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

Zhang, Y.; Wang, B.

doi:10.1107/S1600536811005289

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m371

doi:10.1107/S1600536811005289

Open

access

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

Yi Zhang ^a ^* and Bo Wang ^a

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: yizhang1980@yahoo.com.cn

(Received 24 January 2011; accepted 12 February 2011; online 23 February 2011)

In the title monohydrated salt, (C₆H₁₄N₂)[CuBr₄]·H₂O, the copper(II) ion is coordinated by the four bromide ions in a flattened tetrahedral geometry. In the crystal, the cations, anions and water molecules interact via N—H⋯O, O—H⋯Br and N—H⋯Br hydrogen bonds, forming chains parallel to the b axis. The chains are further linked by O—H⋯Br hydrogen bonds into layers parallel to the bc plane.

Related literature

For related structures, see: Wei & Willett (1996 , 2002 ); Brammer et al. (2002 ); Zhang et al. (2010 ).

Experimental

Crystal data

(C₆H₁₄N₂)[CuBr₄]·H₂O
M_r = 515.39
Monoclinic, P 2₁ /c
a = 9.5171 (19) Å
b = 9.5341 (19) Å
c = 14.952 (3) Å
β = 93.93 (3)°
V = 1353.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 13.40 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.055, T_max = 0.086
13570 measured reflections
3111 independent reflections
2285 reflections with I > 2σ(I)
R_int = 0.124

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.116
S = 1.10
3111 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 1.22 e Å⁻³
Δρ_min = −1.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1W	0.91	2.49	3.121 (8)	127
N2—H2C⋯O1Wⁱ	0.91	1.98	2.788 (7)	147
O1W—H1WA⋯Br4ⁱⁱ	0.85	2.75	3.456 (5)	141
O1W—H1WA⋯Br2ⁱⁱ	0.85	2.86	3.461 (5)	129
O1W—H1WB⋯Br1ⁱⁱⁱ	0.85	2.55	3.319 (5)	152
N1—H1C⋯Br1	0.91	2.61	3.360 (5)	140
N1—H1C⋯Br4	0.91	2.92	3.546 (6)	127
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z; (iii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005289/rz2552sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005289/rz2552Isup2.hkl

checkCIF report

Comment top

Ferroelectric materials have attracted intensive interest not only due to their versatile technological applications in the field of electronics and optics, but also for their importance to the fundamental scientific research. Recently, monosalts of 1,4-diazabicyclo[2.2.2]octane (dabco) including dabcoHBF₄, dabcoHClO₄ and dabcoHReO₄ have been reported to have excellent dielectric and ferroelectric properties (Wei & Willett, 1996, 2002; Brammer et al., 2002). Our group has recently reported the compound (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂].H₂O (Zhang et al., 2010), which also shows good dielectric and ferroelectric properties. Herein we report the synthesis and crystal structure of the title compound, (dabcoH₂)CuBr₄.H₂O.

The asymmetric unit of the title compound contains one (dabcoH₂)²⁺ cation, one [CuBr₄]^2- anion and one water molecules (Fig 1). The copper(II) ion has a flattened tetrahedral coordination geometry provided by the four Br^- ions, with Cu—Br distances ranging from 2.3598 (12) to 2.4070 (12) Å. Generally, the Cu—Br bond lengths and Br—Cu—Br bond angles in a [CuBr₄]^2- anion are not equal to one another but vary with the environment around the Br atoms. As atoms Br1, Br2 and Br4 are involved in hydrogen bonds, the Cu1—Br3 bond length is significantly shorter than the other Cu—Br bonds. The distortion from the ideal tetrahedral geometry is also indicated by the values of the Br—Cu—Br angles, which range from 96.75 (4) to 133.92 (5)°. The H1C and H2C protons of the 1,4-diazoniabicyclo(2.2.2)octane cation and the H1WA hydrogen atom of the water molecule are engaged in bifurcated N—H···Br, N—H···O and O—H···Br hydrogen bonds (Table 1), forming chains parallel to the b axis. The chains are further connected by O—H···Br hydrogen bonds into layers parallel to the (011) plane (Fig. 2).

