Bis(1-tert-butyl-1H-imidazole-κN³)dichloridocobalt(II)

In the crystal structure of the title compound, [CoCl₂(C₇H₁₂N₂)₂], mol­ecular units are formed by coordination of the unsubstituted N atoms of two tert-butyl-substituted imidazole mol­ecules and two chloride ligands, which distinguishes the complex from structures of imidazolium-based dications with tetra­chlorido­cobaltate dianions. There are two crystallographically independent mol­ecules in the asymmetric unit, related by a noncrystallographic inversion centre.

S1. Comment

We have previously reported the syntheses of hexakis(1-isopropylimidazole)calcium(II) dichloride, [Ca(ⁱPrIm)₆]Cl₂, and di-µ-chlorido-bis[tris(1-tert-butylimidazole)chloridocalcium(II)], [(^tBuIm)₃CaCl(µ₂-Cl)₂ClCa(^tBuIm)₃], as well as the complex triaquatris(1-isopropylimidazole)magnesium(II) dichloride, [Mg(ⁱPrIm)₆(H₂O)₃]Cl₂ (Unger et al., 2007). In these cases, we synthesized the complexes from the respective imidazoles and alkaline earth metal salts. We report here the synthesis of bis(1-tert-butyl-1H-imidazole-κN³)dichloridocobalt(II), (I), starting from the bis-imidazolium salt.

The Co^II cation of (I) is coordinated in a distorted tetrahedral geometry by two chloride ligands [Co—Cl = 2.2588 (6) and 2.2603 (5) Å] and two 1-tert-butyl-1H-imidazole ligands, which coordinate via N atoms [Co—N = 2.013 (2) and 2.019 (2) Å]. These bond lengths are not significantly longer than in the analogous methyl-substituted complex bis(methylimidazole)CoCl₂ (Mukerjee et al., 2000). Even the N—Co—N angle is comparable [^tBu = 109.65 (7)° versus Me = 110.6 (1)°], which shows that the steric demand of the larger tert-butyl group has no influence on the coordination geometry. The most obvious difference is that in the methyl-substituted case, the H atoms on C2 of the imidazole ligand point in different directions, while in the tert-butyl case, both H atoms are oriented on the same side of the complex. By quenching the reaction with elemental sulfur we could show that the free carbene is formed under the reaction conditions but decomposes relatively quickly. The H atoms in the methylene bridge are acidic and not stable towards the base potassium bis(trimethylsilyl)amide (KHMDS), as we found large amounts of tert-butylimidazole in the solution. These form the observed product, which crystallized from the tetrahydrofuran solution.

In the asymmetric unit of (I) there are two crystallographically independent molecules, A (including atom Co1) and B (atom Co2) (Fig. 1). They are related by a noncrystallographic inversion centre. As can be seen from the Cl—Co—N—C torsion angles (Table 1), the core geometry of molecules A and B differs only slightly. As a consequence of their acidity, imidazole atoms H11, H31, H81, H211, H231 and H281 take part in C—H···Cl contacts (Table 2 and Figs. 2 and 3). Six contacts are shorter than the sum of the relevant van der Waals radii (2.95 Å; Bondi, 1964).

The most striking feature of (I) in the solid state is a head-to-tail arrangement of molecules A and B. Atoms Cl1 and Cl3 of both molecules take part in bifurcated hydrogen-bond bridges (Fig. 2). These dimers connect to form an infinite double layer parallel to the ab plane via Cl2···H231 and Cl4···H31 contacts (Fig. 3).

Related literature

For related literature, see: Bondi (1964); Caballero et al. (2001); Cotton et al. (1961); Douthwaite et al. (1999, 2001, 2002); Herrmann et al. (1996); Mukerjee et al. (2000); Sheldrick (2008); Unger et al. (2007).

S2. Experimental

The bisimidazolium salt was previously deprotonated by sodium hexamethyldisilazan in tetrahydrofuran and the formation of the free carbene could be independently confirmed (Douthwaite et al., 1999). The corresponding nickel and palladium NHC complexes have been described in the literature (Douthwaite et al., 2001, 2002) and the addition of sulfur leads to the dithiones (Caballero et al., 2001; Herrmann et al., 1996). However, in this instance, the addition of bis(triphenylphosphane)cobalt(II) chloride (Cotton et al., 1961) did not lead to the expected formation of the biscarbene complex, and instead we isolated the N-coordinated complex, (I). [Recrystallisation from which solvent?] The crystal selected was fixed in a capillary with perfluorinated ether and transferred to the diffractometer.

