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

Rong, T.

doi:10.1107/S1600536811020782

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m889

doi:10.1107/S1600536811020782

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1-Chloromethyl-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 26 April 2011; accepted 30 May 2011; online 11 June 2011)

In the crystal structure of the title compound, (C₇H₁₅ClN₂)[CuCl₄], a weak intermolecular N—H⋯Cl hydrogen bond is observed between the organic dication and the tetrahedral [CuCl₄]²⁻ anion. The organic dication is distorted, as indicated by the N—C—C—N torsion angles, which range from 16.76 (4) to 19.54 (3)°.

Related literature

For related 1,4-diazabicyclo[2.2.2]octane tetrachloridocuprate(II) and tetrachloridocobaltate(II) structures, and related references therein, see: Sun & Qu (2005 ); Qu & Sun (2005 ). For phase transitions of ferroelectric materials, see: Zhang et al. (2008 ); Ye et al. (2009 ).

Experimental

Crystal data

(C₇H₁₅ClN₂)[CuCl₄]
M_r = 368.00
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.878 (4) Å
b = 11.167 (4) Å
c = 12.201 (4) Å
V = 1345.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.59 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.465, T_max = 0.596
6091 measured reflections
3072 independent reflections
2865 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.055
S = 1.01
3072 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), with 1298 Friedel pairs
Flack parameter: 0.006 (11)

Table 1
Selected bond lengths (Å)

Cl2—Cu1	2.2537 (8)
Cl3—Cu1	2.2539 (9)
Cl4—Cu1	2.2559 (9)
Cl5—Cu1	2.2088 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Cl2	0.91	2.60	3.270 (2)	131
N2—H2C⋯Cl3	0.91	2.54	3.252 (2)	136

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: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020782/si2354sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020782/si2354Isup2.hkl

checkCIF report

Comment top

The title compound (I), (Fig. 1), consists of protonated 1-(chloridomethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium dications and [CuCl₄]^2- anions. The organic dication is distorted, as indicated by the N—C—C—N torsion angles, which range from 16.76 (4) to 19.54 (3)°. In the structure of 1,4-dimethyl-1,4-diazonia[2.2.2]octane tetrachloridocuprate(II), of two independent dications one is almost undistorted with torsion angles between 0.6 (6) and 0.9 (5)°, whereas the other dication is distorted exhibiting torsion angles in the range of 5.5 (5) and 7.9 (5)° (Sun & Qu, 2005). In the isotypic cobalt(II) structure (Qu & Sun, 2005), two independent dications are slightly distorted with torsion angles range between 3.0 (4) and 8.7 (4)°. The [CuCl₄]^2- anion in (I) possesses typical Cu—Cl bonds and its lengths range from 2.209 (1) to 2.2559 (9) Å (Table 1), while the Cl—Cu—Cl angles range from 95.98 (4) to 132.85 (3)°. The bifurcated N—H···(Cl,Cl) hydrogen bonds (Table 2) between the organic dications and the [CuCl₄]^2- anions contribute to the stability of crystal packing (Fig. 2).

The study of ferroelectric materials has received much attention. Some materials have predominantly dielectric-ferroelectric performance.The title compound was studied as part of our work to obtain potential ferroelectric phase transition materials. Unluckily, the compound has no dielectric anomalies in the temperature range 93–453 K, suggesting that it might be only a paraelectric (Zhang et al., 2008; Ye et al., 2009).

Related literature top

For related 1,4-diazabicyclo[2.2.2]octane tetrachloridocuprate(II) and tetrachloridocobaltate(II) structures, and related references therein, see: Sun & Qu (2005); Qu & Sun (2005). For phase transitions of ferroelectric materials, see: Zhang et al. (2008); Ye et al. (2009).

Experimental top

1, 4-diazabicyclo [2.2.2]octane (5.6 g, 0.05 mol) was added in dichloromethane (20 ml) and the mixture was refluxed for 8 h. On standing for about 16 h at room temperature, the white precipitate of 1-(chloridomethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium chloride was obtained.