Related literature top

For related structures, see: Wei & Willett (1996, 2002); Brammer et al. (2002); Zhang et al. (2010).

Experimental top

To a concentrated HBr water solution (50 ml) 1,4-diazabicyclo[2.2.2]octane (10 mmol, 1.12 g) and of CuBr₂.2H₂O (10 mmol, 2.60 g) were added with stirring. Brown single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of the solvent over a period of a week at room temperature. The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε= C/(T–T₀)), suggesting that the title compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 93 K and 362 K (m. p. 99 °C).

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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) are omitted.

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

Crystal data top

(C₆H₁₄N₂)[CuBr₄]·H₂O	F(000) = 972
M_r = 515.39	D_x = 2.529 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2622 reflections
a = 9.5171 (19) Å	θ = 3.0–27.5°
b = 9.5341 (19) Å	µ = 13.40 mm⁻¹
c = 14.952 (3) Å	T = 298 K
β = 93.93 (3)°	Polyhedron, brown
V = 1353.5 (5) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	3111 independent reflections
Radiation source: fine-focus sealed tube	2285 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.124
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.055, T_max = 0.086	l = −19→19
13570 measured reflections

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0225P)² + 2.0506P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3111 reflections	Δρ_max = 1.22 e Å⁻³
128 parameters	Δρ_min = −1.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0204 (7)

Crystal data top

(C₆H₁₄N₂)[CuBr₄]·H₂O	V = 1353.5 (5) Å³
M_r = 515.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5171 (19) Å	µ = 13.40 mm⁻¹
b = 9.5341 (19) Å	T = 298 K
c = 14.952 (3) Å	0.20 × 0.20 × 0.20 mm
β = 93.93 (3)°