S3. Refinement

H atoms were constrained to an ideal geometry using the standard riding model implemented in SHELXL97 (Sheldrick, 2008). H atoms were fixed with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, or C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms.

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The head-to-tail arrangement of molecules A and B. Dashed lines indicate hydrogen bonds.
	Fig. 3. A stereoview of (I), showing the hydrogen-bonding network. Dashed lines indicate hydrogen bonds.

Bis(1-tert-butyl-1H-imidazole-κN³)dichloridocobalt(II)

Crystal data

[CoCl2(C7H12N2)2]	F(000) = 1576
Mr = 378.20	Dx = 1.368 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7031 reflections
a = 14.1054 (1) Å	θ = 1.5–25.4°
b = 14.5470 (1) Å	µ = 1.23 mm^−1
c = 18.7059 (2) Å	T = 173 K
β = 106.9542 (3)°	Fragment, blue
V = 3671.47 (5) Å^3	0.33 × 0.33 × 0.05 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	6741 independent reflections
Radiation source: Nonius FR 591 rotating-anode	5547 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 18 pixels mm^-1	θmax = 25.4°, θmin = 1.5°
ϕ and ω rotation scans	h = −17→17
Absorption correction: multi-scan [applied during the scaling procedure (DENZO; Otwinowski & Minor, 1997)]	k = −17→17
Tmin = 0.857, Tmax = 1.000	l = −22→21
74460 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.03	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + (0.0321P)^2 + 2.5029P] where P = (Fo^2 + 2Fc^2)/3
6741 reflections	(Δ/σ)max = 0.001
391 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3
0 constraints

Special details

Experimental. Diffractometer operator E. Herdtweck scan speed 2 × 30 s per film repetition 1 dx 40 933 films measured in 8 data sets set 1: phi-scan with delta_phi = 1.0 set 2 to 9: omega-scans with delta_omega = 1.0

