Poly[4,4′-(propane-1,3-di­yl)­dipyri­dinium bis­{tetra­aqua­bis­(μ₂-5-carboxybenzene-1,2,4-tri­carboxyl­ato)bis­[μ₂-1,3-bis­(4-pyrid­yl)propane]­dicobalt(II)} penta­hydrate]

The title polymeric compound, {(C₁₃H₁₆N₂)[Co(C₁₀H₃O₈)(C₁₃H₁₄N₂)(H₂O)₂]₂·5H₂O}_n, is an ionic structure comprising an anionic two-dimensional mesh characterized by a {[Co(Hbtc)(bpp)(H₂O)₂]⁻}₂ motif [Hbtc is 5-carboxybenzene-1,2,4-tri­carboxyl­ate and bpp is 1,3-bis­(4-pyrid­yl)propane], with inter­spersed 4,4′-(propane-1,3-di­yl)dipyridinium cations, denoted (H₂bpp)²⁺, and water mol­ecules providing the charge balance and structure stabilization. The reticular mesh consists of two independent types of [Co(H₂O)₂]²⁺ cationic nodes (lying on inversion centres), inter­connected in the [01] direction by two independent sets of neutral bridging bpp ligands, both types of ligands being split by non-equivalent twofold axes. One set is formed by genuinely symmetric moieties, while those in the second set are only symmetric by disorder in the central propane bridge. These chains contain only one type of Co^II centre and one type of bpp ligand; the metal cations therein are laterally bridged by Hbtc anions, thus forming transverse chains of alternating types of Co^II cations. The elemental motif of the resulting grid is a highly distorted parallelogram, with metal–­metal distances of 13.5242 (14) Å in the bpp direction and 9.105 (2) Å in the Hbtc direction, and a large inter­nal angle of 138.42 (18)°. These two-dimensional structures have a profusion of hydrogen-bonding interactions with each other, either directly (with the aqua mol­ecules as donors and the Hbtc anions as acceptors) or mediated by the unbound (H₂bpp)²⁺ cations and water mol­ecules of hydration. These inter­actions generate a very complex hydrogen-bonding scheme involving all of the available N—H and O—H groups and which links these two-dimensional grids into a three-dimensional network.

S1. Comment

Multidentate ligands are basic in the design of metal–organic coordination polymers, not only because they can produce unexpected structural motifs (Archer, 2001), but also because the resulting compounds may contain some interesting properties with potential applications as functional materials (Kitagawa et al., 2004; Kondo et al., 1997; Fujita et al., 1994; Yoghi et al., 2001). Some of the properties analysed in these ligands are flexibility and multidenticity, which when adequately combined in the same compound often lead to intriguing structural topologies. 1,3-Bis(4-pyridyl)propane (bpp) is an excellent example of the first group. The ligand, an analogue of 4,4'-bipyridine, possesses variable flexibility and functionality owing to the introduction of three methylene groups between the two pyridine (py) rings (Zhang et al., 2010; Carlucci et al., 1997; Plater et al., 2000). Its binding diversity is limited, since it can present only two possible coordination modes, viz. either through its two pyridine N atoms [by far the most frequent one, accounting for an overwhelming 95% of the reported cases in the CSD (Cambridge Structural Database) (Allen, 2002)], or just through one of them. But even within this almost unique µ₂-mode the flexibility allowed by the central (saturated) bridge allows for at least two different conformations, very clearly differentiated by their internal N···N distance: (a) bridging, covering more than 90% of the entries in the CSD and the ligand displaying a fully stretched geometry, reflected in an N···N range of 7.5–10.5 Å and (b) chelating, with the ligand heavily bent onto itself. Even if this second group is in the minority, there is a clear bimodal distribution of N···N distances within the group: a subgroup falling into an N···N range of 5.5–6.5 Å, displaying a rather `twisted' chelating geometry with no direct interaction between offset py groups, and the conformation with an N···N range of 3.8–4.2 Å, which could be termed face-to-face chelating with a clear π–π interaction between stacking py groups.

On the other hand, benzene-1,2,4,5-tetracarboxylic acid (H₄btc) is an outstanding representative of multidentate ligands with eight possible active sites available for coordination and/or hydrogen bonding (Chu et al., 2001; Rochon Fernande & Massarweh, 2000; Bok et al., 2005). In addition, the rotational degree of freedom of its four carboxyate groups gives the ligand an astonishing variety of binding modes, in a surprising mixture of bridging and chelation. It was clear then that the simultaneous presence of these two ingredients in a single complex should in principle give rise to interesting (and at the same time unpredictable) crystal structures, and therefore we decided to investigate the system. We report herein our first successful result, the cobalt(II) title polymeric complex formulated as {(H₂bpp)[Co(Hbtc)(bpp)(H₂O)₂]₂.5H₂O}_n, (I).

