Tetra­aqua­bis­(2,6-diamine-7H-purine-κN⁹)cobalt(II) benzene-1,2,4,5-tetra­carboxyl­ate tetra­hydrate

The title compound, [Co(C₅H₇N₆)₂(H₂O)₄](C₁₀H₂O₈)·4H₂O, is an ionic structure comprising a [Co(Hdap)₂(H₂O)₄]⁴⁺ cation (dap is 2,6-diamino­purine) in a general position, two benzene-1,2,4,5-tetra­carboxyl­ate (btc⁴⁻) anions straddling two different inversion centres and four solvent water mol­ecules. The structure presents a remarkable degree of pseudosymmetry, with the Co^II cation lying almost exactly on a noncrystallographic pseudo-inversion centre. The overall spatial arrangement can be described in terms of cationic and anionic chains running along the [111] direction and linked into a three-dimensional network by a very complex hydrogen-bonding scheme in which all the available N—H and O—H groups take part.

S1. Comment

2,6-Diaminopurine, C₅H₆N₆ (hereinafter dap), is an attractive ligand which has not been much explored. Among its many interesting features are an impressive ability to participate in hydrogen bonding, acting as both a (multiple) donor and a (multiple) acceptor, and thus giving rise to extremely complex hydrogen-bonding networks. In its Hdap⁺ protonated state, the group can display a special form of tautomerism known as prototropy, consisting of the relocation of the extra proton, which has the effect of forcing a rearrangement of the charge distribution. The different forms reported so far for the cation are shown in the second scheme, and the electron-density redistribution is evidenced by the different positions of the single and double bonds around the rings. The few known structures containing the Hdap⁺ cation (Cambridge Structural Database, Version 5.3; Allen, 2002) are [M(Hdap⁺)₂.(hpt^2-)₂(H₂O)₂].4H₂O [H₂hpt is homophthalic acid, M is Ni^II (IIa) or Co^II (IIb); Atria, Corsini et al., 2011], bis(Hdap) di-µ-croconato-κ³O,O':O'';κ³O:O',O''-bis[tetraaqua(croconato-κ²O,O')neodymium(III)], (III) (Atria, Morel et al., 2011), and bis(Hdap)(hpt).heptahydrate, (IV) (Atria et al., 2010). All three Hdap⁺ groups appearing in (IIa), (IIb), (III) and (IV) are different, in that protonation takes place at different N sites. The group can also act as a ligand, though with rather restricted coordination capabilities. The molecule is capable of acting as a monocoordinated ligand linking the metal site through one of its lone imidazole N atoms, but this behaviour seems to be rather uncommon in dap chemistry: until very recently only one compound with the molecule binding to a metal centre appeared in the literature (Badura & Vahrenkamp, 2002), and only in the last year have we described compounds (IIa) and (IIb) as members of a new family of isomorphous compounds with the ligand acting in a similar N-monodentate fashion. Pursuing our interest in dap and Hdap⁺ structures, we present herein the title novel cobalt transition metal complex with the molecule acting as a charged singly protonated cation (Hdap⁺), binding the metal in an N-monodentate fashion, [Co^II(Hdap⁺)₂.(H₂O)₄].btc^-4.4H₂O, (I), where H₄btc is 1,2,4,5-benzyltetracarboxylic acid.

Compound (I) is an ionic structure comprising a [Co(Hdap)₂(H₂O)₄]⁴⁺ cationic unit in a general position, charge-balanced by two btc^4- anions straddling two different inversion centres such that two independent half-anions provide the required 4- charge. The structure is completed by four solvent water molecules. The four aqua ligands bound to the Co^II centre (Fig. 1a) form a square-planar array defining the equatorial positions of an octahedron. The apical sites are occupied by two `elongated' Hdap⁺ cations (discussed below), each coordinating via their single imidazole N donor atom. The resulting octahedron is slightly elongated, with a mean value for the equatorial (shortest) Co—O bonds of 2.099 (6) Å, and an average of 2.146 (3) Å for the apical (longest) Co—N ones. Intramolecular bond angles span the narrow ranges 86.28 (4)–92.78 (4) and 175.21 (4)–178.35 (4)°. The structure presents a remarkable pseudosymmetry (pseudo I-centring of the reported triclinic cell), with the Co^II cation lying almost on a non-crystallographic 1 pseudo centre. To facilitate comparison, pseudo-symmetrically related atoms have been labelled similarly (O1W, O1W' etc).

Fig. 1(b) shows the overlap of the whole independent unit and its pseudo-symmetry-related counterpart, without any least-squares fitting, and the correspondence is apparent [mean deviation of the fit is 0.22 (14) Å; see Refinement section for details].

The centrosymmetric btc^4- units are very similar to each other and the four independent carboxylate groups present almost perfect delocalisation [overall C—O range 1.2451 (19)–1.2648 (19)Å]. The groups are, however, rotated around the C—C bond, following the demands posed by the complex hydrogen-bonding scheme, with one of the COO^- groups being almost parallel and the remaining one nearly orthogonal to the plane of the benzyl core [rotation angles 4.9 (1) and 4.0 (1), and 83.3 (1) and 89.8 (1)°, for pseudo-related COO^- groups in each anion].

