(4-Aza-1-azoniabicyclo­[2.2.2]octane-κN4)trichloridocobalt(II)

Zhou, Q.; Zhu, B.-H.

doi:10.1107/S1600536812017199

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m675

doi:10.1107/S1600536812017199

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(4-Aza-1-azoniabicyclo[2.2.2]octane-κN⁴)trichloridocobalt(II)

Qinqin Zhou ^a ^* and Bo-Han Zhu ^a

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhouqinqin623@sina.com

(Received 29 March 2012; accepted 18 April 2012; online 25 April 2012)

In the title compound, [CoCl₃(C₆H₁₃N₂)], the tetrahedrally coordinated Co^II ion has Co—Cl distances ranging from 2.2220 (11) to 2.2449 (9) Å and a Co—N distance of 2.056 (2) Å. In the crystal, N—H⋯Cl hydrogen bonds link molecules into chains in [010]. Weak C—H⋯Cl interactions stabilize further the crystal packing.

Related literature

For background to related ferroelectric materials, see: Fu et al. (2010 ); Zhang et al. (2008 ). For the crystal structure of the Zn analogue of the title compound, see: Wei & Willett (2001 ).

Experimental

Crystal data

[CoCl₃(C₆H₁₃N₂)]
M_r = 278.46
Monoclinic, P 2₁
a = 6.6873 (13) Å
b = 12.433 (3) Å
c = 6.9298 (14) Å
β = 116.96 (3)°
V = 513.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.40 mm⁻¹
T = 293 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.438, T_max = 0.511
5285 measured reflections
2343 independent reflections
2263 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.054
S = 1.06
2343 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 1103 Friedel pairs
Flack parameter: 0.032 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱ	0.89 (3)	2.37 (3)	3.217 (2)	160 (3)
C3—H3A⋯Cl2ⁱⁱ	0.97	2.83	3.603 (3)	137
C3—H3B⋯Cl3ⁱ	0.97	2.72	3.621 (3)	155
C6—H6A⋯Cl3ⁱⁱⁱ	0.97	2.81	3.494 (3)	129
C6—H6A⋯Cl2^iv	0.97	2.82	3.605 (3)	139
C5—H5B⋯Cl2^v	0.97	2.82	3.735 (3)	158
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (iv) x+1, y, z; (v) x+1, y, z+1.

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017199/cv5276sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017199/cv5276Isup2.hkl

checkCIF report

Comment top

The study of ferroelectric materials has received much attention and some materials have predominantly dielectric-ferroelectric performance (Fu et al, 2010; Zhang et al., 2008). The title compound, (I), was prepared in an attempt to obtain analogs to Zn(dabcoH)Cl₃ (Wei & Willett, 2001).

In (I) (Fig. 1), the tetrahedrally coordinated Co^II ion has Co—Cl distances ranging from 2.2224 (11) to 2.2449 (9)Å and a Co—N distance of 2.057 (2) Å. In the crystal structure, intermolecular N—H···Cl hydrogen bonds (Table 1) link molecules into chains in [010]. Weak C—H···Cl interactions (Table 1) stabilize further the crystal packing.

Related literature top

For background to related ferroelectric materials, see: Fu et al. (2010); Zhang et al. (2008). For the crystal structure of Zn analogue of the title compound, see: Wei et al. (2001).

Experimental top

(dabcoH)Cl(10 mmol, 1.48 g) was dissolved in 15 mL water, then CoCl₂^.6H₂O (10 mmol, 2.38 g) in 15 ml water was added and the mixed solution was filtered. After a few days, black microcrystasls were obtained by slow evaporation at room temperature in air.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.

(4-Aza-1-azoniabicyclo[2.2.2]octane-κN⁴)trichloridocobalt(II) top

Crystal data top

[CoCl₃(C₆H₁₃N₂)]	F(000) = 282
M_r = 278.46	D_x = 1.801 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1860 reflections
a = 6.6873 (13) Å	θ = 3.3–27.5°
b = 12.433 (3) Å	µ = 2.40 mm⁻¹
c = 6.9298 (14) Å	T = 293 K
β = 116.96 (3)°	Block, black
V = 513.6 (2) Å³	0.36 × 0.32 × 0.28 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2343 independent reflections
Radiation source: fine-focus sealed tube	2263 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.438, T_max = 0.511	l = −8→8
5285 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)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0178P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.015
2343 reflections	Δρ_max = 0.29 e Å⁻³
113 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1103 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.032 (13)

Crystal data top

[CoCl₃(C₆H₁₃N₂)]	V = 513.6 (2) Å³
M_r = 278.46	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.6873 (13) Å	µ = 2.40 mm⁻¹
b = 12.433 (3) Å	T = 293 K
c = 6.9298 (14) Å	0.36 × 0.32 × 0.28 mm
β = 116.96 (3)°

