Transformations of the chameleon ligand 1,10-phenanthroline-5,6-dione/diol: cis-dichlorido(1,10-phenanthroline-5,6-dione-[kappa]²N,N')-trans-dipyridine­cobalt(II) pyridine disolvate prepared from the diol

The title compound, [CoCl₂(C₅H₅N)₂(C₁₂H₆N₂O₂)]·2C₅H₅N, is a neutral Co^II complex with two chloride anions coordinated in a cis fashion, two pyridine ligands in trans positions and a chelating 1,10-phenanthroline-5,6-dione ligand that completes the octa­hedral coordination geometry. Two pyridine solvent mol­ecules reside in channels (about 7 × 4 Å wide; the closest atom-atom distance within the channel is 10 Å). The three-dimensional structure supporting these channels is held together by C-H...Cl [3.466 (8)-3.670 (9) Å] and C-H...O [3.014 (9)-3.285 (8) Å] hydrogen bonds, and can be viewed as a CsCl or bcu (body-centred cubic) net.

S1. Comment

The N,N'-1,10-phenanthroline-5,6-dione ligand continues to be important for coordination chemistry (Calderazzo et al., 2002; Fujihara et al., 2003; Margiotta et al., 2004; Zhang et al., 2003), analytical chemistry (del Pozo et al., 2005; Gatti et al., 2004; Shabir & Forrow, 2003) and biophysical chemistry (Berger et al., 2004; Wu et al., 2002). The fate of complexes with this ligand in different solutions is therefore an important issue, and we recently showed how seemingly stable and innocent [please clarify what this means in this context] tris(phenanthroline-5,6-dione)–Co^III complexes could yield both Co^II complexes and phenanthroline-5,6-diole complexes over time (Larsson & Öhrström, 2004). This is not the only type of transformation that can occur (Fig. 1), and notably we also detected the complete transformation of the original complex to the bis-hydrated form (Lei & Anson, 1995; Lei et al., 1996) in an aqueous solution (see 1c in Fig. 1).

It is therefore prudent to double check any assignment of the (5,6)-carbon–carbon bond, and the carbon–oxygen bond, in either ones own X-ray structures or structures downloaded from the Cambridge Structural Database (CSD; Allen & Motherwell, 2002) or other sources. This is especially important for room-temperature data since subtle differences in bond lengths are all the evidence that there will be to detect the differences between the dione and the diol in the absence of an unambiguous location of the H atoms in the electron density map. In Fig. 2 are plotted the C—O distances against the C—C distances for diketone and diol fragments found in the CSD (Version 1.7) having different bond assignments. Clearly, the large majority of data are unambigous, but there are also a few cases that, based on these data alone, seem questionable. It can be noted that data in the small grouping at the centre of the graph correspond mainly to semi-quinone radical systems.

Here we report another example of an unexpected transformation, this time from the diol to the dione. The title compound, (I), was first obtained by reacting CoCl₂(s) with N,N'-1,10- phenanthroline-5,6-diole in pyridine. A subsequent preparation using CoCl₂(s) and N,N'-1,10-phenanthroline-5,6-dione in pyridine afforded compound (I) in good yield. The dione assignment was unambiguous [C6—O2 = 1.216 (7) Å, C5—O1 = 1.217 (7) Å and C5—C6 = 1.526 (8) Å]. The O1—C5—C6—O2 torsion angle of 3.406 (s.u.?)° supports this assignment. The slight deviation from planarity is not unusual and is due to asymmetric interactions with a neighbouring complex, the closest O···H interactions in this case being 2.4–2.6 Å [s.u.'s available?]; otherwise, the molecular structure is unremarkable (Fig. 3). All the Co—N and Co—Cl distances are as expected for a Co^II complex. A small deviation from linearity for the N1A—Co—N1B angle [173.58(s.u.?)°] can probably be traced to repulsion with the two chloride anions.