Data collection top

Rigaku SCXmini diffractometer	3111 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2285 reflections with I > 2σ(I)
T_min = 0.055, T_max = 0.086	R_int = 0.124
13570 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.10	Δρ_max = 1.22 e Å⁻³
3111 reflections	Δρ_min = −1.29 e Å⁻³
128 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.13288 (8)	1.07551 (7)	−0.32168 (5)	0.0252 (2)
Br2	0.47455 (8)	1.29945 (9)	−0.17676 (5)	0.0294 (3)
Br3	0.24026 (10)	1.44329 (8)	−0.35401 (5)	0.0343 (3)
Br4	0.12020 (9)	1.24314 (8)	−0.10831 (5)	0.0291 (2)
C1	0.2071 (9)	0.7578 (7)	−0.1967 (5)	0.0250 (18)
H1A	0.1136	0.7276	−0.2186	0.030*
H1B	0.2588	0.7837	−0.2479	0.030*
C2	0.2812 (10)	0.6413 (8)	−0.1464 (5)	0.039 (2)
H2A	0.2182	0.5619	−0.1423	0.046*
H2B	0.3620	0.6113	−0.1776	0.046*
C3	0.1196 (8)	0.8404 (8)	−0.0560 (5)	0.0221 (17)
H3A	0.0265	0.8058	−0.0751	0.027*
H3B	0.1094	0.9204	−0.0170	0.027*
C4	0.2029 (9)	0.7281 (8)	−0.0075 (6)	0.032 (2)
H4A	0.2322	0.7602	0.0524	0.039*
H4B	0.1444	0.6456	−0.0023	0.039*
C5	0.3414 (8)	0.9335 (7)	−0.1063 (5)	0.0265 (19)
H5A	0.3357	1.0120	−0.0654	0.032*
H5B	0.3896	0.9644	−0.1579	0.032*
C6	0.4211 (9)	0.8136 (8)	−0.0601 (6)	0.040 (2)
H6A	0.5019	0.7893	−0.0932	0.048*
H6B	0.4551	0.8418	−0.0001	0.048*
Cu1	0.24156 (9)	1.27018 (9)	−0.24116 (6)	0.0190 (3)
N1	0.1962 (6)	0.8822 (6)	−0.1354 (4)	0.0164 (13)
H1C	0.1478	0.9520	−0.1654	0.020*
N2	0.3277 (6)	0.6913 (6)	−0.0552 (4)	0.0204 (14)
H2C	0.3753	0.6211	−0.0251	0.024*
O1W	0.6324 (6)	0.5717 (5)	−0.0241 (3)	0.0316 (14)
H1WA	0.6670	0.5956	0.0276	0.047*
H1WB	0.6832	0.6044	−0.0638	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0381 (5)	0.0188 (4)	0.0181 (5)	−0.0005 (3)	−0.0012 (4)	−0.0011 (3)
Br2	0.0251 (4)	0.0452 (5)	0.0177 (5)	0.0018 (4)	0.0000 (3)	0.0023 (4)
Br3	0.0557 (6)	0.0281 (5)	0.0180 (5)	−0.0065 (4)	−0.0067 (4)	0.0144 (4)
Br4	0.0378 (5)	0.0327 (5)	0.0182 (5)	0.0007 (4)	0.0138 (4)	0.0031 (3)
C1	0.037 (5)	0.028 (4)	0.010 (4)	−0.003 (4)	0.002 (3)	−0.008 (3)
C2	0.077 (7)	0.025 (5)	0.015 (5)	0.015 (5)	0.009 (5)	−0.004 (4)
C3	0.027 (4)	0.029 (4)	0.010 (4)	0.003 (3)	0.003 (3)	−0.004 (3)
C4	0.046 (5)	0.029 (5)	0.024 (5)	0.009 (4)	0.012 (4)	0.010 (4)
C5	0.035 (4)	0.017 (4)	0.026 (5)	−0.007 (3)	−0.007 (4)	0.006 (3)
C6	0.029 (5)	0.035 (5)	0.054 (6)	−0.001 (4)	−0.011 (4)	0.029 (5)
Cu1	0.0288 (5)	0.0193 (5)	0.0087 (5)	−0.0016 (4)	0.0003 (4)	0.0041 (4)
N1	0.020 (3)	0.019 (3)	0.011 (3)	0.005 (3)	−0.002 (2)	0.007 (3)
N2	0.037 (4)	0.011 (3)	0.013 (3)	0.006 (3)	−0.002 (3)	0.008 (3)
O1W	0.045 (3)	0.027 (3)	0.023 (3)	0.000 (3)	0.008 (3)	0.010 (2)

Geometric parameters (Å, º) top

Br1—Cu1	2.4070 (12)	C4—N2	1.469 (10)
Br2—Cu1	2.3726 (13)	C4—H4A	0.9700
Br3—Cu1	2.3598 (12)	C4—H4B	0.9700
Br4—Cu1	2.3792 (13)	C5—N1	1.502 (9)
C1—C2	1.492 (10)	C5—C6	1.512 (10)
C1—N1	1.507 (9)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—N2	1.471 (9)
C2—N2	1.483 (9)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	N1—H1C	0.9100
C3—N1	1.489 (9)	N2—H2C	0.9100
C3—C4	1.490 (10)	O1W—H1WA	0.8501
C3—H3A	0.9700	O1W—H1WB	0.8500
C3—H3B	0.9700

