Packing forces in di­chlorido­bis­(3,5-diphenyl-1H-pyrazole-[kappa]N²)cobalt(II) di­chloro­methane hemisolvate

The title compound, [CoCl₂(C₁₅H₁₂N₂)₂]·0.5CH₂Cl₂, was crystallized from a binary mixture of di­chloro­methane and hexane and a dimeric supra­molecular structure was isolated. The Co^II centre exhibits a distorted tetra­hedral geometry, with two independent pyrazole-based ligands occupying two coordination sites and two chloride ligands occupying the third and fourth coordination sites. The supra­molecular structure is supported by complementary hydrogen bonding between the pyrazole NH group and the chloride ligand of an adjacent mol­ecule. This hydrogen-bonding motif yields a ten-mem­bered hydrogen-bonded ring. Density functional theory (DFT) simulations at the PBE/6-311G level of theory were used to probe the solid-state structure. These simulations suggest that the chelate undergoes a degree of conformational distortion from the lowest-energy geometry to allow for optimal hydrogen bonding in the solid state.

S1. Introduction

The use of late transition metal complexes anchored on nitro­gen-donor ligands as catalysts in olefin oligomerization and polymerization reactions has witnessed enormous growth since their discovery by Brookhart and co-workers (Brookhart et al., 1995; Ittel et al., 2000). For the past decade, we have been investigating the use of nickel(II), palladium(II) and cobalt(II) complexes of pyrazole and pyrazolyl ligands as catalysts in ethyl­ene and higher olefin polymerization and oligomerization reactions (Ojwach et al., 2005; Mkoyi et al., 2013; Ainooson et al., 2011). We recently reported that [(pyrazolyl­methyl)­pyridine]­nickel(II) complexes not only produce highly active ethyl­ene oligomerization reactions, but also promote tandem Friedel–Crafts alkyl­ation of the toluene solvent used (Ojwach et al., 2009; Budhai et al., 2013; Benade et al., 2011). In our continuing efforts to develop efficient olefin transformation catalysts of late transition metal complexes, the title compound, (I), was synthesized. Activation of the compound to form an active ethyl­ene oligomerization or polymerization catalyst unfortunately resulted in very low activities. We describe herein the solid-state structure and the gas-phase density functional theory (DFT) structure of this cobalt(II) complex.

S2. Experimental

S2.1. Synthesis and crystallization

3,5-Di­phenyl-1H-pyrazole was synthesized by reacting di­benzoyl­methane and hydrazine according to a previously described method (Kitajima et al., 1992). The title compound was prepared by adding a solution of CoCl₂ (0.100 g, 0.770 mmol) in di­chloro­methane (15 ml) to a solution of 3,5-di­phenyl-1H-pyrazole (0.340 g, 1.54 mmol) in di­chloro­methane (15 ml). The resulting blue solution was stirred for 24 h at room temperature. Slow evaporation of the reaction mixture afforded (I). Recrystallization of (I) from di­chloro­methane–hexane [Solvent ratio?] yielded blue crystals suitable for single-crystal X-ray diffraction (yield 0.38 g, 87%). IR (ATR, cm^-1): 1079 (C—C), 1567 (C═N). ESI–MS: m/z (%) 612 [(M + 0.5CH₂Cl₂)⁺, 88%]. Analysis, calculated for C₃₀H₂₄Cl₂CoN₄.0.5CH₂Cl₂: C 59.77, H 4.11, N 9.14%; found: C 58.94, H 4.22, N 9.25%. µ_eff = 4.26 BM.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Pyrazole N-bound and solvent H atoms were located and allowed to refine isotropically. All other H atoms were placed in geometrically calculated positions, with aromatic C—H = 0.93 Å and U_iso(H) = 1.2U_eq.

