1,2-Dimethyl-1,4-diazo­niabicyclo­[2.2.2]octane tetra­chloridocuprate(II)

Rong, T.

doi:10.1107/S1600536811025347

metal-organic compounds

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Volume 67| Part 8| August 2011| Page m1016

doi:10.1107/S1600536811025347

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1,2-Dimethyl-1,4-diazoniabicyclo[2.2.2]octane tetrachloridocuprate(II)

Tao Rong ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: rongtao198806@163.com

(Received 19 June 2011; accepted 28 June 2011; online 2 July 2011)

In the title compound, (C₈H₁₈N₂)[CuCl₄], torsion angles on the ethylene bridges of the 1,4-diazoniabicyclo[2.2.2]octane fragment are in the range 11.9 (5)–15.0 (5)° and the [CuCl₄]²⁻ anion has a strongly distorted tetrahedral geometry. The cation is connected to the anion via three-center N—H⋯Cl hydrogen bonds.

Related literature

For similar compounds exhibiting phase transition, see: Corzo-Suárez et al. (1997 ); Katrusiak (2000 ); Sun & Jin (2002 ).

Experimental

Crystal data

(C₈H₁₈N₂)[CuCl₄]
M_r = 347.58
Orthorhombic, P b c a
a = 13.347 (3) Å
b = 14.187 (3) Å
c = 14.408 (3) Å
V = 2728.2 (9) Å³
Z = 8
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.618, T_max = 0.624
26550 measured reflections
3131 independent reflections
2455 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.123
S = 1.12
3131 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.91	2.54	3.271 (4)	138
N1—H1⋯Cl3	0.91	2.57	3.229 (4)	130

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 & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025347/gk2387sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025347/gk2387Isup2.hkl

checkCIF report

Comment top

The synthesis and characterization of copper halides in which organic ligands link metal centres have attracted much attention. One of the reasons for that is the fact that the copper environment of these compounds can adopt different geometries: tetrahedral, pseudo-tetrahedral or square-planar (Corzo-Suárez et al., 1997). This coordination variety allows the study of the relationship between the different geometries and the structural and magnetic properties of these compounds.

The title compound at room temperature crystallizes in the centrosymmetric Pbca space group and is paraelectric. It contains an isolated distorted (compressed) tetrahedral [CuCl₄]^2- anion, and a protonated (C₈H₁₈N₂)²⁺ cation. In this salt, the N—H⁺ group of the dication forms bifurcated hydrogen bond to two chloride ligands of the adjacent [CuCl₄]^2- anion.

In the cation the C9—N2—C6—C10 torsion angle is 47.9 (6)° and the DABCO fragment is distorted as indicated by the N1—C—C—N2 torsion angles, which range from 11.9 (5)-15.0 (5)° . In contrast to the present case, disorder of the DABCO unit is frequently observed in DABCO salts, such as in DABCO–perchloric acid (1:1) (Katrusiak, 2000) and DABCO–maleic acid (1:2) (Sun & Jin, 2002).

In [CuCl₄]^2- anion distortion from tetrahedral geometry is typically measured by the value of the trans Cl—Cu—Cl angle and by the dihedral angle between CuCl₂ planes. In the present case, the two 'trans' angles are 131.30°(5) and 131.22° (6) and the dihedral angle between the CuCl₂ planes is 65.72 (5).

The dielectric measurements (capacitance and dielectric loss measurements) on the powder samples pressed into tablets with a conducting carbon glue depositing on it, were carried out with an automatic impedance TongHui2828 Analyzer. Dielectric permittivity of the compound was tested to investigate the possibility of ferroelectric phase transitions. In the temperature range 80- 423 K no dielectric anomaly was observed revealing no phase transition in the studied temperature range.

Related literature top

For similar compounds exhibiting phase transition, see: Corzo-Suárez et al. (1997); Katrusiak (2000); Sun & Jin (2002).

