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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m973.
Published online 2009 July 22. doi:  10.1107/S160053680902813X
PMCID: PMC2977123

1,4-Diazo­niabicyclo­[2.2.2]octane tetra­bromidocadmate(II) monohydrate

Abstract

The metal atom in the anion of the title salt, (C6H14N2)[CdBr4]·H2O, shows a slightly distorted tetra­hedral coordination. The water mol­ecule is involved in three hydrogen bonds, viz. one N—H(...)O and two O—H(...)Br, and an N—H(...)Br inter­action consolidates the three-dimensional network.

Related literature

For other ammonium tetra­bromidocadmates, see: Al-Far & Ali (2008 [triangle]); Battaglia et al. (1991 [triangle]); Chen et al. (2006 [triangle]); Geselle & Fuess (1994 [triangle]); Hatano et al. (2008 [triangle]); Ishihara et al. (2002 [triangle], 2006 [triangle]); Ravikumar et al. (1995 [triangle]); Waskowska (1994 [triangle]); Zhang & Fang (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m973-scheme1.jpg

Experimental

Crystal data

  • (C6H14N2)[CdBr4]·H2O
  • M r = 564.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m973-efi1.jpg
  • a = 8.6323 (1) Å
  • b = 11.8736 (2) Å
  • c = 13.5619 (2) Å
  • V = 1390.05 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 13.04 mm−1
  • T = 296 K
  • 0.30 × 0.15 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.111, T max = 0.562 (expected range = 0.103–0.521)
  • 10779 measured reflections
  • 2451 independent reflections
  • 2267 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.187
  • S = 1.36
  • 2451 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 2.21 e Å−3
  • Δρmin = −2.09 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1021 Friedel pairs
  • Flack parameter: 0.14 (3)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902813X/tk2504sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902813X/tk2504Isup2.hkl

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

Acknowledgments

We thank the University of Malaya (RG020/09AFR) for supporting this study.

supplementary crystallographic information

Experimental

Triethylenediammonium dibromide was prepared from the reaction of triethylenediamine (1 g, 1.68 mmol) with bromine (1:2) in the presence of excess hydrobromic acid. To this was added cadmium chloride hemipentahydrate (0.38 g, 1.68 mmol) in ethanol (50 ml). The mixture was heated for an hour. The filtered solution when allow to evaporate slowly yielded colorless crystals.

Refinement

C- and N-bound H atoms were placed at calculated positions (C–H 0.97Å and N–H 0.86 Å) and were treated as riding on their parent atoms with U(H) set to 1.2Ueq(C, N). The water-bound H atoms were placed in chemically sensible positions on the basis of hydrogen bonding interactions but were not refined.

The final difference Fourier map had a peak 0.2 Å from Cd1 and a hole 0.4 Å from Br4.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of [C6H14N2][CdBr4].H2O at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

(C6H14N2)[CdBr4]·H2OF(000) = 1048
Mr = 564.25Dx = 2.696 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6547 reflections
a = 8.6323 (1) Åθ = 2.8–28.2°
b = 11.8736 (2) ŵ = 13.04 mm1
c = 13.5619 (2) ÅT = 296 K
V = 1390.05 (4) Å3Block, colorless
Z = 40.30 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer2451 independent reflections
Radiation source: fine-focus sealed tube2267 reflections with I > 2σ(I)
graphiteRint = 0.034
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.111, Tmax = 0.562k = −14→14
10779 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.187w = 1/[σ2(Fo2) + (0.1P)2 + 5P] where P = (Fo2 + 2Fc2)/3
S = 1.36(Δ/σ)max = 0.001
2451 reflectionsΔρmax = 2.21 e Å3
128 parametersΔρmin = −2.09 e Å3
0 restraintsAbsolute structure: Flack (1983), 1021 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.14 (3)

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

xyzUiso*/Ueq
Cd10.25482 (11)0.47127 (8)1.00019 (6)0.0410 (3)
Br10.3099 (2)0.28309 (13)0.91553 (12)0.0596 (5)
Br20.4870 (2)0.59802 (15)0.95680 (13)0.0579 (5)
Br30.2467 (2)0.46741 (14)1.19150 (10)0.0552 (4)
Br40.0032 (2)0.56945 (19)0.95508 (17)0.0741 (6)
O1W1.151 (3)0.265 (2)0.6666 (18)0.144 (9)
H111.19650.21500.63360.216*
H121.20160.27460.71890.216*
N10.6148 (13)0.4081 (10)0.7757 (7)0.040 (3)
H10.52720.42150.80340.048*
N20.8660 (14)0.3708 (12)0.6978 (13)0.063 (4)
H20.95230.35770.66820.076*
C10.725 (2)0.3684 (14)0.8530 (12)0.056 (4)
H1A0.68600.30080.88460.067*
H1B0.73960.42600.90290.067*
C20.882 (2)0.3435 (18)0.7975 (16)0.086 (8)
H2A0.96470.38770.82640.104*
H2B0.90830.26450.80420.104*
C30.5912 (16)0.3214 (11)0.7016 (12)0.045 (3)
H3A0.51210.34490.65510.054*
H3B0.55770.25190.73260.054*
C40.7409 (17)0.3035 (13)0.6494 (9)0.047 (3)
H4A0.73080.32620.58100.056*
H4B0.76790.22420.65100.056*
C50.6697 (19)0.5139 (11)0.7291 (11)0.044 (3)
H5A0.67810.57290.77830.052*
H5B0.59680.53820.67900.052*
C60.824 (2)0.4924 (13)0.6836 (17)0.066 (5)
H6A0.90160.54000.71430.079*
H6B0.82060.51000.61380.079*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.0398 (5)0.0445 (6)0.0387 (5)0.0007 (4)0.0034 (5)−0.0059 (4)
Br10.0813 (11)0.0441 (8)0.0535 (8)0.0002 (8)0.0191 (7)−0.0081 (7)
Br20.0570 (9)0.0650 (10)0.0515 (8)−0.0032 (8)−0.0029 (7)0.0044 (7)
Br30.0546 (8)0.0682 (10)0.0428 (7)0.0061 (9)0.0040 (7)0.0035 (6)
Br40.0606 (11)0.0862 (13)0.0756 (12)0.0076 (10)−0.0051 (9)−0.0244 (10)
O1W0.150 (18)0.153 (19)0.129 (16)0.073 (17)0.022 (14)0.012 (15)
N10.037 (5)0.063 (7)0.020 (5)−0.003 (5)0.003 (4)−0.009 (5)
N20.029 (6)0.057 (8)0.104 (12)−0.002 (5)0.019 (7)−0.038 (8)
C10.067 (11)0.051 (9)0.051 (8)0.005 (8)−0.023 (8)0.003 (7)
C20.089 (14)0.071 (12)0.099 (15)0.039 (11)−0.064 (13)−0.051 (11)
C30.036 (6)0.031 (7)0.069 (9)0.000 (5)−0.002 (7)0.000 (6)
C40.045 (7)0.056 (8)0.040 (6)−0.008 (7)−0.005 (7)−0.014 (6)
C50.059 (9)0.026 (6)0.045 (7)0.002 (6)0.007 (7)0.000 (6)
C60.066 (11)0.040 (9)0.091 (12)−0.011 (7)0.035 (10)−0.017 (8)

