A mixed-valence complex of cobalt based on 3-meth­oxy­salicylaldoxime

A new tetra­nuclear mixed-valence cobalt complex, namely di-μ₂-azido-di­azido­diethanol­bis­{μ₂-2-[(hy­droxy­imino)­methyl]-6-methoxy­phenolato}bis{μ₃-6-meth­oxy-2-[(oxido­imino)­methyl]­phenolato}dicobalt(II)dicobalt(III) ethanol disolvate, [Co^II₂Co^III₂(C₈H₇NO₃)₂(C₈H₈NO₃)₂(N₃)₄(C₂H₅OH)₂]·2C₂H₅OH, has been synthesized by the reaction of Co(OAc)₂·4H₂O (OAc is acetate) with 3-meth­oxy­salicylaldoxime (H₂mosao) in an ethanol solution. In the complex, the four Co cations all display distorted octa­hedral coordination environments and they are bridged by two κ²,κ¹,κ¹;μ₃-mosao²⁻ ligands, two κ²,κ²;μ₂-Hmosao⁻ ligands and two μ₂-N₃⁻ anions to form a tetra­nuclear [Co₄N₄O₄] cluster. Adjacent clusters are connected through weak C—H...N and C—H...O inter­actions, resulting in a two-dimensional supra­molecular network parallel to the ac plane. The magnetic properties of the complex have also been studied.

S1. Introduction

There are many reasons for the continuing inter­est in the synthesis and study of multinuclear 3d molecular metal clusters (Koumousi et al., 2013). In particular, clusters containing Mn^III, Fe^III, Co^II and Ni^II usually show fascinating structures and attractive magnetic properties, containing high-spin (S) ground-state values and single-molecule magnetic (SMM) behaviour (Aromi & Brechin, 2006). Owing to their strong coordination ability (Milions et al., 2006; Chaudhuri, 2003; Kukushkin & Pombeiro, 1999) and multiple coordination modes, oxime ligands, as old and evergreen ligands, can easily coordinate to metal cations to form complexes with five- or six-membered rings, as well as mono-, di- and multinuclear complexes with inter­esting structures. These complexes have potential applications in organic chemistry, coordination chemistry and materials and biological science, due to their special chemical properties, biological activities and magnetic properties (Koumousi et al., 2012; Hołyńska et al., 2013; Esteban et al., 2012). Therefore, studies of oxime coordination complexes are significant. Given these considerations, we were inter­ested in the syntheses and properties of oxime coordination complexes and reported a novel enneanuclear manganese coordination complex, [Mn₉O₄(Me-sao)₆(MeO)₃(O₂CMe)₃(OH)(MeOH)₂].2.5DMF (Me-saoH₂ = 2-hy­droxy­phenyl­ethano­neoxime and DMF is di­methyl­formamide), which contains 9-MC-3 and 15-MC-6 (MC denotes a metallacrown) onset-stacked MCs and shows SMM properties (Wang et al., 2011). As part of our continuing investigation of oxime coordination complexes, we have now synthesized a new cobalt complex, [Co₂^IICo₂^III(mosao)₂(Hmosao)₂(N₃)₄(EtOH)₂].2EtOH, (I), which is a novel example of a mixed-valence Co₄ cluster coordinated by oxime ligands, from the reaction of Co(OAc)₂.4H₂O (OAc is acetate) with the polydentate 3-meth­oxy­salicylaldoxime (H₂mosao) ligand in ethanol solution through the solvent evaporation method.

S2. Experimental

S2.1. Synthesis and crystallization

All analytical grade chemicals were obtained commercially and used without further purification. H₂mosao was synthesized as described in the literature (Xu et al. 2004). Complex (I) was prepared by the solvent evaporation method. H₂mosao (0.0334 g, 0.2 mmol) and Co(OAc)₂.4H₂O (OAc is acetate; 0.0498 g, 0.2 mmol) were dissolved in ethanol (20 ml). The solution was then stirred for 0.5 h and NaN₃ (0.0130 g, 0.2 mmol) was added. After stirring for 6 h, the solution was filtered and the filtrate was left undisturbed to give black crystals of (I) (yield 0.0266 g, 42.6% based on Co). Analysis, calculated for C₄₀H₅₄Co₄N₁₆O₁₆ (%): H 4.35, C 38.41, N 17.92; found: H 4.42, C 38.37, N 17.88.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms of the H₂mosao and hy­droxy groups were located in difference Fourier maps but were allowed to ride in the refinement, with aryl C—H = 0.93 Å and O—H = 0.85 Å, and U_iso(H) = 1.2U_eq(C,O), and with methyl C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C). The remaining H atoms were positioned in geometrically idealized positions and constrained to ride on their parent atoms, with methyl­ene C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C), and with methyl C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C).