Regarding the protonated Hdap⁺ cation, to our knowledge the only reported structures containing the species are those labelled (II) to (IV) above, but none of them is strictly comparable with (I). Structure (III) bears the same proton disposition (see second scheme), but in this structure the cation is not coordinated. On the other hand, complexes (IIa) and (IIb) bear the same coordination behaviour but the protonation takes place at different sites (see second scheme) and this has important consequences in the way in which both three-dimensional structures are built up. In structures (IIa) and (IIb), the extra H atom is located midway between the two amino groups (at N31), thus leaving the remaining atom N41 free to make a strong intramolecular hydrogen bond accepting one aqua H atom. In (I) instead, it is precisely atom N41 at the protonated site, thus precluding this particular type of interaction but promoting in turn a stronger hydrogen-bonding link to the surrounding anions. As already suggested, intermolecular interactions are by far the most distinctive feature in these dap-containing structures. In the case of (I), there is an extremely large number of different possible donors (a total of 28, all of them involved in hydrogen bonding), and a comparable number of possible acceptors and aromatic rings liable to be involved in π–π contacts. Table 2 shows the most important hydrogen bonds and Table 3 presents π–π interactions. The net result of their presence is a tightly bound three-dimensional structure, rather difficult to describe in the usual terms of a constructive process starting from strongly linked elemental bricks, further interlinked by weaker forces. However, inspection of Fig. 2 suggests one possible (though certainly not unique) description in terms of the interlinkage of cationic (heavy dark lines) and anionic (weaker lines) chains, running along the [111] direction and seen in projection in the figure. Figs. 3(a) and 3(b) give, in turn, individual views of each of these one-dimensional structures.

The anion/solvent water chain (Fig. 3a) is sustained internally by a network of hydrogen bonds, involving solvent water molecules as donors and a mixture of water and btc^4- carboxylate O atoms as acceptors. The cationic chain (Fig 3b) is, in turn, linked by π–π contacts between overlapping dap units, presented in detail in Table 3. This leaves 20 H atoms available for hydrogen bonding with the anion/solvent water chain, constituting the main factor in the assembly of the three-dimensional structure.

Related literature

For related literature, see: Allen (2002); Atria et al. (2010); Atria, Corsini, Herrera, Garland & Baggio (2011); Atria, Morel, Garland & Baggio (2011); Badura & Vahrenkamp (2002).

S2. Experimental

2,6-Diaminopurine (0.300 g, 2 mmol) and cobalt acetate tetrahydrate (0.498 g, 2 mmol) were dissolved in water–ethanol (2:1 v/v, 10 ml) and the mixture kept under reflux for 10 min. An aqueous solution (40 ml) of 1,2,4,5-benzenetetracarboxylic acid (0.508 g, 2 mmol) and NaOH (0.080 g, 2 mmol) was added to this mixture, which was kept under reflux for another 4 h. Slow evaporation at room temperature for two weeks yielded single crystals of (I) suitable for X-ray diffraction.

S3. Refinement

The amine groups exhibited slightly different geometries, as assessed by the deviations of the amine H atoms from the least-squares mean plane through the other atoms in the diaminopurine moieties: the C—NH₂ group at N51 is essentially planar, although slightly rotated around the C—N bond [with deviations of -0.15 (2) and 0.12 (2) Å from the mean plane]. In contrast, the other three amines exhibit different types and degrees of pyramidalization at the N atom. At N51', only one H atom lies significantly out of the plane [deviations of 0.02 (2) and -0.10 (2) Å], while the deviations are greater at N61 [0.33 (2) and 0.24 (2) Å] and at N61' [0.34 (2) and 0.23 (2) Å]. This varying degree of planarity for NH₂ groups is not uncommon for aromatic rings carrying two amino groups and might be due to the ability of the delocalized π-system of the ring to accommodate charge from one amino group, but not more (Linden, 2010).

The striking pseudo-I-centring in the true primitive triclinic cell exhibited by structure (I) (see Fig. 1b) requires some additional description. The true unit cell is the primitive one reported herein, leading to a mean I/σ(I) of 17.3 for all reflections and 9.1 for those with h+k+l = 2n+1 (I-centring violations).

The pseudo-centring effect on the intensities does not arise (as it more typically does) from a heavy atom lying on a special position and the rest of the structure evolving more or less independently, but rather from a collective effect where all individual deviations from the pseudo-symmetry are rather small. This can be seen both in Fig. 1(b) and, more quantitatively, from the small mean-square deviation of the separation of pseudo-related atoms and the (also small) s.u.: 0.22 (14) Å. Finally, an independent structure resolution and refinement of the structure, using an `I-centred cell' [viz. including the (1/2 + x, 1/2 + y, 1/2 + z) symmetry operation] and the same data set, but purged of I-centring violations, could be performed without any substantial problems, converging perfectly acceptably, as can be seen from the following values for the `I-centred' refinement (the corresponding values for the true primitive cell are given in parentheses): N_total = 11306 (22822), N_unique= 3112 (6235), N_I>2σ(I) = 2965 (5525), N_parameters = 255 (506), N_restraints = 12 (24), R₁ = 0.0370 (0.0348), wR₂ = 0.0992 (0.0930), S = 1.056 (1.049).

The main difficulty found during the structure resolution in the `centred' I1 space group involved the location of the water H atoms, where those of O4W in particular appeared somewhat disordered. The reason for this is clearly seen in Figs. 1(b) and 3(a), where the positions of the `pseudo-equivalent' atoms O4W and O4W' appear as the most conspicuous deviation from the pseudo-inversion symmetry, the pseudo-centres being shown as `crossed circles' in Fig. 3(a).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. (a) The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, with independent atoms shown as heavy bonds and filled ellipsoids, and symmetry-related atoms as hollow bonds and empty ellipsoids. Primed atoms are related to unprimed ones by the `pseudo-inversion' at (1/4, 1/4, 1/4). (b) Schematic overlap of the independent unit and its `pseudo-inverted' counterpart. No least-squares fit was performed. [Symmetry codes: (i) -x + 2, -y, -z + 1; (ii) -x - 1, -y + 1, -z.]
	Fig. 2. A packing view of (I), drawn along the [111] direction of the cationic and anionic chains, which are therefore seen in projection. The former are shown in bold. H atoms have been omitted for clarity.
	Fig. 3. The chain formation in (I). (a) The anionic hydrogen-bonded chain, with embedded pseudo-inversion centres (shown as crossed circles). (b) The cationic chain formed by π–π interactions. [Symmetry codes: (i) x, y, z + 1; (ii) -x + 1, -y, -z + 1; (iii) -x, -y + 1, -z + 1.]

