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

Wei, B.

doi:10.1107/S1600536810047495

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1672

https://doi.org/10.1107/S1600536810047495

Open

access

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

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 12 October 2010; accepted 16 November 2010; online 27 November 2010)

In the title salt, (C₈H₁₅N₃)[CdBr₄], four Br atoms coordinate the Cd^II 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 ); Chen et al. (2010 ); Wang et al. (2005 ); Xiong et al. (2002 ); Ye et al. (2006 ).

Experimental

Crystal data

(C₈H₁₅N₃)[CdBr₄]
M_r = 585.27
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.033
wR(F²) = 0.079
S = 0.76
3518 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Br1ⁱ	0.90	2.85	3.466 (4)	127
N1—H1C⋯Br2ⁱⁱ	0.90	2.69	3.325 (4)	128
N1—H1C⋯Br4ⁱ	0.90	3.11	3.711 (4)	126
C2—H2B⋯Br3ⁱⁱⁱ	0.97	2.83	3.765 (5)	162
C4—H4B⋯Br1	0.97	2.85	3.643 (4)	140
C7—H7A⋯Br3^iv	0.97	2.90	3.626 (4)	132
C7—H7B⋯Br2ⁱⁱⁱ	0.97	2.78	3.683 (4)	154
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047495/bh2319sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047495/bh2319Isup2.hkl

checkCIF report

Comment top

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 CdBr₄^2- 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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

(C₈H₁₅N₃)[CdBr₄]	F(000) = 1088
M_r = 585.27	D_x = 2.533 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4263 reflections
a = 8.610 (3) Å	θ = 2.4–27.5°
b = 14.071 (4) Å	µ = 11.82 mm⁻¹
c = 12.702 (4) Å	T = 293 K
β = 94.136 (4)°	Prism, colourless
V = 1534.9 (8) Å³	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	3518 independent reflections
Radiation source: fine-focus sealed tube	2861 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.470, T_max = 1.000	l = −16→16
16630 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 0.76	w = 1/[σ²(F_o²) + (0.0502P)² + 0.2386P] where P = (F_o² + 2F_c²)/3
3518 reflections	(Δ/σ)_max = 0.018
145 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.88 e Å⁻³
0 constraints

Crystal data top

(C₈H₁₅N₃)[CdBr₄]	V = 1534.9 (8) Å³
M_r = 585.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.610 (3) Å	µ = 11.82 mm⁻¹
b = 14.071 (4) Å	T = 293 K
c = 12.702 (4) Å	0.2 × 0.2 × 0.2 mm
β = 94.136 (4)°

