20.97424 (5)0.81384 (9)0.18848 (3)0.0491 (2)
P10.52097 (10)0.74245 (15)0.67295 (7)0.0260 (3)
P20.26999 (11)0.73716 (17)0.83560 (8)0.0336 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.053 (4)0.061 (4)0.027 (3)−0.003 (3)−0.015 (2)0.004 (2)
C20.027 (3)0.037 (3)0.041 (3)−0.001 (2)−0.010 (2)−0.003 (2)
C30.054 (3)0.045 (3)0.039 (3)0.018 (3)0.011 (3)0.008 (2)
C40.034 (3)0.025 (2)0.026 (2)0.0043 (19)−0.0025 (19)0.0012 (18)
C50.064 (4)0.044 (3)0.040 (3)−0.024 (3)0.007 (3)−0.005 (3)
C60.038 (3)0.023 (2)0.035 (3)−0.004 (2)−0.008 (2)−0.0012 (19)
C70.040 (3)0.038 (3)0.035 (3)0.004 (2)0.004 (2)−0.008 (2)
C80.048 (3)0.060 (4)0.040 (3)−0.005 (3)0.017 (3)−0.013 (3)
N10.045 (3)0.032 (2)0.026 (2)−0.0003 (18)0.0029 (19)0.0015 (16)
N20.027 (2)0.0226 (18)0.029 (2)0.0039 (15)−0.0020 (16)−0.0014 (15)
O10.0329 (19)0.0411 (19)0.0284 (17)0.0070 (15)−0.0029 (15)0.0076 (15)
O20.052 (2)0.0301 (18)0.042 (2)−0.0086 (16)0.0173 (17)0.0011 (15)
O30.047 (2)0.0254 (17)0.048 (2)0.0046 (15)0.0133 (17)0.0055 (15)
O40.041 (2)0.058 (2)0.0319 (19)0.0148 (18)−0.0095 (16)−0.0110 (17)
O50.053 (2)0.040 (2)0.085 (3)−0.0016 (19)0.014 (2)−0.010 (2)
O60.054 (3)0.088 (3)0.033 (2)−0.016 (2)0.0131 (19)−0.014 (2)
O70.084 (3)0.047 (2)0.055 (3)0.016 (2)−0.007 (2)−0.005 (2)
O80.063 (3)0.113 (4)0.045 (2)−0.044 (3)0.020 (2)−0.022 (3)
Br10.0384 (3)0.0382 (3)0.0377 (3)0.0004 (2)0.0016 (2)−0.0041 (2)
Br20.0453 (4)0.0619 (4)0.0406 (3)−0.0004 (3)0.0118 (3)−0.0015 (3)
P10.0294 (6)0.0237 (6)0.0251 (6)0.0022 (5)0.0035 (5)0.0006 (4)
P20.0386 (7)0.0318 (7)0.0308 (7)−0.0040 (5)0.0064 (6)−0.0031 (5)

Geometric parameters (Å, °)

