Bis(cyclo­hexyl­ammonium) tetra­bromido­cuprate(II)

Han, M.T.

doi:10.1107/S1600536812011117

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m448

doi:10.1107/S1600536812011117

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Bis(cyclohexylammonium) tetrabromidocuprate(II)

Meng Ting Han ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: saltfish777@gmail.com

(Received 22 February 2012; accepted 14 March 2012; online 21 March 2012)

The structure of the title salt, (C₆H₁₄N)₂[CuBr₄], is built up from cyclohexylammonium cations and tetrabromidocuprate anions, the latter being located on an inversion center. In the crystal, anions and cations are interconnected by N—H⋯Br hydrogen bonds, forming ribbons parallel to [0-11].

Related literature

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling (1999 ); Homes et al. (2001 ). For the synthesis of a variety of compounds with potential piezoelectric and ferroelectric properties, see: Fu et al. (2009 ); Hang et al. (2009 ). For the synthesis of the title compound, see: Willett (2004 ).

Experimental

Crystal data

(C₆H₁₄N)₂[CuBr₄]
M_r = 583.51
Monoclinic, P 2₁ /c
a = 14.372 (3) Å
b = 7.6483 (15) Å
c = 9.1561 (18) Å
β = 106.89 (3)°
V = 963.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 9.42 mm⁻¹
T = 293 K
0.33 × 0.28 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.056, T_max = 0.152
9579 measured reflections
2199 independent reflections
1468 reflections with I > 2σ(I)
R_int = 0.092
2 standard reflections every 150 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.095
S = 1.03
2199 reflections
88 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Br2ⁱ	0.89	2.60	3.474 (4)	166
N1—H1C⋯Br2ⁱⁱ	0.89	2.56	3.445 (4)	174
N1—H1E⋯Br3ⁱⁱⁱ	0.89	2.62	3.341 (4)	138
Symmetry codes: (i) x, y+1, z-1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011117/bh2418sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011117/bh2418Isup2.hkl

checkCIF report

Comment top

At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling, 1999; Homes et al. 2001). Recently we have reported the synthesis of a variety of compounds (Fu et al., 2009; Hang et al., 2009), which have potential piezoelectric and ferroelectric properties. In order to find more dielectric ferroelectric materials, we investigated the physical properties of the title compound (Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 0.42 to 6.6), suggesting that this compound should be not a real ferroelectrics or that no phase transition occurs within the measured temperature range. Similarly, below the melting point (443 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed. Herein, we report the synthesis and crystal structure of the title compound.

The structure of the title compound is shown in Fig. 1. There are one half CuBr₄^2- anion and one cyclohexylammonium cation in the asymmetric unit. The cyclohexyl ring has the chair conformation. As it can be seen from the packing diagram (Fig. 2), ions are connected via intermolecular N—H···Br hydrogen bonds to form a one dimensional chain in the crystal. Dipole–dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling (1999); Homes et al. (2001). For the synthesis of a variety of compounds with potential piezoelectric and ferroelectric properties, see: Fu et al. (2009); Hang et al. (2009). For the synthesis of the title compound, see: Willett (2004).

Experimental top

Crystals of the title compound were grown by evaporation of an aqueous solution containing a 2:1 ratio of cyclohexylammonium bromide and copper(II) bromide. A few drops of hydrobromic acid were added to the solution to avoid hydrolysis of the Cu(II) ion (Willett, 2004).

Structure description top

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling (1999); Homes et al. (2001). For the synthesis of a variety of compounds with potential piezoelectric and ferroelectric properties, see: Fu et al. (2009); Hang et al. (2009). For the synthesis of the title compound, see: Willett (2004).

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis showing the hydrogen bonds network. Some of the H atoms have been omitted for clarity.