S3. Results and discussion

As shown in Fig. 1, in complex (I) the asymmetric unit contains two crystallographically independent cobalt cations (Co1 and Co2), one mosao^2- ligand, one Hmosao^- ligand, two N₃^- anions, one coordinated ethanol molecule and one free ethanol molecule. Atom Co1 is present in a distorted six-coordinated o­cta­hedral coordination environment, where the equatorial plane is occupied by two phenolate O atoms (O2 and O5), and by two oxime N atoms (N1 and N8) from one mosao^2- ligand and one Hmosao^- ligand. The axial positions are occupied by two N atoms (N2 and N5) from two N₃^- anions. Atom Co2 also adopts a distorted o­cta­hedral geometry and exhibits an NO₅ environment, utilizing two O atoms (O5 and O6) from one Hmosao^- ligand, two O atoms [O1 and O1ⁱ; symmetry code: (i) -x + 1, -y + 1, -z + 1] from two mosao^2- ligands, one N atom (N2ⁱ) from an N₃^- anion and one O atom (O7) from an ethanol molecule. The mosao^2- ligand bridges three Co centres (Co1, Co2 and Co2ⁱ) through phenolate and oxime O atoms, adopting a [κ²,κ¹,κ¹;µ₃-mosao]^2- coordination mode (shown in Fig. 2a). The Hmosao^- ligand bridges two Co centres (Co1 and Co2) through phenolate O, oxime N and meth­oxy O atoms, adopting a [κ²,κ²;µ₂-Hmosao]^- coordination mode (shown in Fig. 2b). There are two kinds of N₃^- anion, one of which bridges Co1 and Co2ⁱ through one N atom, adopting a µ₂-coordination mode, while the other coordinates to Co1 as a monodentate terminal ligand. Thus, atoms Co1 and Co2 and their symmetry-related counterparts (Co1ⁱ and Co2ⁱ) are connected by two mosao^2- ligands, two Hmosao^- ligands and two µ₂-N₃^- anions to form a tetra­nuclear [Co₄N₄O₄] cluster.

The Co—O and Co—N bond lengths for atom Co1 (Table 2) average 1.927 Å, which is close to the previously reported bond lengths for Co^III cations (Ferguson et al., 2007; Chibotaru et al., 2008), indicating that Co1 is in a 3+ valence state. The Co—O and Co—N bond lengths for Co2 (Table 2) average 2.074 Å, which is close to the previously reported bond lengths for Co^II cations (Ferguson et al., 2007; Chibotaru et al., 2008), suggesting that Co2 has a 2+ valence state. In order to confirm these valence-state attributions, bond-valence sum (BVS) calculations (Brown & Altermatt, 1985; Thorp, 1992) were performed for these two Co centres. The BVS calculation for Co1 (3.38) indicates a 3+ valence state, whereas that for Co2 (2.09) agrees with a 2+ valence state. As the complex is neutral, it follows from the charge balance that two H₂mosao ligands should be mono-deprotonated (i.e. Hmosao^-) and the other two should be doubly deprotonated (i.e. mosao^2-), leading to the formula [Co^II₂Co^III₂(mosao)₂(Hmosao)₂(N₃)₄(EtOH)₂].2EtOH. To confirm the above conclusion further, BVS calculations were performed for the O atoms of the hy­droxy groups of the H₂mosao ligands, which revealed minor deviations from the expected values of 2 valence units (v.u.) for atoms O1 (1.68), O2 (1.85) and O5 (2.05) and 1 v.u. for atom O4 (0.94). Thus, uncoordinated atom O4 is protonated, which is similar to previously reported results (Guo et al., 2011).

Among the previously reported cobalt complexes, most Co₄ clusters are based on carbonyl ligands (Fliedel et al. 2010; De Silva et al. 2001; Darensbourg et al. 1986). However, oxime ligands usually coordinate to cobalt to form mononuclear complexes (Karabocek et al., 2012; Dutta & Gupta, 2011) and examples of multinuclear complexes are relatively scarce (Stamatatos et al. 2005, 2007). In addition, Co cations exist in a single oxidation state (Co^II or Co^III) in most cobalt complexes based on oxime ligands (Liu et al. 2003; Wei et al., 2011). Complex (I) is a novel example of mixed-valence Co₄ cluster coordinated by oxime ligands.

Complex (I) shows a two-dimensional supra­molecular network formed by weak C—H···N and C—H···O inter­actions. As shown in Fig. 3, adjacent clusters are connected to each other by weak C—H···N inter­actions and extend along the a axis to give a supra­molecular chain, with C···N3ⁱⁱ = 3.567 (12) Å [symmetry code: (ii) x - 1, y, z]. Adjacent supra­molecular chains are further linked by weak C—H···O inter­actions and expand along the c axis to yield a two-dimensional supra­molecular network. The C8···O4ⁱⁱⁱ distance is 3.231 (12) Å [symmetry code: (iii) -x, -y, -z]. In addition, there are two kinds of hydrogen bond (O8—H8···N5 and O7—H7A···O8) between the Co₄ cluster and the free ethanol molecule (Fig. 4). The O8···N5 and O7···O8 distances are 2.969 (10) and 2.619 (10) Å, respectively. Full geometric details of the hydrogen bonds are given in Table 3.

