Intramolecular hydrogen bonding in dichlorido­bis(3,5-di-tert-butyl-1H-pyrazole-κN²)cobalt(II) as a consequence of ligand steric bulk

The title compound, [CoCl₂(C₁₁H₂₀ClN₂)₂], forms two intra­molecular hydrogen bonds [graph set S(5)] between the N atoms of the pyrazole ligands and the chloride ligands. This hydrogen-bonding motif is uncommon among related compounds but occurs here because of the bulk of tert-butyl substituents on the pyrazole ligands which shield the central metal atom to a significantly larger extent than pyrazole ligands with smaller 3,5-substituents.

S1. Comment

Pyrazole and pyrazolyl transition metal complexes continue to be investigated as catalysts in ethylene oligomerization and polymerization reactions (Ojwach et al., 2010). The ability of such metal complexes to catalyze the formation of polyethylene depends on the electrophilicity and steric bulk of the catalysts. Both of these factors are usually dictated by the nature and size of substituents on the pyrazolyl unit. However, in the polymer catalysts bis(pyrazole) nickel (Nelana et al., 2004), pyrazole palladium (Li et al., 2002) and pyrazolyl palladium complexes (Guzei et al., 2003; Mohlala et al., 2005) the high electrophilic metal centers ensure rapid insertion regardless of the steric bulk of these catalysts. In an extension of this study we prepared the title compound, (I), which had appreciably lower catalytic activity than its nickel and palladium analogues.

The coordination geometry of the Co atom in (I) is distorted tetrahedral. The metric parameters for bond distances and angles about the cobalt center are similar to those in six related compounds where a cobalt atom binds to two monodentate chloride ligands and two monodentate substituted pyrazole ligands (Table 1) [Cambridge Structural Database (CSD), version 1.12, August 2010 update; Allen, 2002]. However the N1—Co1—N3 angle in (I) is significantly larger and falls outside of the range of measurements for the related compounds in the CSD. This larger than expected angle can be attributed to the two intramolecular hydrogen bonds in (I) absent in similar compounds.

In complex (I) there are two intramolecular hydrogen bonds of the type N—H···Cl formed between the pyrazole and chloride ligands. It has been shown that Cl atoms coordinated to transition metals may act as moderately strong hydrogen-bond acceptors (Aullón et al., 1998). In the case of (I), however, the hydrogen bonds are considered weak because of the suboptimal N—H···Cl angles averaging 130.0 (13)° (Table 2). These intramolecular hydrogen interactions are described with the graph set S(5) (Bernstein et al., 1995). Compared to the six related compounds in the CSD, (I) is the only compound that forms exactly two intramolecular S(5) N(pz)—H···Cl hydrogen bonds. Several compounds including dichloro-bis(3,5-dimethylpyrazole) cobalt(II) (CSD code FUFVUX02; Guzei & Spencer, 2006), bis(dichloro-(µ₂-bis(3,5-dimethyl-4-pyrazolyl)methane) cobalt(II)) ethanol solvate (CAFXIQ; Foces-Foces et al., 1983) and dichloro-bis(3,5-diethyl-4-methyl-1H-pyrazole) cobalt(II) (DEMPCO10; Agre et al., 1978) form two intermolecular N(pz)—H···Cl hydrogen bonds with the graph set R²₂(10). Another related compound, dichloro-bis(3-methyl-5-phenylpyrazol-2-yl) cobalt(II) (SEHTUU; Verweij et al., 1989), forms only one intramolecular N(pz)—H···Cl S(5) hydrogen bond but cannot form a second intramolecular hydrogen bond with the other pyrazole nitrogen donor. The other N(pz)—Cl distance is too long and the N(pz)—H···Cl angle too acute for SEHTUU to form two S(5) intramolecular bonds as in (I). The protonated pyrazole nitrogen on the two remaining related compounds forms intermolecular and intramolecular hydrogen bonds with oxygen and nitrogen atoms in side chains of the pyrazole rings, respectively (FOYWEW, Leovac et al., 2007 and YOCYAR, Cai et al., 2008).

