metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 CoII 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[Fu, D. W., Dai, J., Ge, J. Z., Ye, H. Y. & Qu, Z. R. (2010). Inorg. Chem. Commun. 13, 282-285.]); Zhang et al. (2008[Zhang, W., Xiong, R. G. & Huang, S. P. D. (2008). J. Am. Chem. Soc. 130, 10468-10469.]). For the crystal structure of the Zn analogue of the title compound, see: Wei & Willett (2001[Wei, M. & Willett, R. D. (2001). Acta Cryst. E57, m167-m168.]).

[Scheme 1]

Experimental

Crystal data
  • [CoCl3(C6H13N2)]

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.438, Tmax = 0.511

  • 5285 measured reflections

  • 2343 independent reflections

  • 2263 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.29 e Å−3

  • Δρmin = −0.33 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1103 Friedel pairs

  • Flack parameter: 0.032 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯Cl2iv 0.97 2.82 3.605 (3) 139
C5—H5B⋯Cl2v 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 CoII 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.

Refinement top

N-bound atom H1 was located on a difference map and isotropically refined. C-bound H atoms were placed in calculated positions (C—H = 0.97 Å), and refined as riding with Uiso(H) = 1.2-1.5 Ueq(C).

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
[Figure 1] 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
Mr = 278.46Dx = 1.801 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1860 reflections
a = 6.6873 (13) Åθ = 3.3–27.5°
b = 12.433 (3) ŵ = 2.40 mm1
c = 6.9298 (14) ÅT = 293 K
β = 116.96 (3)°Block, black
V = 513.6 (2) Å30.36 × 0.32 × 0.28 mm
Z = 2
Data collection top
Rigaku SCXmini
diffractometer
2343 independent reflections
Radiation source: fine-focus sealed tube2263 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.3°
ω scansh = 88
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1616
Tmin = 0.438, Tmax = 0.511l = 88
5285 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.054 w = 1/[σ2(Fo2) + (0.0178P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.015
2343 reflectionsΔρmax = 0.29 e Å3
113 parametersΔρmin = 0.33 e Å3
1 restraintAbsolute structure: Flack (1983), 1103 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.032 (13)
Crystal data top
[CoCl3(C6H13N2)]V = 513.6 (2) Å3
Mr = 278.46Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.6873 (13) ŵ = 2.40 mm1
b = 12.433 (3) ÅT = 293 K
c = 6.9298 (14) Å0.36 × 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)
Tmin = 0.438, Tmax = 0.511Rint = 0.029
5285 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.054Δρmax = 0.29 e Å3
S = 1.06Δρmin = 0.33 e Å3
2343 reflectionsAbsolute structure: Flack (1983), 1103 Friedel pairs
113 parametersAbsolute 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
xyzUiso*/Ueq
Co10.56604 (4)0.11682 (3)0.70822 (5)0.02232 (9)
Cl20.22414 (9)0.06559 (5)0.46983 (10)0.03324 (15)
Cl30.71041 (10)0.24845 (5)0.59195 (11)0.03334 (15)
Cl10.58299 (12)0.15466 (6)1.03206 (12)0.04149 (18)
C30.8485 (4)0.2022 (2)0.8668 (4)0.0297 (6)
H3A0.74990.25920.77950.036*
H3B0.92680.22701.01550.036*
C60.8946 (5)0.1423 (2)0.5520 (5)0.0376 (7)
H6A1.00150.12100.50040.045*
H6B0.80830.20260.46580.045*
N20.7709 (3)0.01327 (16)0.7478 (3)0.0192 (4)
C10.7407 (4)0.0495 (2)0.5324 (4)0.0263 (5)
H1A0.58610.07150.44550.032*
H1B0.77140.01000.45910.032*
C51.0080 (4)0.0144 (2)0.8778 (5)0.0315 (6)
H5A1.04970.06980.80430.038*
H5B1.03020.04291.01640.038*
C20.7144 (4)0.1024 (2)0.8533 (4)0.0292 (6)
H2A0.74350.08070.99820.035*
H2B0.55570.11850.77260.035*
N11.0141 (4)0.17317 (18)0.7836 (4)0.0359 (6)
C41.1569 (4)0.0829 (2)0.9146 (5)0.0417 (8)
H4A1.22890.10211.06690.050*
H4B1.27260.06720.87090.050*
H11.107 (5)0.227 (3)0.801 (5)0.054 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02136 (15)0.01775 (14)0.02842 (17)0.00118 (13)0.01178 (13)0.00032 (14)