On the basis of the structure of (I), the only unpaired electrons will be on the Co^II centres, as the Co^III ions are low-spin (t_2g⁶, S = 0). Therefore, from a magnetic viewpoint, the complex is effectively dinuclear (Stamatatos et al., 2005). Direct-current magnetic susceptibility measurements were performed on polycrystalline samples of (I) in the temperature range 2–300 K in an applied field of 0.1 T. As shown in Fig. 5, the value of χ_MT at 300 K is equal to 6.00 cm³ mol^-1 K (3.00 cm³ mol^-1 K per Co^II), which is within the usual range for o­cta­hedral Co^II in the ⁴T_1g state (Murrie, 2010; Lloret et al., 2008). Upon lowering the temperature, χ_MT remains nearly constant until approximately 160 K. Below 160 K, a slight increase up to a maximum of 6.29 cm³ mol^-1 K at 48 K and a drop to 3.19 cm³ mol^-1 K at 2 K are observed. The increase in χ_MT reveals prevailing ferromagnetic inter­actions between the Co^II centres. The 1/χ_M = f(T) curve fits well the Curie–Weiss law at high temperature (50–300 K), with C = 5.92 cm³ mol^-1 K and θ = 2.93 K (Fig. 5, inset). The positive θ value also indicates ferromagnetic inter­actions between the two Co^II centres. The final decrease is caused by zero-field splitting effects and/or weak inter­molecular anti­ferromagnetic inter­actions.

In summary, a new tetra­nuclear mixed-valence cobalt complex, (I), has been synthesized through the solvent evaporation method. The complex contains two Co^II cations and two Co^III cations. The four Co cations all display distorted six-coordinated o­cta­hedral coordination environments and are bridged by two [κ²,κ¹,κ¹;µ₃-mosao]^2- ligands, two [κ²,κ²;µ₂-Hmosao]^- ligands and two µ₂-N₃^- anions to form a tetra­nuclear [Co₄N₄O₄] cluster. Adjacent clusters are connected through weak C—H···N and C—H···O inter­actions, resulting in a two-dimensional supra­molecular network parallel to the ac plane.

Related literature

For related literature, see:Aromi & Brechin (2006); Brown & Altermatt (1985); Chaudhuri (2003); Chibotaru et al. (2008); Darensbourg et al. (1986); De Silva et al. (2001); Dutta & Gupta (2011); Esteban et al. (2012); Ferguson et al. (2007); Fliedel et al. (2010); Hołyńska et al. (2013); Karabocek et al. (2012); Koumousi et al. (2012, 2013); Kukushkin & Pombeiro (1999); Liu et al. (2003); Milions et al. (2006); Thorp (1992); Stamatatos et al. (2005, 2007); Wang et al. (2011); Wei et al. (2011); Xu et al. (2004).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of complex (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
	Fig. 2. The coordination modes of (a) the mosao^2- ligand and (b) the Hmosao^- ligand.
	Fig. 3. The two-dimensional supramolecular network of complex (I). Dashed lines indicate hydrogen bonds. [Symmetry codes: (ii) x - 1, y, z; (iii) -x, -y, -z.]
	Fig. 4. The hydrogen bonds (dashed lines) between the Co4 cluster and the free ethanol molecule.
	Fig. 5. The temperature dependence of χMT and 1/χM (inset) for complex (I). Colour code: measured values, black; calculated curve, red.

Di-µ₂-azido-diazidodiethanolbis{µ₂-2-[(hydroxyimino)methyl]-6-methoxyphenolato}bis{µ₃-2-[(oxidoimino)methyl]-6-methoxyphenolato}dicobalt(II)dicobalt(III) ethanol disolvate

Crystal data

[Co4(C8H7NO3)2(C8H8NO3)2(N3)4(C2H6O)2]·2C2H6O	Z = 1
Mr = 1250.71	F(000) = 642
Triclinic, P1	Dx = 1.627 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.605 (7) Å	Cell parameters from 931 reflections
b = 10.749 (7) Å	θ = 2.2–21.7°
c = 13.010 (9) Å	µ = 1.36 mm^−1
α = 91.524 (11)°	T = 298 K
β = 107.539 (10)°	Block, black
γ = 93.855 (10)°	0.21 × 0.12 × 0.07 mm
V = 1276.3 (15) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4419 independent reflections
Radiation source: fine-focus sealed tube	2144 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
Tmin = 0.763, Tmax = 0.911	k = −7→12
6405 measured reflections	l = −15→14

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0539P)^2] where P = (Fo^2 + 2Fc^2)/3
4419 reflections	(Δ/σ)max = 0.003
353 parameters	Δρmax = 0.57 e Å^−3
3 restraints	Δρmin = −0.62 e Å^−3