The fact that (I) forms two intramolecular N(pz)—H···Cl hydrogen bonds is likely responsible for the larger than average N—Co—N angle as the Cl—Co—N angles involved in the five-membered hydrogen-bonded rings are significantly smaller [99.93 (10)° and 100.78 (11)°] than the ideal tetrahedral angle. Compound (I) is believed to form the intramolecular rather than intermolecular N(pz)—H···Cl hydrogen bonds, seemingly more popular among related compounds, because the bulky tert-butyl pyrazole substituents in the 3,5-positions prevent molecules of (I) from approaching each other close enough to form intermolecular bonds. To substantiate this line of reasoning we calculated the G-parameters and sizes of the pyrazole ligands in (I) and the six aforementioned complexes. The G-parameter (computed with the program Solid-G, Guzei, 2006) is the percentage of the central metal's coordination sphere shielded by the ligand (Guzei & Wendt, 2006). This methodology is based on solid angles and is illustrated in Fig. 2. Each ligand `casts a shadow' on a sphere of an arbitrary radius centered at the Co atom, and the percentage of the sphere shielded by each ligand is its G-parameter. It has been shown that even small, 2–3% changes in the G-parameters can lead to substantial changes in the mutual ligand arrangement (Fukin et al., 2007). The ligand size is represented by the volume of the smallest parallelepiped circumscribing the free ligand as computed with the WBOX routine in the program OLEX2 (Dolomanov et al., 2009) (Fig. 3). This approach has been previously applied to alkali metal complexes of nonactin (Guzei et al., 2009). Table 3 summarizes the geometric computations. The average G-parameter of the pyrazole ligands in (I) is significantly larger at 25.0 (5)% than that in any of the related compounds. Thus, the approach of other complexes to the Cl ligands and formation of intermolecular bonds are hampered. The average pyrazole ligand volume in (I) is substantially larger than that for all related compounds except for 3,5-dimethyl-4-pyrazolylmethane (Table 3). However, whereas the volume of 3,5-dimethyl-4-pyrazolylmethane is larger than that for (I), this ligand forms an elongated chain directed away from the central cobalt atom. Consequently, it does not crowd the central cobalt atom as much as 3,5-bis-tertbutylpyrazole does in (I) as evidenced by the larger G-parameter of the latter. It appears that the type of the hydrogen bonds in dipyrazole-dichloride complexes of Co^II is dictated by the ligand steric parameters.

Related literature

For related literature, see: Agre et al. (1978); Allen (2002); Aullón et al. (1998); Bernstein et al. (1995); Cai et al. (2008); Dolomanov et al. (2009); Foces-Foces, Cano & García-Blanco (1983); Fukin et al. (2007); Guzei (2006); Guzei & Spencer (2006); Guzei & Wendt (2006); Guzei et al. (2003, 2009); Leovac et al. (2007); Li et al. (2002); Mohlala et al. (2005); Nelana et al. (2004); Ojwach & Darkwa (2010); Verweij et al. (1989).

S2. Experimental

A solution of CoCl₂ (0.58 g, 4.45 mmol) and tertiarybutylpyrazole (1.60 g, 4.44 mmol) in CH₂Cl₂ (20 ml) was stirred at room temperature for 18 h. The resultant blue solution was reduced to about 10 ml, followed by the addition of about 5 ml of hexane. The solution was kept at 269 K for a day to produce blue crystals suitable for X-ray crystallography. Yield: 1.40 g, (64%). Analysis: calculated for C₂₂H₄₀Cl₂N₄Co: C 62.99, H 9.61, N 13.36; found: C 62.60, H 9.70, N 13.55.

S3. Refinement

The crystals of (I) do not survive thermal shock and shatter when immersed into the cold stream of nitrogen at either 100, 150, 200 or 250 K; thus the crystal structure was determined at room temperature. There is positional disorder in the structure of (I). Atom Cl2 is disordered over two positions with a 79 (2)% major component contribution. The tert-butyl groups at atoms C8 and C15 are disordered over two positions with 60.8 (7) and 59.7 (13)% major component contributions. The tert-butyl group at atom C19 is disordered over three positions in a 40.9 (6): 34.1 (7): 25.0 (7)% ratio. The disorder was handled as follows: In the disordered tert-butyl groups, all 1–2 distances were restrained to 1.538 (2) Å and 1–3 distances to 2.512 (2) Å. The displacement parameter of the methyl groups of each disordered tert-butyl group were constrained to be the same. The distances between the Co atom and both parts of the disordered Cl2 atom were restrained to be the same within 0.002 Å and the anisotropic displacement parameters of atoms Cl2 and Cl2A were constrained to be the same. All H atoms were placed in idealized locations, with N—H distances of 0.86 Å, Csp²—H distances of 0.93 Å and Csp³—H distances of 0.96 Å. All H atoms were refined as riding with appropriate displacement parameters of U_iso(H) = U_eq(parent atoms) for all N—H and Csp²—H groups and U_eq(parent atoms) for all Csp³—H groups.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008) and FCF_filter (Guzei, 2007); molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Figures

	Fig. 1. A molecular diagram of (I) drawn with 50% probability ellipsoids. All hydrogen atoms attached to carbon atoms and minor components of disordered atoms were omitted for clarity. Atoms C9—C14 and C20, C21–C22 were refined isotropically. The two intramolecular hydrogen bonds are shown with dashed lines.
	Fig. 2. A diagram of the solid angles of (I) which shows the shielding of the cobalt atom by the various ligands. Pyrazole ligands are shown as red and green, chloride ligands are yellow.

(I)

Crystal data

[CoCl2(C11H20ClN2)2]	F(000) = 1044
Mr = 490.41	Dx = 1.182 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 999 reflections
a = 12.483 (4) Å	θ = 4.3–70.0°
b = 17.516 (7) Å	µ = 6.76 mm^−1
c = 12.604 (4) Å	T = 296 K
β = 90.22 (2)°	Block, blue
V = 2755.9 (17) Å^3	0.45 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker SMART APEXII area-detector diffractometer	5156 independent reflections
Radiation source: fine-focus sealed tube	4195 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
0.50° ω and 0.5 ° ϕ scans	θmax = 70.0°, θmin = 4.3°
Absorption correction: analytical (SADABS; Bruker, 2007)	h = −15→14
Tmin = 0.151, Tmax = 0.236	k = −21→21
44217 measured reflections	l = −15→15