The title compound was synthesized by adding a solution of 1-(chloridomethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium chloride (1.97 g, 10 mmol) in HCl (37%, 20 ml) to a solution of CuCl₂ (8 mmol) in 20 ml H₂O. After a few weeks, brown hygroscopic block crystals of the title compound were obtained on slow evaporation of the solvent.

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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of a packing section of the title compound, stacking along the c axis. Dashed lines indicate hydrogen bonds.

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

Crystal data top

(C₇H₁₅ClN₂)[CuCl₄]	F(000) = 740
M_r = 368.00	D_x = 1.816 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4288 reflections
a = 9.878 (4) Å	θ = 2.5–27.5°
b = 11.167 (4) Å	µ = 2.59 mm⁻¹
c = 12.201 (4) Å	T = 293 K
V = 1345.9 (8) Å³	Block, brown
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	3072 independent reflections
Radiation source: fine-focus sealed tube	2865 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
CCD profile fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.465, T_max = 0.596	l = −15→15
6091 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)] = 0.022	H-atom parameters constrained
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0267P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3072 reflections	Δρ_max = 0.39 e Å⁻³
136 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with 1298 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (11)

Crystal data top

(C₇H₁₅ClN₂)[CuCl₄]	V = 1345.9 (8) Å³
M_r = 368.00	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.878 (4) Å	µ = 2.59 mm⁻¹
b = 11.167 (4) Å	T = 293 K
c = 12.201 (4) Å	0.30 × 0.25 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	3072 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2865 reflections with I > 2σ(I)
T_min = 0.465, T_max = 0.596	R_int = 0.032
6091 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.055	Δρ_max = 0.39 e Å⁻³
S = 1.01	Δρ_min = −0.36 e Å⁻³
3072 reflections	Absolute structure: Flack (1983), with 1298 Friedel pairs
136 parameters	Absolute structure parameter: 0.006 (11)
0 restraints

