1,4,8,11-Tetra-azoniacyclo-tetra-decane tetra-chloridocobaltate(II) dichloride.

The asymmetric unit of the title compound, (C(10)H(28)N(4))[CoCl(4)]Cl(2), contains two half-mol-ecules of the macrocycle, which are both completed by crystallographic inversion symmetry. In the dianion, the Co(2+) cation is tetra-hedrally coordinated by four Cl atoms; the Co-Cl bond lengths correlate with the number of hydrogen bonds that the chloride ions accept. The crystal cohesion is supported by electrostatic inter-actions which, together with numerous N-H⋯Cl, N-H⋯(Cl,Cl) and C-H⋯Cl hydrogen bonds, lead to a three-dimensional network.

Related literature

For background to organic–inorganic hybrid networks and their properties, see: Bu et al. (2001 ▶); Mitzi et al. (1999 ▶). For hydrogen-bonding in supra­molecular networks, see: Brammer et al. (2002 ▶). For related structures, see: El Glaoui et al. (2009 ▶); Jakubas et al. (2005 ▶); Adamski et al. (2009 ▶); Boyd & McFadyen (2007 ▶); n class="Chemical">Hashizume et al. (1999 ▶).

Experimental

Crystal data

(C10H28N4)[n class="Chemical">CoCl4]Cl2

M = 475.99

Triclinic,

a = 7.4058 (10) Å

b = 8.1244 (10) Å

c = 17.147 (1) Å

α = 84.36 (2)°

β = 85.56 (2)°

γ = 77.84 (2)°

V = 1001.97 (19) Å3

Z = 2

Mo Kα radiation

μ = 1.66 mm−1

T = 293 K

0.20 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

21712 measured reflections

4375 independent reflections

4023 reflections with I > 2σ(I)

R int = 0.012

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.098

S = 1.13

4375 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.99 e Å−3

Δρmin = −0.70 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025079/hb5513sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025079/hb5513Isup2.hkl

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

(C10H28N4)[CoCl4]Cl2	Z = 2
Mr = 475.99	F(000) = 490
Triclinic, P1	Dx = 1.578 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4058 (10) Å	Cell parameters from 25 reflections
b = 8.1244 (10) Å	θ = 12–15°
c = 17.147 (1) Å	µ = 1.66 mm−1
α = 84.36 (2)°	T = 293 K
β = 85.56 (2)°	Prism, blue
γ = 77.84 (2)°	0.20 × 0.15 × 0.10 mm
V = 1001.97 (19) Å3

Enraf–Nonius CAD-4 diffractometer	Rint = 0.012
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 2.4°
graphite	h = −9→2
non–profiled ω/2θ scans	k = −10→10
21712 measured reflections	l = −21→21
4375 independent reflections	2 standard reflections every 120 min
4023 reflections with I > 2σ(I)	intensity decay: −1%

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0484P)2 + 1.0784P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max = 0.001
4375 reflections	Δρmax = 0.99 e Å−3
191 parameters	Δρmin = −0.69 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0098 (15)