Experimental top

To a mixture of iodomethane (10 mmol) and chloroform (15 ml) at 273 K was added dropwise a chloroform solution of 2-methyl-1,4-diazabicyclo[2.2.2]octane (10.2 mmol) resulting in 1,2-methyl-1,4-diazabicyclo[2.2.2]octane iodide. To the mixture of 1,2-methyl-1,4-diazabicyclo[2.2.2]octane iodide (4 mmol,1.07 g) and water (7 ml), concentrated hydrochloric acid (12 mmol) was added dropwise. Concentrated hydrochloric acid was also added dropwise to a mixture of CuCl₂ (2 mmol,0.341 g) and ethanol (5 ml). The two solutions were then mixed and stirred for 20 minutes. The resulting precipitate was dissolved in water. Yellow crystals suitable for X-ray analysis were formed after several weeks on slow evaporation of the solvent at room temperature (m.p. > 473 K).

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 & Putz, 2005); software used to prepare material for publication: SHELXL97 (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. Dashed lines indicate hydrogen bonds.
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Dashed lines indicate hydrogen bonds.

1,2-Dimethyl-1,4-diazoniabicyclo[2.2.2]octane tetrachloridocuprate(II) top

Crystal data top

(C₈H₁₈N₂)[CuCl₄]	F(000) = 1416
M_r = 347.58	D_x = 1.692 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7516 reflections
a = 13.347 (3) Å	θ = 3.1–27.5°
b = 14.187 (3) Å	µ = 2.36 mm⁻¹
c = 14.408 (3) Å	T = 293 K
V = 2728.2 (9) Å³	Prism, yellow
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	3131 independent reflections
Radiation source: fine-focus sealed tube	2455 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ scan	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.618, T_max = 0.624	l = −18→18
26550 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0447P)² + 4.3147P] where P = (F_o² + 2F_c²)/3
3131 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

