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

Lo, K.M.; Ng, S.W.

doi:10.1107/S160053680902813X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m973

doi:10.1107/S160053680902813X

Open

access

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

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^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 ); 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

Crystal data

(C₆H₁₄N₂)[CdBr₄]·H₂O
M_r = 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 ) 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[F² > 2σ(F²)] = 0.057
wR(F²) = 0.187
S = 1.36
2451 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 2.21 e Å⁻³
Δρ_min = −2.09 e Å⁻³
Absolute structure: Flack (1983 ), 1021 Friedel pairs
Flack parameter: 0.14 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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 ).

Supporting information

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

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

checkCIF report

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.

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

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]·H₂O	F(000) = 1048
M_r = 564.25	D_x = 2.696 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6547 reflections
a = 8.6323 (1) Å	θ = 2.8–28.2°
b = 11.8736 (2) Å	µ = 13.04 mm⁻¹
c = 13.5619 (2) Å	T = 296 K
V = 1390.05 (4) Å³	Block, colorless
Z = 4	0.30 × 0.15 × 0.05 mm

Data collection top

Bruker SMART APEX diffractometer	2451 independent reflections
Radiation source: fine-focus sealed tube	2267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.111, T_max = 0.562	k = −14→14
10779 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.1P)² + 5P] where P = (F_o² + 2F_c²)/3
S = 1.36	(Δ/σ)_max = 0.001
2451 reflections	Δρ_max = 2.21 e Å⁻³
128 parameters	Δρ_min = −2.09 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1021 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.14 (3)

Crystal data top

(C₆H₁₄N₂)[CdBr₄]·H₂O	V = 1390.05 (4) Å³
M_r = 564.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.6323 (1) Å	µ = 13.04 mm⁻¹
b = 11.8736 (2) Å	T = 296 K
c = 13.5619 (2) Å	0.30 × 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)
T_min = 0.111, T_max = 0.562	R_int = 0.034
10779 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.187	Δρ_max = 2.21 e Å⁻³
S = 1.36	Δρ_min = −2.09 e Å⁻³
2451 reflections	Absolute structure: Flack (1983), 1021 Friedel pairs
128 parameters	Absolute structure parameter: 0.14 (3)
0 restraints