In contrast, the intermolecular interactions are worth a closer analysis. Despite the many aromatic molecules there are no obvious π–π interactions, but there is some indication of a σ–π interaction between the lone pairs on the N atoms and the electron-deficient part of the phenanthrolinedione ligand; the N···C distances vary between 2.65 and 2.94 Å [s.u.'s available?]. These interactions will, however, be weak, and consequently the non-classical hydrogen-bonds between ketones or coordinated chlorides and aromatic CH H atoms reported in Table 1 may dominate among the intermolecular forces. These interactions are in agreement with other, recently published, studies on MCl₂(L) complexes, where the C—H···Cl interactions were inferred to be as crucial for the resulting structure (Balamurugan et al., 2004; Xuan et al., 2003).

Consequently, taking the C—H···Cl and C—H···O interactions as defining the three-dimensional connectivity, it has a distorted CsCl-type net or, according to the nomenclature described by O'Keeffe & Yaghi (2005) and Öhrström & Larsson (2005), a bcu (body centred cubic) arrangement. A previous example of this type of net was found for the coordination polymer [La(2,2'-bipyridine-N,N'-dioxide)₄](CF₃SO₃)₃·4.2MeOH (Long et al., 2001). In the relatively spaceous channels thus formed, the pyridine molecules cocrystallize with the complex (Fig. 4). These solvent molecules occupy 38% of the unit-cell volume as calculated using PLATON (Spek, 2003).

From the average values of the principal mean-square atomic displacement U factors of the C atoms it can be deduced that the solvent pyridine molecules are more flexible than the coordinated pyridine ligands, as the mean U factors are larger by 40%. The low `solvent' U_eq for atom N5 may also indicate dissorder of the solvent pyridine molecules, but the introduction of further modeling does not seem meaningful.

In conclusion, although (I) cannot be claimed as being porous, or having other intersting properties associated with three- dimensional nets, this study underlines the utility of network analysis (Öhrström & Larsson, 2005) for the understanding of `small molecule' crystal structures.

Related literature

For related literature, see: Allen & Motherwell (2002); Balamurugan et al. (2004); Berger et al. (2004); Calderazzo et al. (2002); Fujihara et al. (2003); Gatti et al. (2004); Larsson & Öhrström (2004); Lei & Anson (1995); Lei et al. (1996); Long et al. (2001); Margiotta et al. (2004); O'Keeffe & Yaghi (2005); Pozo et al. (2005); Shabir & Forrow (2003); Spek (2003); Wu et al. (2002); Xuan et al. (2003); Yamada et al. (1992); Zhang et al. (2003); Öhrström & Larsson (2005).

S2. Experimental

N,N'-1,10-Phenanthroline-5,6-diole (Wu et al., 2002) was prepared from N,N'-1,10-phenanthroline-5,6-dione (Yamada et al., 1992). The later was prepared from N,N'-1,10-phenanthroline (Aldrich). Literature procedures were used in both cases, and the identity of the diol was confirmed by its physical characteristics (colour and solubility) as well as IR and NMR measurements. Compound (I) was first obtained by reacting CoCl₂(s) with N,N'-1,10- phenanthroline-5,6-diole in pyridine, and crystals suitable for X-ray analysis were selected directly from the product of this reaction. In a subsequent more controlled reaction, compound (I) was prepared by the reaction of CoCl₂·6H₂O (12 mg, 0.05 mmol) dissolved in pyridine (1.5 ml) and N,N'- 1,10-phenanthroline-5,6-dione (10 mg, 0.05 mmol) dissolved in pyridine (4.5 ml). The solutions were mixed at room temperature, giving a deep orange solution, and after 1 h, orange uniform cubic crystals started to appear. These were filtered off, and washed twice with pyridine (1.5 ml) and twice with dichloromethane (3 ml) (yield 21 mg, 69%). The identity of the crystals was confirmed by single-crystal X-ray diffraction.

