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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1527.
Published online 2010 June 5. doi:  10.1107/S1600536810019926
PMCID: PMC3006882

1-Cyano­methyl-4-aza-1-azonia­bicyclo­[2.2.2]octane bromide dihydrate

Abstract

In the crystal structure of the title compound, C8H14N3 +·Br·2H2O, inter­molecular O—H(...)O and O—H(...)Br hydrogen bonding occurs. The water mol­ecules are connected into chains extending in the a-axis direction. The bromide anions are connected to the water mol­ecules, forming 10-membered rings. The cations are connected to the anions via weak C—H(...)Br inter­actions. Two carbon atoms of the cation are disordered and were refined using a split model (occupancy ratio 0.70:0.3).

Related literature

For uses of DABCO (1,4-biaza­bicyclo­[2.2.2]octa­ne) and its derivatives, see: Basaviah et al. (2003 [triangle]); Chen et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1527-scheme1.jpg

Experimental

Crystal data

  • C8H14N3 +·Br·2H2O
  • M r = 268.16
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1527-efi1.jpg
  • a = 7.461 (5) Å
  • b = 12.008 (7) Å
  • c = 13.236 (8) Å
  • V = 1185.8 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.45 mm−1
  • T = 293 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.701, T max = 1.000
  • 13047 measured reflections
  • 2711 independent reflections
  • 2219 reflections with I > 2σ(I)
  • R int = 0.073

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.077
  • S = 1.01
  • 2711 reflections
  • 140 parameters
  • 101 restraints
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.29 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1134 Friedel pairs
  • Flack parameter: 0.033 (14)

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/S1600536810019926/nc2186sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019926/nc2186Isup2.hkl

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

supplementary crystallographic information

Comment

1,4-Diazabicyclo[2.2.2]octane (DABCO) is used as a organocatalyst for a large number of reactions because of its nucleophilicity (Basaviah et al., 2003) and some of its derivatives are ferroelectrics (Chen et al., 2010). The structure determination of the title compound was performed within a project on the electric properties of 1,4-Diazabicyclo[2.2.2]octane derivatives. Within this project the crystals of the title compound were obtained by accident.

In the crystal stucture of the title compound two C atoms of the cation are disordered (Fig. 1). The cations and anions are connected by weak intermolecular C—H···Br interactions. The bromide anions are additionally linked to the water molecules via intermolecular O—H···Br hydrogen bonding and the water molecules are connected into chains that elongate in the direction of the a axis (Fig. 2). Each water molecule act as hydrogen bond donor and acceptor. The bromide anions and the water molecules forming ten-membered rings.

Experimental

1,4-Diaza-bicyclo[2.2.2]octane (dabco) (0.05?mol, 5.6?g) and bromoacetonitrile (0.1?mol, 12.00?g) were dissolved in CH3CN(40?ml). The mixture was stirred for 1?h leading to a white precipitate of the title compound whish was filtered off, washed with acetonitrile and dried. Yield: 80%. Afterwards a mixture of 1-(cyanomethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane bromide (0.01?mol 2.32?g) and tetrafluoro-borate sodium (0.01?mol 1.10?g) in H2O (20?ml) was stirred until a clear solution was obtained. On slow evaporation of the solvent colourless plate crystals of the title compand suitable for X-ray analysis were obtained accidently.

The dielectric constant of the title compound as a function of temperature goes smoothly between 93 and 363?K and there is no dielectric anomaly observed within the measured temperature range.

Refinement

The C—H H atoms were positioned with idealized geometry and refined using a riding model (Uiso(H) = 1.2 Ueq(C). The O—H H atoms were located in difference map, their bond lengths set to ideal values and finally they were refined using a riding model (Uiso(H) = 1.5 Ueq(O). Two carbon atoms are disordered and were refined using a split model and sof of 0.7 and 0.3. The C atoms with lower occupancy were refined only isotropic. The absolute structure was determined on the basis of 1134 Friedel-pairs.

Figures

Fig. 1.
Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30% probability level. Disordering is shown with full and open bonds.
Fig. 2.
Crystal structure of the title compound with view along the a axis. Disordered C and H atoms are omitted and intermolecular hydrogen bonding is shown as dashed lines.