Data collection top

Rigaku Mercury CCD diffractometer	3518 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2861 reflections with I > 2σ(I)
T_min = 0.470, T_max = 1.000	R_int = 0.068
16630 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 0.76	Δρ_max = 0.61 e Å⁻³
3518 reflections	Δρ_min = −0.88 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
Cd1	0.78773 (4)	0.22670 (2)	0.50861 (3)	0.02924 (11)
Br1	0.82000 (6)	0.40556 (3)	0.46315 (4)	0.03047 (13)
Br2	0.79028 (6)	0.24284 (3)	0.71414 (4)	0.03420 (13)
Br3	0.52068 (6)	0.15357 (3)	0.45098 (4)	0.03464 (13)
Br4	1.03019 (6)	0.13565 (3)	0.45657 (4)	0.03694 (14)
C8	0.4254 (6)	0.4480 (3)	0.6975 (4)	0.0314 (11)
N2	0.6179 (4)	0.5753 (2)	0.7314 (3)	0.0205 (7)
C5	0.9032 (5)	0.5513 (3)	0.7405 (4)	0.0328 (11)
H5A	0.9784	0.5564	0.8008	0.039*
H5B	0.9444	0.5081	0.6898	0.039*
N1	0.8754 (4)	0.6469 (2)	0.6913 (3)	0.0242 (8)
H1C	0.9610	0.6750	0.6691	0.029*
C6	0.7506 (6)	0.5138 (3)	0.7750 (4)	0.0378 (12)
H6A	0.7350	0.4490	0.7501	0.045*
H6B	0.7532	0.5132	0.8515	0.045*
C4	0.6267 (5)	0.5849 (3)	0.6140 (3)	0.0294 (10)
H4A	0.5365	0.6195	0.5842	0.035*
H4B	0.6263	0.5224	0.5819	0.035*
C3	0.7744 (5)	0.6376 (3)	0.5904 (3)	0.0283 (10)
H3A	0.8293	0.6027	0.5387	0.034*
H3B	0.7486	0.7000	0.5620	0.034*
C2	0.6364 (6)	0.6733 (3)	0.7808 (4)	0.0316 (11)
H2A	0.5586	0.7160	0.7484	0.038*
H2B	0.6215	0.6696	0.8557	0.038*
C7	0.4643 (5)	0.5354 (3)	0.7579 (3)	0.0279 (10)
H7A	0.4677	0.5215	0.8328	0.034*
H7B	0.3835	0.5825	0.7424	0.034*
N3	0.3933 (6)	0.3830 (3)	0.6497 (4)	0.0459 (12)
C1	0.7981 (5)	0.7107 (3)	0.7646 (4)	0.0300 (10)
H1A	0.7909	0.7744	0.7354	0.036*
H1B	0.8590	0.7135	0.8318	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02631 (19)	0.03071 (19)	0.0309 (2)	−0.00124 (14)	0.00314 (15)	0.00137 (14)
Br1	0.0324 (3)	0.0264 (2)	0.0335 (3)	0.00131 (19)	0.0088 (2)	−0.00169 (18)
Br2	0.0285 (3)	0.0477 (3)	0.0266 (3)	0.0031 (2)	0.0034 (2)	0.0044 (2)
Br3	0.0287 (3)	0.0421 (3)	0.0334 (3)	−0.0064 (2)	0.0042 (2)	−0.0070 (2)
Br4	0.0334 (3)	0.0351 (3)	0.0433 (3)	0.0054 (2)	0.0086 (2)	0.0016 (2)
C8	0.029 (3)	0.026 (2)	0.039 (3)	−0.008 (2)	0.003 (2)	0.010 (2)
N2	0.0180 (18)	0.0228 (18)	0.0213 (18)	0.0003 (14)	0.0053 (15)	0.0002 (14)
C5	0.023 (2)	0.032 (3)	0.043 (3)	0.007 (2)	0.003 (2)	0.002 (2)
N1	0.0148 (18)	0.031 (2)	0.029 (2)	−0.0028 (15)	0.0094 (15)	−0.0017 (15)
C6	0.027 (3)	0.034 (3)	0.052 (3)	0.008 (2)	−0.003 (2)	0.015 (2)
C4	0.027 (3)	0.045 (3)	0.016 (2)	−0.004 (2)	0.0037 (19)	−0.0024 (18)
C3	0.025 (2)	0.035 (3)	0.026 (2)	−0.002 (2)	0.007 (2)	0.0022 (18)
C2	0.033 (3)	0.031 (2)	0.033 (3)	−0.003 (2)	0.015 (2)	−0.013 (2)
C7	0.020 (2)	0.033 (2)	0.032 (3)	−0.0025 (19)	0.0067 (19)	0.0061 (19)
N3	0.051 (3)	0.032 (2)	0.053 (3)	−0.012 (2)	−0.004 (2)	0.011 (2)
C1	0.028 (2)	0.028 (2)	0.035 (3)	−0.003 (2)	0.008 (2)	−0.0084 (19)

Geometric parameters (Å, º) top

Cd1—Br3	2.5766 (8)	N1—H1C	0.8997
Cd1—Br4	2.5760 (8)	C6—H6A	0.9700
Cd1—Br1	2.6015 (9)	C6—H6B	0.9700
Cd1—Br2	2.6191 (10)	C4—C3	1.521 (6)
C8—N3	1.122 (6)	C4—H4A	0.9700
C8—C7	1.475 (6)	C4—H4B	0.9700
N2—C7	1.497 (5)	C3—H3A	0.9700
N2—C6	1.506 (5)	C3—H3B	0.9700
N2—C4	1.505 (5)	C2—C1	1.516 (6)
N2—C2	1.519 (5)	C2—H2A	0.9700
C5—N1	1.495 (5)	C2—H2B	0.9700
C5—C6	1.510 (7)	C7—H7A	0.9700
C5—H5A	0.9700	C7—H7B	0.9700
C5—H5B	0.9700	C1—H1A	0.9700
N1—C1	1.485 (5)	C1—H1B	0.9700
N1—C3	1.501 (5)

