A new trinuclear cobalt(II) complex: deca­aqua-1κ³O,2κ⁴O,3κ³O-bis­(benzene-1,3,5-tricarboxyl­ato)-1κO,3κO-di-μ-4,4′-bipyridine-1:2κ²N:N′;2:3κ²N:N′-di-4,4′-bipyridine-1κN,3κN-tricobalt(II) 4,4′-bipyridine solvate octa­hydrate

The principal building units in the title compound, [Co₃(C₉H₃O₆)₂(C₁₀H₈N₂)₄(H₂O)₁₀]·C₁₀H₈N₂·8H₂O, are the linear centrosymmetric tricobalt(II) complex mol­ecules resulting from two square-pyramidal [Co(btc)(bpy)(H₂O)₃]⁻ entities (bpy is 4,4′-bipyridine and btc is the benzene-1,3,5-tricarboxyl­ate trianion) bridged by one trans-[Co(bpy)₂(H₂O)₄]²⁺ unit. The trinuclear complex mol­ecules are assembled into infinite chains through inter­molecular O—H...N hydrogen bonds and π–π stacking inter­actions between adjacent monodentate bpy ligands. The chains and uncoordinated bpy mol­ecules are further assembled into two-dimensional open layers, which are stacked in a staggered manner to give a three-dimensional supra­molecular architecture with the solvent water mol­ecules in the cavities.

S1. Comment

Recently, the design and synthesis of metal–organic frameworks (MOFs) has been a field of increasing interest, due to their potential applications as functional materials (Tu et al., 2003; Mandal et al., 2000; Reynolds & Coucouvanis, 1998). In general, the strategy to design MOFs relies on the utilization of multidentate O- and/or N-donor bridging ligands. For this, benzencarboxylic acids like terephthalic acid, benzene-1,3,5-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid and mellitic acid etc., in combination with some linear N-donor ligands such as 4,4'-bipyridine, 1,2-bis-(4-pyridyl)ethane etc., are extensively employed to construct one-, two- and three-dimensional coordination polymers (Groeneman et al., 1999; Shattock et al., 2005; Wu et al., 2002; Cui, 2005; Chui et al., 1999). However, few reports of polynuclear complex molecules from the self-assembly of transition metal cations with benzene-1,3,5-tricarboxylic acid (TMA) and 4,4'-bipyridine (bpy) have been published to date. Here, we present the title novel trinuclear cobalt complex, [Co₃(H₂O)₁₀(C₁₀H₈N₂)₄(C₉H₃O₆)₂]·C₁₀H₈N₂·8H₂O, (I), which was obtained from the hydrothermal reaction of bpy, benzene-1,3,5-tricarboxylic acid and CoCl₂·6H₂O at 443 K.

As shown in Fig. 1, compound (I) consists of solvent water molecules, bpy molecules and linear centrosymmetric trinuclear [Co₃(H₂O)₁₀(C₁₀H₈N₂)₄(C₉H₃O₆)₂] complex molecules, where the middle Co1 atom at an inversion centre is bridged to two distal Co2 atoms by two bidentate bpy ligands. Both crystallographically independent Co atoms are in nearly identical trans-CoN₂O₄ environments with normal Co—N and Co—O bond lengths (Lightfoot & Snedden, 1999). The octahedral N₂O₄ donor set around the Co1 atoms arises from two N atoms of different bridging bpy ligands and four aqua O atoms, while the coordination geometry of the Co2 atoms is defined by three aqua O atoms, one O atom of the monodentate TMA anion, and two N atoms of one bidentate bpy and one monodentate bpy, respectively. The monodentate TMA anions are nearly perpendicular to the principal axis through the Co atoms of the trinuclear molecule. To the best of our knowledge, complex (I) represents a rare example of a compound with the TMA anion acting as a monodentate ligand (Guillou et al., 2000).

The carboxylic acid groups are found to be twisted from the plane defined by the C atoms to different extents. The largest dihedral angle of 13.3 (3)° is found for the coordinated group, due to the formation of an intramolecular hydrogen bond between the uncoordinated atom O6 and an aqua ligand, with O3···O6 = 2.775 (4) Å; the dihedral angles for the uncoordinated groups are 4.7 (8) and 5.0 (7)°, respectively [Please specify the atoms]. The uncoordinated carboxylic acid O atoms are each involved in double hydrogen bonds to both aqua ligands and uncoordinated H₂O molecules.