Tetraaquabis(2,6-diamine-7H-purine-κN⁹)cobalt(II) benzene-1,2,4,5-tetracarboxylate tetrahydrate

Crystal data

[Co(C5H7N6)2(H2O)4]C10H2O8·4H2O	Z = 2
Mr = 755.51	F(000) = 782
Triclinic, P1	Dx = 1.780 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5730 (3) Å	Cell parameters from 9999 reflections
b = 11.9386 (4) Å	θ = 1.3–27.8°
c = 15.6694 (6) Å	µ = 0.71 mm^−1
α = 91.026 (1)°	T = 150 K
β = 94.732 (1)°	Polyhedron, pink
γ = 92.794 (1)°	0.54 × 0.19 × 0.16 mm
V = 1409.84 (9) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	6235 independent reflections
Radiation source: sealed tube	5525 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
CCD rotation images, thin slices scans	θmax = 27.8°, θmin = 1.3°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −9→9
Tmin = 0.82, Tmax = 0.89	k = −15→15
22822 measured reflections	l = −20→19

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.4507P] where P = (Fo^2 + 2Fc^2)/3
6235 reflections	(Δ/σ)max < 0.001
550 parameters	Δρmax = 0.90 e Å^−3
36 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. Least-squares planes (x,y,z in crystal coordinates) through the diaminopurine groupos and deviations from them (* indicates atom used to define plane)

6.2520 (0.0012) x + 6.0335 (0.0032) y - 3.4652 (0.0045) z = 2.7395 (0.0029)

* -0.0732 (0.0012) C11 * 0.0699 (0.0013) C21 * 0.0213 (0.0012) C31 * -0.0089 (0.0013) C41 * 0.0618 (0.0013) C51 * -0.0251 (0.0011) N11 * -0.0276 (0.0011) N21 * -0.0133 (0.0011) N31 * 0.0865 (0.0011) N41 * -0.0109 (0.0010) N51 * -0.0804 (0.0010) N61 -0.3330 (0.0211) H61A -0.2394 (0.0202) H61B -0.1435 (0.0202) H51A 0.1125 (0.0199) H51B

Rms deviation of fitted atoms = 0.0524

6.4788 (0.0011) x + 5.0703 (0.0034) y - 4.7591 (0.0044) z = 1.6853 (0.0005)

Angle to previous plane (with approximate esd) = 6.77 ( 0.04 )

* 0.0490 (0.0012) C11' * -0.0167 (0.0013) C21' * -0.0164 (0.0013) C31' * 0.0033 (0.0013) C41' * -0.0474 (0.0013) C51' * -0.0139 (0.0011) N11' * 0.0511 (0.0011) N21' * -0.0088 (0.0012) N31' * -0.0672 (0.0012) N41' * -0.0141 (0.0010) N51' * 0.0811 (0.0010) N61' 0.3380 (0.0207) H61C 0.2289 (0.0201) H61D 0.0163 (0.0200) H51C -0.1006 (0.0202) H51D