Bis(cyclohexylammonium) tetrabromidocuprate(II) top

Crystal data top

(C₆H₁₄N)₂[CuBr₄]	F(000) = 566
M_r = 583.51	D_x = 2.012 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2203 reflections
a = 14.372 (3) Å	θ = 2.3–27.5°
b = 7.6483 (15) Å	µ = 9.42 mm⁻¹
c = 9.1561 (18) Å	T = 293 K
β = 106.89 (3)°	Block, sepia
V = 963.0 (3) Å³	0.33 × 0.28 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	1468 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.092
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.056, T_max = 0.152	l = −11→11
9579 measured reflections	2 standard reflections every 150 reflections
2199 independent reflections	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.024P)²] where P = (F_o² + 2F_c²)/3
2199 reflections	(Δ/σ)_max = 0.001
88 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³
0 constraints

Crystal data top

(C₆H₁₄N)₂[CuBr₄]	V = 963.0 (3) Å³
M_r = 583.51	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.372 (3) Å	µ = 9.42 mm⁻¹
b = 7.6483 (15) Å	T = 293 K
c = 9.1561 (18) Å	0.33 × 0.28 × 0.20 mm
β = 106.89 (3)°

Data collection top

Rigaku SCXmini diffractometer	1468 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.092
T_min = 0.056, T_max = 0.152	2 standard reflections every 150 reflections
9579 measured reflections	intensity decay: none
2199 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	Δρ_max = 0.62 e Å⁻³
2199 reflections	Δρ_min = −0.77 e Å⁻³
88 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.0000	1.0000	0.0342 (2)
Br2	0.17788 (4)	0.00282 (7)	1.09313 (6)	0.03796 (18)
Br3	0.00212 (4)	0.25662 (7)	0.84636 (6)	0.04466 (19)
N1	0.1634 (3)	0.9201 (6)	0.4590 (4)	0.0399 (11)
H1E	0.1113	0.9760	0.4690	0.060*
H1C	0.1627	0.8100	0.4898	0.060*
H1D	0.1627	0.9216	0.3615	0.060*
C1	0.4344 (4)	1.0010 (7)	0.6360 (6)	0.0484 (16)
H1A	0.4396	1.1186	0.5994	0.058*
H1B	0.4905	0.9351	0.6282	0.058*
C2	0.4348 (5)	1.0087 (7)	0.8026 (6)	0.0525 (17)
H2A	0.4376	0.8909	0.8429	0.063*
H2B	0.4923	1.0709	0.8618	0.063*
C3	0.3442 (4)	1.1006 (8)	0.8188 (6)	0.0497 (16)
H3A	0.3442	1.0960	0.9247	0.060*
H3B	0.3459	1.2225	0.7906	0.060*
C4	0.2518 (4)	1.0177 (7)	0.7197 (5)	0.0389 (14)
H4A	0.1961	1.0857	0.7260	0.047*
H4B	0.2453	0.9006	0.7563	0.047*
C5	0.2537 (4)	1.0092 (6)	0.5542 (5)	0.0309 (12)
H5A	0.2542	1.1290	0.5166	0.037*
C6	0.3421 (4)	0.9158 (8)	0.5364 (5)	0.0400 (14)
H6A	0.3419	0.9197	0.4304	0.048*
H6B	0.3403	0.7941	0.5654	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0304 (6)	0.0312 (5)	0.0383 (5)	−0.0027 (4)	0.0055 (4)	0.0048 (4)
Br2	0.0322 (4)	0.0389 (3)	0.0412 (3)	−0.0035 (3)	0.0082 (3)	0.0022 (2)
Br3	0.0428 (4)	0.0384 (3)	0.0463 (3)	−0.0101 (3)	0.0026 (3)	0.0103 (3)
N1	0.031 (3)	0.046 (3)	0.039 (2)	0.005 (2)	0.004 (2)	0.006 (2)
C1	0.035 (4)	0.066 (4)	0.044 (3)	0.004 (3)	0.011 (3)	0.008 (3)
C2	0.043 (4)	0.066 (4)	0.039 (3)	−0.001 (3)	−0.002 (3)	−0.001 (3)
C3	0.060 (5)	0.052 (4)	0.037 (3)	−0.008 (3)	0.012 (3)	−0.015 (3)
C4	0.030 (4)	0.048 (4)	0.036 (3)	0.004 (3)	0.006 (3)	−0.004 (3)
C5	0.030 (3)	0.029 (3)	0.031 (3)	−0.001 (3)	0.006 (2)	0.001 (2)
C6	0.032 (4)	0.058 (4)	0.032 (3)	0.002 (3)	0.013 (3)	−0.005 (3)