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.205	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1082P)^2 + 2.7564P] where P = (Fo^2 + 2Fc^2)/3
5156 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.72 e Å^−3
65 restraints	Δρmin = −0.41 e Å^−3

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	Occ. (<1)
Co1	0.23606 (5)	0.79519 (4)	0.95931 (5)	0.0605 (3)
Cl1	0.36640 (9)	0.70482 (9)	0.96600 (10)	0.0871 (4)
Cl2	0.2946 (7)	0.9178 (2)	0.9659 (4)	0.0954 (14)	0.79 (2)
Cl2A	0.3332 (18)	0.9043 (9)	0.9505 (11)	0.0954 (14)	0.21 (2)
N1	0.1684 (3)	0.79250 (17)	0.8112 (2)	0.0530 (8)
N2	0.2053 (3)	0.85209 (18)	0.7522 (2)	0.0566 (8)
H2	0.2460	0.8877	0.7764	0.068*
N3	0.1523 (2)	0.76712 (19)	1.0909 (2)	0.0517 (7)
N4	0.1915 (3)	0.70424 (18)	1.1403 (2)	0.0539 (8)
H4	0.2474	0.6798	1.1197	0.065*
C1	0.0740 (5)	0.6531 (3)	0.8891 (4)	0.0931 (17)
H1A	0.1498	0.6469	0.8991	0.140*
H1B	0.0386	0.6055	0.9028	0.140*
H1C	0.0478	0.6913	0.9370	0.140*
C2	−0.0684 (4)	0.6887 (4)	0.7603 (6)	0.1011 (19)
H2A	−0.0932	0.7278	0.8076	0.152*
H2B	−0.1048	0.6417	0.7755	0.152*
H2C	−0.0829	0.7036	0.6883	0.152*
C3	0.0888 (6)	0.6144 (3)	0.7015 (5)	0.107 (2)
H3A	0.0685	0.6265	0.6299	0.161*
H3B	0.0560	0.5671	0.7222	0.161*
H3C	0.1652	0.6096	0.7061	0.161*
C4	0.0515 (3)	0.6778 (2)	0.7752 (3)	0.0551 (9)
C5	0.1094 (3)	0.7507 (2)	0.7452 (3)	0.0475 (8)
C6	0.1082 (3)	0.7848 (2)	0.6449 (3)	0.0549 (9)
H6	0.0721	0.7675	0.5849	0.066*
C7	0.1706 (3)	0.84834 (18)	0.6525 (2)	0.0528 (8)
C8	0.2020 (3)	0.90874 (17)	0.5701 (2)	0.0664 (11)
C9	0.1567 (7)	0.8870 (4)	0.4610 (3)	0.0988 (15)*	0.608 (7)
H9A	0.1860	0.9203	0.4080	0.148*	0.608 (7)
H9B	0.0801	0.8920	0.4617	0.148*	0.608 (7)
H9C	0.1756	0.8352	0.4450	0.148*	0.608 (7)
C10	0.3253 (3)	0.9135 (4)	0.5639 (6)	0.0988 (15)*	0.608 (7)
H10A	0.3454	0.9573	0.5227	0.148*	0.608 (7)
H10B	0.3526	0.8682	0.5309	0.148*	0.608 (7)
H10C	0.3546	0.9181	0.6342	0.148*	0.608 (7)
C11	0.1579 (7)	0.98706 (19)	0.6039 (5)	0.0988 (15)*	0.608 (7)
H11A	0.1881	1.0011	0.6713	0.148*	0.608 (7)
H11B	0.0813	0.9843	0.6098	0.148*	0.608 (7)
H11C	0.1766	1.0247	0.5518	0.148*	0.608 (7)
C9A	0.2206 (10)	0.8694 (4)	0.4622 (3)	0.0988 (15)*	0.392 (7)
H9D	0.2380	0.9072	0.4099	0.148*	0.392 (7)
H9E	0.1567	0.8429	0.4410	0.148*	0.392 (7)
H9F	0.2786	0.8337	0.4685	0.148*	0.392 (7)
C10A	0.3047 (6)	0.9497 (5)	0.6051 (7)	0.0988 (15)*	0.392 (7)
H10D	0.3610	0.9130	0.6145	0.148*	0.392 (7)
H10E	0.2923	0.9759	0.6708	0.148*	0.392 (7)
H10F	0.3252	0.9860	0.5517	0.148*	0.392 (7)