S3. Refinement

Crystals of (I) are racemically twinned with a twin scale factor (Flack parameter) of 0.55</span><span style=" font-weight:600;">(3). H atoms were included in calculated positions and refined as riding atoms [C—H = 0.93 Å, with U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalMaker (CrystalMaker, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. Some possible transformations of the N,N'-1,10- phenanthroline-5,6-dione ligand.
	Fig. 2. C—O distances versus C—C distances for diketone and diol fragments found in the CSD having different bond assignments. X is any non-metal. In all runs of the CONQUEST software (Version 1.7; Bruno et al., 2002), the compounds were restricted to those having R values <10% and being error and disorder free; a total of 186 fragments were found.
	Fig. 3. The molecular structure of compound (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. A view of the network structure of compound (I), containing the pyridine solvent molecules. The nodes are Co atoms and the links are defined by C—H···Cl and C—H···O hydrogen bonds giving a bcu or CsCl-type net.

cis-dichlorido(1,10-phenanthroline-5,6-dione-κ²N,N')-trans- dipyridinecobalt(II) pyridine disolvate

Crystal data

[CoCl2(C5H5N)2(C12H6N2O2)]·2C5H5N	F(000) = 1348.0
Mr = 656.44	Dx = 1.417 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5614 reflections
a = 20.3809 (8) Å	θ = 2.0–26.7°
b = 9.5957 (3) Å	µ = 0.77 mm^−1
c = 15.7370 (6) Å	T = 293 K
V = 3077.67 (19) Å^3	Cube, dark orange
Z = 4	0.1 × 0.1 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.000
Graphite monochromator	θmax = 25°, θmin = 2.0°
ω/2θ scans	h = −24→24
4843 measured reflections	k = −11→11
4843 independent reflections	l = −16→16
3663 reflections with I > 2/s(I)

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)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 4.1274P] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.001
5614 reflections	Δρmax = 0.40 e Å^−3
389 parameters	Δρmin = −0.39 e Å^−3
1 restraint	Absolute structure: Flack (1983), 2112 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.56 (2)