Crystal data

C8H14N3+·Br·2H2OF(000) = 552
Mr = 268.16Dx = 1.502 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3350 reflections
a = 7.461 (5) Åθ = 6.3–55.2°
b = 12.008 (7) ŵ = 3.45 mm1
c = 13.236 (8) ÅT = 293 K
V = 1185.8 (13) Å3Prism, colourless
Z = 40.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer2711 independent reflections
Radiation source: fine-focus sealed tube2219 reflections with I > 2σ(I)
graphiteRint = 0.073
Detector resolution: 13.6620 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −15→15
Tmin = 0.701, Tmax = 1.000l = −17→17
13047 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041w = 1/[σ2(Fo2) + (0.0275P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.29 e Å3
2711 reflectionsΔρmin = −0.29 e Å3
140 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
101 restraintsExtinction coefficient: 0.0055 (11)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1134 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.033 (14)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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*/UeqOcc. (<1)
N10.3080 (4)0.2169 (2)0.79551 (19)0.0332 (7)
C10.3169 (6)0.2800 (3)0.8942 (3)0.0470 (10)
H1A0.37250.23430.94580.056*
H1B0.19720.29970.91650.056*
C20.4287 (6)0.3857 (3)0.8761 (3)0.0623 (11)
H2A0.36170.44990.89950.075*
H2B0.53810.38120.91540.075*
C30.2110 (6)0.2873 (3)0.7178 (3)0.0640 (13)
H3A0.08390.28990.73300.077*0.70
H3B0.22620.25560.65090.077*0.70
H3C0.10460.32080.74700.077*0.30
H3D0.17550.24220.66040.077*0.30
C40.2926 (10)0.4068 (6)0.7216 (5)0.053 (2)0.70
H4A0.30340.43640.65360.063*0.70
H4B0.21480.45570.76000.063*0.70
C4'0.349 (2)0.3801 (15)0.6842 (12)0.078 (8)0.30
H4C0.41510.35550.62530.093*0.30
H4D0.28520.44800.66690.093*0.30
C50.4948 (6)0.1953 (3)0.7609 (4)0.0645 (12)
H5A0.49480.14340.70480.077*0.70
H5B0.56540.16380.81540.077*0.70
H5C0.49240.16610.69260.077*0.30
H5D0.54970.13980.80420.077*0.30
C60.5746 (11)0.3096 (5)0.7274 (8)0.0645 (12)0.70
H6A0.69870.31440.74890.077*0.70
H6B0.57180.31480.65430.077*0.70
C6'0.6115 (17)0.3066 (10)0.7634 (12)0.078 (8)0.30
H6C0.69080.30710.82150.094*0.30
H6D0.68300.31350.70250.094*0.30
N20.4744 (4)0.4012 (3)0.7705 (3)0.0493 (8)
C70.2164 (5)0.1068 (3)0.8091 (3)0.0435 (9)
H7A0.21390.06760.74500.052*
H7B0.28360.06190.85680.052*
C80.0335 (6)0.1213 (3)0.8459 (3)0.0488 (10)
N3−0.1082 (6)0.1335 (3)0.8753 (3)0.0724 (11)
Br10.08721 (5)−0.01932 (3)0.56114 (3)0.05169 (15)
O10.4108 (4)0.1366 (2)0.4565 (2)0.0779 (9)
H1O10.35190.09800.49530.117*
H2O10.49700.14180.49460.117*
O20.2440 (4)0.3445 (2)0.4497 (2)0.0736 (9)
H1O20.28870.28230.44480.110*
H2O20.32070.39320.44580.110*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0371 (15)0.0258 (15)0.0368 (16)0.0016 (13)−0.0012 (12)−0.0057 (12)
C10.061 (3)0.042 (2)0.038 (2)−0.0100 (19)0.0000 (18)−0.0081 (16)
C20.063 (3)0.049 (2)0.074 (3)−0.022 (3)0.012 (3)−0.017 (2)
C30.079 (3)0.056 (3)0.057 (2)−0.013 (3)−0.027 (2)0.021 (2)
C40.070 (4)0.044 (4)0.044 (4)0.010 (3)0.003 (3)0.012 (3)
C4'0.12 (2)0.036 (10)0.081 (15)−0.034 (12)−0.028 (13)0.018 (10)
C50.051 (2)0.041 (2)0.101 (3)0.0023 (19)0.032 (2)−0.009 (2)
C60.051 (2)0.041 (2)0.101 (3)0.0023 (19)0.032 (2)−0.009 (2)
C6'0.076 (13)0.085 (13)0.072 (13)−0.067 (12)0.050 (10)−0.046 (10)
N20.0519 (19)0.0353 (17)0.061 (2)−0.0021 (15)0.0030 (16)0.0087 (16)
C70.051 (2)0.0298 (19)0.049 (2)−0.0041 (18)0.0025 (19)0.0010 (16)
C80.052 (3)0.042 (2)0.052 (2)−0.0124 (19)−0.0037 (19)−0.0013 (18)
N30.058 (3)0.072 (3)0.087 (3)−0.014 (2)0.004 (2)−0.012 (2)
Br10.0441 (2)0.0516 (2)0.0595 (2)0.00308 (19)−0.00010 (19)−0.00776 (18)
O10.0656 (19)0.0689 (19)0.099 (2)0.0058 (19)−0.008 (2)0.0238 (17)
O20.0561 (18)0.0486 (17)0.116 (3)−0.0053 (15)−0.009 (2)0.0014 (18)

Geometric parameters (Å, °)

