Di­chloro­tetra­kis[3-(4-pyrid­yl)-1H-pyrazole]cobalt(II) aceto­nitrile tetra­solvate: an infinite hydrogen-bonded network, in an instant

Reaction of 3-(4-pyrid­yl)pyrazole (4pypz) with cobalt(II) chloride in acetonitrile affords the title complex, [CoCl₂(C₈H₇N₃)₄]·4CH₃CN, within seconds of addition, as purple X-ray quality crystals. The mol­ecule has C4 symmetry. The metal ion exhibits a trans-N₄Cl₂ octa­hedral geometry, with the four 3-(4-pyrid­yl)-1H-pyrazole ligands coordinating through their pyridyl N-atom donors; one coordinated chloride ion forms hydrogen bonds with the pyrazole rings from four separate units. This configuration creates an infinite three-dimensional coordination network containing channels that are filled with acetonitrile solvent mol­ecules.

Comment

We have extensively studied the structural and photophysical properties of metal complexes with the scorpionate ligand hydro­tris[3-(2-pyrid­yl)pyrazol-1-yl]borate (Tp^2py) (Davies, Adams, Pope et al., 2005; Davies, Adams & Ward, 2005; Davies et al., 2004; Beeby et al., 2002; Ward et al., 2001; Jones, Amoroso et al., 1997; Amoroso et al., 1994). The potentially tridentate ligand 3-(2-pyrid­yl)pyrazole (2pypz), a precursor to (Tp^2py), has also proven to be of inter­est, with a range of coordination modes being displayed depending on whether the pyrazole unit is neutral or deprotonated (Ward, Fleming et al., 1998; Ward, Mann et al., 1998; Jones, Jeffery et al., 1997). Accordingly, we have prepared the isomeric ligand 3-(4-pyrid­yl)pyrazole (4pypz) (Adams et al., 2005), which can no longer act as a chelate but in principle can act as a bridging ligand whose coordination mode will again depend on whether the pyrazole unit is deprotonated.

Linear bridging ligands commonly give rise to infinite coordination polymers (Fujita et al., 1996; Choudhury et al., 2002; Zheng et al., 2005; Subramanian & Zaworotko, 1995); `bent' bridging ligands, arising here from the combination of six- and five-membered rings, are less explored. As a result, we decided to explore the coordination chemistry of the 4pypz ligand. In this paper, we describe the synthesis and structure of the title complex, [CoCl₂(4pypz)₄]·4MeCN, (I), a new hydrogen-bonded coordination network based on 4pypz, in which the 4pypz ligand combines a metal coordination site and a hydrogen-bond donor site. Mulyana et al. (2005) recently described complexes of the isomeric ligand 4-(4-pyrid­yl)­pyrazole, in which the ligand could be either cationic (proton­ated) and monodentate or anionic (deprotonated) and tridentate; in the former case, the network structure is propagated by hydrogen bonding between mononuclear units, whereas in the latter case, the ligand coordinates to three metal ions, resulting in a genuine coordination network.

Reaction of 4pypz with anyhdrous cobalt(II) chloride in acetonitrile afforded a blue solution from which, a few seconds after addition, purple X-ray quality crystals of complex (I) began to appear. In contrast to the behaviour displayed by 4-(4-pyrid­yl)pyrazole (Mulyana et al., 2005), 3-(4-pyrid­yl)­pyrazole remains neutral upon coordination. The cobalt(II) centre retains both chloride ions in a trans arrangement and coordinates to the pyridyl termini of four separate 4pypz ligands around the equatorial plane (Fig. 1), giving a trans-N₄Cl₂ pseudo-octa­hedral coordination geometry. Only one 4pypz arm is located in the asymmetric unit, the Cl—Co—Cl axis (parallel to the c axis) being a fourfold rotation axis such that the Co and Cl atoms have 25% occupancy in the asymmetric unit. The Co1—N1 bond length of 2.1648 (12) Å is typical of pyrid­yl–cobalt(II) coordination (Long & Clarke, 1978). One Co—Cl bond is significantly longer than the other, viz. Co1—Cl1 = 2.5775 (11) Å and Co1—Cl2 = 2.3962 (12) Å.