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 > 2/s(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
Co	0.54522 (3)	0.68554 (6)	0.97138 (4)	0.02775 (17)
Cl1	0.55557 (7)	0.80833 (14)	1.10139 (8)	0.0390 (3)
Cl2	0.42987 (5)	0.63387 (13)	0.97290 (10)	0.0360 (3)
O1	0.8147 (2)	0.6117 (4)	0.7392 (3)	0.0499 (11)
O2	0.7218 (2)	0.4929 (4)	0.6367 (3)	0.0547 (12)
N1	0.64974 (19)	0.7098 (4)	0.9448 (2)	0.0296 (11)
N2	0.56013 (19)	0.5820 (4)	0.8478 (3)	0.0296 (10)
C1	0.6943 (3)	0.7735 (5)	0.9941 (3)	0.0354 (14)
H1	0.6804	0.8119	1.0453	0.042*
C2	0.7598 (2)	0.7850 (5)	0.9723 (5)	0.0372 (12)
H2	0.789	0.8303	1.0084	0.045*
C3	0.7812 (3)	0.7297 (6)	0.8981 (4)	0.0380 (14)
H3	0.8252	0.7353	0.8831	0.046*
C4	0.7362 (2)	0.6643 (5)	0.8445 (3)	0.0306 (12)
C5	0.7578 (3)	0.6068 (6)	0.7624 (4)	0.0380 (14)
C6	0.7063 (3)	0.5370 (6)	0.7063 (3)	0.0387 (14)
C7	0.6380 (3)	0.5290 (5)	0.7382 (3)	0.0321 (13)
C8	0.5885 (3)	0.4681 (6)	0.6909 (3)	0.0376 (13)
H4	0.5976	0.4295	0.638	0.045*
C9	0.5262 (3)	0.4651 (6)	0.7224 (4)	0.0398 (14)
H5	0.4926	0.4244	0.691	0.048*
C10	0.5131 (3)	0.5222 (6)	0.8006 (3)	0.0339 (13)
H6	0.4704	0.5195	0.8214	0.041*
C11	0.6215 (2)	0.5863 (5)	0.8174 (3)	0.0273 (11)
C12	0.6712 (2)	0.6559 (5)	0.8715 (3)	0.0277 (12)
N3	0.5671 (2)	0.4837 (5)	1.0316 (3)	0.0344 (11)
C13	0.6202 (3)	0.4663 (7)	1.0795 (4)	0.0497 (16)
H7	0.6469	0.543	1.0903	0.06*
C14	0.6372 (3)	0.3397 (7)	1.1134 (5)	0.065 (2)
H8	0.6756	0.3315	1.1451	0.078*
C15	0.5980 (3)	0.2247 (7)	1.1010 (5)	0.0605 (19)
H9	0.6092	0.1375	1.1224	0.073*
C16	0.5418 (3)	0.2455 (7)	1.0556 (5)	0.062 (2)
H10	0.5121	0.1728	1.0483	0.074*
C17	0.5291 (3)	0.3735 (7)	1.0207 (4)	0.0496 (16)
H11	0.4916	0.3835	0.9875	0.06*
N4	0.5274 (2)	0.8753 (5)	0.8985 (3)	0.0368 (11)
C18	0.5669 (3)	0.9848 (7)	0.9076 (4)	0.0533 (17)
H12	0.5994	0.9815	0.9491	0.064*
C19	0.5617 (4)	1.1023 (8)	0.8584 (5)	0.072 (2)
H13	0.5891	1.1785	0.867	0.086*
C20	0.5139 (4)	1.1034 (8)	0.7953 (5)	0.075 (2)
H14	0.5108	1.1794	0.7589	0.09*
C21	0.4731 (4)	0.9983 (8)	0.7865 (5)	0.070 (2)
H15	0.4394	1.0005	0.7467	0.083*
C22	0.4824 (3)	0.8830 (7)	0.8395 (4)	0.0527 (16)
H16	0.4548	0.8068	0.8323	0.063*
N5	0.3183 (3)	1.1758 (6)	1.1769 (4)	0.0494 (14)
C23	0.3485 (4)	1.1873 (9)	1.1014 (6)	0.088 (3)
H23	0.3533	1.2758	1.0781	0.106*
C24	0.3729 (4)	1.0742 (12)	1.0561 (7)	0.104 (3)
H24	0.3926	1.0859	1.0032	0.124*
C25	0.3669 (5)	0.9431 (12)	1.0927 (9)	0.111 (4)
H25	0.3844	0.8647	1.0664	0.134*
C26	0.3347 (7)	0.9326 (11)	1.1682 (7)	0.112 (4)
H26	0.3291	0.8462	1.1939	0.134*
C27	0.3107 (5)	1.0501 (9)	1.2058 (5)	0.081 (3)
H27	0.2871	1.0394	1.2559	0.097*
C29	0.1650 (4)	0.8247 (8)	1.3146 (7)	0.087 (3)
H18	0.128	0.8602	1.2876	0.105*
C28	0.1973 (4)	0.7117 (8)	1.2824 (6)	0.068 (2)
H17	0.182	0.6732	1.2319	0.082*
C30	0.1878 (4)	0.8830 (8)	1.3861 (7)	0.088 (3)
H19	0.167	0.9612	1.4083	0.106*
N6	0.2493 (2)	0.6537 (5)	1.3190 (4)	0.0509 (14)
C31	0.2708 (3)	0.7124 (7)	1.3905 (5)	0.0577 (18)
H21	0.3071	0.6737	1.4174	0.069*