Through an intermolecular hydrogen bond between the uncoordinated pyridyl N atom and the aqua ligand opposite to the coordinated carboxylic acid O7 atom [O1···N4ⁱ = 2.828 (5) Å; symmetry code: (i) −x + 2, −y − 1, −z + 2], the trinuclear complex molecules are assembled into infinite chains extending in the [021] and [02sc/Desktop/publCIF/symbols/bar1.png" height="12" />] directions. The resulting chains are stabilized by intermolecular π–π stacking interactions between adjacent monodentate bpy ligands (mean interplanar distance = 3.56 Å). The uncoordinated bpy molecules are each sandwiched between two adjacent bridging bpy ligands of different chains, and are engaged in π–π stacking interactions and in hydrogen bonds to one aqua ligand bonded to the middle Co1 atom, with O5···N5 = 2.895 (5) Å, leading to a two-dimensional open supramolecular layer parallel to (100) with the TMA ligands pendent on both sides (Fig. 2).

The layers are stacked in a staggered manner, with TMA ligands of one layer occupying the apertures of a neighbouring one, and interlocked by interlayer hydrogen bonds [O2···O9^iv = 2.733 (4) Å and O5···O11^iv = 2.858 (4) Å; symmetry code: (iv) −x + 3/2, y + 1/2, −z + 3/2]. The uncoordinated water molecules are located between the layers and participate in extensive hydrogen bonds, which make a substantial contribution to the stabilization of the crystal structure. The uncoordinated bpy molecule is twisted, with a dihedral angle of 8.8 (2)° between the two pyridyl components, while the mono- and bidentate bpy ligands are twisted with dihedral angles between the component rings of 4.9 (1) and 12.8 (2)°, indicating significant coordination effects.

S2. Experimental

A 23 ml Teflon-lined autoclave charged with a mixture of CoCl₂·6H₂O (0.237 g, 1.0 mmol), benzene-1,3,5-tricarboxylic acid (0.105 g, 0.5 mmol), NaOH (0.03 g, 1.5 mmol) and H₂O (10.0 ml) was heated at 443 K for 120 h, then cooled to 373 K at a rate of 5 K h⁻¹ and held at this temperature for 10 h, followed by further cooling to room temperature [Rate for this step?]. The mixture was filtered and slow evaporation of the pink filtrate at room temperature yielded rose-coloured [Red below?] crystals of (I) (yield ca 5%, based on the initial CoCl₂·6H₂O input).

S3. Refinement

H atoms bonded to C atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. Water H atoms were found in a difference Fourier synthesis and refined with the O—H bonds fixed as initially found and U_iso(H) = 1.2U_eq(O).

Computing details

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

Figures

	Fig. 1. A view of the complex molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 45% probability level. H atoms have been omitted for clarity. [Symmetry codes: (x) −x + 2, −y + 1, −z + 1; (xi) −x, −y, −z + 1.]
	Fig. 2. The two-dimensional supramolecular layer in (I), parallel to (100).

decaaqua-1κ³O,2κ⁴O,3κ³O-bis(benzene-1,3,5-tricarboxylato)- 1κO,3κO-di-µ-4,4'-bipyridine-1:2κ²N:N';2:3κ²N:N'-di-4,4'-bipyridine- 1κN,3κN-tricobalt(II) 4,4'-bipyridine solvate octahydrate

Crystal data

[Co3(C9H3O6)2(C10H8N2)4(H2O)10]·C10H8N2·8H2O	F(000) = 1762
Mr = 1696.23	Dx = 1.513 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 25 reflections
a = 13.193 (3) Å	θ = 10–25°
b = 13.982 (3) Å	µ = 0.75 mm^−1
c = 20.193 (4) Å	T = 298 K
β = 91.36 (3)°	Block, red
V = 3723.8 (13) Å^3	0.31 × 0.27 × 0.22 mm
Z = 2

Data collection

Siemens P4 diffractometer	4457 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 27.5°, θmin = 1.8°
θ/2θ scans	h = −1→17
Absorption correction: ψ scan (North et al., 1968)	k = −1→18
Tmin = 0.527, Tmax = 0.601	l = −26→26
10423 measured reflections	3 standard reflections every 97 reflections
8535 independent reflections	intensity decay: none

