1,4-Diazo­niabi­cyclo­[2.2.2]­octane tetra­chloro­cobaltate

The title compound, (C₆H₁₄N₂)[CoCl₄], is isostructural with (C₆H₁₄N₂)[MCl₄] (M = Cu, Zn) and contains doubly protonated dabconium C₆H₁₄N₂²⁺ cations and [CoCl₄]²⁻ tetrahedra. These species interact by way of bifurcated N—H...(Cl,Cl) hydrogen bonds to form corrugated chains. The chains interact by way of van der Waals forces and C—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.078
• Data-to-parameter ratio = 22.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), arose as a side product during our synthetic investigations of organically templated cobalt phosphate networks (Cowley & Chippindale, 1999; Natarajan et al., 2000). It is isostructural with (C₆H₁₄N₂)[MCl₄] (M = Cu, Zn), as described by Viossat et al. (1984) and Brammer et al. (2002), for the copper and zinc congeners, respectively.

In (I), the [CoCl₄]²⁻ tetrahedron shows slight geometrical deviations from regularity with d_av(Co—Cl) = 2.2746 (6) Å and θ_av(Cl—Co—Cl) = 109.49 (2)° [spread of angles = 104.56 (2)–114.76 (2)°]. The dabconium (1,4-diazoniabicyclo[2.2.2]octane) cation has typical geometrical parameters [d_av(N—C) = 1.502 (3) Å, d_av(C—C) = 1.530 (3) Å, θ_av(C—N—C) = 110.3 (2)° and θ_av(N—C—C) = 108.6 (2)°].

The component species in (I) interact by way of bifurcated N—H···(Cl,Cl) hydrogen bonds (Table 2), resulting in each chloride ion acting as an acceptor with typical (Brammer et al., 2001) geometrical parameters of d_av(N···Cl) = 3.298 (2) Å and θ_av(N—H···Cl) = 131.9°. The energetics of these interactions, and their possible role as synthons in supramolecular chemistry are described in detail by Brammer et al. (2002). In (I), these bonds (Fig. 2) result in corrugated polymeric chains which propagate along [001]. The unit-cell packing perpendicular to the chains involves van der Waals forces (Fig. 3) and C—H···Cl hydrogen bonds (Brammer et al., 2002; Table 2), assuming these are not merely an artefact of the crystal packing.

S2. Experimental

10 ml of 1 M CoCl₂ solution, 10 ml of 1M H₃PO₄ solution and 0.5 g dabco (C₆H₁₂N₂) were mixed together in a plastic bottle and heated to 373 K for 24 h, resulting in a blue solution. The solution was cooled to room temperature, and platy crystals of (I) grew as water slowly evaporated from the increasingly viscous liquors over several weeks.

S3. Refinement

H atoms were placed in idealized locations and refined by riding on their parent atom, with U_iso(H) = 1.2U_eq(parent atom) in each case.

Computing details

Data collection: COLLECT (Enraf-Nonius, 1999); cell refinement: COLLECT; data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Asymmetric unit of (I) (50% diaplcaement ellipsoids, arbitrary spheres for the H atoms, C—H H atoms omitted for clarity and hydrogen bonds indicated by dashed lines).
	Fig. 2. Hydrogen-bonding scheme in (I), leading to corrugated chains of alternating dabconium cations and [CoCl4]^2− tetrahedra. Colour key: CoCl4 tetrahedra blue, Cl atoms green, C atoms blue, N atoms purple, H atoms grey (all radii arbitrary; C—H H atoms omitted for clarity). The H···Cl portions of the bifurcated N—H···(Cl,Cl) hydrogen bonds are coloured yellow.
	Fig. 3. Unit-cell packing in (I), viewed down [010]. The colour key as in Fig. 2.