Rms deviation of fitted atoms = 0.0420

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

	x	y	z	Uiso*/Ueq
Co1	0.25925 (2)	0.256490 (15)	0.250449 (11)	0.01303 (8)
N11	0.27315 (17)	0.37228 (10)	0.35769 (8)	0.0161 (3)
N21	0.18154 (17)	0.51238 (10)	0.43706 (8)	0.0156 (3)
H21	0.128 (2)	0.5752 (10)	0.4475 (11)	0.019*
N31	0.42566 (17)	0.36306 (10)	0.61342 (8)	0.0161 (3)
N41	0.44273 (17)	0.28240 (11)	0.47497 (8)	0.0165 (3)
H41	0.479 (2)	0.2261 (11)	0.4465 (10)	0.020*
N51	0.28004 (18)	0.52575 (11)	0.63327 (8)	0.0181 (3)
H51A	0.295 (3)	0.5193 (17)	0.6888 (6)	0.032 (5)*
H51B	0.231 (2)	0.5872 (11)	0.6163 (12)	0.027 (5)*
N61	0.56414 (19)	0.19776 (11)	0.59478 (9)	0.0204 (3)
H61A	0.560 (3)	0.1920 (18)	0.6503 (6)	0.035 (6)*
H61B	0.575 (3)	0.1403 (12)	0.5602 (11)	0.031 (5)*
C11	0.1777 (2)	0.46408 (12)	0.35920 (9)	0.0167 (3)
H11	0.1139	0.4919	0.3100	0.020*
C21	0.28839 (19)	0.44879 (12)	0.49095 (9)	0.0153 (3)
C31	0.33078 (19)	0.44820 (12)	0.58048 (9)	0.0147 (3)
C41	0.47532 (19)	0.28250 (12)	0.56148 (9)	0.0159 (3)
C51	0.34096 (19)	0.36389 (12)	0.44036 (9)	0.0153 (3)
O12	1.02000 (15)	−0.29966 (9)	0.45194 (7)	0.0226 (2)
O22	1.14275 (15)	−0.26819 (9)	0.58488 (7)	0.0214 (2)
O32	0.56420 (14)	0.08420 (9)	0.42258 (7)	0.0173 (2)
O42	0.70410 (15)	0.05395 (9)	0.30503 (7)	0.0211 (2)
C12	1.03724 (19)	−0.11312 (12)	0.50715 (9)	0.0138 (3)
C22	0.89942 (19)	−0.07996 (12)	0.44996 (9)	0.0142 (3)
H22	0.8310	−0.1352	0.4155	0.017*
C32	0.86024 (19)	0.03209 (12)	0.44238 (9)	0.0132 (3)
C42	1.06953 (19)	−0.23598 (12)	0.51543 (9)	0.0152 (3)
C52	0.69869 (19)	0.06054 (11)	0.38474 (9)	0.0141 (3)
O1W	0.25414 (15)	0.11736 (9)	0.33084 (7)	0.0181 (2)
H1WA	0.195 (2)	0.0582 (12)	0.3110 (13)	0.036 (6)*
H1WB	0.3489 (17)	0.0958 (15)	0.3578 (12)	0.029 (5)*
O2W	0.53611 (14)	0.25465 (9)	0.25907 (7)	0.0190 (2)
H2WB	0.585 (3)	0.1926 (11)	0.2659 (13)	0.037 (6)*
H2WA	0.588 (3)	0.2912 (14)	0.2218 (11)	0.046 (7)*
O3W	0.63152 (17)	0.38970 (10)	0.77701 (8)	0.0276 (3)
H3WB	0.608 (3)	0.3391 (14)	0.8127 (10)	0.040 (6)*
H3WA	0.562 (2)	0.3774 (17)	0.7321 (8)	0.041 (6)*
O4W	0.38692 (17)	0.17111 (10)	0.75683 (8)	0.0276 (3)
H4WB	0.422 (3)	0.1838 (16)	0.8098 (7)	0.046 (7)*
H4WA	0.355 (3)	0.1018 (10)	0.7513 (14)	0.069 (8)*
N11'	0.24934 (17)	0.14407 (10)	0.14173 (8)	0.0167 (3)
N21'	0.32333 (17)	−0.00662 (10)	0.06828 (8)	0.0158 (3)
H21'	0.363 (2)	−0.0734 (9)	0.0634 (11)	0.019*
N31'	0.07271 (17)	0.13285 (10)	−0.11176 (8)	0.0166 (3)
N41'	0.08464 (17)	0.23128 (11)	0.02163 (8)	0.0169 (3)
H41'	0.045 (2)	0.2883 (11)	0.0493 (11)	0.020*
N51'	0.19608 (19)	−0.03866 (11)	−0.12541 (8)	0.0189 (3)
H51C	0.165 (3)	−0.0424 (16)	−0.1795 (6)	0.029 (5)*
H51D	0.245 (2)	−0.0979 (12)	−0.1038 (12)	0.027 (5)*
N61'	−0.04210 (19)	0.30745 (11)	−0.10094 (8)	0.0201 (3)
H61C	−0.043 (3)	0.3059 (18)	−0.1568 (6)	0.033 (6)*
H61D	−0.044 (3)	0.3690 (11)	−0.0689 (11)	0.029 (5)*
C11'	0.3354 (2)	0.04830 (12)	0.14365 (9)	0.0172 (3)
H11'	0.3986	0.0222	0.1937	0.021*
C21'	0.22164 (19)	0.05710 (12)	0.01194 (9)	0.0149 (3)
C31'	0.16405 (19)	0.04779 (12)	−0.07644 (9)	0.0146 (3)
C41'	0.03984 (19)	0.22221 (12)	−0.06385 (9)	0.0160 (3)
C51'	0.17998 (19)	0.14866 (12)	0.05923 (9)	0.0147 (3)
O12'	−0.53044 (16)	0.79153 (9)	0.07469 (8)	0.0261 (3)
O22'	−0.66860 (17)	0.77295 (9)	−0.05571 (8)	0.0288 (3)
O32'	−0.05782 (14)	0.42296 (9)	0.08041 (7)	0.0178 (2)
O42'	−0.22780 (15)	0.40999 (9)	0.19016 (7)	0.0210 (2)
C12'	−0.54332 (19)	0.61232 (12)	0.00435 (9)	0.0140 (3)
C22'	−0.40548 (19)	0.57313 (12)	0.05830 (9)	0.0149 (3)
H22'	−0.3409	0.6235	0.0984	0.018*
C32'	−0.36054 (19)	0.46175 (12)	0.05463 (9)	0.0135 (3)
C42'	−0.5839 (2)	0.73471 (12)	0.00781 (10)	0.0173 (3)
C52'	−0.2045 (2)	0.42694 (11)	0.11306 (9)	0.0147 (3)
O1W'	0.25618 (15)	0.39672 (9)	0.17111 (7)	0.0181 (2)
H1WC	0.313 (2)	0.4574 (11)	0.1863 (13)	0.039 (6)*
H1WD	0.1575 (16)	0.4140 (15)	0.1449 (11)	0.026 (5)*
O2W'	−0.01877 (14)	0.24682 (9)	0.24857 (7)	0.0176 (2)
H2WD	−0.073 (3)	0.3030 (13)	0.2284 (12)	0.042 (6)*