Fig. 1 presents the asymmetric unit of (I), which consists of two independent metal ions residing on two different centres of symmetry, two halves of coordinated bpp ligands, two coordinated water molecules and one singly protonated Hbtc. The halving of both coordinated bpp ligands takes place by way of two different twofold rotation axes: in unit 2 (as defined by its trailing number in Fig. 1) the axis bisects the central propane C atom, and thus defines a true symmetry for the ligand, while in unit 3 (after its trailing number in Fig. 1) this is just an `average symmetry' built up around a disordered central propane group (in broken lines in Fig. 1) (see Refinement for details). The independent set is completed by half of a doubly protonated H<sub>2</sub>bpp<sup>2+</sup> cation (hereafter unit 4) also split through the central propane atoms by the same twofold axis halving unit 2, and two and a half water solvates. Fig. 1 presents the minimum formula unit having chemical sense, formulated as (H<sub>2</sub>bpp)[Co(Hbtc)(bpp)(H<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>.5H<sub>2</sub>O; in this figure, the effect of the symmetry operations involved (1 on Co1, Co2, a twofold rotation through C72, C74 and O5W, on one side and C73'' on the other) is apparent. Both Co<sup>II</sup> cations present similar CoN<sub>2</sub>O<sub>4</sub> octahedral environments, with the same ligands: one N from bpp, one O from Hbtec and one aqua molecule, plus their symmetry-related counterparts. The octahedra are quite regular and display similar mean Co—O/N distances [with ranges from 2.1215 (14) to 2.1463 (19) Å], apart from Co2—O81 = 2.0755 (14) Å. The maximum angular deviations from 90° for cis coordination angles are also larger for Co2 [3.06 (6) and 4.18 (7)°, respectively]. All three ligands (one Hbtc and two bpp) act in a similar µ<sub>2</sub>-bridging mode: the two bpp ones in the usual role as a spacer, through the two outermost N atoms; the Hbtc<sup>3-</sup> anion, binding laterally through two, noncontiguous carboxylates and `offering' the opposite side for hydrogen bonding. This µ₂,κO,O' mode in H_nbtc (n = 0–4) is found rather infrequently in the literature: a search of the CSD (Version 5.3; Allen, 2002) showed 309 complexes having the group as a ligand, with only four of them presenting this binding mode. On the other hand, the µ₂,κN,N' mode in bpp is by far the most most common: 379 cases out of 403 complexes (CSD) exhibit this mode. The averaging effect of resonance in the C—O distances in the non-protonated carboxylates is uneven, though clear, with percentage C—O bond differences of 0.4, 2.6 and 2.8%, as compared with 8.0% for the protonated one.

The crystal structure can be described as an anionic two-dimensional mesh characterized by a [Co(H₂O)₂(bpp)(Hbtc)]^2-₂ motif, with interspersed (H₂bpp)²⁺ cations and water molecules providing for charge balance and structure stabilization. The grid consists of two independent types of [Co(H₂O)₂]²⁺ nodes (lying on inversion centres), interconnected along the [101] direction by two independent sets of bridging bpp ligands. One set is formed by the genuinely symmetric moieties, while those in the second set are formed by the disordered ones. These chains do not mix cobalt centres nor bpp ligands and thus contain only Co1/bpp2 and Co2/bpp3 units, respectively; metal cations in contiguous chains are laterally bridged by Hbtc^3- anions, to form new, transversal chains of alternating Co1/Co2 cations (Fig. 2; A···A). The elemental motive [motif?] of the resulting grid is a higlhy distorted parallelogram (Fig. 2), with intermetal distances of 13.5242 (18) Å along [101] (the bpp direction) and 9.105 (2) Å along [100] (the Hbtc one); distortion is best assessed by the large internal angle of 138.42 (16)°.

These two-dimensional structures have a profuse hydrogen-bonding interaction with each other. Fig. 3 presents a simplified packing view where intra/inter-grid hydrogen bonds (not mediated by unbound anions or water solvates) are shown. In particular, there are two interactions internal to the coordination polyhedra (entries 1–2 in Table 1) defining two R(6) rings labelled as `a' and `b' in Fig. 3. Adjacent two-dimensional structures, in turn, interact directly along the [100] direction through the hydrogen bonds involving the remaining H atoms of the two aqua (Table 1), to form three different connecting loops [`c', R<sup>4</sup><sub>4</sub>(20); `d' and `e', R₂²(18)]. In addition to these interactions there are a large number of strong O—H···O, N—H···O hydrogen bonds, mediated by the 1,3-bis(4-pyridinium) propane anion and the solvation water molecules (Table 1), and some weaker non-conventional C—H···O and C—H···Cg bonds which give a strong three-dimensional coherence to the structure of (I).

In order to compare the structure of (I) with some related analogues we searched the CSD (Allen, 2002) and found another compound constructed from the same constituent components as (I), viz. catena[(OH₂)(btc)₂(bpp)Co₅], (II) (Jia et al., 2007). As analysed for (I), a general scheme of cobalt nodes interlinked by btc and bpp ligands, but which, irrespective of these basic similarities in components and general architecture, displays an absolutely different structure, with (II) being definitely three-dimensional. In the structure of (II) the btc acts in an extremely complex µ₈ mode with all its available O atoms engaged in coordination, and defining on its own the three-dimensional structural cage. The bpp ligands, in turn, even if bound to the metal centres play only a secondary role, folded into a nearly circular shape [N···N: 5.628 (2) Å] and filling the voids within the `elementary cells' defined by the btc groups which build up the grid.

This contrasts with (I), where the `first rank' structural building blocks can be shown to be the parallel [1,0,1] chains defined by the [fully stretched, N···N: 9.346 (2) Å] bpps, and where the Hbtc units appear to act as `second rank' interchain µ₂ connectors, to form the (010) two-dimensional structures (Fig. 2) and, via hydrogen bonding, promote the interactions between planes (Fig. 3).

There are many possible reasons for the varying behaviour of the btc and bpp (synthesis conditions, ligand ratio etc.) and their analysis exceeds the scope of this report; the examples given, however, clearly show the versatility with which both ligands can adapt in different circumstances.

Related literature

For related literature, see: Allen (2002); Archer (2001); Bok et al. (2005); Carlucci et al. (1997); Chu et al. (2001); Fujita et al. (1994); Jia et al. (2007); Kondo et al. (1997); Plater et al. (2000); Rochon Fernande & Massarweh (2000); Yoghi & Zaworotko (2001); Zhang et al. (2010).