(I)

Crystal data

(C6H14N2)[CoCl4]	F(000) = 636
Mr = 314.92	Dx = 1.795 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4875 (2) Å	Cell parameters from 4880 reflections
b = 6.7174 (2) Å	θ = 2.9–27.5°
c = 18.3121 (5) Å	µ = 2.35 mm^−1
β = 92.8420 (1)°	T = 120 K
V = 1165.62 (5) Å^3	Plate, blue
Z = 4	0.36 × 0.22 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer	2654 independent reflections
Radiation source: fine-focus sealed tube	2304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω and ϕ scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −11→12
Tmin = 0.485, Tmax = 0.835	k = −8→8
9112 measured reflections	l = −23→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.0946P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2654 reflections	Δρmax = 0.57 e Å^−3
119 parameters	Δρmin = −0.74 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0121 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.76747 (3)	0.44364 (4)	0.116913 (15)	0.01312 (12)
Cl1	0.80551 (5)	0.27988 (8)	0.01143 (3)	0.01763 (15)
Cl2	0.59883 (5)	0.67296 (8)	0.08530 (3)	0.01968 (15)
Cl3	0.96144 (5)	0.59193 (8)	0.17013 (3)	0.01931 (15)
Cl4	0.68874 (6)	0.23386 (8)	0.20440 (3)	0.01823 (15)
N1	0.69890 (17)	0.7051 (3)	−0.07765 (9)	0.0126 (4)
H1	0.6720	0.6221	−0.0401	0.015*
N2	0.77093 (18)	0.9255 (2)	−0.17843 (10)	0.0125 (4)
H2	0.7974	1.0083	−0.2161	0.015*
C1	0.6877 (2)	0.5907 (3)	−0.14826 (11)	0.0153 (5)
H3	0.5898	0.5428	−0.1576	0.018*
H4	0.7511	0.4736	−0.1452	0.018*
C2	0.6041 (2)	0.8838 (3)	−0.08040 (12)	0.0148 (4)
H5	0.6127	0.9568	−0.0334	0.018*
H6	0.5046	0.8419	−0.0890	0.018*
C3	0.8490 (2)	0.7691 (3)	−0.06160 (12)	0.0156 (4)
H7	0.9111	0.6509	−0.0570	0.019*
H8	0.8566	0.8436	−0.0149	0.019*
C4	0.7291 (2)	0.7268 (3)	−0.21025 (12)	0.0187 (5)
H9	0.8090	0.6681	−0.2356	0.022*
H10	0.6486	0.7428	−0.2462	0.022*
C5	0.6484 (2)	1.0179 (3)	−0.14283 (12)	0.0178 (5)
H11	0.5685	1.0345	−0.1792	0.021*
H12	0.6752	1.1510	−0.1235	0.021*
C6	0.8947 (2)	0.9019 (3)	−0.12436 (12)	0.0171 (5)
H13	0.9251	1.0337	−0.1052	0.020*
H14	0.9749	0.8402	−0.1485	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01226 (17)	0.01364 (18)	0.01339 (18)	0.00131 (11)	−0.00008 (12)	−0.00016 (11)
Cl1	0.0197 (3)	0.0173 (3)	0.0159 (3)	0.0005 (2)	−0.0002 (2)	−0.0041 (2)
Cl2	0.0182 (3)	0.0216 (3)	0.0197 (3)	0.0088 (2)	0.0049 (2)	0.0060 (2)
Cl3	0.0131 (3)	0.0212 (3)	0.0236 (3)	−0.0010 (2)	0.0006 (2)	−0.0075 (2)
Cl4	0.0242 (3)	0.0149 (3)	0.0153 (3)	−0.0028 (2)	−0.0008 (2)	0.0017 (2)
N1	0.0120 (8)	0.0115 (9)	0.0146 (9)	−0.0001 (7)	0.0019 (7)	0.0021 (7)
N2	0.0132 (8)	0.0097 (9)	0.0148 (9)	−0.0005 (7)	0.0031 (7)	0.0019 (7)
C1	0.0150 (10)	0.0127 (10)	0.0183 (11)	−0.0026 (9)	0.0020 (9)	−0.0034 (8)
C2	0.0125 (10)	0.0150 (10)	0.0171 (11)	0.0032 (9)	0.0021 (8)	0.0002 (9)
C3	0.0100 (9)	0.0188 (11)	0.0177 (11)	0.0000 (9)	−0.0015 (8)	0.0006 (9)
C4	0.0274 (12)	0.0131 (11)	0.0155 (11)	−0.0030 (10)	0.0011 (9)	−0.0022 (9)
C5	0.0171 (11)	0.0157 (11)	0.0208 (12)	0.0062 (10)	0.0033 (9)	0.0029 (10)
C6	0.0118 (10)	0.0172 (11)	0.0220 (12)	−0.0019 (9)	−0.0010 (9)	0.0023 (9)