Cl20.0236 (3)0.0317 (3)0.0374 (4)0.0042 (3)0.0077 (3)0.0033 (3)
Cl30.0330 (3)0.0271 (3)0.0387 (4)0.0038 (3)0.0151 (3)0.0067 (3)
Cl10.0459 (4)0.0486 (4)0.0399 (4)0.0150 (3)0.0282 (3)0.0172 (3)
C30.0292 (13)0.0218 (12)0.0389 (16)0.0013 (10)0.0162 (12)0.0093 (11)
C60.0531 (18)0.0252 (13)0.0506 (19)0.0018 (12)0.0375 (16)0.0032 (13)
N20.0179 (9)0.0177 (9)0.0221 (11)0.0009 (7)0.0092 (9)0.0003 (8)
C10.0314 (13)0.0262 (13)0.0213 (13)0.0019 (11)0.0119 (11)0.0034 (11)
C50.0211 (12)0.0267 (14)0.0396 (16)0.0022 (10)0.0075 (12)0.0023 (12)
C20.0350 (13)0.0240 (13)0.0374 (15)0.0030 (10)0.0240 (13)0.0069 (11)
N10.0307 (12)0.0215 (11)0.0629 (17)0.0090 (9)0.0278 (12)0.0081 (11)
C40.0169 (12)0.0366 (16)0.061 (2)0.0037 (11)0.0088 (13)0.0122 (15)
Geometric parameters (Å, º) top
Co1—N22.0559 (19)N2—C21.468 (3)
Co1—Cl22.2220 (11)N2—C11.483 (3)
Co1—Cl32.2281 (7)C1—H1A0.9700
Co1—Cl12.2449 (9)C1—H1B0.9700
C3—N11.506 (3)C5—C41.513 (3)
C3—C21.509 (3)C5—H5A0.9700
C3—H3A0.9700C5—H5B0.9700
C3—H3B0.9700C2—H2A0.9700
C6—N11.483 (4)C2—H2B0.9700
C6—C11.511 (3)N1—C41.486 (4)
C6—H6A0.9700N1—H10.89 (3)
C6—H6B0.9700C4—H4A0.9700
N2—C51.466 (3)C4—H4B0.9700
N2—Co1—Cl2105.80 (6)N2—C1—H1B109.3
N2—Co1—Cl3104.73 (6)C6—C1—H1B109.3
Cl2—Co1—Cl3114.22 (3)H1A—C1—H1B108.0
N2—Co1—Cl1107.64 (6)N2—C5—C4111.2 (2)
Cl2—Co1—Cl1111.83 (4)N2—C5—H5A109.4
Cl3—Co1—Cl1111.95 (3)C4—C5—H5A109.4
N1—C3—C2107.37 (19)N2—C5—H5B109.4
N1—C3—H3A110.2C4—C5—H5B109.4
C2—C3—H3A110.2H5A—C5—H5B108.0
N1—C3—H3B110.2N2—C2—C3111.83 (19)
C2—C3—H3B110.2N2—C2—H2A109.2
H3A—C3—H3B108.5C3—C2—H2A109.2
N1—C6—C1107.8 (2)N2—C2—H2B109.2
N1—C6—H6A110.1C3—C2—H2B109.2
C1—C6—H6A110.1H2A—C2—H2B107.9
N1—C6—H6B110.1C6—N1—C4110.3 (2)
C1—C6—H6B110.1C6—N1—C3110.3 (2)
H6A—C6—H6B108.5C4—N1—C3109.1 (2)
C5—N2—C2108.7 (2)C6—N1—H1110 (2)
C5—N2—C1107.81 (17)C4—N1—H1106 (2)
C2—N2—C1108.89 (19)C3—N1—H1111 (2)
C5—N2—Co1111.54 (15)N1—C4—C5108.0 (2)
C2—N2—Co1110.73 (14)N1—C4—H4A110.1
C1—N2—Co1109.05 (14)C5—C4—H4A110.1
N2—C1—C6111.4 (2)N1—C4—H4B110.1
N2—C1—H1A109.3C5—C4—H4B110.1
C6—C1—H1A109.3H4A—C4—H4B108.4
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.89 (3)2.37 (3)3.217 (2)160 (3)
C3—H3A···Cl2ii0.972.833.603 (3)137
C3—H3B···Cl3i0.972.723.621 (3)155
C6—H6A···Cl3iii0.972.813.494 (3)129
C6—H6A···Cl2iv0.972.823.605 (3)139
C5—H5B···Cl2v0.972.823.735 (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)]
Mr278.46
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)6.6873 (13), 12.433 (3), 6.9298 (14)
β (°) 116.96 (3)
V3)513.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)2.40
Crystal size (mm)0.36 × 0.32 × 0.28
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.438, 0.511
No. of measured, independent and
observed [I > 2σ(I)] reflections
5285, 2343, 2263
Rint0.029
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.054, 1.06
No. of reflections2343
No. of parameters113
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.33
Absolute structureFlack (1983), 1103 Friedel pairs
Absolute structure parameter0.032 (13)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.89 (3)2.37 (3)3.217 (2)160 (3)
C3—H3A···Cl2ii0.972.833.603 (3)136.9
C3—H3B···Cl3i0.972.723.621 (3)154.8
C6—H6A···Cl3iii0.972.813.494 (3)128.5
C6—H6A···Cl2iv0.972.823.605 (3)139.1
C5—H5B···Cl2v0.972.823.735 (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

First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationFu, D. W., Dai, J., Ge, J. Z., Ye, H. Y. & Qu, Z. R. (2010). Inorg. Chem. Commun. 13, 282–285.  Web of Science CSD CrossRef CAS Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWei, M. & Willett, R. D. (2001). Acta Cryst. E57, m167–m168.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZhang, W., Xiong, R. G. & Huang, S. P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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