S2. Experimental

An aqueous solution (50 ml) of cobalt(II) acetate (0,164 g, 6.6 mmol) was added to a solution of benzene-1,2,4,5-tetracarboxylic acid (0.168 g, 6.6 mmol) and 4,4-trimethylenedipyridine (0.130 g, 6.6 mmol) in a mixture of ethanol–water (250 ml), which had previously been stirred under reflux for 30 min. The reaction mixture was heated under reflux for 2 h. Single crystals adequate for X-ray diffraction studies were obtained by slow evaporation at room temperature. All reagents and solvents were commercially available and used without additional purification. Elemental analysis was performed with a Carlo–Erba 1108 analyser. Analysis required: C 51.39, H 4.97, N 6.09, O 29.00, Co 8.55%; found: C 51.8, H 4.9, N 6.0, O 28.8, Co 8.6%.

S3. Refinement

All H atoms were clearly visible in difference Fourier maps. They were, however, treated differently. C—H hydrogens were repositioned at their expected locations, and allowed to ride with respect to both coordinates (C—H = 0.93 and 0.99 Å) and isotropic displacement parameters [U_iso(H) = 1.2U_eq(host)]. Those attached to O and N atoms were refined freely. As already stated, the three bpp groups evolve around different twofold axes; in units 2 and 4 the symmetry element passes through the central C atom, and thus the molecules have genuine C2 symmetry, while unit 3 is so only on average, disordered around the symmetry element. This disorder takes place in such a way as to have the two lateral bpy groups reasonably well defined, while linked by a disordered propane group split into two separate components of equal occupancy.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (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. The molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level, with independent (symmetry-related) atoms in heavy (hollow) bonds and filled (empty) ellipsoids. The disordered propane group in one of the bpp ligands is drawn in broken lines. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) -x+1/2, y, -z+3/2; (iv) -x+3/2, y, -z+3/2.]
	Fig. 2. A packing view of (I) along the [010] direction, showing the two-dimensional mesh. In bold, the Co–bpp chains running along [\101], linked by (slanted) Hbtc anions drawn as weak lines, and which define transversal chains (A—A) along [001].
	Fig. 3. A packing view of (I) along [100], orthogonal to the view in Fig. 2. The two-dimensional mesh structures are now seen in projection, as undulating chains (in bold) running horizontally. The nonmediated interplane interactions involving O1W and O2W, linking planes along [010], are shown. For clarity, coordinated bpp groups evolving upwards/downwards, unbound H2bpp cations, water solvent molecules and nonrelevant H atoms have been omitted. [Symmetry code: (i) x, y-1, z.]

Poly[4,4'-(propane-1,3-diyl)dipyridinium bis{tetraaquabis(µ₂-benzene-1,2,4,5-tetracarboxylato)bis[µ₂-1,3- bis(4-pyridyl)propane]dicobalt(II)} pentahydrate]

Crystal data

(C13H16N2)[Co(C10H3O8)(C13H14N2)(H2O)2]·5H2O	F(000) = 1436
Mr = 1379.05	Dx = 1.499 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 8234 reflections
a = 18.068 (4) Å	θ = 2.1–27.0°
b = 9.346 (2) Å	µ = 0.63 mm^−1
c = 18.209 (4) Å	T = 150 K
β = 96.421 (6)°	Blocks, pink
V = 3055.5 (12) Å^3	0.36 × 0.35 × 0.17 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	6749 independent reflections
Radiation source: fine-focus sealed tube	5280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
CCD rotation images, thin slices scans	θmax = 27.9°, θmin = 1.7°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −22→23
Tmin = 0.79, Tmax = 0.89	k = −11→11
24669 measured reflections	l = −23→23