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
Co	0.70021 (4)	0.68008 (4)	0.739869 (18)	0.02545 (12)
Cl1	0.59983 (10)	0.94777 (8)	0.77340 (4)	0.03784 (17)
Cl2	0.98382 (9)	0.53726 (8)	0.77981 (4)	0.03170 (15)
Cl3	0.72293 (9)	0.69599 (9)	0.60513 (3)	0.03302 (16)
Cl4	0.49963 (9)	0.51312 (8)	0.79699 (4)	0.03371 (16)
Cl5	0.13290 (9)	0.05084 (8)	0.62097 (4)	0.03219 (15)
Cl6	0.79324 (9)	0.72834 (9)	0.98838 (4)	0.03847 (17)
N4	0.3477 (3)	0.3336 (3)	0.65786 (12)	0.0285 (4)
H4A	0.3385	0.3878	0.7018	0.034*
H4B	0.3043	0.2383	0.6705	0.034*
N1	1.1540 (3)	0.7804 (3)	0.88701 (12)	0.0287 (4)
H1A	1.0461	0.7781	0.9147	0.034*
H1B	1.1948	0.6781	0.8688	0.034*
N2	1.1506 (3)	0.7095 (2)	1.07369 (12)	0.0260 (4)
H2A	1.0476	0.7014	1.0510	0.031*
H2B	1.1708	0.6263	1.1126	0.031*
N3	0.7691 (3)	0.1442 (3)	0.53021 (13)	0.0288 (4)
H3A	0.7801	0.0709	0.4932	0.035*
H3B	0.8470	0.0955	0.5675	0.035*
C5	0.8823 (4)	1.0892 (3)	1.18244 (15)	0.0317 (5)
H5A	0.7709	1.0990	1.2168	0.038*
H5B	0.9785	1.1149	1.2117	0.038*
C7	0.5487 (3)	0.2847 (3)	0.63236 (14)	0.0266 (5)
H7A	0.6180	0.2286	0.6766	0.032*
H7B	0.5958	0.3855	0.6142	0.032*
C2	1.3114 (3)	0.6829 (3)	1.01371 (15)	0.0293 (5)
H2C	1.3274	0.5700	0.9968	0.035*
H2D	1.4227	0.6890	1.0387	0.035*
C8	0.2242 (3)	0.4440 (3)	0.59907 (15)	0.0282 (5)
H8A	0.0990	0.4699	0.6224	0.034*
H8B	0.2223	0.3819	0.5537	0.034*
C1	1.2914 (3)	0.8090 (3)	0.94166 (14)	0.0276 (5)
H1C	1.2531	0.9223	0.9585	0.033*
H1D	1.4111	0.8016	0.9134	0.033*
C4	0.9406 (4)	0.9072 (3)	1.16103 (15)	0.0308 (5)
H4C	0.9587	0.8328	1.2089	0.037*
H4D	0.8417	0.8787	1.1345	0.037*
C6	0.5756 (3)	0.1671 (3)	0.56660 (15)	0.0274 (5)
H6A	0.5508	0.0582	0.5874	0.033*
H6B	0.4884	0.2139	0.5268	0.033*
C10	0.1664 (3)	0.7006 (3)	0.50678 (16)	0.0297 (5)
H10A	0.1674	0.6241	0.4667	0.036*
H10B	0.0399	0.7333	0.5279	0.036*
C3	1.1177 (4)	0.8759 (3)	1.10836 (17)	0.0336 (6)
H3C	1.1104	0.9656	1.0663	0.040*
H3D	1.2218	0.8794	1.1387	0.040*
C9	0.2862 (4)	0.6085 (3)	0.57213 (18)	0.0371 (6)
H9A	0.2739	0.6784	0.6157	0.045*
H9B	0.4151	0.5849	0.5532	0.045*

	U11	U22	U33	U12	U13	U23
Co	0.02721 (19)	0.02537 (18)	0.02405 (18)	−0.00576 (13)	0.00061 (12)	−0.00424 (12)
Cl1	0.0455 (4)	0.0261 (3)	0.0424 (4)	−0.0072 (3)	−0.0007 (3)	−0.0074 (3)
Cl2	0.0307 (3)	0.0305 (3)	0.0328 (3)	−0.0039 (2)	−0.0015 (2)	−0.0029 (2)
Cl3	0.0324 (3)	0.0433 (4)	0.0248 (3)	−0.0102 (3)	−0.0001 (2)	−0.0059 (2)
Cl4	0.0350 (3)	0.0343 (3)	0.0348 (3)	−0.0141 (3)	0.0055 (2)	−0.0087 (2)
Cl5	0.0361 (3)	0.0301 (3)	0.0321 (3)	−0.0084 (2)	−0.0056 (2)	−0.0048 (2)
Cl6	0.0296 (3)	0.0405 (4)	0.0482 (4)	−0.0144 (3)	0.0001 (3)	−0.0041 (3)
N4	0.0340 (11)	0.0270 (10)	0.0257 (10)	−0.0094 (9)	0.0056 (8)	−0.0071 (8)
N1	0.0315 (11)	0.0259 (10)	0.0297 (10)	−0.0072 (8)	0.0032 (8)	−0.0080 (8)
N2	0.0289 (10)	0.0208 (9)	0.0271 (10)	−0.0036 (8)	0.0004 (8)	−0.0001 (8)
N3	0.0262 (10)	0.0248 (10)	0.0340 (11)	−0.0006 (8)	−0.0022 (8)	−0.0060 (8)
C5	0.0376 (14)	0.0331 (13)	0.0241 (11)	−0.0065 (11)	0.0034 (10)	−0.0066 (10)
C7	0.0286 (12)	0.0254 (11)	0.0263 (11)	−0.0059 (9)	−0.0027 (9)	−0.0030 (9)
C2	0.0253 (11)	0.0258 (11)	0.0351 (13)	−0.0011 (9)	0.0020 (10)	−0.0062 (10)
C8	0.0258 (11)	0.0281 (12)	0.0310 (12)	−0.0055 (9)	0.0033 (9)	−0.0076 (9)
C1	0.0256 (11)	0.0301 (12)	0.0288 (12)	−0.0094 (9)	0.0040 (9)	−0.0067 (9)
C4	0.0355 (13)	0.0282 (12)	0.0280 (12)	−0.0071 (10)	0.0053 (10)	−0.0030 (10)
C6	0.0262 (11)	0.0235 (11)	0.0328 (12)	−0.0051 (9)	0.0007 (9)	−0.0054 (9)
C10	0.0235 (11)	0.0314 (12)	0.0347 (13)	−0.0064 (9)	−0.0006 (10)	−0.0045 (10)
C3	0.0334 (13)	0.0319 (13)	0.0383 (14)	−0.0100 (11)	0.0063 (11)	−0.0151 (11)
C9	0.0392 (14)	0.0281 (13)	0.0475 (16)	−0.0122 (11)	−0.0130 (12)	−0.0003 (11)

