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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1672.
Published online 2010 November 27. doi:  10.1107/S1600536810047495
PMCID: PMC3011683

1-Cyano­methyl-1,4-diazo­niabicyclo­[2.2.2]octane tetra­bromidocadmate(II)

Abstract

In the title salt, (C8H15N3)[CdBr4], four Br atoms coordinate the CdII atom in a distorted tetra­hedral geometry. In the crystal, weak N—H(...)Br inter­actions connect the anion to three symmetry-related cations. The crystal structure also displays very weak C—H(...)Br inter­actions.

Related literature

For background to 1,4-diaza­bicyclo­[2.2.2]octane derivatives and their properties, see: Basavaiah et al. (2003 [triangle]); Chen et al. (2010 [triangle]); Wang et al. (2005 [triangle]); Xiong et al. (2002 [triangle]); Ye et al. (2006 [triangle]).

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Object name is e-66-m1672-scheme1.jpg

Experimental

Crystal data

  • (C8H15N3)[CdBr4]
  • M r = 585.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1672-efi1.jpg
  • a = 8.610 (3) Å
  • b = 14.071 (4) Å
  • c = 12.702 (4) Å
  • β = 94.136 (4)°
  • V = 1534.9 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 11.82 mm−1
  • T = 293 K
  • 0.2 × 0.2 × 0.2 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.470, T max = 1.000
  • 16630 measured reflections
  • 3518 independent reflections
  • 2861 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.079
  • S = 0.76
  • 3518 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.88 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/S1600536810047495/bh2319sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047495/bh2319Isup2.hkl

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

Acknowledgments

The author is grateful to the starter fund of Southeast University for the purchase of the diffractometer.

supplementary crystallographic information

Comment

We are studying the dielectric-ferroelectric materials. 1,4-Diazabicyclo[2.2.2]octane (DABCO) has attracted attention in recent years because of its nucleophilicity (Basavaiah et al., 2003; Xiong et al., 2002) and ferroelectric properties of its derivatives (Chen et al., 2010). For a project on the electric properties of DABCO derivatives (Ye et al., 2006), the title compound was prepared. With no dielectric anomaly observed, the title compound should not be a real ferroelectrics or there may be no distinct phase transition occurring within the measured temperature range (Wang et al., 2005).

The asymmetric unit of the title compound is shown in Fig 1. The Cd atoms are coordinated by four Br atoms with very similar distances in the range 2.5764 (10) to 2.6195 (12) Å. The Br—Cd—Br bond angles are between 98.29 (3) and 116.85 (4)°, which show that the coordination polyhedron can be described as an irregular tetrahedron. Cations (C8H14N3)2+ and anions CdBr42- are connected via weak hydrogen bonds. Weak C—H···Br intramolecular and intermolecular hydrogen bonds also contribute to the stability of the crystal structure, forming one-dimensional chains running along the a axis (Fig. 2).

Experimental

1,4-Diaza-bicyclo[2.2.2]octane (DABCO) (10 mmol, 1.14 g) and bromoacetonitrile (20 mmol, 2.4 g) were dissolved in CH3CN (10 ml) under stirring for 1 h. at room temperature. 1-(Cyanomethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane bromide was obtained by filtering the solid precipitate, then washed with acetonitrile and dried (yield: 90%).

CdBr2 (10 mmol, 0.271 g) and 4 ml 60% HBr were dissolved in MeOH (20 ml) and 1-(cyanomethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane bromide (20 mmol, 0.464 g) dissolved in 10 ml of methanol was added. The mixture was stirred until the solution was clear. After slow evaporation (5 days) of the solvent, colourless plate crystals of the title compound were obtained in about 56% yield.

Refinement

H atoms bonded to C and N atoms were placed in idealized positions [C—H = 0.97 Å and N—H = 0.90 Å] and allowed to ride on their parent atoms with Uiso fixed at 1.2 Ueq(Carrier atom).

Figures

Fig. 1.
The structure of the title compound with labeling scheme and displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
The crystal structure of the title compound viewed down the c axis. Intermolecular interactions are shown as dashed lines.