Geometric parameters (Å, º)

Co1—Cl1	2.2672 (6)	C1—H4	0.9900
Co1—Cl3	2.2694 (6)	C2—C5	1.531 (3)
Co1—Cl2	2.2751 (6)	C2—H5	0.9900
Co1—Cl4	2.2867 (6)	C2—H6	0.9900
N1—C2	1.500 (3)	C3—C6	1.534 (3)
N1—C3	1.503 (3)	C3—H7	0.9900
N1—C1	1.503 (3)	C3—H8	0.9900
N1—H1	0.9300	C4—H9	0.9900
N2—C5	1.496 (3)	C4—H10	0.9900
N2—C4	1.502 (3)	C5—H11	0.9900
N2—C6	1.506 (3)	C5—H12	0.9900
N2—H2	0.9300	C6—H13	0.9900
C1—C4	1.524 (3)	C6—H14	0.9900
C1—H3	0.9900
Cl1—Co1—Cl3	114.76 (2)	N1—C2—H6	110.1
Cl1—Co1—Cl2	104.56 (2)	C5—C2—H6	110.1
Cl3—Co1—Cl2	110.92 (2)	H5—C2—H6	108.4
Cl1—Co1—Cl4	111.66 (2)	N1—C3—C6	108.66 (16)
Cl3—Co1—Cl4	104.82 (2)	N1—C3—H7	110.0
Cl2—Co1—Cl4	110.21 (2)	C6—C3—H7	110.0
C2—N1—C3	109.80 (16)	N1—C3—H8	110.0
C2—N1—C1	111.33 (15)	C6—C3—H8	110.0
C3—N1—C1	109.89 (16)	H7—C3—H8	108.3
C2—N1—H1	108.6	N2—C4—C1	108.49 (17)
C3—N1—H1	108.6	N2—C4—H9	110.0
C1—N1—H1	108.6	C1—C4—H9	110.0
C5—N2—C4	109.99 (16)	N2—C4—H10	110.0
C5—N2—C6	110.77 (16)	C1—C4—H10	110.0
C4—N2—C6	110.10 (16)	H9—C4—H10	108.4
C5—N2—H2	108.6	N2—C5—C2	109.23 (16)
C4—N2—H2	108.6	N2—C5—H11	109.8
C6—N2—H2	108.6	C2—C5—H11	109.8
N1—C1—C4	108.92 (16)	N2—C5—H12	109.8
N1—C1—H3	109.9	C2—C5—H12	109.8
C4—C1—H3	109.9	H11—C5—H12	108.3
N1—C1—H4	109.9	N2—C6—C3	108.29 (16)
C4—C1—H4	109.9	N2—C6—H13	110.0
H3—C1—H4	108.3	C3—C6—H13	110.0
N1—C2—C5	108.05 (16)	N2—C6—H14	110.0
N1—C2—H5	110.1	C3—C6—H14	110.0
C5—C2—H5	110.1	H13—C6—H14	108.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.93	2.77	3.4175 (18)	128
N1—H1···Cl2	0.93	2.46	3.1832 (18)	135
N2—H2···Cl3^i	0.93	2.75	3.3866 (19)	127
N2—H2···Cl4^i	0.93	2.46	3.2064 (18)	138
C1—H3···Cl2^ii	0.99	2.70	3.488 (2)	137
C1—H4···Cl3^iii	0.99	2.82	3.589 (2)	135
C2—H6···Cl4^ii	0.99	2.78	3.588 (2)	140
C3—H7···Cl1^iii	0.99	2.81	3.376 (2)	117
C4—H9···Cl3^i	0.99	2.81	3.409 (2)	119

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z.