(C₈H₁₈N₂)[CuCl₄]	V = 2728.2 (9) Å³
M_r = 347.58	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.347 (3) Å	µ = 2.36 mm⁻¹
b = 14.187 (3) Å	T = 293 K
c = 14.408 (3) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	3131 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2455 reflections with I > 2σ(I)
T_min = 0.618, T_max = 0.624	R_int = 0.059
26550 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.12	Δρ_max = 0.60 e Å⁻³
3131 reflections	Δρ_min = −0.46 e Å⁻³
136 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
N2	0.0533 (2)	0.2734 (2)	0.3412 (2)	0.0377 (7)
N1	0.1522 (3)	0.1255 (2)	0.3722 (2)	0.0435 (8)
H1	0.1883	0.0724	0.3840	0.052*
C4	0.0924 (3)	0.1493 (3)	0.4561 (3)	0.0478 (10)
H4A	0.1354	0.1508	0.5103	0.057*
H4B	0.0411	0.1020	0.4660	0.057*
C7	0.2224 (3)	0.2034 (3)	0.3505 (3)	0.0471 (10)
H7A	0.2677	0.1844	0.3013	0.057*
H7B	0.2619	0.2189	0.4049	0.057*
C3	0.0442 (3)	0.2452 (3)	0.4416 (2)	0.0455 (10)
H3A	−0.0259	0.2426	0.4591	0.055*
H3B	0.0771	0.2917	0.4804	0.055*
C8	0.1625 (3)	0.2886 (3)	0.3202 (3)	0.0463 (10)
H8A	0.1863	0.3442	0.3526	0.056*
H8B	0.1713	0.2987	0.2541	0.056*
C9	−0.0041 (4)	0.3621 (3)	0.3257 (4)	0.0610 (13)
H9A	0.0240	0.4116	0.3629	0.091*
H9B	−0.0729	0.3526	0.3429	0.091*
H9C	−0.0005	0.3793	0.2613	0.091*
C5	0.0852 (4)	0.1073 (3)	0.2931 (3)	0.0571 (12)
H5A	0.0477	0.0496	0.3034	0.069*
H5B	0.1241	0.1001	0.2367	0.069*
C6	0.0129 (3)	0.1911 (3)	0.2836 (3)	0.0511 (11)
H6A	−0.0509	0.1720	0.3115	0.061*
C10	−0.0061 (5)	0.2090 (5)	0.1848 (4)	0.0870 (18)
H10D	−0.0310	0.1526	0.1561	0.130*
H10A	0.0552	0.2276	0.1551	0.130*
H10B	−0.0547	0.2584	0.1786	0.130*
Cu1	0.22240 (4)	−0.07018 (4)	0.54958 (3)	0.04302 (17)
Cl2	0.23258 (8)	−0.22010 (7)	0.59863 (7)	0.0472 (3)
Cl3	0.12745 (8)	−0.09541 (8)	0.42108 (7)	0.0464 (3)
Cl1	0.33647 (9)	0.02455 (9)	0.48415 (9)	0.0607 (3)
Cl4	0.18698 (12)	−0.00003 (10)	0.68313 (9)	0.0759 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0365 (16)	0.0442 (18)	0.0324 (16)	−0.0054 (14)	0.0005 (13)	0.0043 (14)
N1	0.0467 (19)	0.0416 (18)	0.0421 (19)	−0.0007 (15)	0.0007 (16)	0.0007 (15)
C4	0.051 (2)	0.055 (3)	0.037 (2)	−0.002 (2)	0.0083 (19)	0.0096 (19)
C7	0.037 (2)	0.055 (2)	0.049 (2)	−0.0055 (19)	0.0082 (18)	0.004 (2)
C3	0.055 (2)	0.054 (2)	0.0273 (19)	−0.003 (2)	0.0094 (18)	−0.0013 (17)
C8	0.039 (2)	0.052 (2)	0.048 (2)	−0.0090 (19)	0.0066 (19)	0.007 (2)
C9	0.062 (3)	0.054 (3)	0.067 (3)	0.010 (2)	0.002 (2)	0.013 (2)
C5	0.070 (3)	0.053 (3)	0.048 (3)	−0.003 (2)	−0.010 (2)	−0.011 (2)
C6	0.043 (2)	0.071 (3)	0.040 (2)	−0.013 (2)	−0.0079 (19)	−0.007 (2)
C10	0.086 (4)	0.106 (5)	0.069 (4)	0.007 (4)	−0.016 (3)	0.011 (3)
Cu1	0.0504 (3)	0.0431 (3)	0.0355 (3)	0.0047 (2)	0.0013 (2)	−0.0021 (2)
Cl2	0.0558 (6)	0.0447 (6)	0.0411 (5)	0.0091 (5)	0.0000 (5)	0.0026 (4)
Cl3	0.0483 (6)	0.0482 (6)	0.0428 (5)	0.0009 (5)	−0.0049 (4)	0.0037 (4)
Cl1	0.0493 (6)	0.0646 (8)	0.0682 (8)	−0.0106 (5)	−0.0021 (6)	0.0065 (6)
Cl4	0.1097 (11)	0.0628 (8)	0.0550 (8)	0.0211 (8)	0.0109 (7)	−0.0202 (6)

Geometric parameters (Å, º) top

N2—C9	1.491 (5)	C8—H8B	0.9700
N2—C8	1.504 (5)	C9—H9A	0.9600
N2—C3	1.505 (5)	C9—H9B	0.9600
N2—C6	1.530 (5)	C9—H9C	0.9600
N1—C5	1.472 (5)	C5—C6	1.538 (7)
N1—C7	1.483 (5)	C5—H5A	0.9700
N1—C4	1.486 (5)	C5—H5B	0.9700
N1—H1	0.9100	C6—C10	1.469 (6)
C4—C3	1.520 (6)	C6—H6A	0.9800
C4—H4A	0.9700	C10—H10D	0.9600
C4—H4B	0.9700	C10—H10A	0.9600
C7—C8	1.513 (6)	C10—H10B	0.9600
C7—H7A	0.9700	Cu1—Cl4	2.2172 (13)
C7—H7B	0.9700	Cu1—Cl1	2.2390 (13)
C3—H3A	0.9700	Cu1—Cl2	2.2455 (12)
C3—H3B	0.9700	Cu1—Cl3	2.2719 (12)
C8—H8A	0.9700