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating R_factor_obs 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	0.30046 (2)	0.148881 (19)	0.296068 (16)	0.02443 (8)
Cl1	0.22349 (4)	0.16251 (4)	0.17244 (3)	0.03311 (14)
Cl2	0.33651 (4)	0.00521 (3)	0.34197 (3)	0.03122 (13)
N1	0.43252 (13)	0.21302 (11)	0.32086 (9)	0.0244 (4)
N2	0.55196 (13)	0.31650 (11)	0.34675 (10)	0.0246 (4)
N3	0.21723 (13)	0.20424 (12)	0.35646 (10)	0.0276 (4)
N4	0.12648 (13)	0.29509 (12)	0.40414 (10)	0.0283 (4)
C1	0.45390 (16)	0.30200 (14)	0.32959 (12)	0.0258 (5)
H11	0.4059	0.3493	0.3244	0.031*
C2	0.52234 (16)	0.16891 (14)	0.33325 (12)	0.0266 (5)
H21	0.5310	0.1043	0.3309	0.032*
C3	0.59633 (16)	0.23173 (14)	0.34928 (12)	0.0273 (5)
H31	0.6653	0.2197	0.3601	0.033*
C4	0.60243 (17)	0.40801 (14)	0.36558 (13)	0.0296 (5)
C5	0.6005 (2)	0.43318 (17)	0.44427 (14)	0.0441 (7)
H51	0.5317	0.4379	0.4453	0.066*
H52	0.6340	0.4923	0.4587	0.066*
H53	0.6348	0.3855	0.4794	0.066*
C6	0.54547 (18)	0.47873 (15)	0.30912 (15)	0.0380 (6)
H61	0.5412	0.4580	0.2584	0.057*
H62	0.5800	0.5379	0.3187	0.057*
H63	0.4785	0.4857	0.3140	0.057*
C7	0.70808 (18)	0.40011 (17)	0.36149 (16)	0.0433 (6)
H71	0.7450	0.3567	0.3996	0.065*
H72	0.7401	0.4606	0.3704	0.065*
H73	0.7074	0.3780	0.3119	0.065*
C8	0.17982 (16)	0.28800 (15)	0.35556 (12)	0.0283 (5)
H81	0.1895	0.3367	0.3246	0.034*
C9	0.18704 (17)	0.15609 (15)	0.40924 (14)	0.0338 (5)
H91	0.2030	0.0938	0.4228	0.041*
C10	0.13101 (18)	0.21144 (15)	0.43887 (14)	0.0364 (6)
H101	0.1008	0.1955	0.4764	0.044*
C11	0.07807 (17)	0.38122 (15)	0.42007 (14)	0.0332 (5)
C12	0.0119 (2)	0.35709 (18)	0.46857 (18)	0.0528 (8)
H112	0.0527	0.3337	0.5169	0.079*
H121	−0.0358	0.3099	0.4436	0.079*
H123	−0.0237	0.4122	0.4765	0.079*
C13	0.0174 (2)	0.42239 (19)	0.34635 (16)	0.0549 (8)
H131	0.0614	0.4389	0.3164	0.082*
H132	−0.0168	0.4776	0.3560	0.082*
H133	−0.0315	0.3773	0.3191	0.082*
C14	0.15973 (19)	0.44627 (16)	0.46138 (15)	0.0421 (6)
H141	0.1990	0.4173	0.5079	0.063*
H142	0.1303	0.5033	0.4730	0.063*
H143	0.2027	0.4602	0.4300	0.063*
Co2	0.19130 (2)	0.49803 (2)	0.164679 (19)	0.03167 (9)
Cl3	0.26847 (5)	0.49558 (4)	0.28981 (4)	0.03938 (15)
Cl4	0.14925 (5)	0.63903 (4)	0.11322 (4)	0.04224 (16)
N21	0.06229 (14)	0.42985 (13)	0.14949 (12)	0.0372 (5)
N22	−0.05722 (14)	0.33495 (12)	0.15524 (12)	0.0338 (5)
N23	0.28478 (14)	0.44774 (12)	0.11119 (11)	0.0311 (4)
N24	0.39698 (13)	0.36514 (12)	0.07875 (10)	0.0263 (4)