S3. Results and discussion

The solid-state structure of (I) (Fig. 1) shows that the Co^II centre adopts a distorted tetra­hedral coordination geometry. Two of the coordination sites are occupied by two independent monodentate N-donor pyrazole-based ligands, and the third and fourth coordination sites are occupied by two chloride ligands. Table 2 gives selected geometric parameters which illustrate the distorted tetra­hedral geometry. The planes of the phenyl rings of the ligand are not coplanar with the plane of the pyrazole ring. The C8—C7—C6—C5 and C8—C9—C10—C11 torsion angles of one pyrazole ligand are 19.8 (2) and -35.5 (3)°, respectively, while the C23—C22—C21—C20 and C23—C24—C25—C26 torsion angles of the second ligand are 20.1 (2) and 29.5 (2)°, respectively. These torsion angles illustrate the out-of-plane rotation of the phenyl rings relative to the pyrazole rings.

The metal chelate crystallizes as the di­chloro­methane hemisolvate. The C atom of the solvent molecule is located on a twofold rotation axis. The solvent molecule occupies a void of volume 104 ų. There is a short Cl···Cl contact between di­chloro­methane atom Cl1s and atom Cl2 of the metal chelate. However, the solvent molecule is not involved in any meaningful inter­molecular inter­actions.

The cobalt(II) complex forms an inter­esting dimeric supra­molecular structure, supported by complementary hydrogen bonding between the pyrazole NH group and the chloride ligand of an adjacent molecule. This arrangement leads to a ten-membered hydrogen-bonded ring. The dimer has crystallographically imposed inversion symmetry (C_i). Although hydrogen-bond length does not neccessarily correlate linearly with bond strength, due to packing constraints in the lattice (Steiner, 1997), the hydrogen-bond length in (I) (Table 3) is significantly shorter (by 0.422 Å) than the sum of the van der Waals radii of the inter­acting atoms [Standard reference?]. This would imply that it is a moderately strong inter­action. The dimeric structures are linked by weak C—H···Cl inter­actions between o-phenyl atom H11 and atom Cl2. These weak inter­actions link the dimers into a two-dimensional network perpendicular to the c axis.

The structures of the monomer and dimer of the metal chelate in vacuo were calculated using density functional theory (DFT) at the PBE/6-311G level of theory (Perdew et al., 1996, 1997; McLean & Chandler, 1980; Raghavachari et al., 1980; Wachters, 1970; Hay, 1977; Raghavachari & Trucks, 1989) using GAUSSIAN09 (Frisch et al., 2009). X-ray coordinates were used for the input structure. Normal geometry convergence criteria were applied with no symmetry constraints imposed. A lack of negative eigenvalues for the geometry-optimized structures suggests that they are true minima on the global potential energy surface. The experimental (solid-state) and simulated (in vacuo) structures were compared using structural overlays (least-squares fits), calculated using Mercury (Macrae et al., 2008). The similarity of the calculated and experimental structures is illustrated by r.m.s. deviations (RMSDs) for all non-H atoms (Fig. 3).

The most notable difference between the experimental and simulated structures is the coordination environment. The geometry of the Co^II cation could reasonably be described as distorted tetra­hedral for the experimental structure, but the simulated structure approaches a square-planar geometry. This is particularly evident when looking at the N1—Co1—Cl2 and N3—Co1—Cl1 bond angles (Table 2), which are closer to the ideal angle for a square-planar geometry (180°) rather than a tetra­hedral geometry. Similarly, the N3—Co1—N1, N3—Co1—Cl2, N1—Co1—Cl1 and Cl2—Co1—Cl1 bond angles of the DFT-calculated structure approach 90°, the ideal angle for a square-planar geometry. However, despite the differences in the geometry of the metal ion, the dimeric structure retains its C_i symmetry in vacuo.

The partial charge distribution [non-bonding orbital (NBO) charges, measured in electrons] shows that the H atom of the pyrazole NH group carries the largest partial positive charge (0.444 e), while the chloride ligands carry the most negative partial charge (-0.613 e). Therefore, if a hydrogen bond is to be considered a simple electrostatic inter­action then the simulations clearly explain the formation of the complementary N—H···Cl hydrogen bonds.