C1—N11.488 (7)C7—C81.500 (8)
C1—C21.526 (8)C7—N21.517 (6)
C1—H1A0.9700C7—H7A0.9700
C1—H1B0.9700C7—H7B0.9700
C2—N21.501 (6)C8—Br21.945 (5)
C2—H2A0.9700C8—H8A0.9700
C2—H2B0.9700C8—H8B0.9700
C3—N11.501 (6)N1—H1C0.9100
C3—C41.510 (7)O1—P11.549 (4)
C3—H3A0.9700O1—H1D0.8200
C3—H3B0.9700O2—P11.507 (3)
C4—N21.511 (6)O3—P11.505 (3)
C4—H4A0.9700O4—P11.556 (4)
C4—H4B0.9700O4—H4C0.8200
C5—N11.486 (6)O5—P21.550 (4)
C5—C61.519 (7)O5—H5C0.8200
C5—H5A0.9700O6—P21.468 (4)
C5—H5B0.9700O7—P21.554 (4)
C6—N21.509 (6)O7—H7C0.8200
C6—H6A0.9700O8—P21.539 (4)
C6—H6B0.9700O8—H8D0.9600
N1—C1—C2109.1 (4)C8—C7—H7B108.9
N1—C1—H1A109.9N2—C7—H7B108.9
C2—C1—H1A109.9H7A—C7—H7B107.7
N1—C1—H1B109.9C7—C8—Br2107.2 (4)
C2—C1—H1B109.9C7—C8—H8A110.3
H1A—C1—H1B108.3Br2—C8—H8A110.3
N2—C2—C1109.9 (4)C7—C8—H8B110.3
N2—C2—H2A109.7Br2—C8—H8B110.3
C1—C2—H2A109.7H8A—C8—H8B108.5
N2—C2—H2B109.7C5—N1—C1109.8 (4)
C1—C2—H2B109.7C5—N1—C3110.0 (4)
H2A—C2—H2B108.2C1—N1—C3110.0 (4)
N1—C3—C4109.3 (4)C5—N1—H1C109.0
N1—C3—H3A109.8C1—N1—H1C109.0
C4—C3—H3A109.8C3—N1—H1C109.0
N1—C3—H3B109.8C2—N2—C6108.0 (4)
C4—C3—H3B109.8C2—N2—C4108.8 (3)
H3A—C3—H3B108.3C6—N2—C4109.3 (4)
C3—C4—N2110.1 (4)C2—N2—C7112.3 (4)
C3—C4—H4A109.6C6—N2—C7107.2 (4)
N2—C4—H4A109.6C4—N2—C7111.1 (4)
C3—C4—H4B109.6P1—O1—H1D109.5
N2—C4—H4B109.6P1—O4—H4C109.5
H4A—C4—H4B108.2P2—O5—H5C109.5
N1—C5—C6109.0 (4)P2—O7—H7C109.5
N1—C5—H5A109.9P2—O8—H8D109.0
C6—C5—H5A109.9O3—P1—O2112.23 (19)
N1—C5—H5B109.9O3—P1—O1110.5 (2)
C6—C5—H5B109.9O2—P1—O1108.1 (2)
H5A—C5—H5B108.3O3—P1—O4106.7 (2)
N2—C6—C5110.2 (4)O2—P1—O4111.2 (2)
N2—C6—H6A109.6O1—P1—O4108.1 (2)
C5—C6—H6A109.6O6—P2—O8110.1 (3)
N2—C6—H6B109.6O6—P2—O5113.7 (3)
C5—C6—H6B109.6O8—P2—O5104.8 (3)
H6A—C6—H6B108.1O6—P2—O7114.4 (3)
C8—C7—N2113.5 (4)O8—P2—O7111.0 (3)
C8—C7—H7A108.9O5—P2—O7102.3 (2)
N2—C7—H7A108.9
N1—C1—C2—N2−3.1 (6)C1—C2—N2—C461.1 (5)
N1—C3—C4—N2−2.8 (6)C1—C2—N2—C7−175.5 (4)
N1—C5—C6—N2−4.0 (6)C5—C6—N2—C262.0 (5)
N2—C7—C8—Br2178.6 (3)C5—C6—N2—C4−56.2 (5)
C6—C5—N1—C1−58.3 (6)C5—C6—N2—C7−176.8 (4)
C6—C5—N1—C362.8 (6)C3—C4—N2—C2−57.6 (5)
C2—C1—N1—C562.7 (5)C3—C4—N2—C660.1 (5)
C2—C1—N1—C3−58.4 (5)C3—C4—N2—C7178.2 (4)
C4—C3—N1—C5−59.0 (6)C8—C7—N2—C2−60.4 (6)
C4—C3—N1—C162.0 (6)C8—C7—N2—C6−178.9 (4)
C1—C2—N2—C6−57.5 (5)C8—C7—N2—C461.8 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.911.792.667 (6)162
O1—H1D···O60.821.712.519 (5)170
O4—H4C···O3i0.821.802.560 (5)155
O5—H5C···O3i0.821.732.555 (5)179
O7—H7C···O2ii0.821.772.555 (5)159
O8—H8D···Br1iii0.962.183.100 (4)160

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2443).

References

  • Chen, L.-Z., Zhao, H., Ge, J.-Z., Wu, D.-H. & Xiong, R.-G. (2008). Cryst. Growth Des.9, 3828–3831.
  • Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun.12, 994–997.
  • Katrusiak, A. & Szafranski, M. (1999). Phys. Rev. Lett.82, 576–579.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Szafranski, M. & Katrusiak, A. (2008). J. Phys. Chem. B, 112, 6779–6785. [PubMed]
  • Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev.37, 84–100. [PubMed]

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