H2WC	−0.056 (3)	0.2320 (16)	0.2964 (8)	0.040 (6)*
O3W'	−0.13784 (19)	0.09108 (11)	−0.27225 (8)	0.0326 (3)
H3WD	−0.102 (3)	0.1417 (15)	−0.3047 (11)	0.046 (7)*
H3WC	−0.074 (3)	0.099 (2)	−0.2241 (9)	0.060 (8)*
O4W'	0.07752 (19)	0.30298 (12)	−0.27634 (9)	0.0361 (3)
H4WD	0.062 (3)	0.304 (2)	−0.3315 (6)	0.060 (8)*
H4WC	0.175 (2)	0.270 (2)	−0.2651 (13)	0.073 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01317 (12)	0.01397 (12)	0.01175 (12)	0.00283 (8)	−0.00094 (8)	−0.00168 (8)
N11	0.0167 (6)	0.0170 (6)	0.0145 (6)	0.0030 (5)	−0.0003 (5)	−0.0016 (5)
N21	0.0173 (6)	0.0143 (6)	0.0151 (6)	0.0041 (5)	−0.0001 (5)	−0.0004 (5)
N31	0.0174 (6)	0.0165 (6)	0.0142 (6)	0.0009 (5)	−0.0001 (5)	−0.0014 (5)
N41	0.0186 (6)	0.0174 (6)	0.0135 (6)	0.0054 (5)	−0.0002 (5)	−0.0033 (5)
N51	0.0251 (7)	0.0164 (6)	0.0126 (6)	0.0045 (5)	−0.0003 (5)	−0.0026 (5)
N61	0.0261 (7)	0.0190 (7)	0.0164 (6)	0.0076 (5)	−0.0008 (5)	−0.0010 (5)
C11	0.0180 (7)	0.0167 (7)	0.0153 (7)	0.0020 (6)	−0.0001 (6)	−0.0008 (5)
C21	0.0158 (7)	0.0148 (7)	0.0153 (7)	0.0013 (5)	0.0004 (5)	−0.0006 (5)
C31	0.0141 (7)	0.0144 (7)	0.0155 (7)	−0.0013 (5)	0.0014 (5)	−0.0011 (5)
C41	0.0142 (7)	0.0169 (7)	0.0162 (7)	−0.0006 (5)	−0.0003 (5)	−0.0001 (5)
C51	0.0141 (7)	0.0158 (7)	0.0159 (7)	0.0004 (5)	0.0015 (5)	−0.0012 (5)
O12	0.0256 (6)	0.0153 (5)	0.0254 (6)	0.0055 (4)	−0.0078 (5)	−0.0056 (4)
O22	0.0271 (6)	0.0153 (5)	0.0212 (6)	0.0045 (4)	−0.0040 (4)	0.0024 (4)
O32	0.0149 (5)	0.0194 (5)	0.0177 (5)	0.0044 (4)	0.0000 (4)	0.0001 (4)
O42	0.0242 (6)	0.0251 (6)	0.0140 (5)	0.0069 (5)	−0.0017 (4)	−0.0008 (4)
C12	0.0153 (7)	0.0129 (6)	0.0133 (6)	0.0026 (5)	0.0010 (5)	−0.0012 (5)
C22	0.0138 (7)	0.0149 (7)	0.0136 (7)	0.0008 (5)	−0.0005 (5)	−0.0023 (5)
C32	0.0128 (7)	0.0151 (7)	0.0118 (6)	0.0026 (5)	0.0005 (5)	−0.0003 (5)
C42	0.0125 (7)	0.0139 (7)	0.0192 (7)	0.0009 (5)	0.0004 (5)	0.0003 (5)
C52	0.0162 (7)	0.0106 (6)	0.0150 (7)	0.0008 (5)	−0.0021 (5)	−0.0003 (5)
O1W	0.0174 (6)	0.0176 (5)	0.0186 (5)	0.0014 (4)	−0.0040 (4)	0.0012 (4)
O2W	0.0150 (5)	0.0187 (5)	0.0235 (6)	0.0027 (4)	0.0016 (4)	0.0028 (4)
O3W	0.0323 (7)	0.0272 (6)	0.0213 (6)	−0.0072 (5)	−0.0044 (5)	−0.0014 (5)
O4W	0.0340 (7)	0.0262 (6)	0.0220 (6)	−0.0028 (5)	0.0018 (5)	0.0020 (5)
N11'	0.0179 (6)	0.0174 (6)	0.0146 (6)	0.0038 (5)	−0.0002 (5)	−0.0010 (5)
N21'	0.0191 (6)	0.0139 (6)	0.0143 (6)	0.0039 (5)	−0.0005 (5)	−0.0015 (5)
N31'	0.0180 (6)	0.0167 (6)	0.0147 (6)	0.0016 (5)	−0.0003 (5)	−0.0014 (5)
N41'	0.0203 (7)	0.0164 (6)	0.0141 (6)	0.0058 (5)	−0.0004 (5)	−0.0028 (5)
N51'	0.0268 (7)	0.0156 (6)	0.0138 (6)	0.0046 (5)	−0.0025 (5)	−0.0035 (5)
N61'	0.0258 (7)	0.0174 (6)	0.0169 (6)	0.0058 (5)	−0.0021 (5)	−0.0012 (5)
C11'	0.0184 (7)	0.0184 (7)	0.0146 (7)	0.0034 (6)	−0.0005 (6)	−0.0002 (5)
C21'	0.0147 (7)	0.0156 (7)	0.0144 (7)	0.0014 (5)	0.0004 (5)	−0.0001 (5)
C31'	0.0142 (7)	0.0153 (7)	0.0141 (7)	−0.0008 (5)	0.0012 (5)	−0.0001 (5)
C41'	0.0142 (7)	0.0174 (7)	0.0161 (7)	0.0002 (5)	0.0005 (5)	−0.0014 (5)
C51'	0.0135 (7)	0.0154 (7)	0.0152 (7)	0.0018 (5)	0.0012 (5)	−0.0002 (5)
O12'	0.0292 (6)	0.0174 (5)	0.0303 (6)	0.0071 (5)	−0.0073 (5)	−0.0085 (5)
O22'	0.0367 (7)	0.0147 (5)	0.0330 (7)	0.0066 (5)	−0.0129 (5)	0.0021 (5)
O32'	0.0151 (5)	0.0193 (5)	0.0192 (5)	0.0043 (4)	0.0002 (4)	0.0011 (4)
O42'	0.0225 (6)	0.0273 (6)	0.0135 (5)	0.0075 (5)	−0.0009 (4)	0.0006 (4)
C12'	0.0153 (7)	0.0127 (6)	0.0142 (7)	0.0025 (5)	0.0011 (5)	0.0002 (5)
C22'	0.0153 (7)	0.0155 (7)	0.0133 (6)	0.0008 (5)	−0.0009 (5)	−0.0024 (5)
C32'	0.0132 (7)	0.0157 (7)	0.0118 (6)	0.0021 (5)	0.0007 (5)	0.0011 (5)
C42'	0.0151 (7)	0.0138 (7)	0.0226 (7)	0.0012 (5)	0.0003 (6)	−0.0003 (6)
C52'	0.0170 (7)	0.0117 (6)	0.0151 (7)	0.0027 (5)	−0.0015 (5)	−0.0014 (5)
O1W'	0.0188 (6)	0.0163 (5)	0.0182 (5)	0.0007 (4)	−0.0037 (4)	0.0007 (4)
O2W'	0.0154 (5)	0.0208 (5)	0.0168 (5)	0.0037 (4)	0.0005 (4)	0.0013 (4)
O3W'	0.0399 (8)	0.0306 (7)	0.0246 (6)	−0.0111 (6)	−0.0061 (6)	−0.0010 (5)
O4W'	0.0376 (8)	0.0441 (8)	0.0292 (7)	0.0131 (6)	0.0101 (6)	0.0114 (6)