Inter­estingly, the RMSD for the dimeric structure (0.818 Å) is approximately equal to the RMSD for the monomeric structure (0.813 Å). This is an unexpected result, as usually the RMSD would be signifcantly larger when more atoms are used for the least-squares fits, and it would suggest that the dimerization process requires a degree of conformational distortion to allow for optimal hydrogen bonding. The simulations show that the optimized geometry of the dimeric structure in vacuo is 144 kJ mol^-1 lower in energy than the solid-state structure. Seemingly, the stability gained through the hydrogen-bonded inter­actions is large enough to compensate for the fact that the individual monomers, which constitute the dimeric structure, are no longer in their lowest energy conformation. This point is further illustrated by the fact that the RMSD for an overlay of the experimental monomer and a monomer from the DFT-calculated dimer is 0.723 Å, smaller than that for the isolated monomer in vacuo. Similar distortions from the lowest-energy structures have been reported for other hydrogen-bonded dimeric structures (Akerman & Chiazzari, 2014). [Does this also shed light on the lack of catalytic activity?]

Related literature

For related literature, see: Ainooson et al. (2011); Akerman & Chiazzari (2014); Benade et al. (2011); Brookhart et al. (1995); Budhai et al. (2013); Frisch et al. (2009); Hay (1977); Ittel et al. (2000); Kitajima et al. (1992); Macrae et al. (2008); McLean & Chandler (1980); Mkoyi et al. (2013); Ojwach et al. (2005, 2009); Perdew et al. (1996, 1997); Raghavachari & Trucks (1989); Raghavachari et al. (1980); Steiner (1997); Wachters (1970).

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are depicted with a common arbitrary radius. [Symmetry code: (i) -x + 1, y, -z + 1/2.]
	Fig. 2. The hydrogen-bonded dimer of (I), viewed down the c axis. The dimer is supported by complementary hydrogen bonding between the pyrazole NH group and the chloride ligand of an adjacent molecule.
	Fig. 3. Least-squares fit of the non-H atoms of the DFT-calculated (yellow) and X-ray crystal structure (blue) of (I). (Top) The monomer and (bottom) the dimer. RMSD denotes r.m.s. deviation. The differing geometries of the Co^II chelate in the solid state and in the gas phase show the conformational distortion required for optimal hydrogen bonding in the solid state.

Dichloridobis(3,5-diphenyl-1H-pyrazole-κN²)cobalt(II) dichloromethane hemisolvate

Crystal data

[CoCl2(C15H12N2)2]·0.5CH2Cl2	F(000) = 2512
Mr = 612.85	Dx = 1.463 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4835 reflections
a = 13.7980 (9) Å	θ = 1.8–26.0°
b = 20.8958 (16) Å	µ = 0.93 mm^−1
c = 19.2954 (15) Å	T = 100 K
V = 5563.3 (7) Å^3	Needle, blue
Z = 8	0.20 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5453 independent reflections
Radiation source: Incoatec microsource	4835 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and ϕ scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −8→16
Tmin = 0.835, Tmax = 0.946	k = −23→25
26832 measured reflections	l = −23→20