C11A	0.1103 (6)	0.9670 (5)	0.5583 (8)	0.0988 (15)*	0.392 (7)
H11D	0.0900	0.9854	0.6271	0.148*	0.392 (7)
H11E	0.0499	0.9430	0.5248	0.148*	0.392 (7)
H11F	0.1339	1.0091	0.5155	0.148*	0.392 (7)
C12	−0.1155 (3)	0.8468 (4)	1.1660 (8)	0.0803 (12)*	0.587 (14)
H12A	−0.1603	0.8880	1.1422	0.120*	0.587 (14)
H12B	−0.1124	0.8468	1.2421	0.120*	0.587 (14)
H12C	−0.1446	0.7992	1.1415	0.120*	0.587 (14)
C13	0.0506 (6)	0.9276 (2)	1.1738 (7)	0.0803 (12)*	0.587 (14)
H13A	0.1205	0.9353	1.1442	0.120*	0.587 (14)
H13B	0.0569	0.9193	1.2489	0.120*	0.587 (14)
H13C	0.0072	0.9719	1.1610	0.120*	0.587 (14)
C14	−0.0082 (7)	0.8702 (4)	1.0008 (2)	0.0803 (12)*	0.587 (14)
H14A	0.0607	0.8860	0.9754	0.120*	0.587 (14)
H14B	−0.0601	0.9092	0.9856	0.120*	0.587 (14)
H14C	−0.0289	0.8236	0.9663	0.120*	0.587 (14)
C12A	−0.1218 (2)	0.8340 (4)	1.1217 (12)	0.0803 (12)*	0.413 (14)
H12D	−0.1655	0.8789	1.1146	0.120*	0.413 (14)
H12E	−0.1383	0.8088	1.1872	0.120*	0.413 (14)
H12F	−0.1359	0.8001	1.0635	0.120*	0.413 (14)
C13A	0.0168 (10)	0.9184 (4)	1.2065 (7)	0.0803 (12)*	0.413 (14)
H13D	0.0901	0.9349	1.2039	0.120*	0.413 (14)
H13E	0.0020	0.8974	1.2752	0.120*	0.413 (14)
H13F	−0.0296	0.9611	1.1935	0.120*	0.413 (14)
C14A	0.0263 (9)	0.8891 (5)	1.0115 (5)	0.0803 (12)*	0.413 (14)
H14D	0.0195	0.8494	0.9593	0.120*	0.413 (14)
H14E	0.0988	0.9075	1.0125	0.120*	0.413 (14)
H14F	−0.0213	0.9303	0.9941	0.120*	0.413 (14)
C15	−0.0023 (2)	0.85711 (16)	1.1213 (2)	0.0623 (10)
C16	0.0661 (2)	0.78647 (15)	1.1455 (3)	0.0504 (8)
C17	0.0526 (3)	0.7368 (2)	1.2304 (3)	0.0564 (9)
H17	−0.0010	0.7387	1.2814	0.068*
C18	0.1335 (3)	0.68475 (17)	1.2242 (2)	0.0523 (8)
C19	0.1605 (3)	0.61462 (17)	1.2924 (2)	0.0647 (10)
C20	0.0749 (6)	0.5529 (3)	1.2768 (8)	0.0868 (15)*	0.408 (6)
H20A	0.0922	0.5093	1.3197	0.130*	0.408 (6)
H20B	0.0724	0.5381	1.2035	0.130*	0.408 (6)
H20C	0.0063	0.5726	1.2975	0.130*	0.408 (6)
C21	0.1652 (9)	0.6383 (4)	1.4100 (2)	0.0868 (15)*	0.408 (6)
H21A	0.1826	0.5947	1.4528	0.130*	0.408 (6)
H21B	0.0969	0.6583	1.4311	0.130*	0.408 (6)
H21C	0.2192	0.6768	1.4195	0.130*	0.408 (6)
C22	0.2708 (5)	0.5830 (5)	1.2595 (7)	0.0868 (15)*	0.408 (6)
H22A	0.2880	0.5393	1.3021	0.130*	0.408 (6)
H22B	0.3244	0.6217	1.2698	0.130*	0.408 (6)
H22C	0.2688	0.5685	1.1861	0.130*	0.408 (6)
C20A	0.0597 (5)	0.5910 (5)	1.3553 (9)	0.0868 (15)*	0.341 (7)
H20D	0.0008	0.5839	1.3072	0.130*	0.341 (7)
H20E	0.0423	0.6302	1.4055	0.130*	0.341 (7)
H20F	0.0736	0.5441	1.3923	0.130*	0.341 (7)
C21A	0.2511 (8)	0.6338 (4)	1.3703 (8)	0.0868 (15)*	0.341 (7)