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 1.2623P] where P = (Fo^2 + 2Fc^2)/3
6749 reflections	(Δ/σ)max < 0.001
477 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.46 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.5000	0.5000	0.5000	0.01704 (11)
Co2	0.5000	0.5000	1.0000	0.01864 (11)
C11	0.48876 (11)	0.9303 (2)	0.80253 (11)	0.0179 (4)
C21	0.51798 (12)	0.9948 (2)	0.74278 (11)	0.0189 (4)
H21	0.5147	1.0958	0.7373	0.023*
C31	0.55188 (11)	0.9152 (2)	0.69085 (11)	0.0180 (4)
C41	0.55714 (10)	0.7659 (2)	0.69914 (10)	0.0169 (4)
C51	0.53088 (11)	0.7028 (2)	0.76060 (10)	0.0182 (4)
H51	0.5371	0.6027	0.7679	0.022*
C61	0.49583 (10)	0.7817 (2)	0.81157 (10)	0.0170 (4)
C71	0.45052 (11)	1.0234 (2)	0.85379 (11)	0.0188 (4)
C81	0.58081 (11)	0.9933 (2)	0.62667 (12)	0.0204 (4)
C91	0.57758 (11)	0.6627 (2)	0.64005 (10)	0.0167 (4)
C101	0.46370 (11)	0.6936 (2)	0.87045 (11)	0.0180 (4)
O11	0.43006 (9)	0.95596 (17)	0.91189 (9)	0.0275 (4)
H11O	0.412 (2)	1.019 (4)	0.940 (2)	0.072 (11)*
O21	0.43995 (10)	1.15004 (16)	0.84260 (8)	0.0303 (4)
O31	0.55778 (10)	1.11596 (17)	0.61300 (10)	0.0386 (4)
O41	0.62654 (8)	0.92567 (16)	0.59127 (8)	0.0261 (3)
O51	0.52941 (8)	0.65433 (15)	0.58418 (7)	0.0205 (3)
O61	0.63449 (8)	0.58587 (15)	0.65347 (8)	0.0231 (3)
O71	0.40241 (8)	0.63738 (16)	0.85238 (8)	0.0252 (3)
O81	0.50545 (8)	0.67515 (15)	0.93073 (7)	0.0211 (3)
N12	0.42304 (10)	0.40110 (19)	0.56384 (9)	0.0219 (4)
C12	0.35708 (12)	0.3509 (2)	0.53401 (12)	0.0267 (5)
H12	0.3418	0.3702	0.4834	0.032*
C22	0.30992 (13)	0.2720 (3)	0.57354 (12)	0.0295 (5)
H22	0.2631	0.2401	0.5504	0.035*
C32	0.33181 (12)	0.2400 (2)	0.64724 (12)	0.0249 (5)
C42	0.39948 (12)	0.2965 (2)	0.67882 (12)	0.0245 (5)
H42	0.4155	0.2810	0.7297	0.029*
C52	0.44278 (12)	0.3745 (2)	0.63604 (11)	0.0244 (5)
H52	0.4888	0.4115	0.6585	0.029*
C62	0.28542 (13)	0.1503 (2)	0.69342 (13)	0.0285 (5)
H62A	0.3172	0.0760	0.7197	0.034*
H62B	0.2457	0.1016	0.6608	0.034*
C72	0.2500	0.2426 (3)	0.7500	0.0264 (7)
H72	0.2116	0.3049	0.7233	0.032*
N13	0.58874 (10)	0.4057 (2)	0.94744 (10)	0.0267 (4)
C13	0.64402 (14)	0.4857 (3)	0.92498 (15)	0.0394 (6)
H13	0.6470	0.5838	0.9387	0.047*
C23	0.69665 (16)	0.4311 (4)	0.88271 (16)	0.0536 (8)
H23	0.7349	0.4913	0.8684	0.064*
C33	0.69341 (17)	0.2887 (4)	0.86127 (15)	0.0578 (9)
C43	0.63620 (16)	0.2066 (3)	0.88507 (14)	0.0476 (7)
H43	0.6313	0.1087	0.8713	0.057*
C53	0.58662 (14)	0.2673 (3)	0.92862 (13)	0.0333 (5)
H53	0.5495	0.2082	0.9459	0.040*
C63A	0.7470 (5)	0.1788 (8)	0.8258 (4)	0.068 (2)	0.50
H63A	0.7824	0.1360	0.8651	0.082*	0.50
H63B	0.7172	0.1007	0.8005	0.082*	0.50
C73A	0.7900 (4)	0.2585 (8)	0.7702 (3)	0.066 (2)	0.50
H64C	0.8430	0.2835	0.7836	0.079*	0.50
H64D	0.7706	0.2594	0.7171	0.079*	0.50
C63B	0.7545 (3)	0.2613 (8)	0.8086 (3)	0.0466 (15)	0.50
H63C	0.7951	0.2572	0.8499	0.056*	0.50
H63D	0.7404	0.1595	0.8011	0.056*	0.50
N14	0.33837 (10)	0.91781 (19)	0.51918 (10)	0.0225 (4)
H14N	0.3508 (16)	0.977 (3)	0.4789 (16)	0.049 (8)*
C14	0.26605 (12)	0.8888 (2)	0.52268 (12)	0.0272 (5)
H14	0.2293	0.9314	0.4881	0.033*
C24	0.24461 (12)	0.7982 (2)	0.57579 (12)	0.0261 (5)
H24	0.1933	0.7778	0.5776	0.031*
C34	0.29807 (11)	0.7362 (2)	0.62699 (11)	0.0196 (4)
C44	0.37223 (12)	0.7688 (3)	0.62167 (12)	0.0280 (5)
H44	0.4102	0.7291	0.6560	0.034*
C54	0.39095 (12)	0.8588 (3)	0.56664 (12)	0.0286 (5)
H54	0.4419	0.8788	0.5626	0.034*
C64	0.27622 (11)	0.6424 (2)	0.68812 (11)	0.0211 (4)
H64A	0.3194	0.5836	0.7081	0.025*
H64B	0.2357	0.5770	0.6683	0.025*
C74	0.2500	0.7334 (3)	0.7500	0.0195 (6)
H74	0.2086	0.7958	0.7291	0.023*
O1W	0.58851 (9)	0.37203 (18)	0.55185 (8)	0.0225 (3)
H1WA	0.5811 (15)	0.289 (3)	0.5697 (15)	0.042 (8)*
H1WB	0.6096 (17)	0.423 (4)	0.5848 (18)	0.052 (9)*
O2W	0.41393 (9)	0.39625 (19)	0.92896 (9)	0.0249 (3)
H2WA	0.4003 (19)	0.463 (4)	0.8990 (19)	0.060 (10)*
H2WB	0.4199 (18)	0.328 (4)	0.9049 (18)	0.055 (10)*
O3W	0.89175 (11)	0.88639 (18)	0.52078 (9)	0.0314 (4)
H3WA	0.9245 (17)	0.822 (3)	0.5367 (16)	0.049 (9)*