Special details

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

Refinement. Refinement 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 > 2sigma(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	0.31990 (11)	0.37207 (9)	0.28225 (8)	0.0316 (3)
Co2	0.48291 (11)	0.62148 (9)	0.44723 (8)	0.0316 (3)
N1	0.2476 (7)	0.4263 (5)	0.3953 (5)	0.0329 (16)
N2	0.4660 (7)	0.2903 (6)	0.3983 (5)	0.0377 (17)
N3	0.4717 (7)	0.1788 (7)	0.3861 (5)	0.0386 (17)
N4	0.4791 (9)	0.0735 (7)	0.3738 (6)	0.066 (2)
N5	0.1814 (8)	0.4664 (6)	0.1783 (5)	0.047 (2)
N6	0.0900 (8)	0.4107 (6)	0.1048 (6)	0.0504 (19)
N7	−0.0010 (10)	0.3587 (8)	0.0354 (6)	0.088 (3)
N8	0.3885 (7)	0.3070 (6)	0.1684 (5)	0.0410 (18)
O1	0.3453 (5)	0.4931 (4)	0.4826 (4)	0.0331 (13)
O2	0.1930 (5)	0.2284 (4)	0.2579 (4)	0.0372 (13)
O3	0.0106 (6)	0.0481 (5)	0.1475 (4)	0.0573 (17)
O4	0.3189 (7)	0.1964 (6)	0.1148 (5)	0.0611 (18)
H4A	0.260 (8)	0.185 (8)	0.150 (6)	0.073*
O5	0.4567 (5)	0.5176 (4)	0.3076 (4)	0.0320 (12)
O6	0.6325 (6)	0.7183 (4)	0.3801 (4)	0.0426 (14)
O7	0.3360 (7)	0.7451 (6)	0.3747 (4)	0.0501 (15)
H7A	0.326 (9)	0.744 (8)	0.3083 (16)	0.060*
O8	0.2758 (11)	0.7325 (7)	0.1642 (6)	0.111 (3)
H8	0.207 (9)	0.676 (9)	0.148 (10)	0.133*
C1	0.0143 (9)	0.3062 (7)	0.3314 (6)	0.040 (2)
C2	0.0575 (9)	0.2228 (7)	0.2650 (6)	0.038 (2)
C3	−0.0446 (9)	0.1256 (7)	0.2075 (6)	0.040 (2)
C4	−0.1835 (10)	0.1149 (8)	0.2144 (7)	0.058 (3)
H4	−0.2500	0.0507	0.1759	0.070*
C5	−0.2263 (10)	0.2015 (9)	0.2802 (8)	0.067 (3)
H5	−0.3213	0.1942	0.2846	0.080*
C6	−0.1282 (9)	0.2971 (8)	0.3384 (7)	0.054 (3)
H6	−0.1567	0.3543	0.3815	0.065*
C7	0.1210 (6)	0.3976 (5)	0.4027 (5)	0.037 (2)
H7	0.0943	0.4377	0.4574	0.044*
C8	−0.0795 (6)	−0.0604 (5)	0.0950 (5)	0.073 (3)
H8A	−0.1100	−0.1076	0.1472	0.110*
H8B	−0.0248	−0.1110	0.0617	0.110*
H8C	−0.1641	−0.0356	0.0409	0.110*
C9	0.5779 (9)	0.4673 (8)	0.1744 (6)	0.047 (2)
C10	0.5617 (8)	0.5414 (7)	0.2598 (6)	0.038 (2)
C11	0.6599 (9)	0.6477 (7)	0.2967 (6)	0.041 (2)
C12	0.7683 (10)	0.6792 (8)	0.2536 (7)	0.063 (3)
H12	0.8325	0.7493	0.2807	0.076*
C13	0.7832 (11)	0.6055 (8)	0.1676 (8)	0.072 (3)
H13	0.8563	0.6269	0.1364	0.087*
C14	0.6895 (10)	0.5023 (9)	0.1303 (8)	0.067 (3)
H14	0.7001	0.4535	0.0734	0.080*
C15	0.4884 (9)	0.3535 (8)	0.1312 (7)	0.048 (2)
H15	0.5044	0.3116	0.0728	0.058*
C16	0.7177 (10)	0.8318 (7)	0.4188 (7)	0.068 (3)
H16A	0.8192	0.8160	0.4454	0.101*
H16B	0.6878	0.8684	0.4761	0.101*
H16C	0.7039	0.8881	0.3611	0.101*
C17	0.1994 (11)	0.7570 (10)	0.3958 (9)	0.080 (3)
H17A	0.2064	0.7264	0.4665	0.097*
H17B	0.1233	0.7049	0.3430	0.097*
C18	0.1577 (12)	0.8835 (10)	0.3922 (10)	0.101 (4)
H18A	0.2369	0.9372	0.4386	0.151*
H18B	0.0727	0.8875	0.4161	0.151*
H18C	0.1357	0.9101	0.3196	0.151*
C19	0.3144 (17)	0.7972 (17)	0.0928 (11)	0.170 (8)