H21D	0.2673	0.5897	1.4126	0.130*	0.341 (7)
H21E	0.2292	0.6749	1.4156	0.130*	0.341 (7)
H21F	0.3137	0.6487	1.3314	0.130*	0.341 (7)
C22A	0.1942 (11)	0.5480 (3)	1.2204 (5)	0.0868 (15)*	0.341 (7)
H22D	0.1368	0.5360	1.1723	0.130*	0.341 (7)
H22E	0.2103	0.5041	1.2632	0.130*	0.341 (7)
H22F	0.2566	0.5623	1.1808	0.130*	0.341 (7)
C20B	0.0981 (13)	0.6183 (7)	1.3971 (7)	0.0868 (15)*	0.250 (7)
H20G	0.1151	0.5744	1.4396	0.130*	0.250 (7)
H20H	0.0226	0.6189	1.3823	0.130*	0.250 (7)
H20I	0.1175	0.6638	1.4350	0.130*	0.250 (7)
C21B	0.2815 (4)	0.6133 (7)	1.3162 (14)	0.0868 (15)*	0.250 (7)
H21G	0.2984	0.5693	1.3586	0.130*	0.250 (7)
H21H	0.3012	0.6588	1.3540	0.130*	0.250 (7)
H21I	0.3205	0.6109	1.2507	0.130*	0.250 (7)
C22B	0.1294 (16)	0.5415 (2)	1.2317 (8)	0.0868 (15)*	0.250 (7)
H22G	0.1466	0.4977	1.2742	0.130*	0.250 (7)
H22H	0.1683	0.5393	1.1663	0.130*	0.250 (7)
H22I	0.0539	0.5421	1.2169	0.130*	0.250 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0580 (4)	0.0877 (5)	0.0359 (3)	−0.0176 (3)	−0.0003 (3)	0.0057 (3)
Cl1	0.0571 (6)	0.1455 (13)	0.0587 (6)	0.0126 (6)	0.0078 (5)	−0.0006 (6)
Cl2	0.111 (3)	0.1122 (13)	0.0632 (12)	−0.0600 (17)	0.0054 (16)	−0.0109 (9)
Cl2A	0.111 (3)	0.1122 (13)	0.0632 (12)	−0.0600 (17)	0.0054 (16)	−0.0109 (9)
N1	0.0578 (18)	0.0621 (19)	0.0391 (15)	−0.0152 (14)	−0.0013 (13)	0.0054 (13)
N2	0.071 (2)	0.0596 (19)	0.0396 (15)	−0.0220 (15)	−0.0019 (14)	0.0057 (13)
N3	0.0526 (17)	0.0637 (18)	0.0388 (15)	0.0015 (14)	0.0009 (13)	0.0066 (13)
N4	0.0547 (18)	0.066 (2)	0.0410 (16)	0.0102 (14)	0.0020 (13)	0.0040 (13)
C1	0.123 (4)	0.079 (3)	0.077 (3)	−0.037 (3)	−0.013 (3)	0.024 (3)
C2	0.058 (3)	0.109 (4)	0.136 (5)	−0.018 (3)	−0.003 (3)	0.032 (4)
C3	0.135 (5)	0.069 (3)	0.118 (5)	−0.032 (3)	0.053 (4)	−0.020 (3)
C4	0.055 (2)	0.056 (2)	0.055 (2)	−0.0109 (17)	0.0032 (17)	0.0024 (17)
C5	0.0481 (19)	0.051 (2)	0.0429 (18)	−0.0014 (15)	0.0015 (15)	0.0008 (15)
C6	0.064 (2)	0.059 (2)	0.0414 (19)	−0.0083 (17)	−0.0085 (17)	0.0020 (16)
C7	0.063 (2)	0.053 (2)	0.0416 (18)	−0.0023 (17)	−0.0018 (16)	0.0028 (15)
C8	0.088 (3)	0.063 (2)	0.048 (2)	−0.011 (2)	0.001 (2)	0.0121 (18)
C15	0.072 (3)	0.066 (2)	0.048 (2)	0.012 (2)	0.0001 (18)	0.0059 (18)
C16	0.056 (2)	0.055 (2)	0.0399 (18)	−0.0020 (16)	−0.0012 (16)	−0.0004 (15)
C17	0.066 (2)	0.060 (2)	0.0435 (19)	0.0042 (18)	0.0132 (17)	0.0032 (16)
C18	0.062 (2)	0.057 (2)	0.0381 (17)	0.0001 (17)	0.0030 (16)	0.0001 (15)
C19	0.083 (3)	0.057 (2)	0.054 (2)	0.007 (2)	−0.001 (2)	0.0077 (18)