In relation to the mean plane of the four pyridyl N atoms (N_py), the pyridyl and pyrazole rings are twisted by 46.3 and 26.6°, respectively, and by 20.0° with respect to each other. Pyrrolic N10 atoms form the vertices of a perfect square parallel to the ab plane, with a side length of 11.935 Å and rotated by 7° about the c axis with respect to the square face of the unit cell. The mean plane of the four N10 donors lies 0.27 Å below that of the four pyridyl donors because of the twist between the pyridyl and pyrazolyl rings.

Each pyrrolic H atom, H10, is hydrogen bonded to one of the chloride ions of a separate [CoCl₂(4pypz)] unit [N10⋯Cl1 = 3.260 (2) Å, H10⋯Cl1 = 2.41 Å and N10—H10⋯Cl1 = 164°]; there is a square array of four such hydrogen bonds to each Cl1 atom (Fig. 2), generating a hydrogen-bonded sheet of complex mol­ecules in the ab plane. Each Cl1 atom is therefore in a `square-pyramidal' coordination environment, with four equivalent N—H⋯Cl hydrogen bonds in the basal plane and an axial dative bond to atom Co1. Owing to the orientation of the pyrazole rings, the network of hydrogen bonds also extends down the c axis, giving an overall three-dimensional coordination network. Hydrogen-bonding inter­actions between NH donors and Cl acceptors have been studied extensively as a tool for crystal engineering (Brammer et al., 2002; Angeloni & Orpen, 2001; Angeloni et al., 2004).

In addition, the network contains square channels with a cross-section area of 71 Ų, whose perimeters are defined by the ligands. These channels contain four columns of aceto­nitrile solvent mol­ecules, each of which inter­acts weakly via a C—H⋯N hydrogen bond between atom H8 of a pyrazole ring and atom N22 of the acetonitrile mol­ecule (H8⋯N22 = 2.61 Å). These solvent mol­ecules are easily lost from the lattice on drying, as shown by loss of weight on drying and elemental analysis of the dried material.

Finally, we note that the Flack (1983) parameter for this chiral crystal is indicative of racemic twinning.

Figure 1 A view of [CoCl2(4pypz)4]·4MeCN; displacement ellipsoids are shown at the 40% probability level. [Symmetry codes: (A) 1-x, 1-y, -z; (B) 1-y, x, z; (C) y, 1-x, z.]

Figure 2 A view down the c axis, showing the arrangement of four N—H⋯Cl hydrogen bonds (dashed lines) to atom Cl1 at the centre of the figure. The four ligands coordinated to atom Co1 (obscured beneath Cl1) are shown with solid bonds; the four ligands with hollow bonds are coordinated via their pyridyl N-atom donors to separate metal atoms but act as hydrogen-bond donors to the central complex mol­ecule (see Comment).

Experimental

3-(4-Pyrid­yl)-1H-pyrazole was prepared according to the published method of Davies et al. (2003) and a solution (100 mg, 0.69 mmol) in MeCN (10 ml) was added to a solution of anhydrous CoCl₂ (22.4 mg, 0.17 mmol) in MeCN (10 ml); the resulting solution was stirred once and filtered through celite. Upon being left to stand for a few moments, purple X-ray quality crystals began to precipitate out of the blue solution. After the mixture had been left to stand for a few hours, the purple crystals were filtered off and dried, giving opaque pink crystals of [CoCl₂(4pypz)₄]·4MeCN in 30% yield. Analysis found: C 53.4, H 4.2, N 23.4%; calculated for C₃₂H₂₈Cl₂CoN₁₂·4MeCN: C 53.4, H 4.1, N 23.4%. IR (cm⁻¹): 3287 (m), 1614 (s), 1556 (w), 1496 (w), 1456 (m), 1424 (m), 1356 (w), 1290 (w), 1216 (m), 1178 (m), 1122 (w), 1079 (w), 1039 (m), 1014 (m), 947 (m), 843 (s), 758 (s), 740 (s), 701 (s), 663 (w), 622 (m). A crystal for X-ray diffraction analysis was removed directly from the mother liquor, coated in engine oil to clean it of subsidiary grains, and quickly (to prevent loss of MeCN) mounted in a stream of cold N₂ (150 K) on the diffractometer for subsequent analysis.