C32	0.2416 (4)	0.8284 (8)	1.4266 (6)	0.080 (3)
H20	0.2577	0.8677	1.4764	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0229 (3)	0.0349 (3)	0.0254 (3)	0.0002 (3)	0.0011 (4)	0.0000 (4)
Cl1	0.0452 (8)	0.0432 (8)	0.0285 (7)	−0.0039 (6)	0.0069 (6)	−0.0055 (7)
Cl2	0.0219 (5)	0.0477 (7)	0.0386 (7)	0.0011 (5)	−0.0002 (7)	0.0049 (8)
O1	0.041 (3)	0.057 (3)	0.053 (3)	0.004 (2)	0.016 (2)	0.005 (2)
O2	0.062 (3)	0.069 (3)	0.033 (2)	0.017 (2)	0.009 (2)	−0.013 (2)
N1	0.021 (2)	0.042 (3)	0.026 (3)	−0.0026 (19)	0.0029 (15)	−0.0042 (18)
N2	0.024 (2)	0.034 (2)	0.031 (3)	−0.0001 (18)	−0.0034 (18)	−0.001 (2)
C1	0.033 (3)	0.036 (3)	0.037 (4)	−0.005 (2)	−0.005 (2)	−0.009 (2)
C2	0.024 (2)	0.047 (3)	0.040 (3)	−0.008 (2)	−0.012 (3)	0.000 (4)
C3	0.021 (3)	0.049 (4)	0.044 (4)	−0.002 (2)	0.000 (2)	0.003 (3)
C4	0.030 (3)	0.029 (3)	0.032 (3)	0.000 (2)	0.000 (2)	0.003 (2)
C5	0.037 (3)	0.046 (4)	0.031 (3)	0.007 (3)	0.011 (2)	0.005 (3)
C6	0.048 (4)	0.036 (3)	0.032 (3)	0.009 (3)	0.001 (3)	0.000 (3)
C7	0.048 (4)	0.025 (3)	0.024 (3)	0.007 (2)	0.002 (2)	−0.003 (2)
C8	0.050 (4)	0.031 (3)	0.032 (3)	−0.001 (3)	−0.003 (3)	−0.003 (3)
C9	0.048 (4)	0.035 (3)	0.036 (3)	−0.007 (3)	−0.015 (3)	−0.001 (3)
C10	0.025 (3)	0.043 (3)	0.034 (3)	−0.006 (2)	−0.001 (2)	0.006 (3)
C11	0.023 (3)	0.022 (3)	0.036 (3)	0.000 (2)	−0.004 (2)	0.001 (2)
C12	0.021 (3)	0.032 (3)	0.030 (3)	0.001 (2)	0.001 (2)	0.002 (2)
N3	0.034 (3)	0.035 (3)	0.034 (3)	−0.002 (2)	0.000 (2)	−0.004 (2)
C13	0.039 (3)	0.056 (4)	0.054 (4)	−0.006 (3)	−0.012 (3)	0.012 (3)
C14	0.055 (4)	0.064 (5)	0.076 (5)	−0.005 (3)	−0.027 (4)	0.028 (4)
C15	0.068 (5)	0.046 (4)	0.067 (4)	−0.001 (3)	−0.028 (4)	0.018 (3)
C16	0.062 (4)	0.043 (4)	0.080 (6)	−0.015 (4)	−0.022 (4)	0.013 (4)
C17	0.045 (4)	0.047 (4)	0.056 (4)	−0.003 (3)	−0.017 (3)	0.003 (3)
N4	0.045 (3)	0.038 (3)	0.028 (3)	−0.001 (2)	−0.005 (2)	0.000 (2)
C18	0.057 (4)	0.055 (4)	0.048 (4)	−0.006 (3)	−0.010 (3)	0.008 (3)
C19	0.090 (6)	0.056 (5)	0.069 (5)	−0.027 (4)	−0.024 (4)	0.010 (4)
C20	0.092 (6)	0.064 (5)	0.069 (5)	−0.018 (4)	−0.035 (5)	0.023 (4)
C21	0.094 (6)	0.056 (4)	0.058 (5)	−0.013 (4)	−0.036 (4)	0.017 (4)
C22	0.055 (4)	0.048 (4)	0.055 (4)	−0.003 (3)	−0.006 (3)	0.012 (3)
N5	0.047 (3)	0.049 (4)	0.052 (4)	0.004 (3)	−0.002 (3)	−0.013 (3)
C23	0.094 (6)	0.081 (6)	0.089 (6)	−0.015 (5)	0.033 (5)	−0.037 (5)
C24	0.072 (6)	0.125 (9)	0.114 (8)	−0.021 (6)	0.034 (5)	−0.064 (7)
C25	0.078 (7)	0.094 (8)	0.162 (12)	0.019 (6)	−0.018 (7)	−0.070 (8)
C26	0.170 (12)	0.071 (7)	0.094 (8)	0.025 (7)	−0.039 (8)	−0.021 (6)
C27	0.118 (8)	0.063 (6)	0.062 (5)	0.017 (5)	−0.003 (5)	−0.008 (4)
C29	0.052 (5)	0.051 (5)	0.159 (10)	0.008 (4)	−0.006 (5)	−0.006 (6)
C28	0.059 (5)	0.067 (5)	0.079 (6)	0.022 (4)	−0.015 (4)	−0.009 (4)
C30	0.042 (5)	0.048 (5)	0.175 (10)	0.014 (4)	0.015 (5)	−0.036 (6)
N6	0.038 (3)	0.047 (3)	0.067 (4)	0.007 (2)	0.002 (3)	−0.007 (3)
C31	0.048 (4)	0.055 (4)	0.069 (5)	−0.010 (3)	0.007 (3)	−0.011 (4)
C32	0.062 (5)	0.073 (5)	0.105 (6)	−0.008 (4)	0.013 (4)	−0.047 (5)