Geometric parameters (Å, º)

Co1—O2W	2.0911 (11)	O3W—H3WA	0.851 (9)
Co1—O2W'	2.1007 (11)	O4W—H4WB	0.859 (9)
Co1—O1W'	2.1029 (11)	O4W—H4WA	0.852 (9)
Co1—O1W	2.1032 (11)	N11'—C11'	1.3430 (19)
Co1—N11'	2.1439 (12)	N11'—C51'	1.3577 (18)
Co1—N11	2.1492 (12)	N21'—C11'	1.3348 (19)
N11—C11	1.3429 (19)	N21'—C21'	1.3857 (18)
N11—C51	1.3608 (18)	N21'—H21'	0.869 (9)
N21—C11	1.3375 (19)	N31'—C41'	1.3385 (19)
N21—C21	1.3836 (19)	N31'—C31'	1.3570 (19)
N21—H21	0.887 (9)	N41'—C41'	1.3555 (19)
N31—C41	1.3366 (19)	N41'—C51'	1.3643 (19)
N31—C31	1.3581 (19)	N41'—H41'	0.879 (9)
N41—C41	1.3576 (19)	N51'—C31'	1.3190 (19)
N41—C51	1.3630 (19)	N51'—H51C	0.861 (9)
N41—H41	0.869 (9)	N51'—H51D	0.875 (9)
N51—C31	1.3223 (19)	N61'—C41'	1.3348 (19)
N51—H51A	0.874 (9)	N61'—H61C	0.875 (9)
N51—H51B	0.873 (9)	N61'—H61D	0.884 (9)
N61—C41	1.3325 (19)	C11'—H11'	0.9500
N61—H61A	0.877 (9)	C21'—C51'	1.374 (2)
N61—H61B	0.877 (9)	C21'—C31'	1.4178 (19)
C11—H11	0.9500	O12'—C42'	1.2650 (19)
C21—C51	1.370 (2)	O22'—C42'	1.2448 (18)
C21—C31	1.413 (2)	O32'—C52'	1.2634 (18)
O12—C42	1.2617 (18)	O42'—C52'	1.2537 (18)
O22—C42	1.2552 (18)	C12'—C22'	1.393 (2)
O32—C52	1.2610 (18)	C12'—C32'^ii	1.401 (2)
O42—C52	1.2543 (17)	C12'—C42'	1.5088 (19)
C12—C22	1.396 (2)	C22'—C32'	1.390 (2)
C12—C32^i	1.401 (2)	C22'—H22'	0.9500
C12—C42	1.5049 (19)	C32'—C12'^ii	1.401 (2)
C22—C32	1.3894 (19)	C32'—C52'	1.513 (2)
C22—H22	0.9500	O1W'—H1WC	0.846 (9)
C32—C12^i	1.401 (2)	O1W'—H1WD	0.859 (9)
C32—C52	1.5156 (19)	O2W'—H2WD	0.855 (9)
O1W—H1WA	0.857 (9)	O2W'—H2WC	0.842 (9)
O1W—H1WB	0.856 (9)	O3W'—H3WD	0.845 (9)
O2W—H2WB	0.847 (9)	O3W'—H3WC	0.861 (9)
O2W—H2WA	0.845 (9)	O4W'—H4WD	0.863 (9)
O3W—H3WB	0.853 (9)	O4W'—H4WC	0.859 (10)
O2W—Co1—O2W'	175.22 (4)	Co1—O1W—H1WB	121.3 (13)
O2W—Co1—O1W'	92.79 (4)	H1WA—O1W—H1WB	107.0 (13)
O2W'—Co1—O1W'	91.99 (4)	Co1—O2W—H2WB	118.8 (14)
O2W—Co1—O1W	88.93 (4)	Co1—O2W—H2WA	116.2 (15)
O2W'—Co1—O1W	86.29 (4)	H2WB—O2W—H2WA	108.9 (13)
O1W'—Co1—O1W	178.17 (4)	H3WB—O3W—H3WA	107.4 (13)
O2W—Co1—N11'	89.01 (5)	H4WB—O4W—H4WA	107.3 (14)
O2W'—Co1—N11'	90.96 (5)	C11'—N11'—C51'	103.66 (12)
O1W'—Co1—N11'	91.43 (4)	C11'—N11'—Co1	122.11 (10)
O1W—Co1—N11'	89.24 (4)	C51'—N11'—Co1	134.02 (10)
O2W—Co1—N11	90.23 (5)	C11'—N21'—C21'	106.24 (12)
O2W'—Co1—N11	89.90 (4)	C11'—N21'—H21'	121.3 (12)
O1W'—Co1—N11	87.33 (4)	C21'—N21'—H21'	131.9 (12)
O1W—Co1—N11	92.02 (4)	C41'—N31'—C31'	120.31 (13)
N11'—Co1—N11	178.52 (4)	C41'—N41'—C51'	117.92 (13)
C11—N11—C51	103.63 (12)	C41'—N41'—H41'	117.3 (12)
C11—N11—Co1	123.39 (10)	C51'—N41'—H41'	124.7 (12)
C51—N11—Co1	131.73 (10)	C31'—N51'—H51C	122.7 (13)
C11—N21—C21	106.28 (12)	C31'—N51'—H51D	121.3 (13)
C11—N21—H21	123.4 (12)	H51C—N51'—H51D	115.9 (18)
C21—N21—H21	130.3 (12)	C41'—N61'—H61C	113.3 (14)
C41—N31—C31	119.96 (13)	C41'—N61'—H61D	115.7 (13)
C41—N41—C51	117.78 (12)	H61C—N61'—H61D	124.9 (19)
C41—N41—H41	117.0 (12)	N21'—C11'—N11'	113.34 (13)
C51—N41—H41	124.9 (12)	N21'—C11'—H11'	123.3
C31—N51—H51A	121.5 (13)	N11'—C11'—H11'	123.3
C31—N51—H51B	123.8 (13)	C51'—C21'—N21'	105.36 (12)