H3WB	0.8595 (18)	0.876 (3)	0.5461 (17)	0.054 (10)*
O4W	0.77770 (12)	0.8425 (3)	0.61098 (14)	0.0554 (6)
H4WA	0.781 (2)	0.821 (4)	0.653 (2)	0.083 (14)*
H4WB	0.7302 (19)	0.860 (3)	0.6073 (17)	0.054 (9)*
O5W	0.7500	0.7177 (3)	0.7500	0.0312 (5)
H5W	0.7834 (17)	0.672 (3)	0.7726 (18)	0.058 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0193 (2)	0.0179 (2)	0.0144 (2)	−0.00045 (15)	0.00410 (15)	0.00164 (14)
Co2	0.0219 (2)	0.0172 (2)	0.0168 (2)	−0.00188 (15)	0.00214 (15)	0.00409 (14)
C11	0.0192 (9)	0.0179 (10)	0.0168 (9)	0.0009 (8)	0.0026 (8)	−0.0003 (7)
C21	0.0218 (10)	0.0162 (10)	0.0186 (10)	−0.0014 (8)	0.0015 (8)	0.0021 (7)
C31	0.0184 (9)	0.0188 (10)	0.0170 (9)	−0.0010 (8)	0.0027 (8)	0.0036 (8)
C41	0.0157 (9)	0.0189 (10)	0.0157 (9)	0.0006 (8)	0.0005 (7)	−0.0004 (7)
C51	0.0214 (10)	0.0152 (10)	0.0181 (10)	0.0003 (8)	0.0024 (8)	0.0018 (7)
C61	0.0170 (9)	0.0195 (10)	0.0144 (9)	−0.0008 (8)	0.0012 (7)	0.0017 (7)
C71	0.0213 (10)	0.0209 (10)	0.0140 (9)	0.0006 (8)	0.0008 (8)	−0.0010 (8)
C81	0.0196 (10)	0.0203 (11)	0.0218 (10)	−0.0012 (8)	0.0052 (8)	0.0031 (8)
C91	0.0198 (9)	0.0155 (9)	0.0157 (9)	−0.0020 (8)	0.0057 (8)	0.0029 (7)
C101	0.0210 (10)	0.0151 (9)	0.0186 (10)	0.0037 (8)	0.0055 (8)	0.0003 (7)
O11	0.0394 (9)	0.0209 (8)	0.0254 (8)	0.0044 (7)	0.0176 (7)	0.0011 (6)
O21	0.0520 (10)	0.0187 (8)	0.0218 (8)	0.0080 (7)	0.0111 (7)	0.0013 (6)
O31	0.0505 (10)	0.0255 (9)	0.0450 (10)	0.0105 (8)	0.0283 (9)	0.0171 (8)
O41	0.0281 (8)	0.0271 (8)	0.0255 (8)	0.0034 (6)	0.0133 (6)	0.0065 (6)
O51	0.0229 (7)	0.0208 (7)	0.0180 (7)	0.0008 (6)	0.0033 (6)	−0.0005 (5)
O61	0.0227 (7)	0.0245 (8)	0.0219 (7)	0.0055 (6)	0.0019 (6)	−0.0006 (6)
O71	0.0216 (7)	0.0277 (8)	0.0261 (8)	−0.0027 (6)	0.0016 (6)	0.0088 (6)
O81	0.0260 (7)	0.0200 (7)	0.0171 (7)	−0.0024 (6)	0.0011 (6)	0.0042 (5)
N12	0.0253 (9)	0.0231 (9)	0.0181 (8)	−0.0005 (7)	0.0064 (7)	0.0009 (7)
C12	0.0288 (11)	0.0328 (12)	0.0193 (10)	−0.0015 (10)	0.0056 (9)	0.0017 (9)
C22	0.0311 (12)	0.0336 (13)	0.0250 (11)	−0.0075 (10)	0.0079 (9)	−0.0042 (9)
C32	0.0320 (11)	0.0202 (11)	0.0251 (11)	0.0011 (9)	0.0150 (9)	−0.0017 (8)
C42	0.0288 (11)	0.0270 (11)	0.0189 (10)	0.0048 (9)	0.0080 (9)	0.0049 (8)
C52	0.0249 (10)	0.0293 (12)	0.0193 (10)	0.0018 (9)	0.0036 (8)	0.0000 (8)
C62	0.0369 (12)	0.0237 (11)	0.0284 (12)	−0.0044 (10)	0.0187 (10)	−0.0030 (9)
C72	0.0292 (16)	0.0241 (16)	0.0285 (16)	0.000	0.0152 (13)	0.000
N13	0.0281 (9)	0.0255 (10)	0.0271 (10)	0.0034 (8)	0.0062 (8)	0.0061 (8)
C13	0.0340 (13)	0.0371 (14)	0.0494 (16)	0.0049 (11)	0.0147 (12)	0.0168 (12)
C23	0.0417 (15)	0.080 (2)	0.0425 (16)	0.0169 (15)	0.0209 (13)	0.0290 (16)
C33	0.0521 (18)	0.100 (3)	0.0218 (13)	0.0366 (18)	0.0056 (12)	−0.0020 (15)
C43	0.0513 (17)	0.0554 (18)	0.0323 (14)	0.0236 (14)	−0.0121 (13)	−0.0171 (13)
C53	0.0361 (13)	0.0318 (13)	0.0301 (12)	0.0058 (10)	−0.0047 (10)	0.0002 (10)
C63A	0.117 (7)	0.044 (4)	0.055 (4)	−0.006 (4)	0.062 (4)	0.009 (3)
C73A	0.077 (4)	0.094 (5)	0.034 (3)	−0.012 (4)	0.039 (3)	0.011 (3)
C63B	0.046 (3)	0.062 (4)	0.035 (3)	−0.009 (3)	0.018 (3)	−0.020 (3)
N14	0.0255 (9)	0.0244 (10)	0.0189 (9)	0.0012 (7)	0.0081 (7)	0.0032 (7)
C14	0.0220 (10)	0.0336 (12)	0.0261 (11)	0.0032 (9)	0.0025 (9)	0.0066 (9)
C24	0.0187 (10)	0.0336 (12)	0.0263 (11)	−0.0016 (9)	0.0034 (9)	0.0043 (9)
C34	0.0234 (10)	0.0205 (10)	0.0160 (9)	0.0024 (8)	0.0068 (8)	−0.0032 (8)
C44	0.0205 (10)	0.0415 (14)	0.0220 (11)	0.0029 (10)	0.0023 (9)	0.0073 (9)
C54	0.0182 (10)	0.0406 (14)	0.0275 (12)	−0.0001 (9)	0.0048 (9)	0.0057 (10)
C64	0.0236 (10)	0.0219 (10)	0.0189 (10)	0.0022 (8)	0.0074 (8)	0.0012 (8)
C74	0.0205 (14)	0.0210 (14)	0.0173 (13)	0.000	0.0043 (11)	0.000
O1W	0.0275 (8)	0.0188 (8)	0.0216 (8)	−0.0001 (6)	0.0039 (6)	0.0028 (6)
O2W	0.0322 (8)	0.0190 (8)	0.0229 (8)	−0.0018 (7)	0.0005 (7)	0.0025 (7)
O3W	0.0370 (9)	0.0306 (9)	0.0292 (9)	0.0103 (8)	0.0151 (8)	0.0116 (7)
O4W	0.0320 (11)	0.0792 (16)	0.0588 (14)	0.0182 (10)	0.0219 (10)	0.0417 (12)
O5W	0.0289 (13)	0.0325 (13)	0.0303 (13)	0.000	−0.0045 (11)	0.000