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

	x	y	z	U_iso*/U_eq
Cd1	0.25482 (11)	0.47127 (8)	1.00019 (6)	0.0410 (3)
Br1	0.3099 (2)	0.28309 (13)	0.91553 (12)	0.0596 (5)
Br2	0.4870 (2)	0.59802 (15)	0.95680 (13)	0.0579 (5)
Br3	0.2467 (2)	0.46741 (14)	1.19150 (10)	0.0552 (4)
Br4	0.0032 (2)	0.56945 (19)	0.95508 (17)	0.0741 (6)
O1W	1.151 (3)	0.265 (2)	0.6666 (18)	0.144 (9)
H11	1.1965	0.2150	0.6336	0.216*
H12	1.2016	0.2746	0.7189	0.216*
N1	0.6148 (13)	0.4081 (10)	0.7757 (7)	0.040 (3)
H1	0.5272	0.4215	0.8034	0.048*
N2	0.8660 (14)	0.3708 (12)	0.6978 (13)	0.063 (4)
H2	0.9523	0.3577	0.6682	0.076*
C1	0.725 (2)	0.3684 (14)	0.8530 (12)	0.056 (4)
H1A	0.6860	0.3008	0.8846	0.067*
H1B	0.7396	0.4260	0.9029	0.067*
C2	0.882 (2)	0.3435 (18)	0.7975 (16)	0.086 (8)
H2A	0.9647	0.3877	0.8264	0.104*
H2B	0.9083	0.2645	0.8042	0.104*
C3	0.5912 (16)	0.3214 (11)	0.7016 (12)	0.045 (3)
H3A	0.5121	0.3449	0.6551	0.054*
H3B	0.5577	0.2519	0.7326	0.054*
C4	0.7409 (17)	0.3035 (13)	0.6494 (9)	0.047 (3)
H4A	0.7308	0.3262	0.5810	0.056*
H4B	0.7679	0.2242	0.6510	0.056*
C5	0.6697 (19)	0.5139 (11)	0.7291 (11)	0.044 (3)
H5A	0.6781	0.5729	0.7783	0.052*
H5B	0.5968	0.5382	0.6790	0.052*
C6	0.824 (2)	0.4924 (13)	0.6836 (17)	0.066 (5)
H6A	0.9016	0.5400	0.7143	0.079*
H6B	0.8206	0.5100	0.6138	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0398 (5)	0.0445 (6)	0.0387 (5)	0.0007 (4)	0.0034 (5)	−0.0059 (4)
Br1	0.0813 (11)	0.0441 (8)	0.0535 (8)	0.0002 (8)	0.0191 (7)	−0.0081 (7)
Br2	0.0570 (9)	0.0650 (10)	0.0515 (8)	−0.0032 (8)	−0.0029 (7)	0.0044 (7)
Br3	0.0546 (8)	0.0682 (10)	0.0428 (7)	0.0061 (9)	0.0040 (7)	0.0035 (6)
Br4	0.0606 (11)	0.0862 (13)	0.0756 (12)	0.0076 (10)	−0.0051 (9)	−0.0244 (10)
O1W	0.150 (18)	0.153 (19)	0.129 (16)	0.073 (17)	0.022 (14)	0.012 (15)
N1	0.037 (5)	0.063 (7)	0.020 (5)	−0.003 (5)	0.003 (4)	−0.009 (5)
N2	0.029 (6)	0.057 (8)	0.104 (12)	−0.002 (5)	0.019 (7)	−0.038 (8)
C1	0.067 (11)	0.051 (9)	0.051 (8)	0.005 (8)	−0.023 (8)	0.003 (7)
C2	0.089 (14)	0.071 (12)	0.099 (15)	0.039 (11)	−0.064 (13)	−0.051 (11)
C3	0.036 (6)	0.031 (7)	0.069 (9)	0.000 (5)	−0.002 (7)	0.000 (6)
C4	0.045 (7)	0.056 (8)	0.040 (6)	−0.008 (7)	−0.005 (7)	−0.014 (6)
C5	0.059 (9)	0.026 (6)	0.045 (7)	0.002 (6)	0.007 (7)	0.000 (6)
C6	0.066 (11)	0.040 (9)	0.091 (12)	−0.011 (7)	0.035 (10)	−0.017 (8)

Geometric parameters (Å, º) top

Cd1—Br4	2.540 (2)	C1—H1A	0.9700
Cd1—Br1	2.557 (2)	C1—H1B	0.9700
Cd1—Br2	2.574 (2)	C2—H2A	0.9700
Cd1—Br3	2.596 (2)	C2—H2B	0.9700
O1W—H11	0.84	C3—C4	1.49 (2)
O1W—H12	0.84	C3—H3A	0.9700
N1—C3	1.453 (18)	C3—H3B	0.9700
N1—C5	1.484 (18)	C4—H4A	0.9700
N1—C1	1.491 (18)	C4—H4B	0.9700
N1—H1	0.8600	C5—C6	1.49 (2)
N2—C2	1.40 (3)	C5—H5A	0.9700
N2—C4	1.495 (18)	C5—H5B	0.9700
N2—C6	1.50 (2)	C6—H6A	0.9700
N2—H2	0.8600	C6—H6B	0.9700
C1—C2	1.58 (3)