C21	0.03877 (17)	0.34402 (15)	0.15985 (13)	0.0304 (5)
H211	0.0847	0.2945	0.1695	0.036*
C22	−0.0240 (2)	0.47894 (18)	0.13973 (19)	0.0544 (8)
H221	−0.0305	0.5435	0.1322	0.065*
C23	−0.09782 (19)	0.42161 (17)	0.14242 (17)	0.0512 (7)
H231	−0.1649	0.4378	0.1366	0.061*
C24	−0.11329 (18)	0.24870 (16)	0.15900 (14)	0.0367 (6)
C25	−0.1646 (3)	0.2181 (2)	0.07967 (19)	0.0751 (10)
H251	−0.2071	0.2678	0.0527	0.113*
H252	−0.2050	0.1636	0.0806	0.113*
H253	−0.1147	0.2031	0.0544	0.113*
C26	−0.0416 (2)	0.17655 (19)	0.2015 (2)	0.0747 (11)
H261	−0.0783	0.1210	0.2067	0.112*
H262	−0.0062	0.2002	0.2512	0.112*
H263	0.0061	0.1618	0.1742	0.112*
C27	−0.1904 (2)	0.26807 (18)	0.19910 (17)	0.0511 (7)
H271	−0.1575	0.2901	0.2498	0.077*
H272	−0.2271	0.2115	0.2017	0.077*
H273	−0.2366	0.3151	0.1717	0.077*
C28	0.33406 (17)	0.36882 (15)	0.12037 (13)	0.0327 (5)
H281	0.3258	0.3208	0.1525	0.039*
C29	0.31812 (19)	0.49622 (15)	0.06028 (14)	0.0358 (6)
H291	0.2963	0.5559	0.0421	0.043*
C30	0.38653 (19)	0.44621 (15)	0.04013 (13)	0.0362 (6)
H301	0.4210	0.4639	0.0056	0.043*
C31	0.46122 (17)	0.28457 (15)	0.07408 (12)	0.0277 (5)
C32	0.5314 (2)	0.31228 (17)	0.02940 (14)	0.0399 (6)
H321	0.4928	0.3297	−0.0214	0.060*
H322	0.5747	0.2604	0.0271	0.060*
H323	0.5718	0.3646	0.0537	0.060*
C33	0.52081 (19)	0.25800 (18)	0.15311 (13)	0.0415 (6)
H331	0.5605	0.3107	0.1776	0.062*
H332	0.5648	0.2066	0.1511	0.062*
H333	0.4755	0.2396	0.1815	0.062*
C34	0.39420 (19)	0.20611 (16)	0.03560 (15)	0.0406 (6)
H341	0.3566	0.2250	−0.0150	0.061*
H342	0.3482	0.1906	0.0642	0.061*
H343	0.4347	0.1522	0.0329	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02411 (17)	0.02136 (15)	0.02917 (17)	−0.00051 (12)	0.00988 (13)	−0.00353 (12)
Cl1	0.0332 (3)	0.0353 (3)	0.0291 (3)	0.0058 (2)	0.0064 (2)	0.0001 (2)
Cl2	0.0380 (3)	0.0206 (3)	0.0396 (3)	0.0014 (2)	0.0185 (3)	0.0011 (2)
N1	0.0258 (10)	0.0212 (9)	0.0270 (10)	−0.0003 (7)	0.0088 (8)	−0.0001 (7)
N2	0.0256 (10)	0.0204 (9)	0.0283 (10)	−0.0007 (7)	0.0087 (8)	0.0007 (7)
N3	0.0262 (10)	0.0251 (9)	0.0332 (11)	−0.0016 (8)	0.0117 (8)	−0.0063 (8)
N4	0.0273 (10)	0.0234 (9)	0.0372 (11)	0.0000 (8)	0.0144 (9)	−0.0065 (8)
C1	0.0255 (12)	0.0234 (11)	0.0293 (12)	0.0018 (9)	0.0092 (9)	0.0002 (9)
C2	0.0293 (13)	0.0219 (11)	0.0287 (12)	0.0033 (9)	0.0086 (10)	0.0002 (9)
C3	0.0249 (12)	0.0281 (12)	0.0290 (12)	0.0043 (9)	0.0082 (10)	0.0020 (9)