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0229P)^2 + 3.9174P] where P = (Fo^2 + 2Fc^2)/3
5453 reflections	(Δ/σ)max = 0.002
360 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.32505 (12)	0.33872 (7)	0.38532 (8)	0.0170 (3)
H1	0.3846	0.3530	0.4047	0.020*
C1S	0.5000	0.51886 (15)	0.2500	0.0416 (8)
C2	0.28674 (12)	0.36961 (8)	0.32782 (9)	0.0199 (4)
H2	0.3198	0.4052	0.3084	0.024*
C3	0.20017 (12)	0.34882 (8)	0.29834 (9)	0.0204 (4)
H3	0.1740	0.3703	0.2592	0.024*
C4	0.15231 (12)	0.29637 (8)	0.32656 (8)	0.0190 (3)
H4	0.0940	0.2814	0.3061	0.023*
C5	0.18965 (11)	0.26579 (8)	0.38467 (8)	0.0166 (3)
H5	0.1560	0.2304	0.4041	0.020*
C6	0.27641 (11)	0.28664 (7)	0.41499 (8)	0.0142 (3)
C7	0.31432 (11)	0.25201 (7)	0.47570 (8)	0.0139 (3)
C8	0.29079 (11)	0.18950 (7)	0.49673 (8)	0.0157 (3)
H8	0.2457	0.1614	0.4753	0.019*
C9	0.34617 (11)	0.17703 (7)	0.55457 (8)	0.0143 (3)
C10	0.35515 (11)	0.11975 (7)	0.59828 (8)	0.0149 (3)
C11	0.27413 (12)	0.08122 (7)	0.61126 (8)	0.0177 (3)
H11	0.2129	0.0923	0.5922	0.021*
C12	0.28349 (13)	0.02673 (8)	0.65198 (9)	0.0206 (4)
H12	0.2284	0.0007	0.6609	0.025*
C13	0.37299 (13)	0.01010 (8)	0.67974 (9)	0.0215 (4)
H13	0.3790	−0.0273	0.7074	0.026*
C14	0.45366 (13)	0.04824 (8)	0.66705 (9)	0.0207 (4)
H14	0.5148	0.0369	0.6860	0.025*
C15	0.44488 (12)	0.10297 (8)	0.62664 (8)	0.0171 (3)
H15	0.5000	0.1291	0.6183	0.020*
C16	0.27288 (12)	0.56116 (8)	0.37405 (9)	0.0189 (3)
H16	0.3374	0.5460	0.3787	0.023*
C17	0.25198 (13)	0.60959 (8)	0.32697 (9)	0.0215 (4)
H17	0.3024	0.6277	0.2998	0.026*
C18	0.15729 (13)	0.63167 (8)	0.31952 (9)	0.0231 (4)
H18	0.1433	0.6648	0.2873	0.028*
C19	0.08346 (12)	0.60546 (8)	0.35903 (9)	0.0225 (4)
H19	0.0188	0.6202	0.3535	0.027*
C20	0.10401 (12)	0.55754 (8)	0.40671 (9)	0.0184 (3)
H20	0.0534	0.5401	0.4342	0.022*
C21	0.19875 (11)	0.53473 (7)	0.41458 (8)	0.0160 (3)
C22	0.21675 (11)	0.48260 (7)	0.46387 (8)	0.0156 (3)
C23	0.15326 (11)	0.43827 (7)	0.49217 (8)	0.0162 (3)
H23	0.0855	0.4353	0.4839	0.019*