Geometric parameters (Å, º)

Co1—N3	2.025 (3)	C13—H13B	0.9600
Co1—N1	2.046 (3)	C13—H13C	0.9600
Co1—Cl2A	2.267 (2)	C14—C15	1.5375 (19)
Co1—Cl2	2.2698 (19)	C14—H14A	0.9600
Co1—Cl1	2.2713 (16)	C14—H14B	0.9600
N1—C5	1.330 (5)	C14—H14C	0.9600
N1—N2	1.363 (4)	C12A—C15	1.5456 (19)
N2—C7	1.328 (4)	C12A—H12D	0.9600
N2—H2	0.8600	C12A—H12E	0.9600
N3—C16	1.323 (4)	C12A—H12F	0.9600
N3—N4	1.356 (4)	C13A—C15	1.5355 (19)
N4—C18	1.328 (5)	C13A—H13D	0.9600
N4—H4	0.8600	C13A—H13E	0.9600
C1—C4	1.525 (6)	C13A—H13F	0.9600
C1—H1A	0.9600	C14A—C15	1.5368 (19)
C1—H1B	0.9600	C14A—H14D	0.9600
C1—H1C	0.9600	C14A—H14E	0.9600
C2—C4	1.520 (6)	C14A—H14F	0.9600
C2—H2A	0.9600	C15—C16	1.534 (3)
C2—H2B	0.9600	C16—C17	1.390 (5)
C2—H2C	0.9600	C17—C18	1.364 (5)
C3—C4	1.521 (7)	C17—H17	0.9300
C3—H3A	0.9600	C18—C19	1.536 (2)
C3—H3B	0.9600	C19—C20	1.5323 (19)
C3—H3C	0.9600	C19—C21A	1.5330 (19)
C4—C5	1.515 (5)	C19—C20B	1.5370 (19)
C5—C6	1.398 (5)	C19—C22A	1.5377 (19)
C6—C7	1.361 (5)	C19—C22B	1.5397 (19)
C6—H6	0.9300	C19—C21B	1.5398 (19)
C7—C8	1.535 (3)	C19—C21	1.5411 (19)
C8—C10A	1.5328 (19)	C19—C22	1.5427 (19)
C8—C9	1.5337 (19)	C19—C20A	1.5461 (19)
C8—C11	1.5391 (19)	C20—H20A	0.9600
C8—C11A	1.5408 (19)	C20—H20B	0.9600
C8—C9A	1.5431 (19)	C20—H20C	0.9600
C8—C10	1.5440 (19)	C21—H21A	0.9600
C9—H9A	0.9600	C21—H21B	0.9600
C9—H9B	0.9600	C21—H21C	0.9600
C9—H9C	0.9600	C22—H22A	0.9600
C10—H10A	0.9600	C22—H22B	0.9600
C10—H10B	0.9600	C22—H22C	0.9600
C10—H10C	0.9600	C20A—H20D	0.9600
C11—H11A	0.9600	C20A—H20E	0.9600
C11—H11B	0.9600	C20A—H20F	0.9600
C11—H11C	0.9600	C21A—H21D	0.9600
C9A—H9D	0.9600	C21A—H21E	0.9600
C9A—H9E	0.9600	C21A—H21F	0.9600
C9A—H9F	0.9600	C22A—H22D	0.9600
C10A—H10D	0.9600	C22A—H22E	0.9600
C10A—H10E	0.9600	C22A—H22F	0.9600
C10A—H10F	0.9600	C20B—H20G	0.9600
C11A—H11D	0.9600	C20B—H20H	0.9600
C11A—H11E	0.9600	C20B—H20I	0.9600
C11A—H11F	0.9600	C21B—H21G	0.9600
C12—C15	1.5329 (19)	C21B—H21H	0.9600
C12—H12A	0.9600	C21B—H21I	0.9600
C12—H12B	0.9600	C22B—H22G	0.9600
C12—H12C	0.9600	C22B—H22H	0.9600
C13—C15	1.5476 (19)	C22B—H22I	0.9600
C13—H13A	0.9600
N3—Co1—N1	121.93 (13)	H12E—C12A—H12F	109.5
N3—Co1—Cl2A	121.5 (5)	C15—C13A—H13D	109.5
N1—Co1—Cl2A	101.2 (4)	C15—C13A—H13E	109.5
N3—Co1—Cl2	111.5 (2)	H13D—C13A—H13E	109.5
N1—Co1—Cl2	100.78 (11)	C15—C13A—H13F	109.5
N3—Co1—Cl1	99.93 (10)	H13D—C13A—H13F	109.5
N1—Co1—Cl1	108.13 (11)	H13E—C13A—H13F	109.5
Cl2A—Co1—Cl1	101.9 (7)	C15—C14A—H14D	109.5
Cl2—Co1—Cl1	115.3 (3)	C15—C14A—H14E	109.5
C5—N1—N2	105.5 (3)	H14D—C14A—H14E	109.5
C5—N1—Co1	144.1 (2)	C15—C14A—H14F	109.5
N2—N1—Co1	109.9 (2)	H14D—C14A—H14F	109.5
C7—N2—N1	111.6 (3)	H14E—C14A—H14F	109.5
C7—N2—H2	124.2	C12—C15—C16	110.19 (17)
N1—N2—H2	124.2	C16—C15—C13A	109.87 (17)
C16—N3—N4	105.2 (3)	C16—C15—C14A	109.96 (17)
C16—N3—Co1	141.9 (2)	C13A—C15—C14A	109.81 (17)
N4—N3—Co1	112.8 (2)	C12—C15—C14	109.85 (17)
C18—N4—N3	112.2 (3)	C16—C15—C14	109.94 (17)
C18—N4—H4	123.9	C16—C15—C12A	108.97 (17)