Crystal data

(C8H15N3)[CdBr4]F(000) = 1088
Mr = 585.27Dx = 2.533 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4263 reflections
a = 8.610 (3) Åθ = 2.4–27.5°
b = 14.071 (4) ŵ = 11.82 mm1
c = 12.702 (4) ÅT = 293 K
β = 94.136 (4)°Prism, colourless
V = 1534.9 (8) Å30.2 × 0.2 × 0.2 mm
Z = 4

Data collection

Rigaku Mercury CCD diffractometer3518 independent reflections
Radiation source: fine-focus sealed tube2861 reflections with I > 2σ(I)
graphiteRint = 0.068
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −18→18
Tmin = 0.470, Tmax = 1.000l = −16→16
16630 measured 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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 0.76w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2386P] where P = (Fo2 + 2Fc2)/3
3518 reflections(Δ/σ)max = 0.018
145 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = −0.88 e Å3
0 constraints

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

xyzUiso*/Ueq
Cd10.78773 (4)0.22670 (2)0.50861 (3)0.02924 (11)
Br10.82000 (6)0.40556 (3)0.46315 (4)0.03047 (13)
Br20.79028 (6)0.24284 (3)0.71414 (4)0.03420 (13)
Br30.52068 (6)0.15357 (3)0.45098 (4)0.03464 (13)
Br41.03019 (6)0.13565 (3)0.45657 (4)0.03694 (14)
C80.4254 (6)0.4480 (3)0.6975 (4)0.0314 (11)
N20.6179 (4)0.5753 (2)0.7314 (3)0.0205 (7)
C50.9032 (5)0.5513 (3)0.7405 (4)0.0328 (11)
H5A0.97840.55640.80080.039*
H5B0.94440.50810.68980.039*
N10.8754 (4)0.6469 (2)0.6913 (3)0.0242 (8)
H1C0.96100.67500.66910.029*
C60.7506 (6)0.5138 (3)0.7750 (4)0.0378 (12)
H6A0.73500.44900.75010.045*
H6B0.75320.51320.85150.045*
C40.6267 (5)0.5849 (3)0.6140 (3)0.0294 (10)
H4A0.53650.61950.58420.035*
H4B0.62630.52240.58190.035*
C30.7744 (5)0.6376 (3)0.5904 (3)0.0283 (10)
H3A0.82930.60270.53870.034*
H3B0.74860.70000.56200.034*
C20.6364 (6)0.6733 (3)0.7808 (4)0.0316 (11)
H2A0.55860.71600.74840.038*
H2B0.62150.66960.85570.038*
C70.4643 (5)0.5354 (3)0.7579 (3)0.0279 (10)
H7A0.46770.52150.83280.034*
H7B0.38350.58250.74240.034*
N30.3933 (6)0.3830 (3)0.6497 (4)0.0459 (12)
C10.7981 (5)0.7107 (3)0.7646 (4)0.0300 (10)
H1A0.79090.77440.73540.036*
H1B0.85900.71350.83180.036*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.02631 (19)0.03071 (19)0.0309 (2)−0.00124 (14)0.00314 (15)0.00137 (14)
Br10.0324 (3)0.0264 (2)0.0335 (3)0.00131 (19)0.0088 (2)−0.00169 (18)
Br20.0285 (3)0.0477 (3)0.0266 (3)0.0031 (2)0.0034 (2)0.0044 (2)
Br30.0287 (3)0.0421 (3)0.0334 (3)−0.0064 (2)0.0042 (2)−0.0070 (2)
Br40.0334 (3)0.0351 (3)0.0433 (3)0.0054 (2)0.0086 (2)0.0016 (2)
C80.029 (3)0.026 (2)0.039 (3)−0.008 (2)0.003 (2)0.010 (2)
N20.0180 (18)0.0228 (18)0.0213 (18)0.0003 (14)0.0053 (15)0.0002 (14)
C50.023 (2)0.032 (3)0.043 (3)0.007 (2)0.003 (2)0.002 (2)
N10.0148 (18)0.031 (2)0.029 (2)−0.0028 (15)0.0094 (15)−0.0017 (15)
C60.027 (3)0.034 (3)0.052 (3)0.008 (2)−0.003 (2)0.015 (2)
C40.027 (3)0.045 (3)0.016 (2)−0.004 (2)0.0037 (19)−0.0024 (18)
C30.025 (2)0.035 (3)0.026 (2)−0.002 (2)0.007 (2)0.0022 (18)
C20.033 (3)0.031 (2)0.033 (3)−0.003 (2)0.015 (2)−0.013 (2)
C70.020 (2)0.033 (2)0.032 (3)−0.0025 (19)0.0067 (19)0.0061 (19)
N30.051 (3)0.032 (2)0.053 (3)−0.012 (2)−0.004 (2)0.011 (2)
C10.028 (2)0.028 (2)0.035 (3)−0.003 (2)0.008 (2)−0.0084 (19)