C24	0.20855 (11)	0.39889 (7)	0.53528 (8)	0.0148 (3)
C25	0.17748 (11)	0.34307 (7)	0.57646 (8)	0.0153 (3)
C26	0.09988 (12)	0.30532 (8)	0.55428 (9)	0.0185 (3)
H26	0.0651	0.3169	0.5137	0.022*
C27	0.07335 (12)	0.25110 (8)	0.59117 (9)	0.0235 (4)
H27	0.0203	0.2258	0.5759	0.028*
C28	0.12390 (13)	0.23364 (8)	0.65022 (10)	0.0251 (4)
H28	0.1062	0.1961	0.6749	0.030*
C29	0.20046 (13)	0.27114 (8)	0.67327 (9)	0.0227 (4)
H29	0.2353	0.2592	0.7137	0.027*
C30	0.22614 (12)	0.32621 (8)	0.63722 (9)	0.0192 (3)
H30	0.2771	0.3525	0.6540	0.023*
Cl1	0.48310 (3)	0.342643 (19)	0.65612 (2)	0.01995 (9)
Cl1S	0.51433 (3)	0.47199 (2)	0.32554 (2)	0.03041 (11)
Cl2	0.53993 (3)	0.413550 (18)	0.48609 (2)	0.01836 (9)
Co1	0.424708 (15)	0.366007 (10)	0.550060 (11)	0.01355 (6)
N1	0.38080 (9)	0.27707 (6)	0.51942 (7)	0.0144 (3)
N2	0.40041 (10)	0.22977 (6)	0.56598 (7)	0.0148 (3)
N3	0.30251 (9)	0.41756 (6)	0.53376 (7)	0.0147 (3)
N4	0.30528 (10)	0.46864 (6)	0.48989 (7)	0.0150 (3)
H1S	0.4408 (18)	0.5437 (13)	0.2557 (15)	0.072 (9)*
H101	0.4319 (12)	0.2399 (8)	0.6020 (10)	0.015 (5)*
H102	0.3583 (14)	0.4898 (9)	0.4837 (10)	0.020 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0186 (8)	0.0153 (8)	0.0170 (8)	0.0002 (6)	−0.0004 (6)	−0.0037 (7)
C1S	0.076 (2)	0.0272 (16)	0.0217 (15)	0.000	−0.0016 (16)	0.000
C2	0.0241 (9)	0.0159 (8)	0.0198 (9)	−0.0006 (7)	0.0017 (7)	0.0024 (7)
C3	0.0244 (9)	0.0216 (9)	0.0151 (8)	0.0059 (7)	−0.0016 (7)	0.0026 (7)
C4	0.0162 (8)	0.0218 (9)	0.0191 (9)	0.0021 (7)	−0.0022 (6)	−0.0022 (7)
C5	0.0179 (8)	0.0144 (8)	0.0176 (8)	0.0015 (6)	0.0018 (6)	−0.0011 (6)
C6	0.0174 (8)	0.0122 (7)	0.0131 (8)	0.0028 (6)	0.0015 (6)	−0.0027 (6)
C7	0.0141 (7)	0.0141 (8)	0.0134 (8)	0.0022 (6)	0.0015 (6)	−0.0025 (6)
C8	0.0175 (8)	0.0142 (8)	0.0154 (8)	−0.0004 (6)	−0.0025 (6)	−0.0021 (6)
C9	0.0155 (7)	0.0123 (7)	0.0149 (8)	0.0014 (6)	0.0028 (6)	−0.0026 (6)
C10	0.0199 (8)	0.0126 (8)	0.0123 (8)	0.0021 (6)	−0.0002 (6)	−0.0032 (6)
C11	0.0192 (8)	0.0160 (8)	0.0180 (8)	−0.0005 (6)	−0.0028 (7)	−0.0031 (7)