Data collection top

Rigaku SCXmini diffractometer	2343 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2263 reflections with I > 2σ(I)
T_min = 0.438, T_max = 0.511	R_int = 0.029
5285 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	Δρ_max = 0.29 e Å⁻³
S = 1.06	Δρ_min = −0.33 e Å⁻³
2343 reflections	Absolute structure: Flack (1983), 1103 Friedel pairs
113 parameters	Absolute structure parameter: 0.032 (13)
1 restraint

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
Co1	0.56604 (4)	−0.11682 (3)	0.70822 (5)	0.02232 (9)
Cl2	0.22414 (9)	−0.06559 (5)	0.46983 (10)	0.03324 (15)
Cl3	0.71041 (10)	−0.24845 (5)	0.59195 (11)	0.03334 (15)
Cl1	0.58299 (12)	−0.15466 (6)	1.03206 (12)	0.04149 (18)
C3	0.8485 (4)	0.2022 (2)	0.8668 (4)	0.0297 (6)
H3A	0.7499	0.2592	0.7795	0.036*
H3B	0.9268	0.2270	1.0155	0.036*
C6	0.8946 (5)	0.1423 (2)	0.5520 (5)	0.0376 (7)
H6A	1.0015	0.1210	0.5004	0.045*
H6B	0.8083	0.2026	0.4658	0.045*
N2	0.7709 (3)	0.01327 (16)	0.7478 (3)	0.0192 (4)
C1	0.7407 (4)	0.0495 (2)	0.5324 (4)	0.0263 (5)
H1A	0.5861	0.0715	0.4455	0.032*
H1B	0.7714	−0.0100	0.4591	0.032*
C5	1.0080 (4)	−0.0144 (2)	0.8778 (5)	0.0315 (6)
H5A	1.0497	−0.0698	0.8043	0.038*
H5B	1.0302	−0.0429	1.0164	0.038*
C2	0.7144 (4)	0.1024 (2)	0.8533 (4)	0.0292 (6)
H2A	0.7435	0.0807	0.9982	0.035*
H2B	0.5557	0.1185	0.7726	0.035*
N1	1.0141 (4)	0.17317 (18)	0.7836 (4)	0.0359 (6)
C4	1.1569 (4)	0.0829 (2)	0.9146 (5)	0.0417 (8)
H4A	1.2289	0.1021	1.0669	0.050*
H4B	1.2726	0.0672	0.8709	0.050*
H1	1.107 (5)	0.227 (3)	0.801 (5)	0.054 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02136 (15)	0.01775 (14)	0.02842 (17)	−0.00118 (13)	0.01178 (13)	0.00032 (14)
Cl2	0.0236 (3)	0.0317 (3)	0.0374 (4)	0.0042 (3)	0.0077 (3)	−0.0033 (3)
Cl3	0.0330 (3)	0.0271 (3)	0.0387 (4)	0.0038 (3)	0.0151 (3)	−0.0067 (3)
Cl1	0.0459 (4)	0.0486 (4)	0.0399 (4)	0.0150 (3)	0.0282 (3)	0.0172 (3)
C3	0.0292 (13)	0.0218 (12)	0.0389 (16)	−0.0013 (10)	0.0162 (12)	−0.0093 (11)
C6	0.0531 (18)	0.0252 (13)	0.0506 (19)	−0.0018 (12)	0.0375 (16)	0.0032 (13)
N2	0.0179 (9)	0.0177 (9)	0.0221 (11)	−0.0009 (7)	0.0092 (9)	0.0003 (8)
C1	0.0314 (13)	0.0262 (13)	0.0213 (13)	−0.0019 (11)	0.0119 (11)	0.0034 (11)
C5	0.0211 (12)	0.0267 (14)	0.0396 (16)	0.0022 (10)	0.0075 (12)	0.0023 (12)
C2	0.0350 (13)	0.0240 (13)	0.0374 (15)	−0.0030 (10)	0.0240 (13)	−0.0069 (11)
N1	0.0307 (12)	0.0215 (11)	0.0629 (17)	−0.0090 (9)	0.0278 (12)	−0.0081 (11)
C4	0.0169 (12)	0.0366 (16)	0.061 (2)	−0.0037 (11)	0.0088 (13)	−0.0122 (15)