C4	0.0314 (13)	0.0222 (11)	0.0359 (13)	−0.0069 (9)	0.0110 (10)	0.0008 (9)
C5	0.0572 (18)	0.0350 (14)	0.0399 (15)	−0.0149 (12)	0.0139 (13)	−0.0064 (11)
C6	0.0354 (14)	0.0269 (12)	0.0515 (16)	−0.0029 (10)	0.0123 (12)	0.0099 (11)
C7	0.0283 (14)	0.0367 (14)	0.0641 (18)	−0.0053 (11)	0.0123 (13)	0.0037 (12)
C8	0.0300 (13)	0.0259 (11)	0.0308 (12)	0.0000 (9)	0.0116 (10)	−0.0029 (9)
C9	0.0336 (14)	0.0237 (11)	0.0493 (15)	−0.0008 (10)	0.0203 (12)	0.0011 (10)
C10	0.0404 (15)	0.0277 (12)	0.0502 (15)	−0.0034 (10)	0.0276 (12)	0.0005 (11)
C11	0.0314 (13)	0.0267 (12)	0.0441 (14)	0.0034 (10)	0.0152 (11)	−0.0086 (10)
C12	0.0538 (18)	0.0392 (15)	0.082 (2)	0.0004 (13)	0.0449 (17)	−0.0150 (14)
C13	0.0525 (18)	0.0488 (17)	0.0564 (18)	0.0212 (14)	0.0049 (14)	−0.0115 (14)
C14	0.0408 (15)	0.0309 (13)	0.0563 (17)	−0.0018 (11)	0.0167 (13)	−0.0149 (12)
Co2	0.02576 (18)	0.02496 (17)	0.0472 (2)	0.00152 (12)	0.01513 (15)	0.00222 (13)
Cl3	0.0365 (3)	0.0385 (3)	0.0454 (4)	0.0056 (3)	0.0156 (3)	0.0042 (3)
Cl4	0.0346 (3)	0.0261 (3)	0.0686 (4)	0.0032 (2)	0.0191 (3)	0.0102 (3)
N21	0.0264 (11)	0.0289 (11)	0.0567 (13)	0.0027 (8)	0.0130 (10)	0.0066 (9)
N22	0.0253 (11)	0.0257 (10)	0.0503 (13)	0.0010 (8)	0.0110 (9)	0.0029 (9)
N23	0.0292 (11)	0.0274 (10)	0.0382 (11)	−0.0012 (8)	0.0121 (9)	−0.0013 (8)
N24	0.0291 (10)	0.0254 (9)	0.0265 (10)	−0.0013 (8)	0.0116 (8)	−0.0009 (8)
C21	0.0244 (13)	0.0262 (12)	0.0415 (14)	0.0020 (9)	0.0110 (10)	0.0009 (10)
C22	0.0331 (16)	0.0328 (14)	0.097 (2)	0.0060 (12)	0.0189 (15)	0.0150 (15)
C23	0.0282 (15)	0.0353 (14)	0.091 (2)	0.0063 (11)	0.0188 (15)	0.0119 (14)
C24	0.0322 (14)	0.0260 (12)	0.0536 (16)	−0.0055 (10)	0.0151 (12)	−0.0036 (11)
C25	0.082 (3)	0.079 (2)	0.069 (2)	−0.038 (2)	0.0299 (19)	−0.0321 (19)
C26	0.0395 (18)	0.0327 (16)	0.152 (4)	−0.0001 (13)	0.028 (2)	0.0272 (18)
C27	0.0489 (18)	0.0402 (15)	0.074 (2)	−0.0062 (13)	0.0342 (16)	−0.0022 (14)
C28	0.0353 (14)	0.0309 (13)	0.0357 (13)	0.0032 (10)	0.0164 (11)	0.0053 (10)
C29	0.0441 (15)	0.0232 (12)	0.0419 (14)	−0.0016 (10)	0.0152 (12)	0.0024 (10)
C30	0.0473 (16)	0.0285 (12)	0.0380 (14)	−0.0029 (11)	0.0209 (12)	0.0028 (10)
C31	0.0294 (12)	0.0276 (11)	0.0281 (12)	0.0010 (9)	0.0114 (10)	−0.0023 (9)
C32	0.0471 (16)	0.0393 (14)	0.0424 (15)	0.0004 (12)	0.0273 (13)	−0.0052 (11)
C33	0.0433 (16)	0.0479 (15)	0.0335 (14)	0.0150 (12)	0.0115 (12)	0.0032 (12)
C34	0.0424 (15)	0.0300 (13)	0.0503 (16)	−0.0010 (11)	0.0148 (13)	−0.0076 (11)