C12	0.0264 (9)	0.0148 (8)	0.0205 (9)	−0.0042 (7)	0.0013 (7)	−0.0015 (7)
C13	0.0339 (10)	0.0140 (8)	0.0168 (8)	0.0039 (7)	−0.0005 (7)	0.0014 (7)
C14	0.0229 (9)	0.0231 (9)	0.0163 (8)	0.0078 (7)	−0.0025 (7)	0.0001 (7)
C15	0.0181 (8)	0.0177 (8)	0.0153 (8)	0.0008 (6)	0.0011 (6)	−0.0026 (7)
C16	0.0178 (8)	0.0188 (8)	0.0201 (9)	0.0012 (6)	0.0012 (7)	−0.0036 (7)
C17	0.0242 (9)	0.0205 (9)	0.0196 (9)	−0.0029 (7)	0.0024 (7)	0.0003 (7)
C18	0.0302 (10)	0.0175 (8)	0.0216 (9)	0.0023 (7)	−0.0025 (7)	0.0008 (7)
C19	0.0217 (9)	0.0198 (9)	0.0261 (10)	0.0044 (7)	−0.0035 (7)	−0.0021 (7)
C20	0.0184 (8)	0.0165 (8)	0.0203 (9)	−0.0017 (6)	0.0012 (7)	−0.0024 (7)
C21	0.0191 (8)	0.0129 (8)	0.0159 (8)	−0.0006 (6)	−0.0004 (6)	−0.0039 (6)
C22	0.0162 (8)	0.0140 (8)	0.0165 (8)	0.0015 (6)	−0.0003 (6)	−0.0044 (6)
C23	0.0137 (7)	0.0173 (8)	0.0176 (8)	−0.0004 (6)	0.0006 (6)	−0.0036 (7)
C24	0.0154 (8)	0.0145 (8)	0.0146 (8)	−0.0015 (6)	0.0013 (6)	−0.0037 (6)
C25	0.0152 (7)	0.0138 (8)	0.0169 (8)	0.0006 (6)	0.0051 (6)	−0.0021 (6)
C26	0.0172 (8)	0.0185 (8)	0.0196 (9)	0.0008 (7)	−0.0006 (7)	−0.0011 (7)
C27	0.0220 (9)	0.0191 (9)	0.0293 (10)	−0.0049 (7)	0.0026 (7)	−0.0025 (7)
C28	0.0299 (10)	0.0171 (8)	0.0282 (10)	−0.0002 (7)	0.0085 (8)	0.0042 (7)
C29	0.0243 (9)	0.0250 (9)	0.0187 (9)	0.0043 (7)	0.0028 (7)	0.0021 (7)
C30	0.0176 (8)	0.0220 (9)	0.0181 (9)	−0.0008 (7)	0.0017 (7)	−0.0028 (7)
Cl1	0.0230 (2)	0.0197 (2)	0.0172 (2)	−0.00119 (16)	−0.00586 (16)	−0.00122 (16)
Cl1S	0.0284 (2)	0.0312 (2)	0.0317 (3)	−0.00108 (19)	−0.00016 (19)	0.0107 (2)
Cl2	0.01646 (19)	0.01701 (19)	0.0216 (2)	−0.00379 (15)	0.00254 (15)	−0.00040 (16)
Co1	0.01353 (11)	0.01202 (11)	0.01510 (12)	−0.00101 (8)	−0.00092 (8)	−0.00044 (8)
N1	0.0163 (7)	0.0126 (6)	0.0143 (7)	0.0001 (5)	−0.0004 (5)	−0.0001 (5)
N2	0.0174 (7)	0.0135 (7)	0.0133 (7)	0.0000 (5)	−0.0033 (6)	0.0003 (5)
N3	0.0161 (7)	0.0121 (6)	0.0160 (7)	−0.0017 (5)	0.0012 (5)	−0.0006 (5)
N4	0.0137 (7)	0.0121 (7)	0.0191 (7)	−0.0021 (5)	0.0011 (5)	−0.0001 (5)