Geometric parameters (Å, º) top

Co1—N2	2.0559 (19)	N2—C2	1.468 (3)
Co1—Cl2	2.2220 (11)	N2—C1	1.483 (3)
Co1—Cl3	2.2281 (7)	C1—H1A	0.9700
Co1—Cl1	2.2449 (9)	C1—H1B	0.9700
C3—N1	1.506 (3)	C5—C4	1.513 (3)
C3—C2	1.509 (3)	C5—H5A	0.9700
C3—H3A	0.9700	C5—H5B	0.9700
C3—H3B	0.9700	C2—H2A	0.9700
C6—N1	1.483 (4)	C2—H2B	0.9700
C6—C1	1.511 (3)	N1—C4	1.486 (4)
C6—H6A	0.9700	N1—H1	0.89 (3)
C6—H6B	0.9700	C4—H4A	0.9700
N2—C5	1.466 (3)	C4—H4B	0.9700

N2—Co1—Cl2	105.80 (6)	N2—C1—H1B	109.3
N2—Co1—Cl3	104.73 (6)	C6—C1—H1B	109.3
Cl2—Co1—Cl3	114.22 (3)	H1A—C1—H1B	108.0
N2—Co1—Cl1	107.64 (6)	N2—C5—C4	111.2 (2)
Cl2—Co1—Cl1	111.83 (4)	N2—C5—H5A	109.4
Cl3—Co1—Cl1	111.95 (3)	C4—C5—H5A	109.4
N1—C3—C2	107.37 (19)	N2—C5—H5B	109.4
N1—C3—H3A	110.2	C4—C5—H5B	109.4
C2—C3—H3A	110.2	H5A—C5—H5B	108.0
N1—C3—H3B	110.2	N2—C2—C3	111.83 (19)
C2—C3—H3B	110.2	N2—C2—H2A	109.2
H3A—C3—H3B	108.5	C3—C2—H2A	109.2
N1—C6—C1	107.8 (2)	N2—C2—H2B	109.2
N1—C6—H6A	110.1	C3—C2—H2B	109.2
C1—C6—H6A	110.1	H2A—C2—H2B	107.9
N1—C6—H6B	110.1	C6—N1—C4	110.3 (2)
C1—C6—H6B	110.1	C6—N1—C3	110.3 (2)
H6A—C6—H6B	108.5	C4—N1—C3	109.1 (2)
C5—N2—C2	108.7 (2)	C6—N1—H1	110 (2)
C5—N2—C1	107.81 (17)	C4—N1—H1	106 (2)
C2—N2—C1	108.89 (19)	C3—N1—H1	111 (2)
C5—N2—Co1	111.54 (15)	N1—C4—C5	108.0 (2)
C2—N2—Co1	110.73 (14)	N1—C4—H4A	110.1
C1—N2—Co1	109.05 (14)	C5—C4—H4A	110.1
N2—C1—C6	111.4 (2)	N1—C4—H4B	110.1
N2—C1—H1A	109.3	C5—C4—H4B	110.1
C6—C1—H1A	109.3	H4A—C4—H4B	108.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.89 (3)	2.37 (3)	3.217 (2)	160 (3)
C3—H3A···Cl2ⁱⁱ	0.97	2.83	3.603 (3)	137
C3—H3B···Cl3ⁱ	0.97	2.72	3.621 (3)	155
C6—H6A···Cl3ⁱⁱⁱ	0.97	2.81	3.494 (3)	129
C6—H6A···Cl2^iv	0.97	2.82	3.605 (3)	139
C5—H5B···Cl2^v	0.97	2.82	3.735 (3)	158

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

Experimental details

Crystal data
Chemical formula	[CoCl₃(C₆H₁₃N₂)]
M_r	278.46
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.6873 (13), 12.433 (3), 6.9298 (14)
β (°)	116.96 (3)
V (Å³)	513.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.40
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.438, 0.511
No. of measured, independent and observed [I > 2σ(I)] reflections	5285, 2343, 2263
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.054, 1.06
No. of reflections	2343
No. of parameters	113
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.33
Absolute structure	Flack (1983), 1103 Friedel pairs
Absolute structure parameter	0.032 (13)

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
N1—H1···Cl1ⁱ	0.89 (3)	2.37 (3)	3.217 (2)	160 (3)
C3—H3A···Cl2ⁱⁱ	0.97	2.83	3.603 (3)	136.9
C3—H3B···Cl3ⁱ	0.97	2.72	3.621 (3)	154.8
C6—H6A···Cl3ⁱⁱⁱ	0.97	2.81	3.494 (3)	128.5
C6—H6A···Cl2^iv	0.97	2.82	3.605 (3)	139.1
C5—H5B···Cl2^v	0.97	2.82	3.735 (3)	158.0

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

Acknowledgements

This work was supported by Jiangsu Planned Projects for Postdoctoral Research Funds (grant No. 1101010B).

References

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