Geometric parameters (Å, º)

Co1—N1	2.0128 (17)	Co2—N23	2.0110 (19)
Co1—N3	2.0191 (17)	Co2—N21	2.0185 (19)
Co1—Cl1	2.2587 (6)	Co2—Cl4	2.2699 (6)
Co1—Cl2	2.2604 (6)	Co2—Cl3	2.2757 (7)
N1—C1	1.328 (3)	N21—C21	1.321 (3)
N1—C2	1.378 (3)	N21—C22	1.377 (3)
N2—C1	1.342 (3)	N22—C21	1.338 (3)
N2—C3	1.377 (3)	N22—C23	1.376 (3)
N2—C4	1.502 (3)	N22—C24	1.496 (3)
N3—C8	1.326 (3)	N23—C28	1.327 (3)
N3—C9	1.375 (3)	N23—C29	1.374 (3)
N4—C8	1.342 (3)	N24—C28	1.342 (3)
N4—C10	1.372 (3)	N24—C30	1.368 (3)
N4—C11	1.498 (3)	N24—C31	1.499 (3)
C1—H11	0.9500	C21—H211	0.9500
C2—C3	1.353 (3)	C22—C23	1.346 (4)
C2—H21	0.9500	C22—H221	0.9500
C3—H31	0.9500	C23—H231	0.9500
C4—C7	1.519 (3)	C24—C26	1.513 (4)
C4—C6	1.525 (3)	C24—C25	1.516 (4)
C4—C5	1.525 (3)	C24—C27	1.517 (3)
C5—H51	0.9800	C25—H251	0.9800
C5—H52	0.9800	C25—H252	0.9800
C5—H53	0.9800	C25—H253	0.9800
C6—H61	0.9800	C26—H261	0.9800
C6—H62	0.9800	C26—H262	0.9800
C6—H63	0.9800	C26—H263	0.9800
C7—H71	0.9800	C27—H271	0.9800
C7—H72	0.9800	C27—H272	0.9800
C7—H73	0.9800	C27—H273	0.9800
C8—H81	0.9500	C28—H281	0.9500
C9—C10	1.355 (3)	C29—C30	1.347 (3)
C9—H91	0.9500	C29—H291	0.9500
C10—H101	0.9500	C30—H301	0.9500
C11—C14	1.517 (3)	C31—C33	1.522 (3)
C11—C13	1.518 (4)	C31—C34	1.522 (3)
C11—C12	1.520 (3)	C31—C32	1.524 (3)
C12—H112	0.9800	C32—H321	0.9800
C12—H121	0.9800	C32—H322	0.9800
C12—H123	0.9800	C32—H323	0.9800
C13—H131	0.9800	C33—H331	0.9800
C13—H132	0.9800	C33—H332	0.9800
C13—H133	0.9800	C33—H333	0.9800
C14—H141	0.9800	C34—H341	0.9800
C14—H142	0.9800	C34—H342	0.9800
C14—H143	0.9800	C34—H343	0.9800
N1—Co1—N3	109.65 (7)	N23—Co2—N21	116.50 (8)
N1—Co1—Cl1	109.36 (5)	N23—Co2—Cl4	104.23 (6)
N3—Co1—Cl1	110.70 (6)	N21—Co2—Cl4	105.72 (6)
N1—Co1—Cl2	104.51 (5)	N23—Co2—Cl3	108.64 (6)
N3—Co1—Cl2	105.03 (5)	N21—Co2—Cl3	106.16 (6)
Cl1—Co1—Cl2	117.25 (2)	Cl4—Co2—Cl3	115.96 (3)
C1—N1—C2	105.57 (17)	C21—N21—C22	105.0 (2)
C1—N1—Co1	129.92 (15)	C21—N21—Co2	134.32 (16)
C2—N1—Co1	124.51 (14)	C22—N21—Co2	119.33 (16)
C1—N2—C3	107.08 (17)	C21—N22—C23	106.42 (19)
C1—N2—C4	125.46 (17)	C21—N22—C24	128.23 (19)
C3—N2—C4	127.28 (18)	C23—N22—C24	125.3 (2)
C8—N3—C9	105.77 (18)	C28—N23—C29	105.16 (19)
C8—N3—Co1	130.82 (15)	C28—N23—Co2	130.16 (16)
C9—N3—Co1	123.42 (14)	C29—N23—Co2	124.40 (15)
C8—N4—C10	107.13 (18)	C28—N24—C30	106.52 (18)
C8—N4—C11	125.24 (19)	C28—N24—C31	125.32 (18)
C10—N4—C11	127.49 (18)	C30—N24—C31	128.09 (18)
N1—C1—N2	111.32 (18)	N21—C21—N22	112.13 (19)
N1—C1—H11	124.3	N21—C21—H211	123.9