Geometric parameters (Å, º)

Co—N4	2.182 (5)	C15—H9	0.93
Co—N1	2.183 (4)	C16—C17	1.370 (9)
Co—N2	2.205 (4)	C16—H10	0.93
Co—N3	2.203 (5)	C17—H11	0.93
Co—Cl1	2.3705 (14)	N4—C22	1.307 (8)
Co—Cl2	2.4029 (12)	N4—C18	1.332 (8)
O1—C5	1.217 (7)	C18—C19	1.372 (9)
O2—C6	1.216 (7)	C18—H12	0.93
N1—C1	1.341 (6)	C19—C20	1.391 (10)
N1—C12	1.338 (6)	C19—H13	0.93
N2—C10	1.342 (7)	C20—C21	1.315 (10)
N2—C11	1.339 (6)	C20—H14	0.93
C1—C2	1.383 (7)	C21—C22	1.398 (9)
C1—H1	0.93	C21—H15	0.93
C2—C3	1.355 (8)	C22—H16	0.93
C2—H2	0.93	N5—C27	1.297 (9)
C3—C4	1.396 (7)	N5—C23	1.343 (10)
C3—H3	0.93	C23—C24	1.391 (11)
C4—C12	1.394 (7)	C23—H23	0.93
C4—C5	1.473 (8)	C24—C25	1.389 (14)
C5—C6	1.526 (8)	C24—H24	0.93
C6—C7	1.483 (8)	C25—C26	1.361 (15)
C7—C8	1.384 (7)	C25—H25	0.93
C7—C11	1.404 (7)	C26—C27	1.364 (13)
C8—C9	1.364 (8)	C26—H26	0.93
C8—H4	0.93	C27—H27	0.93
C9—C10	1.373 (8)	C29—C30	1.339 (12)
C9—H5	0.93	C29—C28	1.366 (11)
C10—H6	0.93	C29—H18	0.93
C11—C12	1.482 (7)	C28—N6	1.329 (9)
N3—C17	1.322 (7)	C28—H17	0.93
N3—C13	1.328 (7)	C30—C32	1.373 (12)
C13—C14	1.372 (8)	C30—H19	0.93
C13—H7	0.93	N6—C31	1.332 (9)
C14—C15	1.377 (9)	C31—C32	1.384 (9)
C14—H8	0.93	C31—H21	0.93
C15—C16	1.365 (9)	C32—H20	0.93
N4—Co—N1	88.46 (17)	C13—C14—C15	120.5 (6)
N4—Co—N2	86.31 (16)	C13—C14—H8	119.7
N1—Co—N2	75.21 (15)	C15—C14—H8	119.7
N4—Co—N3	173.64 (17)	C16—C15—C14	116.4 (6)
N1—Co—N3	88.75 (16)	C16—C15—H9	121.8
N2—Co—N3	87.46 (16)	C14—C15—H9	121.8
N4—Co—Cl1	93.07 (13)	C15—C16—C17	120.0 (6)
N1—Co—Cl1	91.46 (11)	C15—C16—H10	120
N2—Co—Cl1	166.66 (11)	C17—C16—H10	120
N3—Co—Cl1	92.72 (12)	N3—C17—C16	123.6 (6)
N4—Co—Cl2	90.82 (13)	N3—C17—H11	118.2
N1—Co—Cl2	168.11 (11)	C16—C17—H11	118.2
N2—Co—Cl2	92.90 (11)	C22—N4—C18	117.1 (5)
N3—Co—Cl2	90.73 (12)	C22—N4—Co	122.5 (4)
Cl1—Co—Cl2	100.43 (5)	C18—N4—Co	120.1 (4)
C1—N1—C12	117.0 (4)	N4—C18—C19	122.7 (6)
C1—N1—Co	126.8 (3)	N4—C18—H12	118.6
C12—N1—Co	116.2 (3)	C19—C18—H12	118.6
C10—N2—C11	118.9 (5)	C18—C19—C20	117.7 (7)
C10—N2—Co	125.6 (4)	C18—C19—H13	121.2
C11—N2—Co	115.4 (3)	C20—C19—H13	121.2