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0637P)^2 + 0.3118P] where P = (Fo^2 + 2Fc^2)/3
8535 reflections	(Δ/σ)max = 0.001
502 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	1.0000	0.5000	0.5000	0.0375 (2)
Co2	0.93710 (4)	−0.16582 (4)	0.81737 (3)	0.03659 (16)
O1	1.0786 (2)	−0.1382 (2)	0.86312 (14)	0.0544 (8)
H1A	1.1179	−0.1772	0.8725	0.065*
H1B	1.0955	−0.0915	0.8844	0.065*
O2	0.8603 (2)	−0.0726 (2)	0.88168 (13)	0.0536 (8)
H2A	0.8032	−0.0570	0.8733	0.064*
H2B	0.8848	−0.0312	0.8997	0.064*
O3	1.0138 (2)	−0.2566 (2)	0.75454 (14)	0.0498 (8)
H3A	1.0635	−0.2543	0.7409	0.060*
H3B	0.9805	−0.2669	0.7200	0.060*
O4	0.8553 (2)	0.5424 (2)	0.52759 (13)	0.0515 (8)
H4A	0.8373	0.5403	0.5671	0.062*
H4B	0.7959	0.5275	0.5090	0.062*
O5	1.0579 (2)	0.5706 (2)	0.58597 (14)	0.0533 (8)
H5A	1.0596	0.5410	0.6230	0.064*
H5B	1.0501	0.6215	0.5882	0.064*
N1	0.9907 (3)	0.3737 (2)	0.55748 (16)	0.0421 (8)
N2	0.9545 (3)	−0.0461 (2)	0.75158 (16)	0.0423 (8)
C1	1.0437 (4)	−0.0106 (4)	0.7361 (3)	0.0644 (14)
H1	1.1018	−0.0418	0.7517	0.077*
C2	1.0551 (4)	0.0706 (3)	0.6978 (3)	0.0664 (15)
H2	1.1197	0.0935	0.6894	0.080*
C3	0.9714 (3)	0.1177 (3)	0.67207 (19)	0.0375 (10)
C4	0.9784 (3)	0.2057 (3)	0.63229 (19)	0.0375 (9)
C5	1.0681 (3)	0.2558 (3)	0.6271 (2)	0.0448 (11)
H5	1.1265	0.2335	0.6487	0.054*
C6	1.0719 (3)	0.3382 (3)	0.5903 (2)	0.0469 (11)
H6	1.1332	0.3707	0.5880	0.056*
C7	0.9034 (3)	0.3259 (3)	0.5626 (2)	0.0544 (12)
H7	0.8457	0.3498	0.5409	0.065*
C8	0.8957 (3)	0.2438 (3)	0.5980 (2)	0.0550 (12)
H8	0.8335	0.2125	0.5993	0.066*
C9	0.8782 (3)	0.0799 (3)	0.6885 (2)	0.0538 (12)
H9	0.8188	0.1088	0.6728	0.065*
C10	0.8735 (3)	−0.0001 (3)	0.7278 (2)	0.0548 (12)
H10	0.8099	−0.0234	0.7383	0.066*
N3	0.9101 (3)	−0.2859 (2)	0.88209 (17)	0.0407 (8)
N4	0.8306 (3)	−0.6939 (3)	1.0847 (2)	0.0626 (11)
C11	0.9029 (4)	−0.3745 (3)	0.8580 (2)	0.0520 (12)
H11	0.9107	−0.3828	0.8127	0.062*
C12	0.8849 (4)	−0.4539 (3)	0.8954 (2)	0.0499 (12)
H12	0.8812	−0.5137	0.8753	0.060*
C13	0.8719 (3)	−0.4459 (3)	0.9629 (2)	0.0393 (10)
C14	0.8562 (3)	−0.5312 (3)	1.0054 (2)	0.0421 (10)
C15	0.8479 (4)	−0.6225 (3)	0.9786 (2)	0.0638 (14)
H15	0.8507	−0.6312	0.9331	0.077*
C16	0.8355 (4)	−0.7000 (4)	1.0195 (3)	0.0698 (15)
H16	0.8302	−0.7602	1.0002	0.084*
C17	0.8379 (4)	−0.6076 (4)	1.1105 (2)	0.0613 (13)
H17	0.8351	−0.6017	1.1563	0.074*
C18	0.8493 (3)	−0.5256 (3)	1.0736 (2)	0.0529 (12)
H18	0.8525	−0.4664	1.0946	0.063*
C19	0.8763 (4)	−0.3539 (3)	0.9879 (2)	0.0565 (13)
H19	0.8666	−0.3436	1.0328	0.068*
C20	0.8948 (4)	−0.2776 (3)	0.9471 (2)	0.0551 (12)
H20	0.8968	−0.2167	0.9656	0.066*
O6	0.8282 (2)	−0.2902 (2)	0.69142 (16)	0.0618 (9)
O7	0.7975 (2)	−0.19143 (19)	0.77475 (13)	0.0438 (7)
O8	0.3753 (3)	−0.3597 (2)	0.58598 (17)	0.0682 (10)