Geometric parameters (Å, º) top

Cu1—Br3ⁱ	2.4201 (6)	C2—H2A	0.9700
Cu1—Br3	2.4201 (6)	C2—H2B	0.9700
Cu1—Br2	2.4488 (9)	C3—C4	1.513 (7)
Cu1—Br2ⁱ	2.4488 (9)	C3—H3A	0.9700
N1—C5	1.500 (6)	C3—H3B	0.9700
N1—H1E	0.8900	C4—C5	1.525 (6)
N1—H1C	0.8900	C4—H4A	0.9700
N1—H1D	0.8900	C4—H4B	0.9700
C1—C6	1.521 (7)	C5—C6	1.507 (7)
C1—C2	1.525 (6)	C5—H5A	0.9800
C1—H1A	0.9700	C6—H6A	0.9700
C1—H1B	0.9700	C6—H6B	0.9700
C2—C3	1.525 (7)

Br3ⁱ—Cu1—Br3	180.0	C4—C3—C2	112.0 (4)
Br3ⁱ—Cu1—Br2	89.59 (3)	C4—C3—H3A	109.2
Br3—Cu1—Br2	90.41 (3)	C2—C3—H3A	109.2
Br3ⁱ—Cu1—Br2ⁱ	90.41 (3)	C4—C3—H3B	109.2
Br3—Cu1—Br2ⁱ	89.59 (3)	C2—C3—H3B	109.2
Br2—Cu1—Br2ⁱ	180.000 (9)	H3A—C3—H3B	107.9
C5—N1—H1E	109.5	C3—C4—C5	110.3 (5)
C5—N1—H1C	109.5	C3—C4—H4A	109.6
H1E—N1—H1C	109.5	C5—C4—H4A	109.6
C5—N1—H1D	109.5	C3—C4—H4B	109.6
H1E—N1—H1D	109.5	C5—C4—H4B	109.6
H1C—N1—H1D	109.5	H4A—C4—H4B	108.1
C6—C1—C2	111.4 (5)	N1—C5—C6	109.6 (4)
C6—C1—H1A	109.3	N1—C5—C4	109.6 (4)
C2—C1—H1A	109.3	C6—C5—C4	112.8 (4)
C6—C1—H1B	109.3	N1—C5—H5A	108.3
C2—C1—H1B	109.3	C6—C5—H5A	108.3
H1A—C1—H1B	108.0	C4—C5—H5A	108.3
C3—C2—C1	111.1 (5)	C5—C6—C1	110.4 (4)
C3—C2—H2A	109.4	C5—C6—H6A	109.6
C1—C2—H2A	109.4	C1—C6—H6A	109.6
C3—C2—H2B	109.4	C5—C6—H6B	109.6
C1—C2—H2B	109.4	C1—C6—H6B	109.6
H2A—C2—H2B	108.0	H6A—C6—H6B	108.1

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Br2ⁱⁱ	0.89	2.60	3.474 (4)	166
N1—H1C···Br2ⁱⁱⁱ	0.89	2.56	3.445 (4)	174
N1—H1E···Br3^iv	0.89	2.62	3.341 (4)	138

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

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N)₂[CuBr₄]
M_r	583.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.372 (3), 7.6483 (15), 9.1561 (18)
β (°)	106.89 (3)
V (Å³)	963.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	9.42
Crystal size (mm)	0.33 × 0.28 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.056, 0.152
No. of measured, independent and observed [I > 2σ(I)] reflections	9579, 2199, 1468
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.095, 1.03
No. of reflections	2199
No. of parameters	88
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.77

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Br2ⁱ	0.89	2.60	3.474 (4)	165.9
N1—H1C···Br2ⁱⁱ	0.89	2.56	3.445 (4)	174.4
N1—H1E···Br3ⁱⁱⁱ	0.89	2.62	3.341 (4)	138.3

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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