N3—N4—H4	123.9	C13A—C15—C12A	109.18 (17)
C4—C1—H1A	109.5	C14A—C15—C12A	109.02 (17)
C4—C1—H1B	109.5	C12—C15—C13	109.25 (17)
H1A—C1—H1B	109.5	C16—C15—C13	108.80 (17)
C4—C1—H1C	109.5	C14—C15—C13	108.78 (17)
H1A—C1—H1C	109.5	N3—C16—C17	109.9 (3)
H1B—C1—H1C	109.5	N3—C16—C15	123.8 (3)
C4—C2—H2A	109.5	C17—C16—C15	126.1 (3)
C4—C2—H2B	109.5	C18—C17—C16	106.4 (3)
H2A—C2—H2B	109.5	C18—C17—H17	126.8
C4—C2—H2C	109.5	C16—C17—H17	126.8
H2A—C2—H2C	109.5	N4—C18—C17	106.3 (3)
H2B—C2—H2C	109.5	N4—C18—C19	122.2 (3)
C4—C3—H3A	109.5	C17—C18—C19	131.6 (3)
C4—C3—H3B	109.5	C20—C19—C18	110.01 (16)
H3A—C3—H3B	109.5	C21A—C19—C18	110.05 (17)
C4—C3—H3C	109.5	C18—C19—C20B	109.70 (17)
H3A—C3—H3C	109.5	C21A—C19—C22A	109.92 (17)
H3B—C3—H3C	109.5	C18—C19—C22A	109.67 (17)
C5—C4—C2	109.4 (4)	C18—C19—C22B	109.46 (17)
C5—C4—C3	108.4 (3)	C20B—C19—C22B	109.49 (17)
C2—C4—C3	108.6 (5)	C18—C19—C21B	109.49 (17)
C5—C4—C1	112.8 (3)	C20B—C19—C21B	109.48 (17)
C2—C4—C1	109.2 (4)	C22B—C19—C21B	109.21 (17)
C3—C4—C1	108.2 (5)	C20—C19—C21	109.73 (17)
N1—C5—C6	109.5 (3)	C18—C19—C21	109.30 (16)
N1—C5—C4	124.8 (3)	C20—C19—C22	109.61 (17)
C6—C5—C4	125.6 (3)	C18—C19—C22	109.28 (16)
C7—C6—C5	106.4 (3)	C21—C19—C22	108.90 (16)
C7—C6—H6	126.8	C21A—C19—C20A	109.27 (17)
C5—C6—H6	126.8	C18—C19—C20A	108.97 (16)
N2—C7—C6	106.9 (3)	C22A—C19—C20A	108.93 (17)
N2—C7—C8	121.5 (3)	C19—C20—H20A	109.5
C6—C7—C8	131.6 (3)	C19—C20—H20B	109.5
C10A—C8—C7	110.14 (17)	H20A—C20—H20B	109.5
C9—C8—C7	109.97 (17)	C19—C20—H20C	109.5
C9—C8—C11	109.78 (17)	H20A—C20—H20C	109.5
C7—C8—C11	109.54 (17)	H20B—C20—H20C	109.5
C10A—C8—C11A	109.74 (17)	C19—C21—H21A	109.5
C7—C8—C11A	109.33 (17)	C19—C21—H21B	109.5
C10A—C8—C9A	109.49 (17)	H21A—C21—H21B	109.5
C7—C8—C9A	109.19 (17)	C19—C21—H21C	109.5
C11A—C8—C9A	108.92 (17)	H21A—C21—H21C	109.5
C9—C8—C10	109.40 (17)	H21B—C21—H21C	109.5
C7—C8—C10	109.23 (17)	C19—C22—H22A	109.5
C11—C8—C10	108.90 (17)	C19—C22—H22B	109.5
C8—C9—H9A	109.5	H22A—C22—H22B	109.5
C8—C9—H9B	109.5	C19—C22—H22C	109.5
C8—C9—H9C	109.5	H22A—C22—H22C	109.5
C8—C10—H10A	109.5	H22B—C22—H22C	109.5
C8—C10—H10B	109.5	C19—C20A—H20D	109.5
C8—C10—H10C	109.5	C19—C20A—H20E	109.5
C8—C11—H11A	109.5	H20D—C20A—H20E	109.5
C8—C11—H11B	109.5	C19—C20A—H20F	109.5
C8—C11—H11C	109.5	H20D—C20A—H20F	109.5
C8—C9A—H9D	109.5	H20E—C20A—H20F	109.5
C8—C9A—H9E	109.5	C19—C21A—H21D	109.5
H9D—C9A—H9E	109.5	C19—C21A—H21E	109.5
C8—C9A—H9F	109.5	H21D—C21A—H21E	109.5
H9D—C9A—H9F	109.5	C19—C21A—H21F	109.5
H9E—C9A—H9F	109.5	H21D—C21A—H21F	109.5
C8—C10A—H10D	109.5	H21E—C21A—H21F	109.5
C8—C10A—H10E	109.5	C19—C22A—H22D	109.5
H10D—C10A—H10E	109.5	C19—C22A—H22E	109.5
C8—C10A—H10F	109.5	H22D—C22A—H22E	109.5
H10D—C10A—H10F	109.5	C19—C22A—H22F	109.5
H10E—C10A—H10F	109.5	H22D—C22A—H22F	109.5
C8—C11A—H11D	109.5	H22E—C22A—H22F	109.5
C8—C11A—H11E	109.5	C19—C20B—H20G	109.5
H11D—C11A—H11E	109.5	C19—C20B—H20H	109.5
C8—C11A—H11F	109.5	H20G—C20B—H20H	109.5