Geometric parameters (Å, °)

Cd1—Br42.540 (2)C1—H1A0.9700
Cd1—Br12.557 (2)C1—H1B0.9700
Cd1—Br22.574 (2)C2—H2A0.9700
Cd1—Br32.596 (2)C2—H2B0.9700
O1W—H110.84C3—C41.49 (2)
O1W—H120.84C3—H3A0.9700
N1—C31.453 (18)C3—H3B0.9700
N1—C51.484 (18)C4—H4A0.9700
N1—C11.491 (18)C4—H4B0.9700
N1—H10.8600C5—C61.49 (2)
N2—C21.40 (3)C5—H5A0.9700
N2—C41.495 (18)C5—H5B0.9700
N2—C61.50 (2)C6—H6A0.9700
N2—H20.8600C6—H6B0.9700
C1—C21.58 (3)
Br4—Cd1—Br1116.87 (7)N2—C2—H2B109.8
Br4—Cd1—Br2110.01 (7)C1—C2—H2B109.8
Br1—Cd1—Br2105.29 (7)H2A—C2—H2B108.2
Br4—Cd1—Br3103.05 (7)N1—C3—C4107.9 (11)
Br1—Cd1—Br3116.00 (7)N1—C3—H3A110.1
Br2—Cd1—Br3105.05 (6)C4—C3—H3A110.1
H11—O1W—H12107.7N1—C3—H3B110.1
C3—N1—C5110.5 (10)C4—C3—H3B110.1
C3—N1—C1110.6 (12)H3A—C3—H3B108.4
C5—N1—C1111.3 (12)C3—C4—N2110.0 (11)
C3—N1—H1108.1C3—C4—H4A109.7
C5—N1—H1108.1N2—C4—H4A109.7
C1—N1—H1108.1C3—C4—H4B109.7
C2—N2—C4111.8 (15)N2—C4—H4B109.7
C2—N2—C6111.8 (15)H4A—C4—H4B108.2
C4—N2—C6106.5 (14)N1—C5—C6108.5 (11)
C2—N2—H2108.9N1—C5—H5A110.0
C4—N2—H2108.9C6—C5—H5A110.0
C6—N2—H2108.9N1—C5—H5B110.0
N1—C1—C2105.7 (13)C6—C5—H5B110.0
N1—C1—H1A110.6H5A—C5—H5B108.4
C2—C1—H1A110.6C5—C6—N2109.1 (12)
N1—C1—H1B110.6C5—C6—H6A109.9
C2—C1—H1B110.6N2—C6—H6A109.9
H1A—C1—H1B108.7C5—C6—H6B109.9
N2—C2—C1109.5 (13)N2—C6—H6B109.9
N2—C2—H2A109.8H6A—C6—H6B108.3
C1—C2—H2A109.8
C3—N1—C1—C260.9 (16)C2—N2—C4—C357.5 (17)
C5—N1—C1—C2−62.3 (16)C6—N2—C4—C3−64.8 (17)
C4—N2—C2—C1−60.2 (17)C3—N1—C5—C6−63.7 (16)
C6—N2—C2—C159.0 (19)C1—N1—C5—C659.6 (16)
N1—C1—C2—N22(2)N1—C5—C6—N22(2)
C5—N1—C3—C458.4 (15)C2—N2—C6—C5−63 (2)
C1—N1—C3—C4−65.3 (15)C4—N2—C6—C559.1 (19)
N1—C3—C4—N26.0 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H11···Br4i0.842.723.15 (3)113
O1w—H12···Br1ii0.842.833.65 (3)167
N1—H1···Br10.862.923.568 (11)134
N2—H2···O1w0.862.042.80 (2)146

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2504).

References

  • Al-Far, R. & Ali, B. F. (2008). J. Chem. Crystallogr.37, 333–341.
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  • Chen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta Cryst. C62, m571–m573. [PubMed]
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  • Westrip, S. P. (2009). publCIF In preparation.
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