H19A	0.2296	0.8400	0.0546	0.204*
H19B	0.3299	0.7372	0.0411	0.204*
C20	0.4329 (14)	0.8852 (11)	0.1172 (10)	0.115 (5)
H20A	0.4475	0.9233	0.1876	0.173*
H20B	0.4145	0.9480	0.0647	0.173*
H20C	0.5191	0.8454	0.1163	0.173*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0354 (7)	0.0309 (7)	0.0251 (6)	−0.0074 (5)	0.0065 (5)	−0.0047 (5)
Co2	0.0381 (7)	0.0288 (7)	0.0242 (6)	−0.0073 (5)	0.0064 (5)	−0.0034 (5)
N1	0.032 (4)	0.034 (4)	0.029 (4)	−0.008 (3)	0.007 (3)	−0.005 (3)
N2	0.043 (4)	0.026 (4)	0.041 (4)	0.001 (3)	0.010 (3)	−0.006 (3)
N3	0.050 (5)	0.032 (4)	0.036 (4)	0.002 (4)	0.017 (3)	0.002 (4)
N4	0.084 (6)	0.040 (5)	0.070 (6)	0.009 (5)	0.020 (5)	−0.008 (4)
N5	0.055 (5)	0.043 (5)	0.033 (4)	−0.010 (4)	0.001 (4)	−0.012 (3)
N6	0.054 (5)	0.042 (5)	0.052 (5)	0.002 (4)	0.010 (4)	0.014 (4)
N7	0.094 (7)	0.074 (7)	0.060 (6)	−0.025 (5)	−0.024 (5)	0.008 (5)
N8	0.051 (5)	0.033 (4)	0.034 (4)	−0.014 (3)	0.011 (4)	−0.014 (3)
O1	0.041 (3)	0.030 (3)	0.023 (3)	−0.011 (2)	0.005 (2)	−0.003 (2)
O2	0.033 (3)	0.038 (3)	0.037 (3)	−0.013 (3)	0.010 (3)	−0.008 (2)
O3	0.066 (4)	0.051 (4)	0.048 (4)	−0.029 (3)	0.015 (3)	−0.017 (3)
O4	0.075 (5)	0.050 (4)	0.060 (4)	−0.021 (3)	0.032 (4)	−0.034 (3)
O5	0.034 (3)	0.028 (3)	0.034 (3)	−0.005 (2)	0.013 (3)	−0.002 (2)
O6	0.052 (4)	0.035 (3)	0.040 (3)	−0.015 (3)	0.018 (3)	−0.010 (3)
O7	0.050 (4)	0.053 (4)	0.048 (4)	0.002 (3)	0.016 (3)	0.004 (3)
O8	0.168 (9)	0.084 (7)	0.047 (5)	−0.028 (5)	−0.011 (5)	0.010 (4)
C1	0.036 (5)	0.040 (5)	0.043 (5)	−0.012 (4)	0.013 (4)	−0.006 (4)
C2	0.034 (5)	0.046 (5)	0.031 (5)	−0.006 (4)	0.006 (4)	0.002 (4)
C3	0.047 (6)	0.049 (6)	0.021 (4)	−0.020 (4)	0.010 (4)	−0.004 (4)
C4	0.050 (6)	0.057 (6)	0.058 (6)	−0.034 (5)	0.012 (5)	−0.008 (5)
C5	0.045 (6)	0.081 (8)	0.066 (7)	−0.018 (5)	0.012 (5)	−0.012 (6)
C6	0.048 (6)	0.062 (6)	0.052 (6)	−0.007 (5)	0.017 (5)	−0.014 (5)
C7	0.038 (5)	0.036 (5)	0.036 (5)	−0.009 (4)	0.013 (4)	−0.002 (4)
C8	0.087 (8)	0.061 (7)	0.066 (7)	−0.036 (6)	0.028 (6)	−0.023 (5)
C9	0.058 (6)	0.048 (6)	0.040 (5)	−0.015 (5)	0.029 (5)	−0.011 (4)
C10	0.040 (5)	0.038 (5)	0.034 (5)	−0.007 (4)	0.011 (4)	−0.002 (4)
C11	0.050 (6)	0.037 (5)	0.036 (5)	−0.008 (4)	0.018 (4)	−0.003 (4)
C12	0.066 (7)	0.060 (7)	0.068 (7)	−0.027 (5)	0.035 (6)	−0.013 (5)
C13	0.082 (8)	0.060 (7)	0.088 (8)	−0.032 (6)	0.056 (7)	−0.015 (6)
C14	0.074 (7)	0.058 (7)	0.081 (8)	−0.016 (5)	0.049 (6)	−0.011 (5)
C15	0.053 (6)	0.054 (6)	0.045 (6)	−0.006 (5)	0.029 (5)	−0.009 (4)
C16	0.084 (8)	0.041 (6)	0.076 (7)	−0.029 (5)	0.030 (6)	−0.014 (5)
C17	0.071 (8)	0.077 (9)	0.102 (9)	0.016 (6)	0.037 (7)	0.014 (7)
C18	0.082 (9)	0.069 (9)	0.156 (13)	0.017 (7)	0.040 (9)	0.004 (8)
C19	0.154 (15)	0.25 (2)	0.074 (10)	−0.112 (14)	0.012 (10)	0.025 (11)
C20	0.116 (12)	0.096 (10)	0.115 (11)	−0.014 (9)	0.012 (9)	0.023 (8)