Geometric parameters (Å, º)

Co1—N12	2.1215 (17)	C72—H72	0.9899
Co1—N12^i	2.1215 (17)	N13—C53	1.337 (3)
Co1—O51	2.1285 (14)	N13—C13	1.347 (3)
Co1—O51^i	2.1285 (14)	C13—C23	1.386 (4)
Co1—O1W^i	2.1312 (15)	C13—H13	0.9500
Co1—O1W	2.1312 (15)	C23—C33	1.386 (5)
Co2—O81	2.0755 (14)	C23—H23	0.9500
Co2—O81^ii	2.0755 (14)	C33—C43	1.395 (5)
Co2—O2W	2.1406 (16)	C33—C63B	1.563 (6)
Co2—O2W^ii	2.1406 (16)	C33—C63A	1.597 (8)
Co2—N13	2.1463 (19)	C43—C53	1.383 (4)
Co2—N13^ii	2.1463 (19)	C43—H43	0.9500
C11—C21	1.398 (3)	C53—H53	0.9500
C11—C61	1.403 (3)	C63A—C73A	1.536 (8)
C11—C71	1.500 (3)	C63A—H63A	0.9900
C21—C31	1.397 (3)	C63A—H63B	0.9900
C21—H21	0.9500	C73A—C63B^iv	1.565 (9)
C31—C41	1.406 (3)	C63B—C33	1.563 (8)
C31—C81	1.519 (3)	C73A—H64C	0.9900
C41—C51	1.394 (3)	C73A—H64D	0.9900
C41—C91	1.521 (3)	C63B—H63C	0.9900
C51—C61	1.392 (3)	C63B—H63D	0.9900
C51—H51	0.9500	N14—C54	1.330 (3)
C61—C101	1.518 (3)	N14—C14	1.343 (3)
C71—O21	1.212 (2)	N14—H14N	0.96 (3)
C71—O11	1.319 (2)	C14—C24	1.374 (3)
C81—O31	1.235 (2)	C14—H14	0.9500
C81—O41	1.272 (3)	C24—C34	1.392 (3)
C91—O61	1.256 (2)	C24—H24	0.9500
C91—O51	1.265 (2)	C34—C44	1.388 (3)
C101—O71	1.237 (2)	C34—C64	1.503 (3)
C101—O81	1.272 (2)	C44—C54	1.379 (3)
O11—H11O	0.87 (4)	C44—H44	0.9500
N12—C12	1.338 (3)	C54—H54	0.9500
N12—C52	1.346 (3)	C64—C74	1.529 (3)
C12—C22	1.388 (3)	C64—H64A	0.9900
C12—H12	0.9500	C64—H64B	0.9900
C22—C32	1.388 (3)	C74—C64^iii	1.529 (3)
C22—H22	0.9500	C74—H74	0.9901
C32—C42	1.395 (3)	O1W—H1WA	0.86 (3)
C32—C62	1.507 (3)	O1W—H1WB	0.82 (3)
C42—C52	1.374 (3)	O2W—H2WA	0.85 (4)
C42—H42	0.9500	O2W—H2WB	0.78 (3)
C52—H52	0.9500	O3W—H3WA	0.87 (3)
C62—C72	1.537 (3)	O3W—H3WB	0.79 (3)
C62—H62A	0.9900	O4W—H4WA	0.79 (4)
C62—H62B	0.9900	O4W—H4WB	0.87 (3)
C72—C62^iii	1.537 (3)	O5W—H5W	0.81 (3)
N12—Co1—N12^i	180.0	C22—C32—C62	122.9 (2)
N12—Co1—O51	91.53 (6)	C42—C32—C62	119.8 (2)
N12^i—Co1—O51	88.47 (6)	C52—C42—C32	119.7 (2)
N12—Co1—O51^i	88.47 (6)	C52—C42—H42	120.2
N12^i—Co1—O51^i	91.53 (6)	C32—C42—H42	120.2
O51—Co1—O51^i	180.0	N12—C52—C42	123.1 (2)
N12—Co1—O1W^i	88.96 (6)	N12—C52—H52	118.4
N12^i—Co1—O1W^i	91.04 (6)	C42—C52—H52	118.4
O51—Co1—O1W^i	93.06 (6)	C32—C62—C72	111.18 (19)
O51^i—Co1—O1W^i	86.94 (6)	C32—C62—H62A	109.4
N12—Co1—O1W	91.04 (6)	C72—C62—H62A	109.4
N12^i—Co1—O1W	88.96 (6)	C32—C62—H62B	109.4
O51—Co1—O1W	86.94 (6)	C72—C62—H62B	109.4
O51^i—Co1—O1W	93.06 (6)	H62A—C62—H62B	108.0
O1W^i—Co1—O1W	180.00 (8)	C62—C72—C62^iii	111.7 (3)
O81—Co2—O81^ii	180.000 (1)	C62—C72—H72	108.8
O81—Co2—O2W	94.05 (6)	C62^iii—C72—H72	109.7
O81^ii—Co2—O2W	85.95 (6)	C53—N13—C13	117.4 (2)
O81—Co2—O2W^ii	85.95 (6)	C53—N13—Co2	120.65 (16)
O81^ii—Co2—O2W^ii	94.05 (6)	C13—N13—Co2	121.58 (16)
O2W—Co2—O2W^ii	180.000 (1)	N13—C13—C23	122.8 (3)
O81—Co2—N13	87.95 (6)	N13—C13—H13	118.6