H51A—N51—H51B	114.7 (18)	C51'—C21'—C31'	119.85 (13)
C41—N61—H61A	113.9 (14)	N21'—C21'—C31'	134.76 (13)
C41—N61—H61B	116.2 (13)	N51'—C31'—N31'	118.97 (13)
H61A—N61—H61B	123.5 (19)	N51'—C31'—C21'	123.20 (13)
N21—C11—N11	113.18 (13)	N31'—C31'—C21'	117.83 (13)
N21—C11—H11	123.4	N61'—C41'—N31'	119.22 (13)
N11—C11—H11	123.4	N61'—C41'—N41'	117.34 (13)
C51—C21—N21	105.50 (13)	N31'—C41'—N41'	123.44 (13)
C51—C21—C31	119.75 (13)	N11'—C51'—N41'	128.10 (13)
N21—C21—C31	134.27 (13)	N11'—C51'—C21'	111.40 (13)
N51—C31—N31	118.90 (13)	N41'—C51'—C21'	120.47 (13)
N51—C31—C21	122.90 (13)	C22'—C12'—C32'^ii	119.58 (13)
N31—C31—C21	118.19 (13)	C22'—C12'—C42'	119.83 (13)
N61—C41—N31	119.42 (13)	C32'^ii—C12'—C42'	120.56 (13)
N61—C41—N41	117.06 (13)	C32'—C22'—C12'	121.28 (13)
N31—C41—N41	123.52 (13)	C32'—C22'—H22'	119.4
N11—C51—N41	128.01 (13)	C12'—C22'—H22'	119.4
N11—C51—C21	111.41 (13)	C22'—C32'—C12'^ii	119.14 (13)
N41—C51—C21	120.53 (13)	C22'—C32'—C52'	117.98 (13)
C22—C12—C32^i	119.63 (13)	C12'^ii—C32'—C52'	122.85 (13)
C22—C12—C42	119.26 (13)	O22'—C42'—O12'	124.37 (14)
C32^i—C12—C42	121.08 (13)	O22'—C42'—C12'	117.45 (13)
C32—C22—C12	121.38 (13)	O12'—C42'—C12'	118.18 (13)
C32—C22—H22	119.3	O42'—C52'—O32'	125.20 (14)
C12—C22—H22	119.3	O42'—C52'—C32'	118.24 (13)
C22—C32—C12^i	118.99 (13)	O32'—C52'—C32'	116.46 (12)
C22—C32—C52	118.28 (13)	Co1—O1W'—H1WC	121.4 (13)
C12^i—C32—C52	122.55 (12)	Co1—O1W'—H1WD	118.9 (12)
O22—C42—O12	124.52 (13)	H1WC—O1W'—H1WD	107.3 (13)
O22—C42—C12	117.99 (13)	Co1—O2W'—H2WD	116.7 (15)
O12—C42—C12	117.49 (13)	Co1—O2W'—H2WC	113.7 (14)
O42—C52—O32	125.07 (13)	H2WD—O2W'—H2WC	108.1 (13)
O42—C52—C32	119.26 (13)	H3WD—O3W'—H3WC	107.3 (14)
O32—C52—C32	115.58 (12)	H4WD—O4W'—H4WC	105.4 (14)
Co1—O1W—H1WA	116.9 (13)
O2W—Co1—N11—C11	134.45 (12)	O2W—Co1—N11'—C11'	51.58 (12)
O2W'—Co1—N11—C11	−50.33 (12)	O2W'—Co1—N11'—C11'	−123.64 (12)
O1W'—Co1—N11—C11	41.67 (12)	O1W'—Co1—N11'—C11'	144.35 (12)
O1W—Co1—N11—C11	−136.62 (12)	O1W—Co1—N11'—C11'	−37.36 (12)
O2W—Co1—N11—C51	−60.57 (13)	O2W—Co1—N11'—C51'	−122.23 (14)
O2W'—Co1—N11—C51	114.65 (13)	O2W'—Co1—N11'—C51'	62.55 (14)
O1W'—Co1—N11—C51	−153.35 (13)	O1W'—Co1—N11'—C51'	−29.47 (14)
O1W—Co1—N11—C51	28.36 (13)	O1W—Co1—N11'—C51'	148.83 (14)
C21—N21—C11—N11	0.56 (17)	C21'—N21'—C11'—N11'	−0.05 (17)
C51—N11—C11—N21	−0.25 (17)	C51'—N11'—C11'—N21'	−0.26 (17)
Co1—N11—C11—N21	168.27 (10)	Co1—N11'—C11'—N21'	−175.69 (10)
C11—N21—C21—C51	−0.62 (16)	C11'—N21'—C21'—C51'	0.34 (16)
C11—N21—C21—C31	−172.40 (16)	C11'—N21'—C21'—C31'	178.11 (16)
C41—N31—C31—N51	178.66 (14)	C41'—N31'—C31'—N51'	−179.30 (14)
C41—N31—C31—C21	−0.4 (2)	C41'—N31'—C31'—C21'	0.3 (2)
C51—C21—C31—N51	−178.09 (14)	C51'—C21'—C31'—N51'	−178.64 (14)
N21—C21—C31—N51	−7.2 (3)	N21'—C21'—C31'—N51'	3.8 (3)
C51—C21—C31—N31	0.9 (2)	C51'—C21'—C31'—N31'	1.8 (2)
N21—C21—C31—N31	171.81 (15)	N21'—C21'—C31'—N31'	−175.69 (15)
C31—N31—C41—N61	−178.16 (13)	C31'—N31'—C41'—N61'	176.53 (13)
C31—N31—C41—N41	2.9 (2)	C31'—N31'—C41'—N41'	−3.8 (2)
C51—N41—C41—N61	175.31 (14)	C51'—N41'—C41'—N61'	−175.25 (13)