Br4—Cd1—Br1	116.87 (7)	N2—C2—H2B	109.8
Br4—Cd1—Br2	110.01 (7)	C1—C2—H2B	109.8
Br1—Cd1—Br2	105.29 (7)	H2A—C2—H2B	108.2
Br4—Cd1—Br3	103.05 (7)	N1—C3—C4	107.9 (11)
Br1—Cd1—Br3	116.00 (7)	N1—C3—H3A	110.1
Br2—Cd1—Br3	105.05 (6)	C4—C3—H3A	110.1
H11—O1W—H12	107.7	N1—C3—H3B	110.1
C3—N1—C5	110.5 (10)	C4—C3—H3B	110.1
C3—N1—C1	110.6 (12)	H3A—C3—H3B	108.4
C5—N1—C1	111.3 (12)	C3—C4—N2	110.0 (11)
C3—N1—H1	108.1	C3—C4—H4A	109.7
C5—N1—H1	108.1	N2—C4—H4A	109.7
C1—N1—H1	108.1	C3—C4—H4B	109.7
C2—N2—C4	111.8 (15)	N2—C4—H4B	109.7
C2—N2—C6	111.8 (15)	H4A—C4—H4B	108.2
C4—N2—C6	106.5 (14)	N1—C5—C6	108.5 (11)
C2—N2—H2	108.9	N1—C5—H5A	110.0
C4—N2—H2	108.9	C6—C5—H5A	110.0
C6—N2—H2	108.9	N1—C5—H5B	110.0
N1—C1—C2	105.7 (13)	C6—C5—H5B	110.0
N1—C1—H1A	110.6	H5A—C5—H5B	108.4
C2—C1—H1A	110.6	C5—C6—N2	109.1 (12)
N1—C1—H1B	110.6	C5—C6—H6A	109.9
C2—C1—H1B	110.6	N2—C6—H6A	109.9
H1A—C1—H1B	108.7	C5—C6—H6B	109.9
N2—C2—C1	109.5 (13)	N2—C6—H6B	109.9
N2—C2—H2A	109.8	H6A—C6—H6B	108.3
C1—C2—H2A	109.8

C3—N1—C1—C2	60.9 (16)	C2—N2—C4—C3	57.5 (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—C1	59.0 (19)	C1—N1—C5—C6	59.6 (16)
N1—C1—C2—N2	2 (2)	N1—C5—C6—N2	2 (2)
C5—N1—C3—C4	58.4 (15)	C2—N2—C6—C5	−63 (2)
C1—N1—C3—C4	−65.3 (15)	C4—N2—C6—C5	59.1 (19)
N1—C3—C4—N2	6.0 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2, −z+3/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)[CdBr₄]·H₂O
M_r	564.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	8.6323 (1), 11.8736 (2), 13.5619 (2)
V (Å³)	1390.05 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.04
Crystal size (mm)	0.30 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.111, 0.562
No. of measured, independent and observed [I > 2σ(I)] reflections	10779, 2451, 2267
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.187, 1.36
No. of reflections	2451
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.21, −2.09
Absolute structure	Flack (1983), 1021 Friedel pairs
Absolute structure parameter	0.14 (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···A	D—H	H···A	D···A	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−1/2, −z+3/2; (ii) x+1, y, z.

Acknowledgements

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

References

Al-Far, R. & Ali, B. F. (2008). J. Chem. Crystallogr. 37, 333–341. Web of Science CSD CrossRef Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Battaglia, L. P., Corradiab, B., Cariatif, K. & Koman, M. (1991). Inorg. Chim. Acta, 187, 141–147. CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, 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
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Geselle, M. & Fuess, H. (1994). Acta Cryst. C50, 1582–1585. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hatano, N., Nakashima, M., Horiuchi, K., Terao, H. & Ishihara, H. (2008). Z. Naturforsch. Teil B, 63, 1181–1186. CAS Google Scholar
Ishihara, H., Horiuchi, K., Gesing, T. M., Dou, S.-Q., Buhl, J. C. & Erk, P. (2002). Z. Natursforsch. 57, 503–508. CAS Google Scholar
Ishihara, 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
Ravikumar, 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
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Waskowska, A. (1994). Z. Kristallogr. 209, 750–754. Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Zhang, H. & Fang, L. (2005). Acta Cryst. E61, m101–m102. CSD CrossRef IUCr Journals Google Scholar