Geometric parameters (Å, º)

Co1—O2	1.860 (5)	C2—C3	1.411 (10)
Co1—N1	1.900 (6)	C3—C4	1.362 (11)
Co1—N8	1.927 (6)	C4—C5	1.411 (11)
Co1—O5	1.928 (5)	C4—H4	0.9300
Co1—N5	1.948 (7)	C5—C6	1.384 (11)
Co1—N2	1.995 (7)	C5—H5	0.9300
Co2—O1	2.005 (5)	C6—H6	0.9300
Co2—O7	2.041 (6)	C7—H7	0.9300
Co2—O5	2.047 (5)	C8—H8A	0.9600
Co2—N2^i	2.103 (6)	C8—H8B	0.9600
Co2—O1^i	2.121 (5)	C8—H8C	0.9600
Co2—O6	2.124 (5)	C9—C14	1.397 (10)
Co2—Co2^i	2.975 (3)	C9—C10	1.403 (10)
N1—C7	1.267 (7)	C9—C15	1.443 (10)
N1—O1	1.382 (6)	C10—C11	1.406 (10)
N2—N3	1.212 (8)	C11—C12	1.354 (10)
N2—Co2^i	2.103 (6)	C12—C13	1.402 (11)
N3—N4	1.148 (8)	C12—H12	0.9300
N5—N6	1.199 (8)	C13—C14	1.360 (11)
N6—N7	1.151 (9)	C13—H13	0.9300
N8—C15	1.278 (9)	C14—H14	0.9300
N8—O4	1.384 (7)	C15—H15	0.9300
O1—Co2^i	2.121 (5)	C16—H16A	0.9600
O2—C2	1.330 (8)	C16—H16B	0.9600
O3—C3	1.362 (9)	C16—H16C	0.9600
O3—C8	1.429 (7)	C17—C18	1.441 (12)
O4—H4A	0.840 (10)	C17—H17A	0.9700
O5—C10	1.349 (8)	C17—H17B	0.9700
O6—C11	1.406 (8)	C18—H18A	0.9600
O6—C16	1.413 (8)	C18—H18B	0.9600
O7—C17	1.432 (10)	C18—H18C	0.9600
O7—H7A	0.839 (10)	C19—C20	1.383 (14)
O8—C19	1.301 (14)	C19—H19A	0.9700
O8—H8	0.839 (10)	C19—H19B	0.9700
C1—C2	1.396 (10)	C20—H20A	0.9600
C1—C6	1.396 (10)	C20—H20B	0.9600
C1—C7	1.455 (8)	C20—H20C	0.9600
O2—Co1—N1	90.1 (2)	C4—C3—C2	120.8 (8)
O2—Co1—N8	86.6 (2)	O3—C3—C2	113.6 (7)
N1—Co1—N8	176.5 (3)	C3—C4—C5	119.8 (8)
O2—Co1—O5	178.1 (2)	C3—C4—H4	120.1
N1—Co1—O5	91.2 (2)	C5—C4—H4	120.1
N8—Co1—O5	92.1 (2)	C6—C5—C4	120.7 (9)
O2—Co1—N5	93.8 (2)	C6—C5—H5	119.7
N1—Co1—N5	91.4 (3)	C4—C5—H5	119.7
N8—Co1—N5	90.0 (3)	C5—C6—C1	118.9 (8)
O5—Co1—N5	87.6 (2)	C5—C6—H6	120.5
O2—Co1—N2	90.2 (2)	C1—C6—H6	120.5
N1—Co1—N2	84.8 (3)	N1—C7—C1	124.5 (6)
N8—Co1—N2	94.1 (3)	N1—C7—H7	117.8
O5—Co1—N2	88.5 (2)	C1—C7—H7	117.8
N5—Co1—N2	174.4 (2)	O3—C8—H8A	109.5
O1—Co2—O7	99.1 (2)	O3—C8—H8B	109.5
O1—Co2—O5	87.59 (18)	H8A—C8—H8B	109.5
O7—Co2—O5	94.2 (2)	O3—C8—H8C	109.5
O1—Co2—N2^i	91.5 (2)	H8A—C8—H8C	109.5
O7—Co2—N2^i	94.5 (2)	H8B—C8—H8C	109.5
O5—Co2—N2^i	171.3 (2)	C14—C9—C10	118.8 (7)
O1—Co2—O1^i	87.8 (2)	C14—C9—C15	117.5 (7)
O7—Co2—O1^i	173.1 (2)	C10—C9—C15	123.7 (7)
O5—Co2—O1^i	85.44 (18)	O5—C10—C9	123.9 (7)
N2^i—Co2—O1^i	85.9 (2)	O5—C10—C11	118.2 (7)
O1—Co2—O6	164.47 (18)	C9—C10—C11	117.9 (7)
O7—Co2—O6	86.8 (2)	C12—C11—C10	122.4 (7)
O5—Co2—O6	77.60 (18)	C12—C11—O6	123.7 (7)
N2^i—Co2—O6	102.5 (2)	C10—C11—O6	113.9 (7)
O1^i—Co2—O6	86.4 (2)	C11—C12—C13	119.5 (8)
O1—Co2—Co2^i	45.44 (15)	C11—C12—H12	120.2
O7—Co2—Co2^i	144.54 (18)	C13—C12—H12	120.2
O5—Co2—Co2^i	85.12 (15)	C14—C13—C12	119.2 (8)
N2^i—Co2—Co2^i	88.06 (19)	C14—C13—H13	120.4
O1^i—Co2—Co2^i	42.34 (13)	C12—C13—H13	120.4