Special details top

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
C1	0.4179 (3)	1.0325 (2)	0.3874 (2)	0.0310 (6)
H1A	0.4300	0.9982	0.3150	0.037*
H1B	0.3385	1.0836	0.3859	0.037*
C2	0.3989 (3)	0.9330 (2)	0.4717 (2)	0.0267 (6)
H2A	0.3256	0.9533	0.5212	0.032*
H2B	0.3760	0.8586	0.4350	0.032*
C3	0.6657 (3)	1.0334 (2)	0.4017 (2)	0.0303 (6)
H3A	0.7419	1.0735	0.4359	0.036*
H3B	0.6844	1.0253	0.3240	0.036*
C4	0.6448 (3)	0.9099 (2)	0.4533 (2)	0.0286 (6)
H4A	0.6235	0.8517	0.3968	0.034*
H4B	0.7269	0.8845	0.4902	0.034*
C5	0.5303 (3)	1.1391 (2)	0.5373 (2)	0.0288 (6)
H5A	0.4426	1.1748	0.5519	0.035*
H5B	0.5998	1.1973	0.5551	0.035*
C6	0.5486 (3)	1.0273 (2)	0.6064 (2)	0.0282 (6)
H6A	0.6388	1.0263	0.6380	0.034*
H6B	0.4834	1.0269	0.6659	0.034*
C7	0.5329 (3)	0.8043 (2)	0.6006 (2)	0.0336 (6)
H7A	0.6137	0.8040	0.6457	0.040*
H7B	0.5382	0.7367	0.5510	0.040*
Cl1	0.39073 (9)	0.78795 (7)	0.68465 (6)	0.0493 (2)
N1	0.5285 (2)	0.91796 (17)	0.53523 (16)	0.0212 (4)
N2	0.5402 (2)	1.10429 (17)	0.41845 (17)	0.0255 (4)
H2C	0.5438	1.1716	0.3765	0.031*
Cl2	0.36056 (6)	1.33367 (5)	0.33718 (6)	0.03068 (15)
Cl3	0.69739 (6)	1.35292 (6)	0.36324 (6)	0.03568 (16)
Cl4	0.42453 (7)	1.63249 (5)	0.36275 (5)	0.03390 (16)
Cl5	0.55993 (8)	1.49699 (6)	0.59012 (6)	0.04221 (18)
Cu1	0.51283 (3)	1.45593 (3)	0.41718 (3)	0.02648 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0292 (13)	0.0314 (14)	0.0325 (15)	−0.0047 (12)	−0.0084 (11)	0.0029 (11)
C2	0.0233 (13)	0.0228 (13)	0.0339 (14)	−0.0040 (10)	−0.0025 (11)	−0.0032 (11)
C3	0.0237 (12)	0.0379 (14)	0.0294 (14)	0.0008 (12)	0.0058 (11)	0.0033 (12)
C4	0.0255 (13)	0.0314 (13)	0.0289 (14)	0.0070 (12)	0.0048 (11)	0.0014 (11)
C5	0.0342 (15)	0.0215 (12)	0.0305 (13)	−0.0036 (12)	0.0031 (12)	−0.0053 (10)
C6	0.0338 (14)	0.0260 (13)	0.0248 (14)	−0.0091 (11)	0.0016 (10)	−0.0047 (10)
C7	0.0426 (16)	0.0270 (13)	0.0312 (15)	−0.0047 (12)	−0.0017 (13)	0.0070 (11)
Cl1	0.0659 (6)	0.0429 (4)	0.0392 (4)	−0.0177 (4)	0.0166 (4)	0.0024 (3)
N1	0.0226 (10)	0.0194 (9)	0.0217 (10)	−0.0025 (8)	−0.0004 (9)	−0.0012 (8)
N2	0.0260 (10)	0.0214 (10)	0.0292 (11)	−0.0023 (9)	−0.0003 (10)	0.0027 (9)
Cl2	0.0259 (3)	0.0249 (3)	0.0412 (4)	−0.0006 (3)	−0.0059 (3)	−0.0022 (3)
Cl3	0.0241 (3)	0.0314 (3)	0.0516 (4)	0.0000 (3)	−0.0010 (3)	−0.0042 (3)
Cl4	0.0505 (4)	0.0211 (3)	0.0302 (3)	0.0052 (3)	−0.0030 (3)	−0.0007 (3)
Cl5	0.0568 (5)	0.0438 (4)	0.0260 (3)	0.0048 (4)	−0.0066 (3)	−0.0006 (3)
Cu1	0.02908 (17)	0.02223 (14)	0.02814 (16)	0.00119 (14)	−0.00354 (14)	−0.00133 (13)

Geometric parameters (Å, º) top

C1—N2	1.499 (3)	C5—C6	1.518 (3)
C1—C2	1.526 (3)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—N1	1.511 (3)
C2—N1	1.506 (3)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	C7—N1	1.499 (3)
C3—N2	1.484 (3)	C7—Cl1	1.748 (3)
C3—C4	1.530 (3)	C7—H7A	0.9700
C3—H3A	0.9700	C7—H7B	0.9700
C3—H3B	0.9700	N2—H2C	0.9100
C4—N1	1.526 (3)	Cl2—Cu1	2.2537 (8)
C4—H4A	0.9700	Cl3—Cu1	2.2539 (9)
C4—H4B	0.9700	Cl4—Cu1	2.2559 (9)
C5—N2	1.504 (3)	Cl5—Cu1	2.2088 (11)