O9	0.5273 (3)	−0.4224 (2)	0.57082 (16)	0.0657 (9)
O10	0.3427 (2)	−0.0757 (2)	0.74079 (17)	0.0661 (9)
O11	0.4831 (2)	−0.0183 (2)	0.79003 (16)	0.0602 (9)
C26	0.6608 (3)	−0.2301 (3)	0.70391 (18)	0.0367 (9)
C27	0.6173 (3)	−0.2925 (3)	0.65817 (19)	0.0395 (10)
H27	0.6575	−0.3377	0.6376	0.047*
C28	0.5145 (3)	−0.2882 (3)	0.64280 (19)	0.0397 (10)
C29	0.4566 (3)	−0.2177 (3)	0.6723 (2)	0.0435 (10)
H29	0.3877	−0.2140	0.6619	0.052*
C30	0.4991 (3)	−0.1524 (3)	0.71719 (19)	0.0380 (10)
C31	0.6014 (3)	−0.1607 (3)	0.73255 (19)	0.0376 (9)
H31	0.6310	−0.1185	0.7629	0.045*
C32	0.4690 (4)	−0.3611 (3)	0.5967 (2)	0.0482 (11)
C33	0.4363 (3)	−0.0762 (3)	0.7515 (2)	0.0455 (11)
C34	0.7709 (3)	−0.2389 (3)	0.7244 (2)	0.0382 (10)
O12	0.2526 (3)	0.0897 (3)	0.7986 (2)	0.1036 (14)
H12A	0.2765	0.0379	0.7956	0.124*
H12B	0.2390	0.0871	0.8384	0.124*
O14	0.6659 (2)	0.5340 (2)	0.46908 (16)	0.0652 (9)
H14A	0.6221	0.5374	0.4962	0.078*
H14B	0.6630	0.4843	0.4512	0.078*
O15	0.8267 (2)	0.5240 (2)	0.65939 (14)	0.0538 (8)
H15A	0.8799	0.5062	0.6768	0.065*
H15B	0.8237	0.5780	0.6657	0.065*
N5	1.0290 (4)	0.7758 (3)	0.5824 (2)	0.0734 (13)
C21	1.1038 (6)	0.8357 (5)	0.5755 (4)	0.120 (3)
H21	1.1672	0.8182	0.5927	0.144*
C22	1.0949 (5)	0.9238 (5)	0.5443 (4)	0.111 (3)
H22	1.1517	0.9629	0.5417	0.133*
C23	1.0060 (4)	0.9540 (3)	0.5176 (2)	0.0522 (12)
C24	0.9273 (4)	0.8906 (4)	0.5257 (3)	0.0838 (18)
H24	0.8630	0.9060	0.5090	0.101*
C25	0.9423 (5)	0.8048 (4)	0.5580 (3)	0.0874 (19)
H25	0.8866	0.7649	0.5626	0.105*
O13	0.2887 (3)	0.2683 (3)	0.7596 (3)	0.127 (2)
H13B	0.2767	0.2160	0.7699	0.153*
H13A	0.2628	0.3153	0.7517	0.153*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0384 (5)	0.0363 (4)	0.0376 (4)	−0.0023 (4)	−0.0031 (3)	0.0103 (4)
Co2	0.0400 (3)	0.0315 (3)	0.0382 (3)	−0.0019 (3)	−0.0023 (2)	0.0046 (2)
O1	0.062 (2)	0.0374 (16)	0.0629 (19)	−0.0067 (15)	−0.0264 (16)	0.0058 (14)
O2	0.062 (2)	0.0466 (18)	0.0518 (18)	0.0056 (16)	−0.0003 (16)	−0.0076 (15)
O3	0.0419 (17)	0.0553 (19)	0.0523 (17)	0.0003 (15)	0.0026 (14)	−0.0031 (15)
O4	0.0414 (17)	0.069 (2)	0.0440 (16)	−0.0018 (16)	0.0007 (14)	0.0082 (15)
O5	0.067 (2)	0.0434 (17)	0.0491 (17)	−0.0079 (16)	−0.0110 (16)	0.0057 (14)
N1	0.042 (2)	0.041 (2)	0.0428 (19)	−0.0014 (18)	−0.0054 (17)	0.0090 (16)
N2	0.044 (2)	0.0360 (19)	0.046 (2)	−0.0026 (18)	−0.0042 (17)	0.0096 (16)
C1	0.046 (3)	0.064 (3)	0.082 (4)	0.003 (3)	−0.011 (3)	0.041 (3)
C2	0.039 (3)	0.065 (3)	0.095 (4)	−0.005 (3)	−0.003 (3)	0.048 (3)
C3	0.040 (2)	0.037 (2)	0.036 (2)	0.002 (2)	0.0004 (19)	0.0040 (18)
C4	0.043 (2)	0.033 (2)	0.037 (2)	0.003 (2)	0.0018 (19)	0.0034 (18)
C5	0.041 (3)	0.043 (2)	0.050 (3)	0.005 (2)	−0.004 (2)	0.013 (2)
C6	0.042 (3)	0.044 (2)	0.055 (3)	−0.008 (2)	−0.003 (2)	0.010 (2)
C7	0.044 (3)	0.055 (3)	0.064 (3)	−0.002 (2)	−0.014 (2)	0.026 (3)
