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

Abstract

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,

• a = 9.878 (4) Å

• b = 11.167 (4) Å

• c = 12.201 (4) Å

• V = 1345.9 (8) ų

• 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[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 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)

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Positional parameters of all H atoms bonded to C and N atoms were calculated geometrically and were allowed to ride on the C and N atoms to which they are bonded, with respective C—H and N—H distances of 0.97 Å and 0.91 Å and with U_iso(H) = 1.2U_eq(C, N).

Figures

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.

Crystal data

(C7H15ClN2)[CuCl4]	F(000) = 740
Mr = 368.00	Dx = 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

Rigaku Mercury2 diffractometer	3072 independent reflections
Radiation source: fine-focus sealed tube	2865 reflections with I > 2σ(I)
graphite	Rint = 0.032
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 2.5°
CCD profile fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.465, Tmax = 0.596	l = −15→15
6091 measured reflections

Refinement

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(Fo2) + (0.0267P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
3072 reflections	Δρmax = 0.39 e Å−3
136 parameters	Δρmin = −0.36 e Å−3
0 restraints	Absolute structure: Flack (1983), with 1298 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.006 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.