Co—Cl1	2.2609 (8)	C7—C6	1.523 (3)
Co—Cl2	2.2950 (9)	C7—H7A	0.9700
Co—Cl3	2.2963 (7)	C7—H7B	0.9700
Co—Cl4	2.3170 (8)	C2—C1	1.521 (4)
N4—C7	1.500 (3)	C2—H2C	0.9700
N4—C8	1.509 (3)	C2—H2D	0.9700
N4—H4A	0.9000	C8—C9	1.522 (4)
N4—H4B	0.9000	C8—H8A	0.9700
N1—C1	1.503 (3)	C8—H8B	0.9700
N1—C5i	1.515 (3)	C1—H1C	0.9700
N1—H1A	0.9000	C1—H1D	0.9700
N1—H1B	0.9000	C4—C3	1.523 (4)
N2—C3	1.495 (3)	C4—H4C	0.9700
N2—C2	1.506 (3)	C4—H4D	0.9700
N2—H2A	0.9000	C6—H6A	0.9700
N2—H2B	0.9000	C6—H6B	0.9700
N3—C6	1.500 (3)	C10—N3ii	1.506 (3)
N3—C10ii	1.506 (3)	C10—C9	1.521 (4)
N3—H3A	0.9000	C10—H10A	0.9700
N3—H3B	0.9000	C10—H10B	0.9700
C5—N1i	1.515 (3)	C3—H3C	0.9700
C5—C4	1.524 (4)	C3—H3D	0.9700
C5—H5A	0.9700	C9—H9A	0.9700
C5—H5B	0.9700	C9—H9B	0.9700
Cl1—Co—Cl2	117.71 (3)	N2—C2—H2D	108.6
Cl1—Co—Cl3	106.35 (3)	C1—C2—H2D	108.6
Cl2—Co—Cl3	106.05 (3)	H2C—C2—H2D	107.6
Cl1—Co—Cl4	109.41 (3)	N4—C8—C9	113.0 (2)
Cl2—Co—Cl4	103.43 (3)	N4—C8—H8A	109.0
Cl3—Co—Cl4	114.17 (3)	C9—C8—H8A	109.0
C7—N4—C8	116.34 (19)	N4—C8—H8B	109.0
C7—N4—H4A	108.2	C9—C8—H8B	109.0
C8—N4—H4A	108.2	H8A—C8—H8B	107.8
C7—N4—H4B	108.2	N1—C1—C2	113.2 (2)
C8—N4—H4B	108.2	N1—C1—H1C	108.9
H4A—N4—H4B	107.4	C2—C1—H1C	108.9
C1—N1—C5i	115.3 (2)	N1—C1—H1D	108.9
C1—N1—H1A	108.5	C2—C1—H1D	108.9
C5i—N1—H1A	108.5	H1C—C1—H1D	107.8
C1—N1—H1B	108.5	C3—C4—C5	113.2 (2)
C5i—N1—H1B	108.5	C3—C4—H4C	108.9
H1A—N1—H1B	107.5	C5—C4—H4C	108.9
C3—N2—C2	114.07 (19)	C3—C4—H4D	108.9
C3—N2—H2A	108.7	C5—C4—H4D	108.9
C2—N2—H2A	108.7	H4C—C4—H4D	107.7
C3—N2—H2B	108.7	N3—C6—C7	110.9 (2)
C2—N2—H2B	108.7	N3—C6—H6A	109.5
H2A—N2—H2B	107.6	C7—C6—H6A	109.5
C6—N3—C10ii	117.64 (19)	N3—C6—H6B	109.5
C6—N3—H3A	107.9	C7—C6—H6B	109.5
C10ii—N3—H3A	107.9	H6A—C6—H6B	108.1
C6—N3—H3B	107.9	N3ii—C10—C9	112.8 (2)
C10ii—N3—H3B	107.9	N3ii—C10—H10A	109.0
H3A—N3—H3B	107.2	C9—C10—H10A	109.0
N1i—C5—C4	114.7 (2)	N3ii—C10—H10B	109.0
N1i—C5—H5A	108.6	C9—C10—H10B	109.0
C4—C5—H5A	108.6	H10A—C10—H10B	107.8
N1i—C5—H5B	108.6	N2—C3—C4	112.5 (2)
C4—C5—H5B	108.6	N2—C3—H3C	109.1
H5A—C5—H5B	107.6	C4—C3—H3C	109.1
N4—C7—C6	110.50 (19)	N2—C3—H3D	109.1
N4—C7—H7A	109.6	C4—C3—H3D	109.1
C6—C7—H7A	109.6	H3C—C3—H3D	107.8
N4—C7—H7B	109.6	C10—C9—C8	108.7 (2)
C6—C7—H7B	109.6	C10—C9—H9A	109.9
H7A—C7—H7B	108.1	C8—C9—H9A	109.9
N2—C2—C1	114.7 (2)	C10—C9—H9B	109.9
N2—C2—H2C	108.6	C8—C9—H9B	109.9
C1—C2—H2C	108.6	H9A—C9—H9B	108.3