C8	0.040 (3)	0.056 (3)	0.068 (3)	−0.011 (2)	−0.008 (2)	0.026 (3)
C9	0.040 (3)	0.053 (3)	0.068 (3)	0.008 (2)	−0.002 (2)	0.022 (2)
C10	0.039 (3)	0.052 (3)	0.074 (3)	−0.003 (2)	0.001 (2)	0.027 (3)
N3	0.039 (2)	0.039 (2)	0.045 (2)	−0.0052 (17)	−0.0027 (16)	0.0040 (17)
N4	0.060 (3)	0.059 (3)	0.068 (3)	−0.006 (2)	−0.009 (2)	0.025 (2)
C11	0.076 (3)	0.044 (3)	0.036 (2)	−0.006 (3)	0.002 (2)	0.000 (2)
C12	0.067 (3)	0.033 (2)	0.050 (3)	−0.007 (2)	0.000 (2)	0.000 (2)
C13	0.032 (2)	0.040 (2)	0.046 (2)	−0.0008 (19)	−0.0069 (19)	0.006 (2)
C14	0.030 (2)	0.044 (3)	0.052 (3)	0.006 (2)	−0.0027 (19)	0.013 (2)
C15	0.089 (4)	0.045 (3)	0.057 (3)	0.003 (3)	−0.002 (3)	0.011 (2)
C16	0.090 (4)	0.045 (3)	0.075 (4)	0.003 (3)	−0.002 (3)	0.013 (3)
C17	0.068 (3)	0.063 (3)	0.053 (3)	−0.006 (3)	−0.005 (3)	0.017 (3)
C18	0.059 (3)	0.054 (3)	0.046 (3)	−0.007 (2)	−0.006 (2)	0.011 (2)
C19	0.084 (4)	0.043 (3)	0.042 (2)	−0.007 (3)	0.007 (2)	0.006 (2)
C20	0.080 (4)	0.039 (3)	0.047 (3)	−0.006 (2)	−0.001 (2)	−0.005 (2)
O6	0.0410 (18)	0.067 (2)	0.077 (2)	0.0069 (17)	−0.0012 (17)	−0.0314 (19)
O7	0.0408 (17)	0.0451 (17)	0.0452 (16)	0.0003 (14)	−0.0067 (14)	−0.0058 (14)
O8	0.049 (2)	0.073 (2)	0.082 (2)	−0.0045 (18)	−0.0104 (18)	−0.0170 (19)
O9	0.061 (2)	0.064 (2)	0.071 (2)	0.0112 (19)	−0.0162 (18)	−0.0221 (18)
O10	0.042 (2)	0.063 (2)	0.093 (3)	0.0086 (17)	−0.0033 (18)	−0.0141 (19)
O11	0.0474 (19)	0.055 (2)	0.078 (2)	0.0013 (17)	0.0021 (17)	−0.0198 (18)
C26	0.040 (2)	0.034 (2)	0.036 (2)	−0.0047 (19)	0.0015 (18)	0.0008 (18)
C27	0.040 (2)	0.035 (2)	0.043 (2)	−0.001 (2)	0.0023 (19)	−0.0011 (19)
C28	0.041 (3)	0.038 (2)	0.040 (2)	−0.001 (2)	−0.0003 (19)	−0.0026 (19)
C29	0.036 (2)	0.049 (3)	0.046 (2)	−0.001 (2)	−0.002 (2)	0.004 (2)
C30	0.038 (2)	0.030 (2)	0.045 (2)	−0.0003 (19)	0.0016 (19)	0.0033 (18)
C31	0.041 (2)	0.033 (2)	0.039 (2)	−0.002 (2)	0.0005 (18)	−0.0033 (19)
C32	0.042 (3)	0.051 (3)	0.051 (3)	0.002 (2)	−0.005 (2)	−0.001 (2)
C33	0.042 (3)	0.040 (3)	0.055 (3)	0.004 (2)	0.002 (2)	0.002 (2)
C34	0.036 (2)	0.033 (2)	0.045 (2)	−0.005 (2)	−0.001 (2)	0.001 (2)
O12	0.103 (3)	0.096 (3)	0.113 (3)	0.009 (3)	0.028 (3)	−0.010 (3)
O14	0.061 (2)	0.066 (2)	0.068 (2)	−0.0074 (18)	−0.0036 (18)	−0.0015 (18)
O15	0.057 (2)	0.0441 (17)	0.0602 (19)	0.0055 (16)	0.0012 (16)	0.0009 (15)
N5	0.082 (4)	0.062 (3)	0.076 (3)	−0.004 (3)	−0.003 (3)	0.005 (2)
C21	0.096 (5)	0.098 (5)	0.163 (7)	−0.036 (5)	−0.048 (5)	0.052 (5)
C22	0.084 (5)	0.084 (5)	0.162 (7)	−0.043 (4)	−0.046 (5)	0.046 (5)
C23	0.060 (3)	0.046 (3)	0.051 (3)	−0.010 (3)	−0.001 (3)	−0.011 (2)
C24	0.054 (3)	0.070 (4)	0.128 (5)	−0.003 (3)	0.012 (3)	0.031 (4)
C25	0.076 (4)	0.068 (4)	0.118 (5)	−0.013 (4)	0.019 (4)	0.021 (4)
O13	0.063 (3)	0.107 (4)	0.214 (6)	0.025 (3)	0.047 (3)	0.051 (4)

Geometric parameters (Å, º)

Co1—O4^i	2.087 (3)	C13—C19	1.383 (6)
Co1—O4	2.087 (3)	C13—C14	1.487 (6)
Co1—N1	2.118 (3)	C14—C18	1.386 (6)
Co1—N1^i	2.118 (3)	C14—C15	1.390 (6)
Co1—O5	2.123 (3)	C15—C16	1.374 (6)
Co1—O5^i	2.123 (3)	C15—H15	0.9300
Co2—O7	2.045 (3)	C16—H16	0.9300
Co2—O3	2.075 (3)	C17—C18	1.378 (6)
Co2—O1	2.099 (3)	C17—H17	0.9300
Co2—O2	2.115 (3)	C18—H18	0.9300
Co2—N2	2.153 (3)	C19—C20	1.374 (6)
Co2—N3	2.163 (3)	C19—H19	0.9300
O1—H1A	0.7722	C20—H20	0.9300
O1—H1B	0.8108	O6—C34	1.245 (5)
O2—H2A	0.7981	O7—C34	1.258 (5)
O2—H2B	0.7524	O8—C32	1.250 (5)
O3—H3A	0.7179	O9—C32	1.273 (5)
O3—H3B	0.8273	O10—C33	1.249 (5)
O4—H4A	0.8376	O11—C33	1.272 (5)
O4—H4B	0.8861	C26—C31	1.382 (5)
O5—H5A	0.8543	C26—C27	1.385 (5)
O5—H5B	0.7198	C26—C34	1.506 (6)
N1—C7	1.338 (5)	C27—C28	1.386 (6)
N1—C6	1.341 (5)	C27—H27	0.9300
N2—C1	1.321 (6)	C28—C29	1.390 (6)
N2—C10	1.327 (5)	C28—C32	1.496 (6)
C1—C2	1.382 (6)	C29—C30	1.394 (6)
C1—H1	0.9300	C29—H29	0.9300
C2—C3	1.377 (6)	C30—C31	1.383 (5)
C2—H2	0.9300	C30—C33	1.526 (6)
C3—C9	1.385 (6)	C31—H31	0.9300
C3—C4	1.473 (5)	O12—H12A	0.7926
C4—C5	1.382 (6)	O12—H12B	0.8287
C4—C8	1.385 (6)	O14—H14A	0.8069
C5—C6	1.373 (6)	O14—H14B	0.7841
C5—H5	0.9300	O15—H15A	0.8152
C6—H6	0.9300	O15—H15B	0.7665
C7—C8	1.358 (6)	N5—C25	1.299 (7)
C7—H7	0.9300	N5—C21	1.303 (7)
C8—H8	0.9300	C21—C22	1.388 (8)
C9—C10	1.374 (6)	C21—H21	0.9300
C9—H9	0.9300	C22—C23	1.347 (8)
C10—H10	0.9300	C22—H22	0.9300
N3—C11	1.334 (5)	C23—C24	1.377 (7)
N3—C20	1.337 (5)	C23—C23^ii	1.476 (9)
N4—C17	1.318 (6)	C24—C25	1.378 (8)
N4—C16	1.321 (6)	C24—H24	0.9300
C11—C12	1.368 (6)	C25—H25	0.9300
C11—H11	0.9300	O13—H13B	0.7772
C12—C13	1.381 (6)	O13—H13A	0.7557
C12—H12	0.9300
O4^i—Co1—O4	180.000 (1)	C11—N3—Co2	120.8 (3)
O4^i—Co1—N1	88.56 (12)	C20—N3—Co2	123.8 (3)
O4—Co1—N1	91.44 (12)	C17—N4—C16	116.6 (4)
O4^i—Co1—N1^i	91.44 (12)	N3—C11—C12	124.3 (4)
O4—Co1—N1^i	88.56 (12)	N3—C11—H11	117.8
N1—Co1—N1^i	180.00 (14)	C12—C11—H11	117.8