O81^ii—Co2—N13	92.05 (6)	C23—C13—H13	118.6
O2W—Co2—N13	94.19 (7)	C13—C23—C33	120.0 (3)
O2W^ii—Co2—N13	85.81 (7)	C13—C23—H23	120.0
O81—Co2—N13^ii	92.05 (6)	C33—C23—H23	120.0
O81^ii—Co2—N13^ii	87.95 (6)	C23—C33—C43	116.8 (3)
O2W—Co2—N13^ii	85.81 (7)	C23—C33—C63B	108.7 (4)
O2W^ii—Co2—N13^ii	94.19 (7)	C43—C33—C63B	134.4 (4)
C21—C11—C61	118.75 (18)	C23—C33—C63A	136.3 (4)
C21—C11—C71	118.32 (18)	C43—C33—C63A	106.0 (4)
C61—C11—C71	122.93 (17)	C53—C43—C33	120.2 (3)
C31—C21—C11	121.97 (18)	C53—C43—H43	119.9
C31—C21—H21	119.0	C33—C43—H43	119.9
C11—C21—H21	119.0	N13—C53—C43	122.8 (3)
C21—C31—C41	119.03 (18)	N13—C53—H53	118.6
C21—C31—C81	118.66 (17)	C43—C53—H53	118.6
C41—C31—C81	122.31 (18)	C54—N14—C14	120.89 (19)
C51—C41—C31	118.74 (18)	C54—N14—H14N	121.4 (18)
C51—C41—C91	115.54 (17)	C14—N14—H14N	117.5 (18)
C31—C41—C91	124.92 (17)	N14—C14—C24	120.7 (2)
C61—C51—C41	122.18 (18)	N14—C14—H14	119.7
C61—C51—H51	118.9	C24—C14—H14	119.7
C41—C51—H51	118.9	C14—C24—C34	119.9 (2)
C51—C61—C11	119.22 (18)	C14—C24—H24	120.0
C51—C61—C101	114.99 (17)	C34—C24—H24	120.0
C11—C61—C101	125.66 (17)	C44—C34—C24	117.70 (19)
O21—C71—O11	123.24 (19)	C44—C34—C64	121.01 (18)
O21—C71—C11	122.45 (18)	C24—C34—C64	121.23 (18)
O11—C71—C11	114.31 (17)	C54—C44—C34	120.1 (2)
O31—C81—O41	125.62 (19)	C54—C44—H44	119.9
O31—C81—C31	117.62 (18)	C34—C44—H44	119.9
O41—C81—C31	116.76 (17)	N14—C54—C44	120.6 (2)
O61—C91—O51	126.58 (18)	N14—C54—H54	119.7
O61—C91—C41	118.90 (17)	C44—C54—H54	119.7
O51—C91—C41	114.11 (17)	C34—C64—C74	110.51 (17)
O71—C101—O81	126.78 (18)	C34—C64—H64A	109.5
O71—C101—C61	116.39 (17)	C74—C64—H64A	109.5
O81—C101—C61	116.52 (17)	C34—C64—H64B	109.5
C71—O11—H11O	108 (2)	C74—C64—H64B	109.5
C91—O51—Co1	135.64 (13)	H64A—C64—H64B	108.1
C101—O81—Co2	124.58 (13)	C64—C74—C64^iii	112.4 (2)
C12—N12—C52	117.30 (18)	C64—C74—H74	109.1
C12—N12—Co1	122.60 (14)	C64^iii—C74—H74	109.1
C52—N12—Co1	119.81 (14)	Co1—O1W—H1WA	122.3 (19)
N12—C12—C22	123.1 (2)	Co1—O1W—H1WB	105 (2)
N12—C12—H12	118.4	H1WA—O1W—H1WB	109 (3)
C22—C12—H12	118.4	Co2—O2W—H2WA	101 (2)
C12—C22—C32	119.4 (2)	Co2—O2W—H2WB	125 (2)
C12—C22—H22	120.3	H2WA—O2W—H2WB	106 (3)
C32—C22—H22	120.3	H3WA—O3W—H3WB	104 (3)
C22—C32—C42	117.3 (2)	H4WA—O4W—H4WB	95 (3)
C61—C11—C21—C31	1.9 (3)	O1W—Co1—N12—C12	−132.00 (17)
C71—C11—C21—C31	−177.49 (18)	O51—Co1—N12—C52	−45.38 (16)
C11—C21—C31—C41	−0.4 (3)	O51^i—Co1—N12—C52	134.62 (16)
C11—C21—C31—C81	178.78 (18)	O1W^i—Co1—N12—C52	−138.41 (16)
C21—C31—C41—C51	−2.5 (3)	O1W—Co1—N12—C52	41.59 (16)
C81—C31—C41—C51	178.44 (18)	C52—N12—C12—C22	−1.2 (3)
C21—C31—C41—C91	166.84 (18)	Co1—N12—C12—C22	172.53 (17)
C81—C31—C41—C91	−12.3 (3)	N12—C12—C22—C32	−1.3 (4)
C31—C41—C51—C61	3.8 (3)	C12—C22—C32—C42	3.3 (3)
