metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 16 July 2009; accepted 17 July 2009; online 22 July 2009)

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[Al-Far, R. & Ali, B. F. (2008). J. Chem. Crystallogr. 37, 333-341.]); Battaglia et al. (1991[Battaglia, L. P., Corradiab, B., Cariatif, K. & Koman, M. (1991). Inorg. Chim. Acta, 187, 141-147.]); Chen et al. (2006[Chen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta Cryst. C62, m571-m573.]); Geselle & Fuess (1994[Geselle, M. & Fuess, H. (1994). Acta Cryst. C50, 1582-1585.]); Hatano et al. (2008[Hatano, N., Nakashima, M., Horiuchi, K., Terao, H. & Ishihara, H. (2008). Z. Naturforsch. Teil B, 63, 1181-1186.]); Ishihara et al. (2002[Ishihara, H., Horiuchi, K., Gesing, T. M., Dou, S.-Q., Buhl, J. C. & Erk, P. (2002). Z. Natursforsch. 57, 503-508.], 2006[Ishihara, H., Koriuchi, K., Svoboda, I., Fuess, H., Gesing, T. M., Buhl, J. C. & Terao, H. (2006). Z. Naturforsch. Teil B, 61, 69-72.]); Ravikumar et al. (1995[Ravikumar, K., Venkata Lakshmi, N., Swamy, G. Y. S. K. & Chandra Mohan, K. (1995). Acta Cryst. C51, 1556-1558.]); Waskowska (1994[Waskowska, A. (1994). Z. Kristallogr. 209, 750-754.]); Zhang & Fang (2005[Zhang, H. & Fang, L. (2005). Acta Cryst. E61, m101-m102.]).

[Scheme 1]

Experimental

Crystal data
  • (C6H14N2)[CdBr4]·H2O

  • Mr = 564.25

  • Orthorhombic, P 21 21 21

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.111, Tmax = 0.562 (expected range = 0.103–0.521)

  • 10779 measured reflections

  • 2451 independent reflections

  • 2267 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1021 Friedel pairs

  • Flack parameter: 0.14 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1w—H11⋯Br4i 0.84 2.72 3.15 (3) 113
O1w—H12⋯Br1ii 0.84 2.83 3.65 (3) 167
N1—H1⋯Br1 0.86 2.92 3.568 (11) 134
N2—H2⋯O1w 0.86 2.04 2.80 (2) 146
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
1,4-Diazoniabicyclo[2.2.2]octane tetrabromidocadmate(II) monohydrate top
Crystal data top
(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 top
Bruker SMART APEX
diffractometer
2451 independent reflections
Radiation source: fine-focus sealed tube2267 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.111, Tmax = 0.562k = 1414
10779 measured reflectionsl = 1616
Refinement top
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) = 0.187 w = 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 methodsAbsolute structure parameter: 0.14 (3)
Crystal data top
(C6H14N2)[CdBr4]·H2OV = 1390.05 (4) Å3
Mr = 564.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.6323 (1) ŵ = 13.04 mm1
b = 11.8736 (2) ÅT = 296 K
c = 13.5619 (2) Å0.30 × 0.15 × 0.05 mm
Data collection top
Bruker SMART APEX
diffractometer
2451 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2267 reflections with I > 2σ(I)
Tmin = 0.111, Tmax = 0.562Rint = 0.034
10779 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.187Δρmax = 2.21 e Å3
S = 1.36Δρmin = 2.09 e Å3
2451 reflectionsAbsolute structure: Flack (1983), 1021 Friedel pairs
128 parametersAbsolute structure parameter: 0.14 (3)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, º) top
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—C262.3 (16)C6—N2—C4—C364.8 (17)
C4—N2—C2—C160.2 (17)C3—N1—C5—C663.7 (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—C563 (2)
C1—N1—C3—C465.3 (15)C4—N2—C6—C559.1 (19)
N1—C3—C4—N26.0 (17)
Hydrogen-bond geometry (Å, º) top
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, y1/2, z+3/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula(C6H14N2)[CdBr4]·H2O
Mr564.25
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)8.6323 (1), 11.8736 (2), 13.5619 (2)
V3)1390.05 (4)
Z4
Radiation typeMo Kα
µ (mm1)13.04
Crystal size (mm)0.30 × 0.15 × 0.05
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.111, 0.562
No. of measured, independent and
observed [I > 2σ(I)] reflections
10779, 2451, 2267
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.187, 1.36
No. of reflections2451
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.21, 2.09
Absolute structureFlack (1983), 1021 Friedel pairs
Absolute structure parameter0.14 (3)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top
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, y1/2, z+3/2; (ii) x+1, y, z.
 

Acknowledgements

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

References

First citationAl-Far, R. & Ali, B. F. (2008). J. Chem. Crystallogr. 37, 333–341.  Web of Science CSD CrossRef Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBattaglia, L. P., Corradiab, B., Cariatif, K. & Koman, M. (1991). Inorg. Chim. Acta, 187, 141–147.  CAS Google Scholar
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta Cryst. C62, m571–m573.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGeselle, M. & Fuess, H. (1994). Acta Cryst. C50, 1582–1585.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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First citationIshihara, H., Horiuchi, K., Gesing, T. M., Dou, S.-Q., Buhl, J. C. & Erk, P. (2002). Z. Natursforsch. 57, 503–508.  CAS Google Scholar
First citationIshihara, H., Koriuchi, K., Svoboda, I., Fuess, H., Gesing, T. M., Buhl, J. C. & Terao, H. (2006). Z. Naturforsch. Teil B, 61, 69–72.  CAS Google Scholar
First citationRavikumar, K., Venkata Lakshmi, N., Swamy, G. Y. S. K. & Chandra Mohan, K. (1995). Acta Cryst. C51, 1556–1558.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWaskowska, A. (1994). Z. Kristallogr. 209, 750–754.  Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationZhang, H. & Fang, L. (2005). Acta Cryst. E61, m101–m102.  CSD CrossRef IUCr Journals Google Scholar

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