O6—Co2—Co2^i	127.23 (16)	C13—C14—C9	122.2 (8)
C7—N1—O1	116.4 (5)	C13—C14—H14	118.9
C7—N1—Co1	125.8 (4)	C9—C14—H14	118.9
O1—N1—Co1	117.4 (4)	N8—C15—C9	123.9 (7)
N3—N2—Co1	116.9 (5)	N8—C15—H15	118.1
N3—N2—Co2^i	121.5 (5)	C9—C15—H15	118.1
Co1—N2—Co2^i	114.9 (3)	O6—C16—H16A	109.5
N4—N3—N2	178.7 (8)	O6—C16—H16B	109.5
N6—N5—Co1	118.8 (6)	H16A—C16—H16B	109.5
N7—N6—N5	177.9 (10)	O6—C16—H16C	109.5
C15—N8—O4	113.4 (6)	H16A—C16—H16C	109.5
C15—N8—Co1	129.2 (5)	H16B—C16—H16C	109.5
O4—N8—Co1	117.3 (5)	O7—C17—C18	113.2 (9)
N1—O1—Co2	115.7 (4)	O7—C17—H17A	108.9
N1—O1—Co2^i	107.8 (4)	C18—C17—H17A	108.9
Co2—O1—Co2^i	92.2 (2)	O7—C17—H17B	108.9
C2—O2—Co1	125.1 (5)	C18—C17—H17B	108.9
C3—O3—C8	117.7 (6)	H17A—C17—H17B	107.7
N8—O4—H4A	97 (6)	C17—C18—H18A	109.5
C10—O5—Co1	126.9 (4)	C17—C18—H18B	109.5
C10—O5—Co2	115.0 (4)	H18A—C18—H18B	109.5
Co1—O5—Co2	115.8 (2)	C17—C18—H18C	109.5
C11—O6—C16	119.0 (6)	H18A—C18—H18C	109.5
C11—O6—Co2	112.4 (4)	H18B—C18—H18C	109.5
C16—O6—Co2	127.9 (5)	O8—C19—C20	124.2 (12)
C17—O7—Co2	123.8 (6)	O8—C19—H19A	106.3
C17—O7—H7A	112 (6)	C20—C19—H19A	106.3
Co2—O7—H7A	110 (6)	O8—C19—H19B	106.3
C19—O8—H8	123 (9)	C20—C19—H19B	106.3
C2—C1—C6	121.1 (7)	H19A—C19—H19B	106.4
C2—C1—C7	120.4 (7)	C19—C20—H20A	109.5
C6—C1—C7	118.3 (7)	C19—C20—H20B	109.5
O2—C2—C1	122.3 (7)	H20A—C20—H20B	109.5
O2—C2—C3	119.0 (7)	C19—C20—H20C	109.5
C1—C2—C3	118.7 (7)	H20A—C20—H20C	109.5
C4—C3—O3	125.6 (7)	H20B—C20—H20C	109.5
O2—Co1—N1—C7	−27.2 (6)	O1—Co2—O5—Co1	3.1 (3)
N8—Co1—N1—C7	−47 (5)	O7—Co2—O5—Co1	−95.9 (3)
O5—Co1—N1—C7	154.2 (6)	N2^i—Co2—O5—Co1	87.1 (14)
N5—Co1—N1—C7	66.6 (6)	O1^i—Co2—O5—Co1	91.1 (3)
N2—Co1—N1—C7	−117.4 (6)	O6—Co2—O5—Co1	178.4 (3)
O2—Co1—N1—O1	146.2 (5)	Co2^i—Co2—O5—Co1	48.6 (2)
N8—Co1—N1—O1	127 (4)	O1—Co2—O6—C11	3.4 (10)
O5—Co1—N1—O1	−32.4 (5)	O7—Co2—O6—C11	−109.4 (5)
N5—Co1—N1—O1	−120.0 (5)	O5—Co2—O6—C11	−14.4 (5)
N2—Co1—N1—O1	56.0 (5)	N2^i—Co2—O6—C11	156.7 (5)
O2—Co1—N2—N3	33.5 (6)	O1^i—Co2—O6—C11	71.7 (5)
N1—Co1—N2—N3	123.5 (6)	Co2^i—Co2—O6—C11	59.5 (5)
N8—Co1—N2—N3	−53.2 (6)	O1—Co2—O6—C16	−167.2 (8)
O5—Co1—N2—N3	−145.2 (6)	O7—Co2—O6—C16	80.0 (7)
N5—Co1—N2—N3	170 (3)	O5—Co2—O6—C16	175.0 (7)
O2—Co1—N2—Co2^i	−118.4 (3)	N2^i—Co2—O6—C16	−13.9 (7)
N1—Co1—N2—Co2^i	−28.4 (3)	O1^i—Co2—O6—C16	−98.9 (7)
N8—Co1—N2—Co2^i	154.9 (3)	Co2^i—Co2—O6—C16	−111.0 (7)
O5—Co1—N2—Co2^i	62.9 (3)	O1—Co2—O7—C17	25.4 (7)
N5—Co1—N2—Co2^i	18 (3)	O5—Co2—O7—C17	113.6 (7)
Co1—N2—N3—N4	94 (41)	N2^i—Co2—O7—C17	−66.8 (7)
Co2^i—N2—N3—N4	−116 (41)	O1^i—Co2—O7—C17	−159.7 (15)
O2—Co1—N5—N6	−26.2 (7)	O6—Co2—O7—C17	−169.1 (7)
N1—Co1—N5—N6	−116.3 (7)	Co2^i—Co2—O7—C17	26.1 (8)