N1—C1—C2	123.2 (5)	C21—C20—C19	120.8 (7)
N1—C1—H1	118.4	C21—C20—H14	119.6
C2—C1—H1	118.4	C19—C20—H14	119.6
C3—C2—C1	119.5 (5)	C20—C21—C22	117.3 (7)
C3—C2—H2	120.2	C20—C21—H15	121.4
C1—C2—H2	120.2	C22—C21—H15	121.4
C2—C3—C4	119.1 (5)	N4—C22—C21	124.3 (6)
C2—C3—H3	120.5	N4—C22—H16	117.8
C4—C3—H3	120.5	C21—C22—H16	117.8
C3—C4—C12	117.8 (5)	C27—N5—C23	116.2 (7)
C3—C4—C5	120.2 (5)	N5—C23—C24	123.6 (9)
C12—C4—C5	122.0 (5)	N5—C23—H23	118.2
O1—C5—C4	122.2 (5)	C24—C23—H23	118.2
O1—C5—C6	120.0 (5)	C25—C24—C23	117.5 (10)
C4—C5—C6	117.8 (5)	C25—C24—H24	121.2
O2—C6—C7	122.1 (5)	C23—C24—H24	121.2
O2—C6—C5	119.7 (5)	C26—C25—C24	118.1 (9)
C7—C6—C5	118.2 (5)	C26—C25—H25	120.9
C8—C7—C11	118.0 (5)	C24—C25—H25	120.9
C8—C7—C6	121.6 (5)	C25—C26—C27	119.4 (11)
C11—C7—C6	120.4 (5)	C25—C26—H26	120.3
C9—C8—C7	119.5 (5)	C27—C26—H26	120.3
C9—C8—H4	120.3	N5—C27—C26	125.0 (10)
C7—C8—H4	120.3	N5—C27—H27	117.5
C8—C9—C10	119.9 (5)	C26—C27—H27	117.5
C8—C9—H5	120	C30—C29—C28	118.4 (8)
C10—C9—H5	120	C30—C29—H18	120.8
N2—C10—C9	121.8 (5)	C28—C29—H18	120.8
N2—C10—H6	119.1	N6—C28—C29	123.8 (8)
C9—C10—H6	119.1	N6—C28—H17	118.1
N2—C11—C7	121.9 (5)	C29—C28—H17	118.1
N2—C11—C12	116.6 (4)	C29—C30—C32	120.5 (7)
C7—C11—C12	121.5 (5)	C29—C30—H19	119.7
N1—C12—C4	123.4 (5)	C32—C30—H19	119.7
N1—C12—C11	116.5 (4)	C28—N6—C31	116.8 (6)
C4—C12—C11	120.1 (4)	N6—C31—C32	123.1 (7)
C17—N3—C13	116.8 (5)	N6—C31—H21	118.4
C17—N3—Co	121.9 (4)	C32—C31—H21	118.4
C13—N3—Co	121.3 (4)	C30—C32—C31	117.3 (8)
N3—C13—C14	122.5 (6)	C30—C32—H20	121.3
N3—C13—H7	118.7	C31—C32—H20	121.3
C14—C13—H7	118.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H5···Cl1^i	0.93	2.81	3.642 (7)	149
C20—H14···Cl1^ii	0.93	2.82	3.466 (8)	127
C8—H4···Cl2^i	0.93	2.73	3.588 (6)	154
C30—H19···Cl2^iii	0.93	2.77	3.670 (9)	162
C14—H8···O1^iv	0.93	2.59	3.115 (9)	116
C15—H9···O1^iv	0.93	2.42	3.014 (9)	122
C2—H2···O2^v	0.93	2.56	3.285 (8)	135

Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) −x+1, −y+2, z−1/2; (iii) −x+1/2, y+1/2, z+1/2; (iv) −x+3/2, y−1/2, z+1/2; (v) −x+3/2, y+1/2, z+1/2.