N2—C1—H11	124.3	N22—C21—H211	123.9
C3—C2—N1	109.55 (18)	C23—C22—N21	109.7 (2)
C3—C2—H21	125.2	C23—C22—H221	125.1
N1—C2—H21	125.2	N21—C22—H221	125.1
C2—C3—N2	106.48 (19)	C22—C23—N22	106.7 (2)
C2—C3—H31	126.8	C22—C23—H231	126.7
N2—C3—H31	126.8	N22—C23—H231	126.7
N2—C4—C7	109.03 (18)	N22—C24—C26	109.0 (2)
N2—C4—C6	108.52 (18)	N22—C24—C25	108.0 (2)
C7—C4—C6	110.05 (19)	C26—C24—C25	111.5 (3)
N2—C4—C5	107.37 (17)	N22—C24—C27	109.43 (19)
C7—C4—C5	111.1 (2)	C26—C24—C27	109.5 (2)
C6—C4—C5	110.6 (2)	C25—C24—C27	109.4 (2)
C4—C5—H51	109.5	C24—C25—H251	109.5
C4—C5—H52	109.5	C24—C25—H252	109.5
H51—C5—H52	109.5	H251—C25—H252	109.5
C4—C5—H53	109.5	C24—C25—H253	109.5
H51—C5—H53	109.5	H251—C25—H253	109.5
H52—C5—H53	109.5	H252—C25—H253	109.5
C4—C6—H61	109.5	C24—C26—H261	109.5
C4—C6—H62	109.5	C24—C26—H262	109.5
H61—C6—H62	109.5	H261—C26—H262	109.5
C4—C6—H63	109.5	C24—C26—H263	109.5
H61—C6—H63	109.5	H261—C26—H263	109.5
H62—C6—H63	109.5	H262—C26—H263	109.5
C4—C7—H71	109.5	C24—C27—H271	109.5
C4—C7—H72	109.5	C24—C27—H272	109.5
H71—C7—H72	109.5	H271—C27—H272	109.5
C4—C7—H73	109.5	C24—C27—H273	109.5
H71—C7—H73	109.5	H271—C27—H273	109.5
H72—C7—H73	109.5	H272—C27—H273	109.5
N3—C8—N4	111.20 (19)	N23—C28—N24	111.7 (2)
N3—C8—H81	124.4	N23—C28—H281	124.2
N4—C8—H81	124.4	N24—C28—H281	124.2
C10—C9—N3	109.3 (2)	C30—C29—N23	109.6 (2)
C10—C9—H91	125.3	C30—C29—H291	125.2
N3—C9—H91	125.3	N23—C29—H291	125.2
C9—C10—N4	106.6 (2)	C29—C30—N24	107.1 (2)
C9—C10—H101	126.7	C29—C30—H301	126.5
N4—C10—H101	126.7	N24—C30—H301	126.5
N4—C11—C14	107.50 (18)	N24—C31—C33	108.29 (17)
N4—C11—C13	108.55 (19)	N24—C31—C34	108.13 (18)
C14—C11—C13	111.1 (2)	C33—C31—C34	111.1 (2)
N4—C11—C12	108.68 (19)	N24—C31—C32	108.98 (18)
C14—C11—C12	110.3 (2)	C33—C31—C32	109.7 (2)
C13—C11—C12	110.6 (2)	C34—C31—C32	110.61 (19)
C11—C12—H112	109.5	C31—C32—H321	109.5
C11—C12—H121	109.5	C31—C32—H322	109.5
H112—C12—H121	109.5	H321—C32—H322	109.5
C11—C12—H123	109.5	C31—C32—H323	109.5
H112—C12—H123	109.5	H321—C32—H323	109.5
H121—C12—H123	109.5	H322—C32—H323	109.5
C11—C13—H131	109.5	C31—C33—H331	109.5
C11—C13—H132	109.5	C31—C33—H332	109.5
H131—C13—H132	109.5	H331—C33—H332	109.5
C11—C13—H133	109.5	C31—C33—H333	109.5
H131—C13—H133	109.5	H331—C33—H333	109.5
H132—C13—H133	109.5	H332—C33—H333	109.5
C11—C14—H141	109.5	C31—C34—H341	109.5
C11—C14—H142	109.5	C31—C34—H342	109.5
H141—C14—H142	109.5	H341—C34—H342	109.5
C11—C14—H143	109.5	C31—C34—H343	109.5
H141—C14—H143	109.5	H341—C34—H343	109.5