Crystal data

• [CoCl₂(C₈H₇N₃)₄]·4C₂H₃N

• M_r = 874.71

• Tetragonal, I 4

• a = 15.649 (2) Å

• c = 8.653 (2) Å

• V = 2119.0 (6) ų

• Z = 2

• D_x = 1.371 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 1005 reflections

• θ = 5.4–53.8°

• μ = 0.58 mm⁻¹

• T = 150 (2) K

• Block, purple

• 0.31 × 0.31 × 0.19 mm

Data collection

• Bruker SMART 1000 diffractometer

• ω scans

• Absorption correction: multi-scan(SADABS; Sheldrick, 1996)T_min = 0.840, T_max = 0.898

• 11871 measured reflections

• 2407 independent reflections

• 2197 reflections with I > 2σ(I)

• R_int = 0.032

• θ_max = 27.5°

• h = −20 → 19

• k = −20 → 20

• l = −11 → 11

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.029

• wR(F²) = 0.069

• S = 0.97

• 2407 reflections

• 138 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0477P)² + 0.1612P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max = 0.001

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

• Absolute structure: Flack (1983), 1094 Friedel pairs

• Flack parameter: 0.418 (14)

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

S1. Comment

We have extensively studied the structural and photophysical properties of metal complexes with the scorpionate ligand hydrotris[3-(2-pyridyl)pyrazol-1-yl]borate (Tp^2py) (Davies, Adams, Pope et al., 2005; Davies, Adams & Ward, 2005; Davies et al., 2004; Beeby et al., 2002; Ward et al., 2001; Jones, Amoroso et al., 1997; Amoroso et al., 1994). The potentially tridentate ligand 3-(2-pyridyl)pyrazole (2pypz), a precursor to (Tp^2py), has also proven to be of interest with a range of coordination modes being displayed depending on whether the pyrazole unit is neutral or deprotonated (Ward, Fleming et al., 1998; Ward, Mann et al., 1998; Jones, Jeffery et al., 1997). Accordingly, we have prepared the isomeric ligand 3-(4-pyridyl)pyrazole (4pypz) (Adams et al., 2005), which can no longer act as a chelate but in principle can act as a bridging ligand whose coordination mode will again depend on whether the pyrazole is deprotonated.

Linear bridging ligands commonly give rise to infinite coordination polymers (Fujita et al., 1996; Choudhury et al., 2002; Zheng et al., 2005; Subramanian & Zaworotko, 1995); `bent' bridging ligands, arising here from the combination of six- and five-membered rings, are less explored. As a result, we decided to explore the coordination chemistry of the 4pypz ligand. In this paper, we describe the synthesis and structure of the title complex, [Co(4pypz)₄Cl₂]·4(MeCN), (I), a new hydrogen-bonded coordination network based on 4pypz, in which the ligand 4pypz combines a metal coordination site and a hydrogen- bond donor site. Mulyana et al. (2005) recently described complexes of the isomeric ligand 4-(4-pyridyl)pyrazole, in which the ligand could be either cationic (protonated) and monodentate, or anionic (deprotonated) and tridentate; in the former case, the network structure is propagated by hydrogen bonding between mononuclear units, whereas in the latter case, the ligand coordinates to three metal ions, resulting in a genuine coordination network.

Reaction of 4pypz with anyhdrous cobalt(II) chloride in acetonitrile afforded a blue solution from which, a few s after addition, purple X-ray quality crystals of complex (I) began to appear. In contrast to the behaviour displayed by 4-(4-pyridyl)pyrazole (Mulyana et al., 2005), our ligand 3-(4-pyridyl)pyrazole remains neutral upon coordination. The cobalt(II) centre retains both chloride ions in a trans arrangement and coordinates to the pyridyl termini of four separate 4pypz ligands around the equatorial plane (Fig. 1), giving a trans-N₄Cl₂ pseudo-octahedral coordination geometry. Only one 4pypz arm is located in the asymmetric unit, with the Cl—Co—Cl axis (parallel to the c axis) being a fourfold rotation axis such that the Co and Cl atoms have 25% occupancy in the asymmetric unit. The Co1—N1 bond length of 2.1648 (12) Å is typical of pyridyl–Co^II coordination (Long & Clarke, 1978). One Co—Cl bond is significantly longer than the other [Co1—Cl1 = 2.5775 (11) Å and Co1—Cl2 = 2.3962 (12) Å].

In relation to the mean plane of the four pyridyl N atoms (N_py), the pyridyl and pyrazole rings are twisted 46.3 and 26.6°, respectively, and 20.0° with respect to each other. Pyrrolic atoms N10 form the vertices of a perfect square parallel to the ab plane, with a side length of 11.935 Å and rotated by 7° about the c axis with respect to the square face of the unit cell. The mean plane of the four N10 donors lies 0.27 Å below that of the four pyridyl donors because of the twist between the pyridyl and pyrazolyl rings.

Each pyrrolic H atom, H10, is hydrogen bonded to one of the chloride ions of a separate [Co(4pypz)Cl₂] unit [N10···Cl1 = 3.260 (2) Å, H10···Cl1 = 2.41 Å and N10—H10···Cl1 = 164°]; there is a square array of four such hydrogen bonds to each Cl1 atom (Fig. 2), generating a hydrogen-bonded sheet of complex molecules in the ab plane. Each Cl1 atom is therefore in a `square pyramidal' coordination environment, with four equivalent N—H···Cl hydrogen bonds in the basal plane and an axial dative bond to atom Co1. Owing to the orientation of the pyrazole rings, the network of hydrogen bonds also extends down the c axis, giving an overall three-dimensional coordination network. Hydrogen-bonding interactions between NH donors and Cl acceptors have been extensively studied as a tool for crystal engineering (Brammer et al., 2002; Angeloni & Orpen, 2001; Angeloni et al., 2004).

In addition, the network contains square channels with a cross section area of 71 Ų, whose perimeters are defined by the ligands. These channels contain four columns of acetonitrile solvent molecules (Fig. 2), each of which interacts weakly via a C—H···N hydrogen bond between atom H8 of a pyrazole ring and atom N22 of the acetonitrile (H8···N22 = 2.61 Å). These solvent molecules are easily lost from the lattice on drying, as shown by loss of weight on drying and elemental analysis of the dried material.

Finally, we note that the Flack parameter for this chiral crystal [0.42 (1)] is indicative of racemic twinning.

S2. Experimental

3-(4-Pyridyl)pyrazole was prepared according to the published method (Davies et al., 2003). 3-(4-Pyridyl)pyrazole (100 mg, 0.69 mmol) in MeCN (10 ml) was added to a solution of anhydrous CoCl₂ (22.4 mg, 0.17 mmol) in MeCN (10 ml); the solution was stirred once and filtered through celite. Upon being left to stand for a few moments, purple X-ray quality crystals began to precipitate out of the blue solution. After the mixture had been left to stand for a few hours, the purple crystals were filtered off from the filtrate and dried, to give opaque pink crystals of [Co(4pypz)₄Cl₂]·0.5H₂O in 30% yield. Found: C 53.4, H 4.2, N 23.4%; calculated for C₃₂H₂₈N₁₂CoCl₂·0.5H₂O: C 53.4, H 4.1, N 23.4%. IR (cm⁻¹): 3287 (m), 1614 (s), 1556 (w), 1496 (w), 1456 (m), 1424 (m), 1356 (w), 1290 (w), 1216 (m), 1178 (m), 1122 (w), 1079 (w), 1039 (m), 1014 (m), 947 (m), 843 (s), 758 (s), 740 (s), 701 (s), 663 (w), 622 (m). A crystal for X-ray diffraction analysis was removed directly from the mother liquor, coated in engine oil to clean it of subsidiary grains, and quickly (to prevent loss of MeCN) mounted in a stream of cold N₂ (150 K) on the diffractometer for subsequent analysis.

S3. Refinement

(type here to add refinement details)

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of [Co(4pypz)4Cl2]·4MeCN; displacement ellipsoids are shown at the 40% probability level.

Fig. 2. A view down the c axis, showing the arrangement of four N—H···Cl hydrogen bonds (dashed lines) to atom Cl1 at the centre of the figure. The four ligands coordinated to atom Co1 [obscured beneath Cl1] are shown with solid bonds; the four ligands with hollow bonds are coordinated via their pyridyl donors to separate metal atoms, but act as hydrogen-bond donors to the central complex molecule (see main text).

Dichlorotetrakis[3-(4-pyridyl)-1H-pyrazole]cobalt(II) acetonitrile tetrasolvate

Crystal data

[CoCl2(C8H7N3)4]·4C2H3N	Dx = 1.371 Mg m^−3
Mr = 874.71	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1005 reflections
a = 15.649 (2) Å	θ = 5.4–53.8°
c = 8.653 (2) Å	µ = 0.58 mm^−1
V = 2119.0 (6) Å^3	T = 150 K
Z = 2	Block, purple
F(000) = 906	0.31 × 0.31 × 0.19 mm

Data collection

Bruker smart 1000 diffractometer	2407 independent reflections
Radiation source: fine-focus sealed tube	2197 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 100 pixels mm^-1	θmax = 27.5°, θmin = 1.8°
ω scans	h = −20→19
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −20→20
Tmin = 0.840, Tmax = 0.898	l = −11→11
11871 measured reflections

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)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0477P)^2 + 0.1612P] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
2407 reflections	Δρmax = 0.27 e Å^−3
138 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1094 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.418 (14)

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	0.5000	0.5000	0.60360 (5)	0.01697 (11)
Cl1	0.5000	0.5000	0.30573 (9)	0.01661 (18)
Cl2	0.5000	0.5000	0.88052 (10)	0.0226 (2)
N1	0.61477 (8)	0.57695 (8)	0.5918 (2)	0.0199 (3)
C2	0.67856 (11)	0.56009 (11)	0.4937 (2)	0.0218 (4)
H2	0.6727	0.5126	0.4261	0.026*
C3	0.75269 (11)	0.60825 (11)	0.4852 (2)	0.0214 (4)
H3	0.7965	0.5934	0.4141	0.026*
C4	0.76236 (10)	0.67881 (10)	0.5821 (2)	0.0203 (3)
C5	0.69552 (12)	0.69721 (11)	0.6832 (2)	0.0240 (4)
H5	0.6988	0.7453	0.7498	0.029*
C6	0.62435 (11)	0.64488 (11)	0.6856 (2)	0.0232 (4)
H6	0.5800	0.6575	0.7571	0.028*
C7	0.84086 (10)	0.73069 (10)	0.5793 (2)	0.0211 (3)
C8	0.92180 (12)	0.70787 (13)	0.5244 (2)	0.0299 (4)
H8	0.9379	0.6558	0.4761	0.036*
C9	0.97277 (12)	0.77667 (13)	0.5554 (2)	0.0321 (5)
H9	1.0319	0.7821	0.5329	0.039*
N10	0.92289 (10)	0.83472 (9)	0.6236 (2)	0.0341 (4)
H10	0.9415	0.8849	0.6544	0.041*
N11	0.84134 (10)	0.80904 (10)	0.6406 (2)	0.0328 (4)
C20	0.89595 (19)	0.63238 (18)	−0.0833 (3)	0.0521 (7)
H20A	0.8347	0.6229	−0.0998	0.078*
H20B	0.9288	0.5967	−0.1550	0.078*
H20C	0.9094	0.6927	−0.1017	0.078*
C21	0.91795 (15)	0.61014 (13)	0.0738 (3)	0.0404 (5)
N22	0.93422 (16)	0.59211 (15)	0.1974 (3)	0.0588 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01450 (13)	0.01450 (13)	0.0219 (2)	0.000	0.000	0.000
Cl1	0.0146 (3)	0.0146 (3)	0.0207 (4)	0.000	0.000	0.000
Cl2	0.0232 (3)	0.0232 (3)	0.0213 (4)	0.000	0.000	0.000
N1	0.0178 (6)	0.0192 (6)	0.0228 (7)	−0.0001 (5)	0.0000 (7)	−0.0009 (7)
C2	0.0192 (8)	0.0207 (8)	0.0254 (9)	−0.0006 (6)	−0.0016 (7)	−0.0051 (7)
C3	0.0182 (8)	0.0219 (8)	0.0241 (9)	−0.0008 (6)	0.0015 (6)	−0.0045 (7)
C4	0.0197 (7)	0.0182 (7)	0.0228 (9)	−0.0015 (6)	−0.0024 (7)	0.0030 (7)
C5	0.0265 (9)	0.0193 (8)	0.0261 (8)	−0.0019 (7)	−0.0015 (8)	−0.0064 (7)
C6	0.0226 (9)	0.0232 (9)	0.0239 (8)	−0.0003 (7)	0.0021 (7)	−0.0044 (7)
C7	0.0221 (7)	0.0195 (7)	0.0216 (9)	−0.0027 (6)	−0.0047 (8)	0.0010 (7)
C8	0.0223 (9)	0.0274 (10)	0.0401 (11)	−0.0031 (7)	0.0002 (8)	−0.0058 (8)
C9	0.0226 (9)	0.0312 (10)	0.0425 (14)	−0.0067 (8)	−0.0021 (8)	−0.0009 (8)
N10	0.0280 (8)	0.0215 (7)	0.0527 (12)	−0.0101 (6)	−0.0063 (9)	−0.0044 (8)
N11	0.0251 (8)	0.0248 (8)	0.0485 (12)	−0.0050 (6)	−0.0033 (7)	−0.0044 (7)
C20	0.0626 (18)	0.0510 (16)	0.0426 (14)	−0.0094 (13)	−0.0086 (12)	0.0044 (10)
C21	0.0440 (12)	0.0339 (11)	0.0433 (15)	0.0007 (8)	−0.0036 (11)	−0.0074 (10)
N22	0.0786 (17)	0.0534 (14)	0.0444 (13)	0.0072 (12)	−0.0138 (12)	−0.0053 (11)

Geometric parameters (Å, º)

Co1—N1^i	2.1648 (12)	C5—H5	0.9500
Co1—N1	2.1648 (13)	C6—H6	0.9500
Co1—N1^ii	2.1648 (12)	C7—N11	1.336 (2)
Co1—N1^iii	2.1648 (12)	C7—C8	1.399 (3)
Co1—Cl2	2.3962 (12)	C8—C9	1.366 (3)
Co1—Cl1	2.5775 (11)	C8—H8	0.9500
N1—C2	1.337 (2)	C9—N10	1.335 (3)
N1—C6	1.346 (2)	C9—H9	0.9500
C2—C3	1.385 (2)	N10—N11	1.346 (2)
C2—H2	0.9500	N10—H10	0.8800
C3—C4	1.395 (2)	C20—C21	1.446 (4)
C3—H3	0.9500	C20—H20A	0.9800
C4—C5	1.393 (3)	C20—H20B	0.9800
C4—C7	1.473 (2)	C20—H20C	0.9800
C5—C6	1.383 (3)	C21—N22	1.135 (3)
N1^i—Co1—N1	174.61 (10)	C6—C5—C4	119.47 (16)
N1^i—Co1—N1^ii	89.873 (5)	C6—C5—H5	120.3
N1—Co1—N1^ii	89.873 (5)	C4—C5—H5	120.3
N1^i—Co1—N1^iii	89.873 (5)	N1—C6—C5	123.25 (16)
N1—Co1—N1^iii	89.873 (5)	N1—C6—H6	118.4
N1^ii—Co1—N1^iii	174.61 (10)	C5—C6—H6	118.4
N1^i—Co1—Cl2	92.69 (5)	N11—C7—C8	111.34 (15)
N1—Co1—Cl2	92.69 (5)	N11—C7—C4	120.27 (15)
N1^ii—Co1—Cl2	92.69 (5)	C8—C7—C4	128.33 (15)
N1^iii—Co1—Cl2	92.69 (5)	C9—C8—C7	105.12 (17)
N1^i—Co1—Cl1	87.31 (5)	C9—C8—H8	127.4
N1—Co1—Cl1	87.31 (5)	C7—C8—H8	127.4
N1^ii—Co1—Cl1	87.31 (5)	N10—C9—C8	106.35 (17)
N1^iii—Co1—Cl1	87.31 (5)	N10—C9—H9	126.8
Cl2—Co1—Cl1	180.0	C8—C9—H9	126.8
C2—N1—C6	117.12 (14)	C9—N10—N11	113.54 (15)
C2—N1—Co1	122.65 (11)	C9—N10—H10	123.2
C6—N1—Co1	120.23 (12)	N11—N10—H10	123.2
N1—C2—C3	123.46 (15)	C7—N11—N10	103.65 (15)
N1—C2—H2	118.3	C21—C20—H20A	109.5
C3—C2—H2	118.3	C21—C20—H20B	109.5
C2—C3—C4	119.34 (15)	H20A—C20—H20B	109.5
C2—C3—H3	120.3	C21—C20—H20C	109.5
C4—C3—H3	120.3	H20A—C20—H20C	109.5
C3—C4—C5	117.35 (15)	H20B—C20—H20C	109.5
C3—C4—C7	121.12 (16)	N22—C21—C20	179.1 (3)
C5—C4—C7	121.52 (16)

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