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

In the title compound, [CoCl(3)(C(6)H(13)N(2))], the tetra-hedrally 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 mol-ecules into chains in [010]. Weak C-H⋯Cl inter-actions 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 = 278.46

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 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 ▶), 1103 Friedel pairs

Flack parameter: 0.032 (13)

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017199/cv5276sup1.cif

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

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

[CoCl3(C6H13N2)]	F(000) = 282
Mr = 278.46	Dx = 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

Rigaku SCXmini diffractometer	2343 independent reflections
Radiation source: fine-focus sealed tube	2263 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
Tmin = 0.438, Tmax = 0.511	l = −8→8
5285 measured reflections

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(Fo2) + (0.0178P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.015
2343 reflections	Δρmax = 0.29 e Å−3
113 parameters	Δρmin = −0.33 e Å−3
1 restraint	Absolute structure: Flack (1983), 1103 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.032 (13)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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

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···Cl2iv	0.97	2.82	3.605 (3)	139
C5—H5B···Cl2v	0.97	2.82	3.735 (3)	158

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⋯Cl2iv	0.97	2.82	3.605 (3)	139
C5—H5B⋯Cl2v	0.97	2.82	3.735 (3)	158

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .