A two-dimensional hydrogen-bonded water layer in the structure of a cobalt(III) cubane complex

A tetranuclear Co^III oxide complex with cubane topology, tetra­kis­(2,2′-bi­pyridine-κ²N,N′)di-μ₂-carbonato-κ⁴O:O′-tetra-μ₃-oxido-tetra­cobalt(III) penta­deca­hydrate, [Co₄(CO₃)₂O₄(C₁₀H₈N₂)₄]·15H₂O, with an unbounded hydrogen-bonded water layer, has been synthesized by reaction of CoCO₃ and 2,2′-bi­pyridine. The solvent water mol­ecules form a hydrogen-bonded net with tetra­meric and penta­meric water clusters as subunits. The Co₄O₄ cubane-like cores are sandwiched between the water layers, which are further stacked into a three-dimensional metallo-supra­molecular network.

S1. Introduction

In the past few years, metal complexes containing hydrogen-bonded water clusters have attracted a great deal of attention in the field of supra­molecular chemistry and crystal engineering, because studying the behaviour of water clusters can provide insight into the mutual inter­action of unusual properties which are of importance in many physical, chemical and biological processes (Yang et al., 2008; Moorthy et al., 2002; Wu & Lin, 2005; Liu et al., 2007; Cheng et al., 2006; Jin & Che, 2007). The theoretical and experimental study of flexible hydrogen-bonded water clusters can provide direct information on how the clusters were formed and how they inter­link in various geometries under diverse environments (Ghosh & Bharadwaj, 2004; Atwood et al., 2001; Müller et al., 2003; Meng et al., 2010). During the past decade, a variety of water clusters, such as trimers (Ghosh & Bharadwaj, 2005), tetra­mers (Zuhayra et al., 2006), penta­mers (Zabel et al., 1986), hexamers (Saha & Nangia, 2006), o­cta­mers (Khatua et al., 2010), decamers (Yoshizawa et al., 2005), dodecamers (Song & Ma, 2007), tetra­decamers (Ghosh et al., 2005), hexadecamers (Bi et al., 2009) and o­cta­decamers (Luan et al., 2006), and one-dimensional chains (Saha & Nangia, 2005), one-dimensional tapes (Cheng et al., 2006), two-dimensional layers (Zhang et al., 2005) and three-dimensional structures have been reported (Carballo et al., 2005). However, studies of these clusters linking to form larger clusters, especially two- and three-dimensional networks, are rare (Yang et al., 2008; Li et al., 2008). In this paper, we present an inter­esting structure, a cubane-like tetra­nuclear oxide-bridged cobalt(III) complex, namely [Co₄(CO₃)₂(µ₃-O)₄(bpy)₄].15H₂O (bpy is 2,2'-bi­pyridine), (I), including isolated two-dimensional water cluster layers.

S2. Experimental

S2.1. Synthesis and crystallization

All chemicals and solvents were commercially available and were used without further purification. A purple precipitate resulted from the addition of Na₂CO₃ (1.0 ml, 1.0 M) to an aqueous solution of CoCl₂.6H₂O (0.1594 g, 0.67 mmol) in H₂O (5 ml); it was separated by centrifugation and washed with distilled water four times, then transferred into a solution of 2,2'-bi­pyridine (0.1062 g, 0.67 mmol) in methanol (10 ml) and water (10 ml). To the resulting red solution (pH = 11.24), Na₂CO₃ (1.0 ml, 1.0 M) was added dropwise to adjust the pH to 12.21. The mixture obtained was allowed to stand at room temperature for 12 d to afford black–red needle-shaped crystals of (I).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in geometrically calculated positions and were refined using a riding model, with C—H = 0.93 Å [Added text OK?] and with U_iso(H) = 1.2U_eq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and refined with the O—H distance restrained to 0.85 (1) Å, while the H atoms of the multiply split atom O19 could not be positioned reliably and were omitted from a difference Fourier map. Finally, all non-H atoms, except O19, were refined with anisotropic displacement parameters.

S3. Results and discussion

Hydrated complex (I) crystallizes in the orthorhombic space group Pnma, with a two-dimensional supra­molecular water cluster layer and an oxide-bridged Co₄O₄ cubane-like core. The cubane-like tetra­nuclear unit can be understood as a tetra­mer joined by two trimers (Fig. 1). The Co^III cations and O atoms are located at alternating corners of a pseudo-cube. Each Co^III cation is coordinated by two bpy N atoms, one carbonate O atom and three oxide O atoms, forming an o­cta­hedral CoN₂O₄ coordination geometry. Atom Co1 lies in a general posiiton (Wyckoff site 8d), while atoms Co2 and Co3 are halved by a mirror plane (Wyckoff sites 4c). The Co1—N/O bond lengths fall in the range 1.876 (2)–1.950 (2) Å, and the cisoid and transoid N/O—Co1—N/O angles are in the ranges 81.62 (9)–97.73 (10) and 172.79 (9)–177.04 (10)°, respectively. For atom Co2, the corresponding ranges are 1.878 (2)–1.947 (2) Å, and 81.61 (16)–96.77 (10) and 173.63 (12)–176.58 (10)°, and for atom Co3 they are 1.878 (2)–1.947 (2) Å, and 81.05 (15)–98.05 (10) and 172.21 (13)–176.77 (10)°. All of these bonding parameters are within normal values and confirm a slightly distorted o­cta­hedral coordination for the cations.

Three crystallographically distinct Co^III cations are corner-shared via an O atom to form a trimer, and these are in turn bridged to generate a Co₄O₄ cubane-like core (Fig. 1). The cuboidal core is distorted, with all the O—Co—O angles being smaller than 90° while all the Co—O—Co angles are larger than 90°. The intra- and inter­trimeric Co···Co separations vary from 2.6645 (9) to 2.8582 (7) Å (Table 2). The resulting Co₄O₄ cubane-like cores are capped by two crystallographically distinct carbonate anions, both of them bis­ected by a mirror plane.

It is inter­esting to note that ten symmetry-independent solvent water molecules, by cooperative hydrogen-bonding inter­actions, form a two-dimensional water network comprised of tetra­meric and penta­meric water clusters as subunits (Fig. 2). Water molecules O10, O14, O14ⁱ and O17 [symmetry code: (i) x, -y + 1/2, z] form a special cyclic tetra­meric cluster through hydrogen bonds. Molecules O10 and O17 form pairs of mirror-symmetric hydrogen bonds, viz. O10—H10A···O14 and O17—H17A···O14, respectively (see Fig. 2 and Table 3 for details). With the inclusion of water atoms O11, O12, O16 and O16ⁱ, a cyclic tetra­meric water cluster is formed. In these tetra­meric clusters, the average O···O separation (2.84 Å) is comparable with the value of 2.85 Å in liquid water, where the O···O···O angles are in the range 73.6–98.4° (Eisenberg & Kauzmann, 1969). The hydrogen bonds within the penta­meric core involve atoms O10, O12, O14, O15 and O16. As far as the penta­mer is concerned, the O···O···O angles are in the range 95.8 (2)–112.8 (3)° and the O···O distances range from 2.756 (5) to 2.840 (6) Å (average 2.796 Å), slightly longer than those observed in ice I_h (2.759 Å at 200 K; [Reference?]).

The tetra­meric water clusters and the two crystallographically equivalent penta­meric water clusters are edge-shared into (H₂O)₁₄ clusters (Fig. 2), in which the penta­meric clusters form hydrogen-bonding inter­actions with solvent water molecule O13, and the crystallographically independent tetra­meric water cluster serves as a hydrogen-bond acceptor for atoms O9 and O18. On the whole, the resulting (H₂O)₁₄ clusters are joined together by hydrogen-bonding inter­actions with two kinds of cyclic hexameric groups [one formed by atoms O13, O14, O15, O13^iv, O14^iv and O15^iv, and the other formed by atoms 09ⁱⁱ, O10ⁱⁱ, O11, O14ⁱⁱ, O17ⁱⁱ and O18; symmetry codes: (ii) x, y, z + 1; (iv) -x, -y + 1, -z + 1], extending into a two-dimensional water cluster layer (Fig. 3). Inter­estingly, the Co₄O₄ cubane-like cores are sandwiched between these two-dimensional water cluster layers. Solvent molecules O9, O12, O13 and O15 donate H atoms to carbonate atoms O1, O2, O3 and O5, with O9··· O5 = 2.650 (5), O12···O3 = 2.701 (5), O13···O1ⁱⁱⁱ = 2.823 (3) and O15 ···O2^v = 2.722 (4) Å [symmetry codes: (iii) x - 1/2, -y + 1/2, -z + 3/2; (v) x - 1/2, y, -z + 3/2]. Due to this connection between the Co₄O₄ cubane-like core and the two-dimensional water cluster layers, the overall structure of (I) can be considered as a three-dimensional metallo-supra­molecular network (Fig. 4).

Related literature

For related literature, see: Atwood et al. (2001); Bi et al. (2009); Carballo et al. (2005); Cheng et al. (2006); Eisenberg & Kauzmann (1969); Ghosh & Bharadwaj (2004, 2005); Ghosh, Ribas, Fallah & Bharadwaj (2005); Jin & Che (2007); Khatua et al. (2010); Li et al. (2008); Liu et al. (2007); Luan et al. (2006); Müller et al. (2003); Meng et al. (2010); Moorthy et al. (2002); Saha & Nangia (2005, 2006); Song & Ma (2007); Wu & Lin (2005); Yang et al. (2008); Yoshizawa et al. (2005); Zabel et al. (1986); Zhang et al. (2005); Zuhayra et al. (2006).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the cubane-like tetranuclear oxide-bridged cobalt(III) cluster of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 45% probability level. [Symmetry code: (i) x, -y + 1/2, z.]

Fig. 2. The structure and hydrogen-bond connectivity of the (H₂O)₁₄ cluster of (I). Dashed lines indicate hydrogen bonds. [Significance of green and purple dashed lines?] [Symmetry code: (i) x, -y + 1/2, z.]

Fig. 3. The hydrogen-bonded network of the supramolecular water layer of (I). Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, -y + 1/2, z; (ii) x, y, z + 1; (iv) -x, -y + 1, -z + 1.]

Fig. 4. The three-dimensional supramolecular structure of (I). Dashed lines indicate hydrogen bonds. [Significance of green and purple dashed lines?]

Tetrakis(2,2'-bipyridine-κ²N,N')di-µ₂-carbonato-κ⁴O:O'-tetra-µ₃-oxido-tetracobalt(III) pentadecahydrate

Crystal data

[Co4(CO3)2O4(C10H8N2)4]·15H2O	Dx = 1.597 Mg m^−3
Mr = 1314.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 31250 reflections
a = 30.712 (6) Å	θ = 3.0–27.5°
b = 16.820 (3) Å	µ = 1.28 mm^−1
c = 10.588 (2) Å	T = 293 K
V = 5469.5 (19) Å^3	Needle, red
Z = 4	0.27 × 0.20 × 0.08 mm
F(000) = 2712

Data collection

Rigaku R-AXIS RAPID diffractometer	6456 independent reflections
Radiation source: fine-focus sealed tube	4752 reflections with I > 2σ(I)
Detector resolution: 0 pixels mm^-1	Rint = 0.077
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −39→39
Tmin = 0.742, Tmax = 0.902	k = −21→21
49124 measured reflections	l = −13→12

Refinement

Refinement on F^2	30 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0605P)^2 + 5.6408P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
6455 reflections	Δρmax = 0.69 e Å^−3
435 parameters	Δρmin = −0.41 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.37225 (2)	0.17079 (2)	0.61635 (4)	0.02252 (11)
Co2	0.29076 (2)	0.2500	0.58494 (5)	0.02570 (14)
Co3	0.34589 (2)	0.2500	0.39009 (5)	0.02330 (14)
N1	0.40408 (8)	0.08510 (15)	0.5356 (2)	0.0281 (6)
N2	0.35206 (8)	0.08394 (15)	0.7223 (2)	0.0288 (6)
C1	0.43673 (10)	0.0940 (2)	0.4542 (3)	0.0352 (7)
H1	0.4458	0.1451	0.4329	0.042*
C2	0.45758 (12)	0.0297 (2)	0.4005 (3)	0.0457 (9)
H2	0.4805	0.0372	0.3445	0.055*
C3	0.44386 (14)	−0.0457 (2)	0.4313 (4)	0.0535 (10)
H3	0.4568	−0.0898	0.3937	0.064*
C4	0.41100 (13)	−0.0555 (2)	0.5177 (4)	0.0472 (9)
H4	0.4017	−0.1063	0.5398	0.057*
C5	0.39177 (11)	0.01081 (19)	0.5719 (3)	0.0339 (7)
C6	0.36180 (11)	0.01045 (18)	0.6793 (3)	0.0341 (7)
C7	0.34697 (13)	−0.0568 (2)	0.7403 (4)	0.0512 (10)
H7	0.3520	−0.1070	0.7063	0.061*
C8	0.32442 (15)	−0.0485 (2)	0.8531 (4)	0.0597 (11)
H8	0.3142	−0.0931	0.8956	0.072*
C9	0.31736 (13)	0.0256 (3)	0.9011 (4)	0.0508 (10)
H9	0.3034	0.0321	0.9784	0.061*
C10	0.33128 (11)	0.0915 (2)	0.8326 (3)	0.0362 (7)
H10	0.3260	0.1422	0.8644	0.043*
N3	0.25549 (8)	0.17449 (16)	0.6789 (2)	0.0318 (6)
C11	0.25231 (11)	0.0967 (2)	0.6556 (3)	0.0391 (8)
H11	0.2670	0.0755	0.5867	0.047*
C12	0.22778 (12)	0.0470 (2)	0.7311 (4)	0.0456 (9)
H12	0.2255	−0.0069	0.7125	0.055*
C13	0.20700 (12)	0.0783 (2)	0.8332 (4)	0.0488 (10)
H13	0.1915	0.0453	0.8874	0.059*
C14	0.20892 (12)	0.1585 (2)	0.8561 (3)	0.0435 (9)
H14	0.1945	0.1804	0.9252	0.052*
C15	0.23260 (10)	0.2064 (2)	0.7748 (3)	0.0327 (7)
N4	0.36995 (8)	0.17477 (14)	0.2690 (2)	0.0270 (5)
C16	0.36206 (11)	0.09672 (19)	0.2681 (3)	0.0338 (7)
H16	0.3436	0.0756	0.3292	0.041*
C17	0.38024 (12)	0.0462 (2)	0.1799 (3)	0.0412 (8)
H17	0.3741	−0.0079	0.1809	0.049*
C18	0.40771 (13)	0.0779 (2)	0.0903 (3)	0.0473 (9)
H18	0.4212	0.0448	0.0319	0.057*
C19	0.41513 (13)	0.1589 (2)	0.0876 (3)	0.0434 (9)
H19	0.4331	0.1813	0.0266	0.052*
C20	0.39522 (10)	0.20575 (19)	0.1778 (3)	0.0302 (7)
O1	0.42146 (7)	0.18311 (12)	0.7311 (2)	0.0309 (5)
O2	0.47282 (11)	0.2500	0.8292 (4)	0.0457 (9)
C21	0.43830 (13)	0.2500	0.7630 (4)	0.0264 (9)
O3	0.24590 (10)	0.2500	0.4555 (3)	0.0383 (8)
O4	0.29278 (10)	0.2500	0.2909 (3)	0.0358 (7)
O5	0.22208 (13)	0.2500	0.2613 (4)	0.0860 (17)
C22	0.25351 (15)	0.2500	0.3349 (5)	0.0414 (12)
O6	0.32450 (6)	0.17292 (12)	0.50236 (18)	0.0256 (4)
O7	0.39293 (9)	0.2500	0.5069 (3)	0.0237 (6)
O8	0.33913 (9)	0.2500	0.6964 (3)	0.0249 (6)
O9	0.15327 (12)	0.2500	0.1103 (3)	0.0488 (9)
H9A	0.1350 (12)	0.2500	0.171 (3)	0.073*
H9B	0.1780 (8)	0.2500	0.146 (4)	0.073*
O10	0.09819 (12)	0.2500	0.3115 (4)	0.0572 (10)
H10A	0.0816 (6)	0.2902 (3)	0.306 (9)	0.086*	0.5
O11	0.10672 (15)	0.2500	0.8858 (4)	0.0622 (11)
H11A	0.0794 (4)	0.2500	0.900 (5)	0.093*
H11B	0.1184 (17)	0.2500	0.959 (3)	0.093*
O12	0.16004 (12)	0.2500	0.5109 (4)	0.0540 (10)
H12A	0.1856 (7)	0.2500	0.480 (5)	0.081*
H12B	0.1429 (14)	0.2500	0.448 (3)	0.081*
O13	−0.03833 (10)	0.46137 (16)	0.6997 (3)	0.0564 (7)
H13A	−0.0167 (10)	0.440 (2)	0.664 (4)	0.085*
H13B	−0.0539 (12)	0.4233 (17)	0.726 (4)	0.085*
O14	0.03912 (11)	0.37480 (17)	0.3290 (3)	0.0608 (8)
H14A	0.0333 (17)	0.373 (3)	0.4076 (15)	0.091*
H14B	0.0438 (17)	0.4239 (10)	0.314 (4)	0.091*
O15	0.02680 (10)	0.36692 (18)	0.5865 (3)	0.0586 (8)
H15A	0.0536 (5)	0.361 (3)	0.603 (5)	0.088*
H15B	0.0145 (12)	0.3245 (17)	0.610 (4)	0.088*
O16	0.11259 (11)	0.35189 (17)	0.6700 (3)	0.0589 (7)
H16A	0.1145 (17)	0.324 (2)	0.736 (2)	0.088*
H16B	0.1219 (17)	0.323 (2)	0.610 (3)	0.088*
O17	−0.00369 (16)	0.2500	0.1883 (5)	0.0744 (13)
H17A	0.007 (3)	0.2901 (3)	0.226 (7)	0.112*	0.5
O18	0.02111 (17)	0.2500	0.9347 (6)	0.0947 (17)
H18A	0.009 (2)	0.2500	1.006 (3)	0.142*
H18B	0.0004 (18)	0.2500	0.881 (6)	0.142*
O19A	0.2964 (7)	0.2698 (12)	0.031 (2)	0.0244 (17)*	0.08
O19B	0.2736 (4)	0.3595 (7)	0.0968 (10)	0.0244 (17)*	0.2
O19C	0.2834 (9)	0.3290 (16)	0.066 (2)	0.0244 (17)*	0.08
O19D	0.2570 (5)	0.3741 (9)	0.1129 (14)	0.0244 (17)*	0.14

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0243 (2)	0.01837 (19)	0.0248 (2)	−0.00016 (15)	−0.00006 (16)	0.00011 (15)
Co2	0.0216 (3)	0.0287 (3)	0.0268 (3)	0.000	0.0022 (2)	0.000
Co3	0.0229 (3)	0.0246 (3)	0.0224 (3)	0.000	0.0009 (2)	0.000
N1	0.0280 (13)	0.0255 (13)	0.0308 (13)	0.0028 (10)	−0.0025 (11)	−0.0027 (10)
N2	0.0318 (14)	0.0245 (13)	0.0302 (13)	−0.0033 (11)	−0.0029 (11)	0.0031 (11)
C1	0.0306 (17)	0.0377 (18)	0.0373 (17)	0.0021 (14)	−0.0003 (14)	−0.0050 (14)
C2	0.0371 (19)	0.055 (2)	0.045 (2)	0.0130 (17)	0.0018 (16)	−0.0108 (18)
C3	0.053 (2)	0.049 (2)	0.058 (2)	0.0209 (19)	−0.002 (2)	−0.020 (2)
C4	0.058 (2)	0.0241 (17)	0.059 (2)	0.0087 (16)	−0.006 (2)	−0.0084 (16)
C5	0.0376 (18)	0.0225 (15)	0.0415 (18)	0.0015 (13)	−0.0047 (15)	−0.0028 (13)
C6	0.0367 (17)	0.0221 (15)	0.0434 (18)	−0.0020 (13)	−0.0071 (15)	0.0017 (14)
C7	0.060 (3)	0.0260 (18)	0.068 (3)	−0.0052 (17)	0.003 (2)	0.0073 (18)
C8	0.066 (3)	0.041 (2)	0.072 (3)	−0.011 (2)	0.000 (2)	0.023 (2)
C9	0.053 (2)	0.057 (3)	0.042 (2)	−0.0083 (19)	0.0046 (18)	0.0151 (18)
C10	0.0382 (18)	0.0391 (19)	0.0313 (16)	−0.0021 (15)	0.0002 (14)	0.0054 (14)
N3	0.0228 (13)	0.0383 (15)	0.0342 (14)	−0.0024 (11)	0.0013 (11)	0.0001 (12)
C11	0.0359 (18)	0.0391 (19)	0.0425 (18)	−0.0074 (15)	−0.0028 (15)	−0.0042 (15)
C12	0.043 (2)	0.039 (2)	0.055 (2)	−0.0145 (16)	−0.0026 (18)	−0.0032 (18)
C13	0.044 (2)	0.053 (2)	0.049 (2)	−0.0169 (18)	0.0059 (18)	0.0114 (18)
C14	0.0378 (19)	0.054 (2)	0.0392 (19)	−0.0073 (17)	0.0094 (16)	0.0019 (17)
C15	0.0248 (15)	0.0430 (18)	0.0304 (15)	−0.0009 (14)	0.0018 (13)	0.0017 (14)
N4	0.0284 (13)	0.0263 (13)	0.0262 (12)	−0.0005 (10)	−0.0008 (10)	−0.0014 (10)
C16	0.0355 (17)	0.0300 (17)	0.0359 (17)	−0.0038 (13)	−0.0050 (14)	−0.0002 (14)
C17	0.053 (2)	0.0282 (17)	0.0429 (19)	−0.0008 (15)	−0.0044 (17)	−0.0098 (15)
C18	0.054 (2)	0.045 (2)	0.042 (2)	0.0125 (18)	0.0058 (18)	−0.0167 (17)
C19	0.047 (2)	0.046 (2)	0.0364 (18)	0.0031 (17)	0.0103 (16)	−0.0061 (15)
C20	0.0289 (16)	0.0336 (17)	0.0282 (15)	−0.0011 (13)	0.0011 (13)	−0.0010 (13)
O1	0.0329 (12)	0.0240 (11)	0.0357 (11)	0.0008 (9)	−0.0071 (9)	−0.0014 (9)
O2	0.0378 (19)	0.0310 (18)	0.068 (2)	0.000	−0.0237 (18)	0.000
C21	0.024 (2)	0.028 (2)	0.027 (2)	0.000	0.0014 (17)	0.000
O3	0.0235 (16)	0.059 (2)	0.0322 (17)	0.000	−0.0017 (13)	0.000
O4	0.0307 (17)	0.052 (2)	0.0250 (15)	0.000	−0.0051 (13)	0.000
O5	0.033 (2)	0.178 (6)	0.047 (2)	0.000	−0.0149 (19)	0.000
C22	0.028 (2)	0.062 (3)	0.035 (3)	0.000	−0.004 (2)	0.000
O6	0.0242 (10)	0.0259 (11)	0.0266 (10)	−0.0019 (8)	0.0011 (8)	−0.0013 (8)
O7	0.0255 (15)	0.0220 (14)	0.0236 (14)	0.000	0.0010 (12)	0.000
O8	0.0282 (15)	0.0216 (14)	0.0250 (14)	0.000	0.0025 (12)	0.000
O9	0.043 (2)	0.065 (3)	0.0381 (19)	0.000	−0.0061 (16)	0.000
O10	0.039 (2)	0.064 (3)	0.069 (3)	0.000	0.000 (2)	0.000
O11	0.066 (3)	0.075 (3)	0.046 (2)	0.000	−0.002 (2)	0.000
O12	0.037 (2)	0.075 (3)	0.051 (2)	0.000	0.0074 (17)	0.000
O13	0.0601 (19)	0.0383 (15)	0.0708 (19)	−0.0081 (13)	0.0174 (15)	−0.0004 (14)
O14	0.071 (2)	0.0452 (17)	0.0660 (19)	0.0007 (15)	0.0069 (17)	0.0015 (14)
O15	0.0525 (17)	0.0497 (17)	0.074 (2)	−0.0041 (14)	0.0133 (16)	0.0113 (15)
O16	0.0687 (19)	0.0411 (15)	0.0668 (18)	0.0047 (14)	0.0019 (17)	−0.0021 (14)
O17	0.061 (3)	0.079 (3)	0.083 (3)	0.000	−0.020 (2)	0.000
O18	0.066 (3)	0.120 (5)	0.099 (4)	0.000	−0.025 (3)	0.000

Geometric parameters (Å, º)

Co1—O7	1.876 (2)	C11—H11	0.9300
Co1—O8	1.879 (2)	C12—C13	1.361 (5)
Co1—O6	1.900 (2)	C12—H12	0.9300
Co1—N1	1.940 (2)	C13—C14	1.371 (5)
Co1—N2	1.943 (2)	C13—H13	0.9300
Co1—O1	1.950 (2)	C14—C15	1.385 (5)
Co2—O6	1.876 (2)	C14—H14	0.9300
Co2—O6^i	1.876 (2)	C15—C15^i	1.468 (7)
Co2—O8	1.897 (3)	N4—C16	1.335 (4)
Co2—N3^i	1.943 (3)	N4—C20	1.343 (4)
Co2—N3	1.943 (3)	C16—C17	1.381 (5)
Co2—O3	1.943 (3)	C16—H16	0.9300
Co3—O6	1.878 (2)	C17—C18	1.376 (5)
Co3—O6^i	1.878 (2)	C17—H17	0.9300
Co3—O7	1.902 (3)	C18—C19	1.382 (5)
Co3—O4	1.940 (3)	C18—H18	0.9300
Co3—N4	1.947 (2)	C19—C20	1.381 (5)
Co3—N4^i	1.947 (2)	C19—H19	0.9300
Co1—Co1^i	2.6645 (9)	C20—C20^i	1.489 (6)
Co1—Co2	2.8547 (8)	O1—C21	1.283 (3)
Co1—Co3	2.8582 (7)	O2—C21	1.271 (5)
Co2—Co3	2.6689 (9)	C21—O1^i	1.283 (3)
N1—C1	1.330 (4)	O3—C22	1.298 (6)
N1—C5	1.361 (4)	O4—C22	1.293 (6)
N2—C10	1.337 (4)	O5—C22	1.241 (6)
N2—C6	1.351 (4)	O7—Co1^i	1.8764 (19)
C1—C2	1.380 (5)	O8—Co1^i	1.879 (2)
C1—H1	0.9300	O9—H9A	0.853 (10)
C2—C3	1.376 (6)	O9—H9B	0.849 (10)
C2—H2	0.9300	O10—H10A	0.848 (7)
C3—C4	1.372 (6)	O11—H11A	0.852 (10)
C3—H3	0.9300	O11—H11B	0.850 (10)
C4—C5	1.387 (5)	O12—H12A	0.849 (10)
C4—H4	0.9300	O12—H12B	0.846 (10)
C5—C6	1.463 (5)	O13—H13A	0.844 (10)
C6—C7	1.381 (5)	O13—H13B	0.848 (10)
C7—C8	1.388 (6)	O14—H14A	0.851 (10)
C7—H7	0.9300	O14—H14B	0.852 (10)
C8—C9	1.364 (6)	O15—H15A	0.847 (10)
C8—H8	0.9300	O15—H15B	0.844 (10)
C9—C10	1.392 (5)	O16—H16A	0.846 (10)
C9—H9	0.9300	O16—H16B	0.849 (10)
C10—H10	0.9300	O17—H17A	0.851 (7)
N3—C11	1.335 (4)	O18—H18A	0.852 (10)
N3—C15	1.346 (4)	O18—H18B	0.852 (10)
C11—C12	1.381 (5)	O19A—O19A^i	0.67 (4)
O7—Co1—O8	87.62 (9)	C9—C8—C7	119.5 (4)
O7—Co1—O6	81.70 (10)	C9—C8—H8	120.2
O8—Co1—O6	81.68 (10)	C7—C8—H8	120.2
O7—Co1—N1	94.86 (10)	C8—C9—C10	119.0 (4)
O8—Co1—N1	177.04 (10)	C8—C9—H9	120.5
O6—Co1—N1	97.06 (9)	C10—C9—H9	120.5
O7—Co1—N2	176.49 (10)	N2—C10—C9	121.7 (3)
O8—Co1—N2	95.73 (10)	N2—C10—H10	119.1
O6—Co1—N2	97.73 (10)	C9—C10—H10	119.1
N1—Co1—N2	81.77 (11)	C11—N3—C15	119.4 (3)
O7—Co1—O1	92.70 (11)	C11—N3—Co2	125.9 (2)
O8—Co1—O1	93.62 (11)	C15—N3—Co2	114.7 (2)
O6—Co1—O1	172.79 (9)	N3—C11—C12	121.8 (3)
N1—Co1—O1	87.89 (10)	N3—C11—H11	119.1
N2—Co1—O1	88.13 (10)	C12—C11—H11	119.1
O6—Co2—O6^i	87.44 (12)	C13—C12—C11	118.7 (3)
O6—Co2—O8	81.81 (9)	C13—C12—H12	120.6
O6^i—Co2—O8	81.81 (9)	C11—C12—H12	120.6
O6—Co2—N3^i	176.58 (10)	C12—C13—C14	120.1 (3)
O6^i—Co2—N3^i	95.45 (10)	C12—C13—H13	120.0
O8—Co2—N3^i	96.76 (10)	C14—C13—H13	120.0
O6—Co2—N3	95.45 (10)	C13—C14—C15	119.0 (3)
O6^i—Co2—N3	176.58 (10)	C13—C14—H14	120.5
O8—Co2—N3	96.77 (10)	C15—C14—H14	120.5
N3^i—Co2—N3	81.61 (16)	N3—C15—C14	120.8 (3)
O6—Co2—O3	93.61 (9)	N3—C15—C15^i	113.46 (18)
O6^i—Co2—O3	93.61 (9)	C14—C15—C15^i	125.5 (2)
O8—Co2—O3	173.63 (12)	C16—N4—C20	118.8 (3)
N3^i—Co2—O3	88.05 (10)	C16—N4—Co3	125.1 (2)
N3—Co2—O3	88.05 (10)	C20—N4—Co3	116.1 (2)
O6—Co3—O6^i	87.33 (12)	N4—C16—C17	122.4 (3)
O6—Co3—O7	81.61 (9)	N4—C16—H16	118.8
O6^i—Co3—O7	81.61 (9)	C17—C16—H16	118.8
O6—Co3—O4	92.78 (9)	C18—C17—C16	118.4 (3)
O6^i—Co3—O4	92.78 (9)	C18—C17—H17	120.8
O7—Co3—O4	172.21 (13)	C16—C17—H17	120.8
O6—Co3—N4	95.80 (9)	C17—C18—C19	119.8 (3)
O6^i—Co3—N4	176.77 (10)	C17—C18—H18	120.1
O7—Co3—N4	98.05 (10)	C19—C18—H18	120.1
O4—Co3—N4	87.85 (10)	C20—C19—C18	118.4 (3)
O6—Co3—N4^i	176.77 (10)	C20—C19—H19	120.8
O6^i—Co3—N4^i	95.80 (9)	C18—C19—H19	120.8
O7—Co3—N4^i	98.05 (10)	N4—C20—C19	122.1 (3)
O4—Co3—N4^i	87.85 (10)	N4—C20—C20^i	112.82 (17)
N4—Co3—N4^i	81.05 (15)	C19—C20—C20^i	124.8 (2)
C1—N1—C5	119.7 (3)	C21—O1—Co1	124.7 (2)
C1—N1—Co1	125.5 (2)	O2—C21—O1^i	118.75 (19)
C5—N1—Co1	114.7 (2)	O2—C21—O1	118.75 (19)
C10—N2—C6	119.2 (3)	O1^i—C21—O1	122.5 (4)
C10—N2—Co1	125.8 (2)	C22—O3—Co2	124.5 (3)
C6—N2—Co1	115.0 (2)	C22—O4—Co3	126.1 (3)
N1—C1—C2	121.9 (3)	O5—C22—O4	119.9 (4)
N1—C1—H1	119.1	O5—C22—O3	118.6 (4)
C2—C1—H1	119.1	O4—C22—O3	121.5 (4)
C3—C2—C1	118.9 (3)	Co2—O6—Co3	90.64 (9)
C3—C2—H2	120.5	Co2—O6—Co1	98.24 (9)
C1—C2—H2	120.5	Co3—O6—Co1	98.34 (9)
C4—C3—C2	119.6 (3)	Co1^i—O7—Co1	90.47 (12)
C4—C3—H3	120.2	Co1^i—O7—Co3	98.31 (11)
C2—C3—H3	120.2	Co1—O7—Co3	98.31 (11)
C3—C4—C5	119.5 (4)	Co1—O8—Co1^i	90.34 (12)
C3—C4—H4	120.2	Co1—O8—Co2	98.23 (11)
C5—C4—H4	120.2	Co1^i—O8—Co2	98.23 (11)
N1—C5—C4	120.2 (3)	H9A—O9—H9B	104.9 (16)
N1—C5—C6	113.5 (3)	H11A—O11—H11B	104.8 (17)
C4—C5—C6	125.9 (3)	H12A—O12—H12B	106.0 (17)
N2—C6—C7	121.3 (3)	H13A—O13—H13B	105.9 (16)
N2—C6—C5	113.4 (3)	H14A—O14—H14B	104.6 (16)
C7—C6—C5	125.1 (3)	H15A—O15—H15B	105.9 (17)
C6—C7—C8	119.0 (4)	H16A—O16—H16B	105.1 (16)
C6—C7—H7	120.5	H18A—O18—H18B	104.6 (17)
C8—C7—H7	120.5

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O10	0.85 (1)	1.87 (1)	2.720 (6)	176 (5)
O9—H9B···O5	0.85 (1)	1.82 (2)	2.650 (5)	164 (5)
O10—H10A···O14	0.85 (1)	1.95 (2)	2.781 (4)	168 (9)
O11—H11A···O18	0.85 (1)	1.83 (1)	2.680 (7)	179 (6)
O11—H11B···O9^ii	0.85 (1)	1.93 (1)	2.774 (5)	171 (6)
O12—H12A···O3	0.85 (1)	1.87 (2)	2.701 (5)	166 (5)
O12—H12B···O10	0.85 (1)	2.00 (1)	2.840 (6)	175 (5)
O13—H13A···O15	0.84 (1)	1.99 (2)	2.822 (4)	167 (4)
O13—H13B···O1^iii	0.85 (1)	1.99 (2)	2.823 (3)	165 (4)
O14—H14A···O15	0.85 (1)	1.91 (1)	2.756 (5)	174 (5)
O14—H14B···O13^iv	0.85 (1)	1.94 (2)	2.772 (4)	164 (5)
O15—H15A···O16	0.85 (1)	1.95 (1)	2.791 (5)	170 (5)
O15—H15B···O2^v	0.84 (1)	1.90 (2)	2.722 (4)	163 (4)
O16—H16A···O11	0.85 (1)	2.03 (2)	2.862 (4)	169 (5)
O16—H16B···O12	0.85 (1)	1.99 (2)	2.811 (4)	161 (5)
O17—H17A···O14	0.85 (1)	2.05 (1)	2.891 (4)	171 (4)
O18—H18A···O17^ii	0.85 (1)	1.96 (2)	2.791 (8)	164 (8)
O18—H18B···O2^v	0.85 (1)	2.38 (4)	3.163 (7)	152 (7)

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