O4^i—Co1—O5	92.10 (12)	C11—C12—C13	120.5 (4)
O4—Co1—O5	87.90 (12)	C11—C12—H12	119.8
N1—Co1—O5	87.93 (12)	C13—C12—H12	119.8
N1^i—Co1—O5	92.07 (12)	C12—C13—C19	115.5 (4)
O4^i—Co1—O5^i	87.90 (12)	C12—C13—C14	121.8 (4)
O4—Co1—O5^i	92.10 (12)	C19—C13—C14	122.7 (4)
N1—Co1—O5^i	92.07 (12)	C18—C14—C15	115.6 (4)
N1^i—Co1—O5^i	87.93 (12)	C18—C14—C13	122.8 (4)
O5—Co1—O5^i	180.000 (1)	C15—C14—C13	121.6 (4)
O7—Co2—O3	94.73 (11)	C16—C15—C14	120.0 (5)
O7—Co2—O1	178.63 (12)	C16—C15—H15	120.0
O3—Co2—O1	86.58 (12)	C14—C15—H15	120.0
O7—Co2—O2	85.78 (12)	N4—C16—C15	123.9 (5)
O3—Co2—O2	179.45 (12)	N4—C16—H16	118.1
O1—Co2—O2	92.91 (12)	C15—C16—H16	118.1
O7—Co2—N2	89.13 (12)	N4—C17—C18	123.8 (4)
O3—Co2—N2	92.16 (13)	N4—C17—H17	118.1
O1—Co2—N2	91.24 (12)	C18—C17—H17	118.1
O2—Co2—N2	87.67 (13)	C17—C18—C14	120.1 (5)
O7—Co2—N3	87.62 (12)	C17—C18—H18	120.0
O3—Co2—N3	89.10 (12)	C14—C18—H18	120.0
O1—Co2—N3	91.99 (12)	C20—C19—C13	120.7 (4)
O2—Co2—N3	91.09 (12)	C20—C19—H19	119.7
N2—Co2—N3	176.60 (13)	C13—C19—H19	119.7
Co2—O1—H1A	124.2	N3—C20—C19	123.6 (4)
Co2—O1—H1B	127.7	N3—C20—H20	118.2
H1A—O1—H1B	105.4	C19—C20—H20	118.2
Co2—O2—H2A	120.1	C34—O7—Co2	131.6 (3)
Co2—O2—H2B	124.3	C31—C26—C27	119.4 (4)
H2A—O2—H2B	106.5	C31—C26—C34	119.7 (4)
Co2—O3—H3A	132.1	C27—C26—C34	120.8 (4)
Co2—O3—H3B	111.4	C26—C27—C28	120.6 (4)
H3A—O3—H3B	99.0	C26—C27—H27	119.7
Co1—O4—H4A	121.8	C28—C27—H27	119.7
Co1—O4—H4B	128.7	C27—C28—C29	118.6 (4)
H4A—O4—H4B	97.3	C27—C28—C32	119.1 (4)
Co1—O5—H5A	119.5	C29—C28—C32	122.3 (4)
Co1—O5—H5B	117.4	C28—C29—C30	121.8 (4)
H5A—O5—H5B	115.2	C28—C29—H29	119.1
C7—N1—C6	117.1 (3)	C30—C29—H29	119.1
C7—N1—Co1	121.3 (3)	C31—C30—C29	117.8 (4)
C6—N1—Co1	121.6 (3)	C31—C30—C33	119.6 (4)
C1—N2—C10	116.5 (4)	C29—C30—C33	122.6 (4)
C1—N2—Co2	123.2 (3)	C26—C31—C30	121.7 (4)
C10—N2—Co2	120.2 (3)	C26—C31—H31	119.2
N2—C1—C2	123.4 (4)	C30—C31—H31	119.2
N2—C1—H1	118.3	O8—C32—O9	123.0 (4)
C2—C1—H1	118.3	O8—C32—C28	118.5 (4)
C3—C2—C1	120.4 (4)	O9—C32—C28	118.5 (4)