Br3—Cd1—Br4	116.84 (3)	N2—C4—C3	110.0 (3)
Br3—Cd1—Br1	115.51 (2)	N2—C4—H4A	109.7
Br4—Cd1—Br1	108.83 (2)	C3—C4—H4A	109.7
Br3—Cd1—Br2	105.13 (2)	N2—C4—H4B	109.7
Br4—Cd1—Br2	110.50 (2)	C3—C4—H4B	109.7
Br1—Cd1—Br2	98.28 (2)	H4A—C4—H4B	108.2
N3—C8—C7	178.1 (5)	N1—C3—C4	108.4 (3)
C7—N2—C6	111.2 (3)	N1—C3—H3A	110.0
C7—N2—C4	111.4 (3)	C4—C3—H3A	110.0
C6—N2—C4	109.0 (3)	N1—C3—H3B	110.0
C7—N2—C2	108.3 (3)	C4—C3—H3B	110.0
C6—N2—C2	108.4 (4)	H3A—C3—H3B	108.4
C4—N2—C2	108.5 (3)	C1—C2—N2	109.2 (3)
N1—C5—C6	108.6 (4)	C1—C2—H2A	109.8
N1—C5—H5A	110.0	N2—C2—H2A	109.8
C6—C5—H5A	110.0	C1—C2—H2B	109.8
N1—C5—H5B	110.0	N2—C2—H2B	109.8
C6—C5—H5B	110.0	H2A—C2—H2B	108.3
H5A—C5—H5B	108.3	C8—C7—N2	111.5 (4)
C5—N1—C1	110.3 (3)	C8—C7—H7A	109.3
C5—N1—C3	110.1 (3)	N2—C7—H7A	109.3
C1—N1—C3	109.2 (3)	C8—C7—H7B	109.3
C5—N1—H1C	114.6	N2—C7—H7B	109.3
C1—N1—H1C	110.2	H7A—C7—H7B	108.0
C3—N1—H1C	102.0	N1—C1—C2	109.4 (3)
N2—C6—C5	110.1 (4)	N1—C1—H1A	109.8
N2—C6—H6A	109.6	C2—C1—H1A	109.8
C5—C6—H6A	109.6	N1—C1—H1B	109.8
N2—C6—H6B	109.6	C2—C1—H1B	109.8
C5—C6—H6B	109.6	H1A—C1—H1B	108.2
H6A—C6—H6B	108.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br1ⁱ	0.90	2.85	3.466 (4)	127
N1—H1C···Br2ⁱⁱ	0.90	2.69	3.325 (4)	128
N1—H1C···Br4ⁱ	0.90	3.11	3.711 (4)	126
C2—H2B···Br3ⁱⁱⁱ	0.97	2.83	3.765 (5)	162
C4—H4B···Br1	0.97	2.85	3.643 (4)	140
C7—H7A···Br3^iv	0.97	2.90	3.626 (4)	132
C7—H7B···Br2ⁱⁱⁱ	0.97	2.78	3.683 (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.

Experimental details

Crystal data
Chemical formula	(C₈H₁₅N₃)[CdBr₄]
M_r	585.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.610 (3), 14.071 (4), 12.702 (4)
β (°)	94.136 (4)
V (Å³)	1534.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.82
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.470, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16630, 3518, 2861
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.079, 0.76
No. of reflections	3518
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.88

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br1ⁱ	0.90	2.85	3.466 (4)	127
N1—H1C···Br2ⁱⁱ	0.90	2.69	3.325 (4)	128
N1—H1C···Br4ⁱ	0.90	3.11	3.711 (4)	126
C2—H2B···Br3ⁱⁱⁱ	0.97	2.83	3.765 (5)	162
C4—H4B···Br1	0.97	2.85	3.643 (4)	140
C7—H7A···Br3^iv	0.97	2.90	3.626 (4)	132
C7—H7B···Br2ⁱⁱⁱ	0.97	2.78	3.683 (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.

Acknowledgements

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

References

Basavaiah, D., Rao, A. J. & Satyanarayana, T. (2003). Chem. Rev. 103, 811–892. Web of Science CrossRef PubMed CAS Google Scholar
Chen, L.-Z., Huang, Y., Xiong, R.-G. & Hu, H.-W. (2010). J. Mol. Struct. 963, 16–21. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X.-S., Song, Y.-M. & Xiong, R.-G. (2005). Chin. J. Inorg. Chem. 21, 1030–1033. Google Scholar
Xiong, R. G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z. (2002). Angew. Chem. Int. Ed. 41, 3800–3803. CrossRef CAS Google Scholar
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. Web of Science CSD CrossRef PubMed CAS Google Scholar