C9—N2—C8	110.3 (3)	N2—C8—H8B	109.7
C9—N2—C3	109.1 (3)	C7—C8—H8B	109.7
C8—N2—C3	108.0 (3)	H8A—C8—H8B	108.2
C9—N2—C6	112.5 (3)	N2—C9—H9A	109.5
C8—N2—C6	110.0 (3)	N2—C9—H9B	109.5
C3—N2—C6	106.9 (3)	H9A—C9—H9B	109.5
C5—N1—C7	110.5 (3)	N2—C9—H9C	109.5
C5—N1—C4	110.1 (3)	H9A—C9—H9C	109.5
C7—N1—C4	109.9 (3)	H9B—C9—H9C	109.5
C5—N1—H1	108.7	N1—C5—C6	108.3 (3)
C7—N1—H1	108.7	N1—C5—H5A	110.0
C4—N1—H1	108.7	C6—C5—H5A	110.0
N1—C4—C3	108.6 (3)	N1—C5—H5B	110.0
N1—C4—H4A	110.0	C6—C5—H5B	110.0
C3—C4—H4A	110.0	H5A—C5—H5B	108.4
N1—C4—H4B	110.0	C10—C6—N2	117.0 (4)
C3—C4—H4B	110.0	C10—C6—C5	109.1 (4)
H4A—C4—H4B	108.3	N2—C6—C5	108.7 (3)
N1—C7—C8	108.8 (3)	C10—C6—H6A	107.2
N1—C7—H7A	109.9	N2—C6—H6A	107.2
C8—C7—H7A	109.9	C5—C6—H6A	107.2
N1—C7—H7B	109.9	C6—C10—H10D	109.5
C8—C7—H7B	109.9	C6—C10—H10A	109.5
H7A—C7—H7B	108.3	H10D—C10—H10A	109.5
N2—C3—C4	109.6 (3)	C6—C10—H10B	109.5
N2—C3—H3A	109.8	H10D—C10—H10B	109.5
C4—C3—H3A	109.8	H10A—C10—H10B	109.5
N2—C3—H3B	109.8	Cl4—Cu1—Cl1	103.94 (6)
C4—C3—H3B	109.8	Cl4—Cu1—Cl2	99.49 (5)
H3A—C3—H3B	108.2	Cl1—Cu1—Cl2	131.30 (5)
N2—C8—C7	109.8 (3)	Cl4—Cu1—Cl3	131.22 (6)
N2—C8—H8A	109.7	Cl1—Cu1—Cl3	97.52 (5)
C7—C8—H8A	109.7	Cl2—Cu1—Cl3	98.11 (4)

C5—N1—C4—C3	−69.2 (4)	N1—C7—C8—N2	11.9 (5)
C7—N1—C4—C3	52.8 (4)	C7—N1—C5—C6	−69.6 (5)
C5—N1—C7—C8	54.3 (5)	C4—N1—C5—C6	52.0 (5)
C4—N1—C7—C8	−67.5 (4)	C9—N2—C6—C10	47.8 (6)
C9—N2—C3—C4	173.6 (4)	C8—N2—C6—C10	−75.6 (5)
C8—N2—C3—C4	−66.5 (4)	C3—N2—C6—C10	167.4 (4)
C6—N2—C3—C4	51.8 (4)	C9—N2—C6—C5	171.9 (4)
N1—C4—C3—N2	12.8 (5)	C8—N2—C6—C5	48.6 (4)
C9—N2—C8—C7	171.1 (4)	C3—N2—C6—C5	−68.5 (4)
C3—N2—C8—C7	51.9 (4)	N1—C5—C6—C10	143.7 (4)
C6—N2—C8—C7	−64.3 (4)	N1—C5—C6—N2	15.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.91	2.54	3.271 (4)	138
N1—H1···Cl3	0.91	2.57	3.229 (4)	130

Experimental details

Crystal data
Chemical formula	(C₈H₁₈N₂)[CuCl₄]
M_r	347.58
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	13.347 (3), 14.187 (3), 14.408 (3)
V (Å³)	2728.2 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.36
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	0.618, 0.624
No. of measured, independent and observed [I > 2σ(I)] reflections	26550, 3131, 2455
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.123, 1.12
No. of reflections	3131
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.46

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.91	2.54	3.271 (4)	138
N1—H1···Cl3	0.91	2.57	3.229 (4)	130

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to purchase an X-ray diffractometer.

References

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