H11D—C11A—H11F	109.5	C19—C20B—H20I	109.5
H11E—C11A—H11F	109.5	H20G—C20B—H20I	109.5
C15—C12—H12A	109.5	H20H—C20B—H20I	109.5
C15—C12—H12B	109.5	C19—C21B—H21G	109.5
C15—C12—H12C	109.5	C19—C21B—H21H	109.5
C15—C13—H13A	109.5	H21G—C21B—H21H	109.5
C15—C13—H13B	109.5	C19—C21B—H21I	109.5
C15—C13—H13C	109.5	H21G—C21B—H21I	109.5
C15—C14—H14A	109.5	H21H—C21B—H21I	109.5
C15—C14—H14B	109.5	C19—C22B—H22G	109.5
C15—C14—H14C	109.5	C19—C22B—H22H	109.5
C15—C12A—H12D	109.5	H22G—C22B—H22H	109.5
C15—C12A—H12E	109.5	C19—C22B—H22I	109.5
H12D—C12A—H12E	109.5	H22G—C22B—H22I	109.5
C15—C12A—H12F	109.5	H22H—C22B—H22I	109.5
H12D—C12A—H12F	109.5
N3—Co1—N1—C5	−47.7 (5)	N2—C7—C8—C9A	142.0 (6)
Cl2A—Co1—N1—C5	173.6 (8)	C6—C7—C8—C9A	−37.9 (6)
Cl2—Co1—N1—C5	−171.6 (5)	N2—C7—C8—C10	56.2 (5)
Cl1—Co1—N1—C5	67.0 (5)	C6—C7—C8—C10	−123.7 (5)
N3—Co1—N1—N2	142.1 (2)	N4—N3—C16—C17	1.3 (4)
Cl2A—Co1—N1—N2	3.4 (8)	Co1—N3—C16—C17	176.5 (3)
Cl2—Co1—N1—N2	18.1 (4)	N4—N3—C16—C15	177.2 (3)
Cl1—Co1—N1—N2	−103.2 (2)	Co1—N3—C16—C15	−7.7 (6)
C5—N1—N2—C7	0.3 (4)	C12—C15—C16—N3	157.5 (5)
Co1—N1—N2—C7	174.3 (3)	C13A—C15—C16—N3	−107.0 (7)
N1—Co1—N3—C16	−58.9 (5)	C14A—C15—C16—N3	14.0 (7)
Cl2A—Co1—N3—C16	71.6 (8)	C14—C15—C16—N3	36.3 (5)
Cl2—Co1—N3—C16	59.9 (5)	C12A—C15—C16—N3	133.4 (7)
Cl1—Co1—N3—C16	−177.7 (4)	C13—C15—C16—N3	−82.7 (5)
N1—Co1—N3—N4	116.0 (2)	C12—C15—C16—C17	−27.3 (5)
Cl2A—Co1—N3—N4	−113.5 (8)	C13A—C15—C16—C17	68.2 (7)
Cl2—Co1—N3—N4	−125.2 (3)	C14A—C15—C16—C17	−170.8 (7)
Cl1—Co1—N3—N4	−2.8 (2)	C14—C15—C16—C17	−148.5 (5)
C16—N3—N4—C18	−0.9 (4)	C12A—C15—C16—C17	−51.4 (7)
Co1—N3—N4—C18	−177.6 (2)	C13—C15—C16—C17	92.5 (5)
N2—N1—C5—C6	−0.8 (4)	N3—C16—C17—C18	−1.3 (4)
Co1—N1—C5—C6	−171.3 (4)	C15—C16—C17—C18	−177.1 (3)
N2—N1—C5—C4	179.8 (3)	N3—N4—C18—C17	0.1 (4)
Co1—N1—C5—C4	9.4 (7)	N3—N4—C18—C19	178.9 (3)
C2—C4—C5—N1	117.8 (5)	C16—C17—C18—N4	0.7 (4)
C3—C4—C5—N1	−123.9 (5)	C16—C17—C18—C19	−178.0 (3)
C1—C4—C5—N1	−4.1 (6)	N4—C18—C19—C20	−110.6 (5)
C2—C4—C5—C6	−61.5 (6)	C17—C18—C19—C20	67.9 (6)
C3—C4—C5—C6	56.9 (6)	N4—C18—C19—C21A	80.4 (6)
C1—C4—C5—C6	176.7 (4)	C17—C18—C19—C21A	−101.1 (7)
N1—C5—C6—C7	1.0 (5)	N4—C18—C19—C20B	166.0 (9)
C4—C5—C6—C7	−179.6 (4)	C17—C18—C19—C20B	−15.5 (9)
N1—N2—C7—C6	0.4 (5)	N4—C18—C19—C22A	−40.6 (6)
N1—N2—C7—C8	−179.5 (3)	C17—C18—C19—C22A	137.9 (7)
C5—C6—C7—N2	−0.9 (4)	N4—C18—C19—C22B	−73.9 (9)
C5—C6—C7—C8	179.1 (3)	C17—C18—C19—C22B	104.7 (9)
N2—C7—C8—C10A	21.7 (6)	N4—C18—C19—C21B	45.8 (9)
C6—C7—C8—C10A	−158.2 (6)	C17—C18—C19—C21B	−135.7 (9)
N2—C7—C8—C9	176.3 (5)	N4—C18—C19—C21	128.9 (5)
C6—C7—C8—C9	−3.6 (5)	C17—C18—C19—C21	−52.6 (6)
N2—C7—C8—C11	−63.0 (5)	N4—C18—C19—C22	9.8 (5)
C6—C7—C8—C11	117.1 (5)	C17—C18—C19—C22	−171.7 (6)
N2—C7—C8—C11A	−99.0 (6)	N4—C18—C19—C20A	−159.8 (6)
C6—C7—C8—C11A	81.1 (6)	C17—C18—C19—C20A	18.7 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl2	0.86	2.52	3.131 (4)	129
N2—H2···Cl2A	0.86	2.46	3.099 (13)	131
N4—H4···Cl1	0.86	2.48	3.103 (4)	130