N2—C1—C2	108.56 (19)	N1—C6—C5	109.22 (19)
N2—C1—H1A	110.0	N1—C6—H6A	109.8
C2—C1—H1A	110.0	C5—C6—H6A	109.8
N2—C1—H1B	110.0	N1—C6—H6B	109.8
C2—C1—H1B	110.0	C5—C6—H6B	109.8
H1A—C1—H1B	108.4	H6A—C6—H6B	108.3
N1—C2—C1	108.86 (19)	N1—C7—Cl1	112.18 (19)
N1—C2—H2A	109.9	N1—C7—H7A	109.2
C1—C2—H2A	109.9	Cl1—C7—H7A	109.2
N1—C2—H2B	109.9	N1—C7—H7B	109.2
C1—C2—H2B	109.9	Cl1—C7—H7B	109.2
H2A—C2—H2B	108.3	H7A—C7—H7B	107.9
N2—C3—C4	108.13 (19)	C7—N1—C2	113.10 (19)
N2—C3—H3A	110.1	C7—N1—C6	111.95 (19)
C4—C3—H3A	110.1	C2—N1—C6	108.52 (19)
N2—C3—H3B	110.1	C7—N1—C4	106.10 (19)
C4—C3—H3B	110.1	C2—N1—C4	108.03 (19)
H3A—C3—H3B	108.4	C6—N1—C4	108.98 (18)
N1—C4—C3	108.55 (19)	C3—N2—C1	110.7 (2)
N1—C4—H4A	110.0	C3—N2—C5	109.0 (2)
C3—C4—H4A	110.0	C1—N2—C5	109.21 (19)
N1—C4—H4B	110.0	C3—N2—H2C	109.3
C3—C4—H4B	110.0	C1—N2—H2C	109.3
H4A—C4—H4B	108.4	C5—N2—H2C	109.3
N2—C5—C6	108.37 (19)	Cl5—Cu1—Cl2	132.85 (3)
N2—C5—H5A	110.0	Cl5—Cu1—Cl3	102.39 (3)
C6—C5—H5A	110.0	Cl2—Cu1—Cl3	95.98 (4)
N2—C5—H5B	110.0	Cl5—Cu1—Cl4	100.44 (3)
C6—C5—H5B	110.0	Cl2—Cu1—Cl4	98.27 (4)
H5A—C5—H5B	108.4	Cl3—Cu1—Cl4	132.29 (3)

N2—C1—C2—N1	−16.8 (3)	C5—C6—N1—C4	68.1 (2)
N2—C3—C4—N1	−19.5 (3)	C3—C4—N1—C7	−167.6 (2)
N2—C5—C6—N1	−16.8 (3)	C3—C4—N1—C2	70.9 (2)
Cl1—C7—N1—C2	−52.6 (2)	C3—C4—N1—C6	−46.9 (3)
Cl1—C7—N1—C6	70.4 (2)	C4—C3—N2—C1	−47.8 (3)
Cl1—C7—N1—C4	−170.83 (17)	C4—C3—N2—C5	72.3 (2)
C1—C2—N1—C7	−166.0 (2)	C2—C1—N2—C3	69.9 (3)
C1—C2—N1—C6	69.1 (2)	C2—C1—N2—C5	−50.1 (3)
C1—C2—N1—C4	−48.9 (2)	C6—C5—N2—C3	−51.1 (3)
C5—C6—N1—C7	−174.9 (2)	C6—C5—N2—C1	70.0 (3)
C5—C6—N1—C2	−49.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2	0.91	2.60	3.270 (2)	131
N2—H2C···Cl3	0.91	2.54	3.252 (2)	136

Experimental details

Crystal data
Chemical formula	(C₇H₁₅ClN₂)[CuCl₄]
M_r	368.00
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	9.878 (4), 11.167 (4), 12.201 (4)
V (Å³)	1345.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.59
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.465, 0.596
No. of measured, independent and observed [I > 2σ(I)] reflections	6091, 3072, 2865
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.055, 1.01
No. of reflections	3072
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.36
Absolute structure	Flack (1983), with 1298 Friedel pairs
Absolute structure parameter	0.006 (11)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Cl2—Cu1	2.2537 (8)	Cl4—Cu1	2.2559 (9)
Cl3—Cu1	2.2539 (9)	Cl5—Cu1	2.2088 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2	0.91	2.60	3.270 (2)	130.6
N2—H2C···Cl3	0.91	2.54	3.252 (2)	135.9

Acknowledgements

The author is grateful to the Starter Fund of Southeast University, Nanjing, China.

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