Geometric parameters (Å, °)

Cd1—Br32.5766 (8)N1—H1C0.8997
Cd1—Br42.5760 (8)C6—H6A0.9700
Cd1—Br12.6015 (9)C6—H6B0.9700
Cd1—Br22.6191 (10)C4—C31.521 (6)
C8—N31.122 (6)C4—H4A0.9700
C8—C71.475 (6)C4—H4B0.9700
N2—C71.497 (5)C3—H3A0.9700
N2—C61.506 (5)C3—H3B0.9700
N2—C41.505 (5)C2—C11.516 (6)
N2—C21.519 (5)C2—H2A0.9700
C5—N11.495 (5)C2—H2B0.9700
C5—C61.510 (7)C7—H7A0.9700
C5—H5A0.9700C7—H7B0.9700
C5—H5B0.9700C1—H1A0.9700
N1—C11.485 (5)C1—H1B0.9700
N1—C31.501 (5)
Br3—Cd1—Br4116.84 (3)N2—C4—C3110.0 (3)
Br3—Cd1—Br1115.51 (2)N2—C4—H4A109.7
Br4—Cd1—Br1108.83 (2)C3—C4—H4A109.7
Br3—Cd1—Br2105.13 (2)N2—C4—H4B109.7
Br4—Cd1—Br2110.50 (2)C3—C4—H4B109.7
Br1—Cd1—Br298.28 (2)H4A—C4—H4B108.2
N3—C8—C7178.1 (5)N1—C3—C4108.4 (3)
C7—N2—C6111.2 (3)N1—C3—H3A110.0
C7—N2—C4111.4 (3)C4—C3—H3A110.0
C6—N2—C4109.0 (3)N1—C3—H3B110.0
C7—N2—C2108.3 (3)C4—C3—H3B110.0
C6—N2—C2108.4 (4)H3A—C3—H3B108.4
C4—N2—C2108.5 (3)C1—C2—N2109.2 (3)
N1—C5—C6108.6 (4)C1—C2—H2A109.8
N1—C5—H5A110.0N2—C2—H2A109.8
C6—C5—H5A110.0C1—C2—H2B109.8
N1—C5—H5B110.0N2—C2—H2B109.8
C6—C5—H5B110.0H2A—C2—H2B108.3
H5A—C5—H5B108.3C8—C7—N2111.5 (4)
C5—N1—C1110.3 (3)C8—C7—H7A109.3
C5—N1—C3110.1 (3)N2—C7—H7A109.3
C1—N1—C3109.2 (3)C8—C7—H7B109.3
C5—N1—H1C114.6N2—C7—H7B109.3
C1—N1—H1C110.2H7A—C7—H7B108.0
C3—N1—H1C102.0N1—C1—C2109.4 (3)
N2—C6—C5110.1 (4)N1—C1—H1A109.8
N2—C6—H6A109.6C2—C1—H1A109.8
C5—C6—H6A109.6N1—C1—H1B109.8
N2—C6—H6B109.6C2—C1—H1B109.8
C5—C6—H6B109.6H1A—C1—H1B108.2
H6A—C6—H6B108.1

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···Br1i0.902.853.466 (4)127
N1—H1C···Br2ii0.902.693.325 (4)128
N1—H1C···Br4i0.903.113.711 (4)126
C2—H2B···Br3iii0.972.833.765 (5)162
C4—H4B···Br10.972.853.643 (4)140
C7—H7A···Br3iv0.972.903.626 (4)132
C7—H7B···Br2iii0.972.783.683 (4)154

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2319).

References

  • Basavaiah, D., Rao, A. J. & Satyanarayana, T. (2003). Chem. Rev.103, 811–892. [PubMed]
  • Chen, L.-Z., Huang, Y., Xiong, R.-G. & Hu, H.-W. (2010). J. Mol. Struct.963, 16–21.
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, X.-S., Song, Y.-M. & Xiong, R.-G. (2005). Chin. J. Inorg. Chem.21, 1030–1033.
  • Xiong, R. G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z. (2002). Angew. Chem. Int. Ed.41, 3800–3803. [PubMed]
  • Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K., Fu, D.-W., Chan, P. W. H., Zhu, J.-S., Huang, S. D. & Xiong, R.-G. (2006). J. Am. Chem. Soc.128, 6554–6555. [PubMed]

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