N1—C51.490 (5)C4'—H4D0.9700
N1—C71.499 (4)C5—C61.560 (8)
N1—C11.511 (4)C5—C6'1.595 (12)
N1—C31.515 (5)C5—H5A0.9700
C1—C21.538 (5)C5—H5B0.9700
C1—H1A0.9700C5—H5C0.9700
C1—H1B0.9700C5—H5D0.9700
C2—N21.451 (5)C6—N21.448 (7)
C2—H2A0.9700C6—H6A0.9700
C2—H2B0.9700C6—H6B0.9700
C3—C41.560 (8)C6'—N21.532 (13)
C3—C4'1.579 (14)C6'—H6C0.9700
C3—H3A0.9700C6'—H6D0.9700
C3—H3B0.9700C7—C81.459 (6)
C3—H3C0.9700C7—H7A0.9700
C3—H3D0.9700C7—H7B0.9700
C4—N21.504 (8)C8—N31.136 (5)
C4—H4A0.9700O1—H1O10.8201
C4—H4B0.9700O1—H2O10.8200
C4'—N21.500 (14)O2—H1O20.8201
C4'—H4C0.9700O2—H2O20.8200
C5—N1—C7108.0 (3)N1—C5—C6'111.0 (5)
C5—N1—C1108.2 (3)C6—C5—C6'20.1 (9)
C7—N1—C1111.0 (3)N1—C5—H5A110.3
C5—N1—C3109.6 (3)C6—C5—H5A110.3
C7—N1—C3110.8 (3)C6'—C5—H5A123.7
C1—N1—C3109.2 (3)N1—C5—H5B110.3
N1—C1—C2107.6 (3)C6—C5—H5B110.3
N1—C1—H1A110.2C6'—C5—H5B90.9
C2—C1—H1A110.2H5A—C5—H5B108.6
N1—C1—H1B110.2N1—C5—H5C109.4
C2—C1—H1B110.2C6—C5—H5C93.5
H1A—C1—H1B108.5C6'—C5—H5C109.4
N2—C2—C1112.6 (3)H5A—C5—H5C18.8
N2—C2—H2A109.1H5B—C5—H5C124.1
C1—C2—H2A109.1N1—C5—H5D109.4
N2—C2—H2B109.1C6—C5—H5D127.7
C1—C2—H2B109.1C6'—C5—H5D109.4
H2A—C2—H2B107.8H5A—C5—H5D90.6
N1—C3—C4107.7 (4)H5B—C5—H5D20.4
N1—C3—C4'105.9 (7)H5C—C5—H5D108.0
C4—C3—C4'26.6 (8)N2—C6—C5111.1 (5)
N1—C3—H3A110.2N2—C6—H6A109.4
C4—C3—H3A110.2C5—C6—H6A109.4
C4'—C3—H3A132.1N2—C6—H6B109.4
N1—C3—H3B110.2C5—C6—H6B109.4
C4—C3—H3B110.2H6A—C6—H6B108.0
C4'—C3—H3B86.8N2—C6'—C5104.9 (8)
H3A—C3—H3B108.5N2—C6'—H6C110.8
N1—C3—H3C110.6C5—C6'—H6C110.8
C4—C3—H3C85.7N2—C6'—H6D110.8
C4'—C3—H3C110.6C5—C6'—H6D110.8
H3A—C3—H3C26.3H6C—C6'—H6D108.8
H3B—C3—H3C128.5C6—N2—C2113.8 (5)
N1—C3—H3D110.6C6—N2—C4'84.0 (10)
C4—C3—H3D130.2C2—N2—C4'124.4 (7)
C4'—C3—H3D110.6C6—N2—C4109.2 (5)
H3A—C3—H3D85.1C2—N2—C4102.0 (4)
H3B—C3—H3D25.6C4'—N2—C427.8 (9)
H3C—C3—H3D108.7C6—N2—C6'21.1 (8)
N2—C4—C3109.0 (5)C2—N2—C6'96.9 (6)
N2—C4—H4A109.9C4'—N2—C6'104.3 (10)
C3—C4—H4A109.9C4—N2—C6'127.5 (6)
N2—C4—H4B109.9C8—C7—N1111.2 (3)
C3—C4—H4B109.9C8—C7—H7A109.4
H4A—C4—H4B108.3N1—C7—H7A109.4
N2—C4'—C3108.2 (9)C8—C7—H7B109.4
N2—C4'—H4C110.1N1—C7—H7B109.4
C3—C4'—H4C110.1H7A—C7—H7B108.0
N2—C4'—H4D110.1N3—C8—C7179.2 (5)
C3—C4'—H4D110.1H1O1—O1—H2O194.5
H4C—C4'—H4D108.4H1O2—O2—H2O2111.1
N1—C5—C6106.9 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O1···Br10.822.583.354 (3)159
O2—H1O2···O10.821.982.791 (4)170
O1—H2O1···O2i0.821.992.788 (5)164
O2—H2O2···Br1i0.822.503.314 (3)172
C7—H7A···Br10.972.813.740 (5)161
C7—H7B···Br1ii0.972.923.792 (8)151

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2186).

References

  • Basaviah, D., Rao, A. J. & Satyanarayana, T. (2003). Chem. Rev.103, 811–891. [PubMed]
  • Chen, L. Z., Huang, Y., Xiong, R. G. & Hu, H. W. (2010). J. Mol. Struct.963, 16–21.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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