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl6	0.90	2.26	3.155 (2)	171
N1—H1B···Cl4iii	0.90	2.65	3.370 (2)	138
N1—H1B···Cl2	0.90	2.75	3.315 (2)	122
N2—H2A···Cl6	0.90	2.20	3.090 (2)	170
N2—H2B···Cl2iv	0.90	2.51	3.284 (2)	144
N2—H2B···Cl4iv	0.90	2.95	3.609 (2)	131
N3—H3A···Cl5v	0.90	2.27	3.129 (2)	160
N3—H3B···Cl5iii	0.90	2.32	3.132 (2)	151
N4—H4A···Cl4	0.90	2.50	3.298 (2)	147
N4—H4A···Cl2vi	0.90	2.93	3.508 (2)	123
N4—H4B···Cl5	0.90	2.43	3.192 (2)	143
C2—H2C···Cl6iv	0.97	2.74	3.589 (3)	147
C6—H6B···Cl3ii	0.97	2.80	3.758 (3)	169
C10—H10A···Cl3ii	0.97	2.92	3.820 (3)	155
C3—H3D···Cl1i	0.97	2.74	3.610 (3)	150
C3—H3C···Cl6i	0.97	2.79	3.634 (3)	147

Table 1

Selected bond lengths (Å)

Co—Cl1	2.2609 (8)
Co—Cl2	2.2950 (9)
Co—Cl3	2.2963 (7)
Co—Cl4	2.3170 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl6	0.90	2.26	3.155 (2)	171
N1—H1B⋯Cl4i	0.90	2.65	3.370 (2)	138
N1—H1B⋯Cl2	0.90	2.75	3.315 (2)	122
N2—H2A⋯Cl6	0.90	2.20	3.090 (2)	170
N2—H2B⋯Cl2ii	0.90	2.51	3.284 (2)	144
N2—H2B⋯Cl4ii	0.90	2.95	3.609 (2)	131
N3—H3A⋯Cl5iii	0.90	2.27	3.129 (2)	160
N3—H3B⋯Cl5i	0.90	2.32	3.132 (2)	151
N4—H4A⋯Cl4	0.90	2.50	3.298 (2)	147
N4—H4A⋯Cl2iv	0.90	2.93	3.508 (2)	123
N4—H4B⋯Cl5	0.90	2.43	3.192 (2)	143
C2—H2C⋯Cl6ii	0.97	2.74	3.589 (3)	147
C6—H6B⋯Cl3v	0.97	2.80	3.758 (3)	169
C10—H10A⋯Cl3v	0.97	2.92	3.820 (3)	155
C3—H3D⋯Cl1vi	0.97	2.74	3.610 (3)	150
C3—H3C⋯Cl6vi	0.97	2.79	3.634 (3)	147

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