C51—N41—C41—N31	−5.8 (2)	C51'—N41'—C41'—N31'	5.1 (2)
C11—N11—C51—N41	177.22 (15)	C11'—N11'—C51'—N41'	−177.53 (15)
Co1—N11—C51—N41	10.1 (2)	Co1—N11'—C51'—N41'	−2.9 (2)
C11—N11—C51—C21	−0.17 (16)	C11'—N11'—C51'—C21'	0.48 (17)
Co1—N11—C51—C21	−167.31 (11)	Co1—N11'—C51'—C21'	175.09 (11)
C41—N41—C51—N11	−171.06 (14)	C41'—N41'—C51'—N11'	175.04 (14)
C41—N41—C51—C21	6.1 (2)	C41'—N41'—C51'—C21'	−2.8 (2)
N21—C21—C51—N11	0.50 (17)	N21'—C21'—C51'—N11'	−0.52 (17)
C31—C21—C51—N11	173.73 (13)	C31'—C21'—C51'—N11'	−178.70 (13)
N21—C21—C51—N41	−177.11 (13)	N21'—C21'—C51'—N41'	177.66 (13)
C31—C21—C51—N41	−3.9 (2)	C31'—C21'—C51'—N41'	−0.5 (2)
C32^i—C12—C22—C32	−0.6 (2)	C32'^ii—C12'—C22'—C32'	0.3 (2)
C42—C12—C22—C32	177.58 (13)	C42'—C12'—C22'—C32'	−177.70 (13)
C12—C22—C32—C12^i	0.6 (2)	C12'—C22'—C32'—C12'^ii	−0.3 (2)
C12—C22—C32—C52	−174.68 (13)	C12'—C22'—C32'—C52'	177.67 (13)
C22—C12—C42—O22	−154.07 (14)	C22'—C12'—C42'—O22'	159.42 (14)
C32^i—C12—C42—O22	24.1 (2)	C32'^ii—C12'—C42'—O22'	−18.5 (2)
C22—C12—C42—O12	25.6 (2)	C22'—C12'—C42'—O12'	−20.7 (2)
C32^i—C12—C42—O12	−156.31 (14)	C32'^ii—C12'—C42'—O12'	161.33 (14)
C22—C32—C52—O42	−73.66 (18)	C22'—C32'—C52'—O42'	78.88 (18)
C12^i—C32—C52—O42	111.28 (16)	C12'^ii—C32'—C52'—O42'	−103.25 (17)
C22—C32—C52—O32	102.98 (15)	C22'—C32'—C52'—O32'	−97.61 (16)
C12^i—C32—C52—O32	−72.08 (18)	C12'^ii—C32'—C52'—O32'	80.26 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O12^iii	0.89 (1)	1.74 (1)	2.6234 (16)	172 (2)
N41—H41···O32	0.87 (1)	1.88 (1)	2.7178 (16)	160 (2)
N51—H51A···O42′^iv	0.87 (1)	2.17 (1)	2.9214 (16)	144 (2)
N51—H51B···O22^iii	0.87 (1)	1.94 (1)	2.8096 (17)	174 (2)
N61—H61A···O4W	0.88 (1)	2.22 (2)	2.9832 (18)	146 (2)
N61—H61B···O32	0.88 (1)	2.24 (1)	2.9980 (17)	144 (2)
O1W—H1WA···O3W′^v	0.86 (1)	1.89 (1)	2.7171 (16)	161 (2)
O1W—H1WB···O32	0.86 (1)	1.86 (1)	2.7002 (15)	167 (2)
O2W—H2WA···O42′^vi	0.85 (1)	2.04 (1)	2.8052 (16)	151 (2)
O2W—H2WB···O42	0.85 (1)	2.01 (1)	2.8436 (15)	169 (2)
O3W—H3WA···N31	0.85 (1)	2.05 (1)	2.8924 (17)	170 (2)
O3W—H3WB···O12′^iv	0.85 (1)	2.46 (1)	3.3134 (17)	174 (2)
O4W—H4WA···O42^vii	0.85 (1)	2.06 (1)	2.8722 (17)	160 (2)
O4W—H4WB···O12′^iv	0.86 (1)	1.94 (1)	2.7906 (17)	173 (2)
N21′—H21′···O12′^viii	0.87 (1)	1.84 (1)	2.7008 (17)	168 (2)
N41′—H41′···O32′	0.88 (1)	1.89 (1)	2.7529 (16)	165 (2)
N51′—H51C···O42^ix	0.86 (1)	2.28 (2)	2.9786 (17)	138 (2)
N51′—H51D···O22′^viii	0.88 (1)	1.85 (1)	2.7258 (17)	176 (2)
N61′—H61C···O4W′	0.88 (1)	2.15 (1)	2.9643 (19)	155 (2)
N61′—H61D···O32′	0.88 (1)	2.43 (2)	3.1500 (17)	139 (2)
O1W′—H1WC···O3W^x	0.85 (1)	1.92 (1)	2.7360 (16)	162 (2)
O1W′—H1WD···O32′	0.86 (1)	1.86 (1)	2.7025 (15)	169 (2)
O2W′—H2WC···O22^vii	0.84 (1)	2.07 (1)	2.8569 (15)	156 (2)
O2W′—H2WD···O42′	0.86 (1)	1.85 (1)	2.6951 (15)	169 (2)
O3W′—H3WC···N31′	0.86 (1)	2.03 (1)	2.8863 (18)	175 (2)
O3W′—H3WD···O4W′	0.85 (1)	2.32 (2)	2.9470 (19)	132 (2)
O4W′—H4WC···O4W^xi	0.86 (1)	2.05 (1)	2.903 (2)	172 (3)
O4W′—H4WD···O12^ix	0.86 (1)	1.94 (1)	2.7886 (18)	169 (2)

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