C3—C2—H2	119.8	O10—C33—O11	124.5 (4)
C1—C2—H2	119.8	O10—C33—C30	118.0 (4)
C2—C3—C9	115.8 (4)	O11—C33—C30	117.5 (4)
C2—C3—C4	123.1 (4)	O6—C34—O7	125.1 (4)
C9—C3—C4	121.0 (4)	O6—C34—C26	119.6 (4)
C5—C4—C8	115.7 (4)	O7—C34—C26	115.3 (4)
C5—C4—C3	122.0 (4)	H12A—O12—H12B	97.5
C8—C4—C3	122.4 (4)	H14A—O14—H14B	109.8
C6—C5—C4	120.6 (4)	H15A—O15—H15B	106.1
C6—C5—H5	119.7	C25—N5—C21	114.9 (5)
C4—C5—H5	119.7	N5—C21—C22	124.2 (6)
N1—C6—C5	122.6 (4)	N5—C21—H21	117.9
N1—C6—H6	118.7	C22—C21—H21	117.9
C5—C6—H6	118.7	C23—C22—C21	121.6 (6)
N1—C7—C8	122.6 (4)	C23—C22—H22	119.2
N1—C7—H7	118.7	C21—C22—H22	119.2
C8—C7—H7	118.7	C22—C23—C24	113.7 (5)
C7—C8—C4	121.4 (4)	C22—C23—C23^ii	123.2 (6)
C7—C8—H8	119.3	C24—C23—C23^ii	123.1 (6)
C4—C8—H8	119.3	C23—C24—C25	121.0 (6)
C10—C9—C3	120.1 (4)	C23—C24—H24	119.5
C10—C9—H9	120.0	C25—C24—H24	119.5
C3—C9—H9	120.0	N5—C25—C24	124.6 (6)
N2—C10—C9	123.8 (4)	N5—C25—H25	117.7
N2—C10—H10	118.1	C24—C25—H25	117.7
C9—C10—H10	118.1	H13B—O13—H13A	141.3
C11—N3—C20	115.4 (4)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N4^iii	0.77	2.10	2.828 (5)	156
O1—H1B···O14^iv	0.81	2.09	2.812 (4)	149
O2—H2A···O15^v	0.80	2.15	2.916 (5)	162
O2—H2B···O9^vi	0.75	2.00	2.732 (5)	166
O3—H3A···O13^v	0.72	1.98	2.651 (4)	157
O3—H3B···O6	0.83	2.10	2.773 (4)	138
O4—H4A···O15	0.84	1.89	2.709 (4)	167
O4—H4B···O14	0.89	1.89	2.741 (5)	164
O5—H5A···O11^vi	0.85	2.03	2.858 (5)	162
O5—H5B···N5	0.72	2.18	2.895 (4)	173
O12—H12A···O10	0.79	2.14	2.862 (4)	153
O12—H12B···O8^vii	0.83	2.29	2.994 (5)	142
O13—H13A···O10^vii	0.76	2.07	2.787 (4)	158
O13—H13B···O12	0.78	1.89	2.664 (4)	177
O14—H14A···O9^viii	0.81	2.06	2.848 (5)	166
O14—H14B···O8^ix	0.78	1.96	2.728 (5)	167
O15—H15A···O11^vi	0.82	1.94	2.751 (5)	171
O15—H15B···O6^viii	0.78	1.92	2.677 (4)	172

Symmetry codes: (iii) −x+2, −y−1, −z+2; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+3/2, y−1/2, −z+3/2; (vi) −x+3/2, y+1/2, −z+3/2; (vii) −x+1/2, y+1/2, −z+3/2; (viii) x, y+1, z; (ix) −x+1, −y, −z+1.