C91—C41—C51—C61	−166.48 (17)	C12—C22—C32—C62	−177.6 (2)
C41—C51—C61—C11	−2.2 (3)	C22—C32—C42—C52	−2.9 (3)
C41—C51—C61—C101	173.89 (17)	C62—C32—C42—C52	178.0 (2)
C21—C11—C61—C51	−0.7 (3)	C12—N12—C52—C42	1.6 (3)
C71—C11—C61—C51	178.74 (18)	Co1—N12—C52—C42	−172.28 (16)
C21—C11—C61—C101	−176.33 (18)	C32—C42—C52—N12	0.4 (3)
C71—C11—C61—C101	3.1 (3)	C22—C32—C62—C72	−107.5 (2)
C21—C11—C71—O21	4.8 (3)	C42—C32—C62—C72	71.5 (2)
C61—C11—C71—O21	−174.6 (2)	C32—C62—C72—C62^iii	−169.6 (2)
C21—C11—C71—O11	−174.72 (18)	O81—Co2—N13—C53	−136.85 (17)
C61—C11—C71—O11	5.9 (3)	O81^ii—Co2—N13—C53	43.15 (17)
C21—C31—C81—O31	−17.1 (3)	O2W—Co2—N13—C53	−42.94 (17)
C41—C31—C81—O31	162.0 (2)	O2W^ii—Co2—N13—C53	137.06 (17)
C21—C31—C81—O41	163.35 (19)	O81—Co2—N13—C13	35.79 (19)
C41—C31—C81—O41	−17.5 (3)	O81^ii—Co2—N13—C13	−144.21 (19)
C51—C41—C91—O61	−70.7 (2)	O2W—Co2—N13—C13	129.71 (19)
C31—C41—C91—O61	119.7 (2)	O2W^ii—Co2—N13—C13	−50.29 (19)
C51—C41—C91—O51	102.5 (2)	C53—N13—C13—C23	1.3 (4)
C31—C41—C91—O51	−67.1 (2)	Co2—N13—C13—C23	−171.6 (2)
C51—C61—C101—O71	−80.8 (2)	N13—C13—C23—C33	0.5 (4)
C11—C61—C101—O71	95.0 (2)	C13—C23—C33—C43	−0.8 (4)
C51—C61—C101—O81	93.2 (2)	C13—C23—C33—C63B	174.8 (3)
C11—C61—C101—O81	−91.0 (2)	C13—C23—C33—C63A	−167.8 (5)
O61—C91—O51—Co1	15.8 (3)	C23—C33—C43—C53	−0.7 (4)
C41—C91—O51—Co1	−156.75 (13)	C13—N13—C53—C43	−2.9 (3)
N12—Co1—O51—C91	90.11 (18)	Co2—N13—C53—C43	170.02 (18)
N12^i—Co1—O51—C91	−89.89 (18)	C33—C43—C53—N13	2.7 (4)
O1W^i—Co1—O51—C91	179.15 (18)	C54—N14—C14—C24	0.5 (3)
O1W—Co1—O51—C91	−0.85 (18)	N14—C14—C24—C34	0.4 (3)
O71—C101—O81—Co2	21.1 (3)	C14—C24—C34—C44	−0.4 (3)
C61—C101—O81—Co2	−152.18 (13)	C14—C24—C34—C64	176.9 (2)
O2W—Co2—O81—C101	2.34 (16)	C24—C34—C44—C54	−0.6 (3)
O2W^ii—Co2—O81—C101	−177.66 (16)	C64—C34—C44—C54	−177.8 (2)
N13—Co2—O81—C101	96.39 (16)	C14—N14—C54—C44	−1.5 (3)
N13^ii—Co2—O81—C101	−83.61 (16)	C34—C44—C54—N14	1.5 (4)
O51—Co1—N12—C12	141.03 (17)	C44—C34—C64—C74	99.3 (2)
O51^i—Co1—N12—C12	−38.97 (17)	C24—C34—C64—C74	−77.8 (2)
O1W^i—Co1—N12—C12	48.00 (17)	C34—C64—C74—C64^iii	177.37 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11O···O3W^v	0.87 (4)	1.79 (4)	2.625 (2)	161 (3)
N14—H14N···O41^vi	0.96 (3)	1.66 (3)	2.621 (2)	178 (3)
O1W—H1WA···O31^vii	0.86 (3)	1.87 (3)	2.723 (2)	175 (3)
O1W—H1WB···O61	0.82 (3)	1.99 (3)	2.786 (2)	162 (3)
O2W—H2WA···O71	0.85 (4)	1.84 (4)	2.646 (2)	158 (3)
O2W—H2WB···O21^vii	0.78 (3)	2.07 (4)	2.855 (2)	178 (3)
O3W—H3WA···O81^iv	0.87 (3)	1.91 (3)	2.786 (2)	178 (3)
O3W—H3WB···O4W	0.79 (3)	2.02 (3)	2.805 (3)	178 (3)
O4W—H4WA···O5W	0.79 (4)	2.14 (4)	2.882 (2)	157 (4)
O4W—H4WB···O41	0.87 (3)	1.96 (3)	2.824 (3)	172 (3)
O5W—H5W···O61^iv	0.81 (3)	2.05 (3)	2.8535 (19)	169 (3)

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