N8—Co1—N5—N6	60.5 (7)	Co1—O2—C2—C1	−26.9 (11)
O5—Co1—N5—N6	152.5 (7)	Co1—O2—C2—C3	156.3 (6)
N2—Co1—N5—N6	−163 (2)	C6—C1—C2—O2	−179.1 (8)
Co1—N5—N6—N7	120 (26)	C7—C1—C2—O2	−4.9 (12)
O2—Co1—N8—C15	−178.9 (8)	C6—C1—C2—C3	−2.2 (13)
N1—Co1—N8—C15	−160 (4)	C7—C1—C2—C3	172.0 (7)
O5—Co1—N8—C15	−0.4 (8)	C8—O3—C3—C4	−6.1 (12)
N5—Co1—N8—C15	87.2 (8)	C8—O3—C3—C2	173.9 (6)
N2—Co1—N8—C15	−89.0 (8)	O2—C2—C3—C4	178.6 (8)
O2—Co1—N8—O4	3.6 (6)	C1—C2—C3—C4	1.6 (13)
N1—Co1—N8—O4	23 (5)	O2—C2—C3—O3	−1.4 (11)
O5—Co1—N8—O4	−177.8 (6)	C1—C2—C3—O3	−178.4 (7)
N5—Co1—N8—O4	−90.2 (6)	O3—C3—C4—C5	179.6 (8)
N2—Co1—N8—O4	93.6 (6)	C2—C3—C4—C5	−0.3 (14)
C7—N1—O1—Co2	−144.1 (5)	C3—C4—C5—C6	−0.3 (15)
Co1—N1—O1—Co2	41.8 (6)	C4—C5—C6—C1	−0.3 (15)
C7—N1—O1—Co2^i	114.3 (5)	C2—C1—C6—C5	1.6 (14)
Co1—N1—O1—Co2^i	−59.7 (5)	C7—C1—C6—C5	−172.7 (8)
O7—Co2—O1—N1	68.4 (4)	O1—N1—C7—C1	−166.2 (6)
O5—Co2—O1—N1	−25.5 (4)	Co1—N1—C7—C1	7.3 (10)
N2^i—Co2—O1—N1	163.2 (4)	C2—C1—C7—N1	15.0 (12)
O1^i—Co2—O1—N1	−111.0 (5)	C6—C1—C7—N1	−170.7 (8)
O6—Co2—O1—N1	−42.9 (10)	Co1—O5—C10—C9	6.7 (11)
Co2^i—Co2—O1—N1	−111.0 (5)	Co2—O5—C10—C9	169.0 (7)
O7—Co2—O1—Co2^i	179.39 (19)	Co1—O5—C10—C11	−174.1 (5)
O5—Co2—O1—Co2^i	85.53 (18)	Co2—O5—C10—C11	−11.8 (9)
N2^i—Co2—O1—Co2^i	−85.8 (2)	C14—C9—C10—O5	179.0 (8)
O1^i—Co2—O1—Co2^i	0.0	C15—C9—C10—O5	−3.1 (14)
O6—Co2—O1—Co2^i	68.1 (8)	C14—C9—C10—C11	−0.2 (13)
N1—Co1—O2—C2	36.9 (6)	C15—C9—C10—C11	177.7 (8)
N8—Co1—O2—C2	−144.2 (6)	O5—C10—C11—C12	−179.8 (8)
O5—Co1—O2—C2	168 (6)	C9—C10—C11—C12	−0.5 (13)
N5—Co1—O2—C2	−54.4 (6)	O5—C10—C11—O6	−1.2 (11)
N2—Co1—O2—C2	121.7 (6)	C9—C10—C11—O6	178.1 (7)
O2—Co1—O5—C10	43 (7)	C16—O6—C11—C12	2.9 (12)
N1—Co1—O5—C10	174.2 (6)	Co2—O6—C11—C12	−168.6 (7)
N8—Co1—O5—C10	−4.6 (6)	C16—O6—C11—C10	−175.7 (7)
N5—Co1—O5—C10	−94.5 (6)	Co2—O6—C11—C10	12.8 (9)
N2—Co1—O5—C10	89.4 (6)	C10—C11—C12—C13	1.1 (15)
O2—Co1—O5—Co2	−119 (6)	O6—C11—C12—C13	−177.4 (9)
N1—Co1—O5—Co2	12.0 (3)	C11—C12—C13—C14	−1.0 (16)
N8—Co1—O5—Co2	−166.7 (3)	C12—C13—C14—C9	0.3 (17)
N5—Co1—O5—Co2	103.4 (3)	C10—C9—C14—C13	0.3 (16)
N2—Co1—O5—Co2	−72.7 (3)	C15—C9—C14—C13	−177.7 (9)
O1—Co2—O5—C10	−161.2 (5)	O4—N8—C15—C9	−179.1 (8)
O7—Co2—O5—C10	99.8 (5)	Co1—N8—C15—C9	3.4 (13)
N2^i—Co2—O5—C10	−77.2 (15)	C14—C9—C15—N8	175.7 (9)
O1^i—Co2—O5—C10	−73.3 (5)	C10—C9—C15—N8	−2.2 (15)
O6—Co2—O5—C10	14.1 (5)	Co2—O7—C17—C18	144.9 (8)
Co2^i—Co2—O5—C10	−115.7 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O8	0.84 (1)	1.79 (2)	2.620 (10)	171 (9)
O8—H8···N5	0.84 (1)	2.31 (9)	2.970 (10)	136 (12)
C5—H5···N3^ii	0.93	2.70	3.565 (12)	156
C8—H8C···O4^iii	0.96	2.64	3.229 (8)	120

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