C2—C1—N1	109.2 (6)	C6—C5—H5B	110.1
C2—C1—H1A	109.8	H5A—C5—H5B	108.4
N1—C1—H1A	109.8	N2—C6—C5	109.6 (6)
C2—C1—H1B	109.8	N2—C6—H6A	109.7
N1—C1—H1B	109.8	C5—C6—H6A	109.7
H1A—C1—H1B	108.3	N2—C6—H6B	109.7
N2—C2—C1	109.0 (6)	C5—C6—H6B	109.7
N2—C2—H2A	109.9	H6A—C6—H6B	108.2
C1—C2—H2A	109.9	Br3—Cu1—Br2	99.61 (5)
N2—C2—H2B	109.9	Br3—Cu1—Br4	133.92 (5)
C1—C2—H2B	109.9	Br2—Cu1—Br4	99.64 (5)
H2A—C2—H2B	108.3	Br3—Cu1—Br1	101.57 (4)
N1—C3—C4	107.9 (6)	Br2—Cu1—Br1	130.64 (5)
N1—C3—H3A	110.1	Br4—Cu1—Br1	96.75 (4)
C4—C3—H3A	110.1	C3—N1—C5	110.3 (5)
N1—C3—H3B	110.1	C3—N1—C1	109.4 (5)
C4—C3—H3B	110.1	C5—N1—C1	109.4 (6)
H3A—C3—H3B	108.4	C3—N1—H1C	109.2
N2—C4—C3	110.9 (6)	C5—N1—H1C	109.2
N2—C4—H4A	109.5	C1—N1—H1C	109.2
C3—C4—H4A	109.5	C4—N2—C6	110.2 (6)
N2—C4—H4B	109.5	C4—N2—C2	108.8 (6)
C3—C4—H4B	109.5	C6—N2—C2	110.7 (6)
H4A—C4—H4B	108.1	C4—N2—H2C	109.0
N1—C5—C6	108.0 (6)	C6—N2—H2C	109.0
N1—C5—H5A	110.1	C2—N2—H2C	109.0
C6—C5—H5A	110.1	H1WA—O1W—H1WB	109.5
N1—C5—H5B	110.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1W	0.91	2.49	3.121 (8)	127
N2—H2C···O1Wⁱ	0.91	1.98	2.788 (7)	147
O1W—H1WA···Br4ⁱⁱ	0.85	2.75	3.456 (5)	141
O1W—H1WA···Br2ⁱⁱ	0.85	2.86	3.461 (5)	129
O1W—H1WB···Br1ⁱⁱⁱ	0.85	2.55	3.319 (5)	152
N1—H1C···Br1	0.91	2.61	3.360 (5)	140
N1—H1C···Br4	0.91	2.92	3.546 (6)	127

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

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)[CuBr₄]·H₂O
M_r	515.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.5171 (19), 9.5341 (19), 14.952 (3)
β (°)	93.93 (3)
V (Å³)	1353.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.40
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.055, 0.086
No. of measured, independent and observed [I > 2σ(I)] reflections	13570, 3111, 2285
R_int	0.124
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.116, 1.10
No. of reflections	3111
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.22, −1.29

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
N2—H2C···O1W	0.91	2.49	3.121 (8)	127
N2—H2C···O1Wⁱ	0.91	1.98	2.788 (7)	147
O1W—H1WA···Br4ⁱⁱ	0.85	2.75	3.456 (5)	141
O1W—H1WA···Br2ⁱⁱ	0.85	2.86	3.461 (5)	129
O1W—H1WB···Br1ⁱⁱⁱ	0.85	2.55	3.319 (5)	152
N1—H1C···Br1	0.91	2.61	3.360 (5)	140
N1—H1C···Br4	0.91	2.92	3.546 (6)	127

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

Acknowledgements

This work was supported by the Start-up Projects for Postdoctoral Research Funds (1112000064) and the Major Postdoctoral Research Funds (3212000602) of Southeast University.

References

Brammer, L., Swearingen, J. K., Bruton, E. A. & Sherwood, P. (2002). Proc. Natl Acad. Sci. USA, 99, 4956–4961. Web of Science CSD CrossRef PubMed 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
Wei, M. & Willett, R. D. (1996). Inorg. Chem. 35, 6381–6385. CSD CrossRef PubMed CAS Web of Science Google Scholar
Wei, M. & Willett, R. D. (2002). J. Chem. Crystallogr. 32, 439–445. Web of Science CSD CrossRef CAS Google Scholar
Zhang, W., Ye, H. Y., Cai, H. L., Ge, J. Z., Xiong, R. G. & Huang, S. P. (2010). J. Am. Chem. Soc. 132, 7300–7302. Web of Science CSD CrossRef CAS PubMed Google Scholar