H142—C14—H143	109.5	H342—C34—H343	109.5
Cl1—Co1—N1—C1	78.18 (18)	C10—N4—C11—C14	105.8 (3)
Cl1—Co1—N1—C2	−102.57 (16)	C8—N4—C10—C9	−0.4 (3)
Cl2—Co1—N1—C1	−155.51 (17)	C11—N4—C10—C9	−176.3 (2)
Cl2—Co1—N1—C2	23.74 (17)	C10—N4—C8—N3	0.8 (3)
N3—Co1—N1—C1	−43.4 (2)	C11—N4—C8—N3	176.9 (2)
N3—Co1—N1—C2	135.88 (16)	C8—N4—C11—C13	50.8 (3)
Cl1—Co1—N3—C8	−56.1 (2)	C8—N4—C11—C14	−69.5 (3)
Cl1—Co1—N3—C9	123.24 (17)	C8—N4—C11—C12	171.1 (2)
Cl2—Co1—N3—C8	176.49 (19)	C10—N4—C11—C13	−134.0 (2)
Cl2—Co1—N3—C9	−4.23 (19)	C10—N4—C11—C12	−13.7 (3)
N1—Co1—N3—C8	64.7 (2)	Co2—N21—C22—C23	−170.4 (2)
N1—Co1—N3—C9	−116.03 (18)	C22—N21—C21—N22	1.8 (3)
Cl3—Co2—N21—C21	−64.6 (2)	Co2—N21—C21—N22	167.99 (18)
Cl3—Co2—N21—C22	100.1 (2)	C21—N21—C22—C23	−1.6 (3)
Cl4—Co2—N21—C21	171.7 (2)	C21—N22—C24—C25	−96.7 (3)
Cl4—Co2—N21—C22	−23.6 (2)	C21—N22—C24—C26	24.6 (3)
N23—Co2—N21—C21	56.5 (3)	C23—N22—C21—N21	−1.2 (3)
N23—Co2—N21—C22	−138.8 (2)	C24—N22—C21—N21	175.9 (2)
Cl3—Co2—N23—C28	53.7 (2)	C21—N22—C23—C22	0.2 (3)
Cl3—Co2—N23—C29	−119.31 (19)	C24—N22—C23—C22	−177.1 (2)
Cl4—Co2—N23—C28	178.0 (2)	C23—N22—C24—C25	80.0 (3)
Cl4—Co2—N23—C29	4.9 (2)	C23—N22—C24—C26	−158.8 (3)
N21—Co2—N23—C28	−66.0 (2)	C21—N22—C24—C27	144.4 (3)
N21—Co2—N23—C29	120.93 (19)	C23—N22—C24—C27	−39.0 (3)
Co1—N1—C2—C3	−179.36 (14)	C28—N23—C29—C30	−0.2 (3)
Co1—N1—C1—N2	179.37 (14)	Co2—N23—C29—C30	174.27 (17)
C2—N1—C1—N2	0.0 (2)	Co2—N23—C28—N24	−173.54 (15)
C1—N1—C2—C3	0.1 (2)	C29—N23—C28—N24	0.5 (3)
C3—N2—C4—C7	20.1 (3)	C30—N24—C28—N23	−0.6 (3)
C4—N2—C1—N1	−175.54 (19)	C28—N24—C31—C34	67.2 (3)
C3—N2—C4—C5	−100.4 (3)	C30—N24—C31—C32	10.9 (3)
C3—N2—C4—C6	140.0 (2)	C31—N24—C28—N23	−177.82 (19)
C3—N2—C1—N1	−0.1 (2)	C28—N24—C30—C29	0.4 (3)
C1—N2—C4—C5	74.2 (3)	C31—N24—C30—C29	177.5 (2)
C1—N2—C3—C2	0.1 (2)	C28—N24—C31—C32	−172.5 (2)
C4—N2—C3—C2	175.5 (2)	C28—N24—C31—C33	−53.2 (3)
C1—N2—C4—C6	−45.4 (3)	C30—N24—C31—C34	−109.4 (3)
C1—N2—C4—C7	−165.3 (2)	C30—N24—C31—C33	130.2 (2)
Co1—N3—C8—N4	178.52 (15)	N1—C2—C3—N2	−0.1 (2)
C9—N3—C8—N4	−0.9 (3)	N3—C9—C10—N4	−0.1 (3)
Co1—N3—C9—C10	−178.85 (16)	N21—C22—C23—N22	0.9 (4)
C8—N3—C9—C10	0.6 (3)	N23—C29—C30—N24	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H11···Cl3	0.95	2.82	3.767 (2)	172
C3—H31···Cl4^i	0.95	2.78	3.704 (2)	166
C8—H81···Cl3	0.95	2.73	3.618 (2)	157
C21—H211···Cl1	0.95	2.73	3.669 (2)	169
C23—H231···Cl2^ii	0.95	2.75	3.671 (3)	164
C28—H281···Cl1	0.95	2.80	3.643 (2)	148

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