Geometric parameters (Å, º)

C1—C2	1.388 (2)	C17—C18	1.393 (2)
C1—C6	1.401 (2)	C17—H17	0.9500
C1—H1	0.9500	C18—C19	1.385 (3)
C1S—Cl1S	1.7671 (17)	C18—H18	0.9500
C1S—Cl1S^i	1.7671 (17)	C19—C20	1.389 (2)
C1S—H1S	0.97 (2)	C19—H19	0.9500
C2—C3	1.393 (2)	C20—C21	1.400 (2)
C2—H2	0.9500	C20—H20	0.9500
C3—C4	1.391 (2)	C21—C22	1.467 (2)
C3—H3	0.9500	C22—N4	1.353 (2)
C4—C5	1.390 (2)	C22—C23	1.387 (2)
C4—H4	0.9500	C23—C24	1.397 (2)
C5—C6	1.402 (2)	C23—H23	0.9500
C5—H5	0.9500	C24—N3	1.354 (2)
C6—C7	1.473 (2)	C24—C25	1.475 (2)
C7—N1	1.352 (2)	C25—C30	1.396 (2)
C7—C8	1.406 (2)	C25—C26	1.397 (2)
C8—C9	1.377 (2)	C26—C27	1.387 (2)
C8—H8	0.9500	C26—H26	0.9500
C9—N2	1.350 (2)	C27—C28	1.385 (3)
C9—C10	1.469 (2)	C27—H27	0.9500
C10—C15	1.398 (2)	C28—C29	1.388 (3)
C10—C11	1.400 (2)	C28—H28	0.9500
C11—C12	1.389 (2)	C29—C30	1.391 (2)
C11—H11	0.9500	C29—H29	0.9500
C12—C13	1.390 (2)	C30—H30	0.9500
C12—H12	0.9500	Cl1—Co1	2.2530 (5)
C13—C14	1.391 (3)	Cl2—Co1	2.2446 (4)
C13—H13	0.9500	Co1—N3	2.0253 (13)
C14—C15	1.389 (2)	Co1—N1	2.0422 (13)
C14—H14	0.9500	N1—N2	1.3626 (18)
C15—H15	0.9500	N2—H101	0.846 (18)
C16—C17	1.390 (2)	N3—N4	1.3629 (18)
C16—C21	1.401 (2)	N4—H102	0.863 (19)
C16—H16	0.9500
C2—C1—C6	120.35 (15)	C17—C18—H18	119.9
C2—C1—H1	119.8	C18—C19—C20	119.97 (16)
C6—C1—H1	119.8	C18—C19—H19	120.0
Cl1S—C1S—Cl1S^i	112.68 (17)	C20—C19—H19	120.0
Cl1S—C1S—H1S	107.2 (17)	C19—C20—C21	120.52 (16)
Cl1S^i—C1S—H1S	107.1 (17)	C19—C20—H20	119.7
C1—C2—C3	120.53 (15)	C21—C20—H20	119.7
C1—C2—H2	119.7	C20—C21—C16	119.16 (15)
C3—C2—H2	119.7	C20—C21—C22	118.76 (15)
C4—C3—C2	119.56 (15)	C16—C21—C22	122.07 (14)
C4—C3—H3	120.2	N4—C22—C23	106.28 (14)
C2—C3—H3	120.2	N4—C22—C21	123.61 (14)
C5—C4—C3	120.15 (15)	C23—C22—C21	130.10 (15)
C5—C4—H4	119.9	C22—C23—C24	106.44 (14)
C3—C4—H4	119.9	C22—C23—H23	126.8
C4—C5—C6	120.69 (15)	C24—C23—H23	126.8
C4—C5—H5	119.7	N3—C24—C23	109.90 (14)
C6—C5—H5	119.7	N3—C24—C25	121.17 (14)
C1—C6—C5	118.69 (14)	C23—C24—C25	128.90 (14)
C1—C6—C7	122.44 (14)	C30—C25—C26	118.90 (15)
C5—C6—C7	118.84 (14)	C30—C25—C24	120.80 (14)
N1—C7—C8	109.67 (14)	C26—C25—C24	120.28 (15)
N1—C7—C6	123.16 (14)	C27—C26—C25	120.41 (16)
C8—C7—C6	127.16 (14)	C27—C26—H26	119.8
C9—C8—C7	106.35 (14)	C25—C26—H26	119.8
C9—C8—H8	126.8	C28—C27—C26	120.29 (16)
C7—C8—H8	126.8	C28—C27—H27	119.9
N2—C9—C8	106.57 (14)	C26—C27—H27	119.9
N2—C9—C10	121.64 (14)	C27—C28—C29	119.87 (16)
C8—C9—C10	131.75 (14)	C27—C28—H28	120.1
C15—C10—C11	119.52 (15)	C29—C28—H28	120.1
C15—C10—C9	120.23 (14)	C28—C29—C30	120.05 (16)
C11—C10—C9	120.24 (14)	C28—C29—H29	120.0
C12—C11—C10	119.88 (15)	C30—C29—H29	120.0
C12—C11—H11	120.1	C29—C30—C25	120.42 (16)
C10—C11—H11	120.1	C29—C30—H30	119.8
C11—C12—C13	120.35 (16)	C25—C30—H30	119.8
C11—C12—H12	119.8	N3—Co1—N1	101.08 (5)
C13—C12—H12	119.8	N3—Co1—Cl2	105.60 (4)
C12—C13—C14	120.00 (15)	N1—Co1—Cl2	116.98 (4)
C12—C13—H13	120.0	N3—Co1—Cl1	123.64 (4)
C14—C13—H13	120.0	N1—Co1—Cl1	99.89 (4)
C15—C14—C13	120.05 (16)	Cl2—Co1—Cl1	110.008 (17)
C15—C14—H14	120.0	C7—N1—N2	105.38 (12)
C13—C14—H14	120.0	C7—N1—Co1	137.26 (11)
C14—C15—C10	120.21 (15)	N2—N1—Co1	114.22 (10)
C14—C15—H15	119.9	C9—N2—N1	111.99 (13)
C10—C15—H15	119.9	C9—N2—H101	128.5 (12)
C17—C16—C21	120.02 (15)	N1—N2—H101	117.6 (12)
C17—C16—H16	120.0	C24—N3—N4	105.41 (13)
C21—C16—H16	120.0	C24—N3—Co1	129.83 (11)
C16—C17—C18	120.20 (16)	N4—N3—Co1	119.32 (10)
C16—C17—H17	119.9	C22—N4—N3	111.97 (13)
C18—C17—H17	119.9	C22—N4—H102	127.2 (12)
C19—C18—C17	120.13 (16)	N3—N4—H102	120.7 (12)
C19—C18—H18	119.9

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H102···Cl2^ii	0.86 (2)	2.53 (2)	3.292 (1)	148 (2)

Symmetry code: (ii) −x+1, −y+1, −z+1.