A square two-dimensional polymer of cobalt citrate cubanes

The structure of the title complex, poly[dicaesium(I) hexa­aqua­cobalt(II) [octa­aquatetra-μ-citrato-hexa­cobalt(II)] do­deca­hydrate], {Cs₂[Co(H₂O)₆][Co₆(C₆H₄O₇)₄(H₂O)₈]·12H₂O}_n, at 100 (1) K is formed by layers of a square two-dimensional polymer composed of Co^II citrate cubanes bridged by magnetically active six-coordinate Co^II cations. The polymer has plane symmetry p4mm in the c-axis projection. The cubanes reside on sites of crystallographic symmetry , while the bridging Co^II centres lie on twofold axes. The basic polymeric unit has a charge of 4−, balanced by two Cs⁺ and a [Co(H₂O)₆]²⁺ (symmetry ) cation, which lie in channels between the polymeric layers. Unligated water mol­ecules, of which there are 12 per cubane, enter into an extended intra­layer and layer-bridging hydrogen-bond pattern, which can be described in detail even though not all of the H atoms of the water molecules were located.

Comment

Polynuclear transition metal complexes with cube-shaped cores, generically called cubanes, have been studied for a variety of metals and in a variety of contexts. In recent years, the magnetic properties of cubane complexes of first-row transition elements have been studied, not in small part because the seminal single-mol­ecule magnet (SMM), [Mn₁₂O₁₂(CH₃CO₂)₁₆(H₂O)₄], has a cubane Mn₄O₄ centre (Lis, 1980; Sessoli, Gatteschi et al., 1993; Sessoli, Tsai et al., 1993). The first cobalt-based SMM (Yang et al., 2002) was a cubane, with deprotonated hy­droxy­methyl­pyridine ligands. Murrie et al. (2003a,b) described a Co-based SMM with citrate ligands. Citrate cubanes of six different transition metals were described by Hudson et al. (2006), Moubaraki et al. (2008) and Galloway et al. (2008). The citrate cubanes in these studies were discrete mol­ecules, either with the basic [Co₄(citr)₄]⁸⁻ structure (where citr denotes quadruply de­pro­tonated citric acid, C₆H₄O₇⁴⁻), or with two additional Co^II centres covalently bound at the periphery of the [Co₄(citr)₄]⁸⁻ unit to give a tetraanion. We have previously reported a serrated one-dimensional polymer, the structural building block of which is the [Co₄(citr)₄]⁸⁻ cubane, and which undergoes an unprecedented reversible crosslinking in the crystal structure to form a rhombic two-dimensional cubane polymer (Campo et al., 2008). In the resulting two-dimensional polymer, a Co^II centre within the crosslinked fragment possesses an uncommon CoO₇ coordination environment. The first three-dimensional network based on the same building block was reported recently (Galloway et al., 2010).

We have now prepared a square anionic two-dimensional polymer, octa­aquatetra-μ-citrato-hexa­cobalt(II), the structure of which is related to that of a previously reported two-dimensional polymer containing ethyl­ene glycol, (II). The Rb⁺ and Cs⁺ salts of (II) suffer severe structural disorder but have inter­esting magnetic properties; these are the subject of another report (Burzurí et al., 2011). In what follows, we report the structure of the title hydrated double salt of this polymer, viz. {Cs₂[Co(H₂O)₆]{[Co₄(C₆H₄O₇)₄][μ-Co(H₂O)₄]₂}·12H₂O}_n, (I), which is the first of the square two-dimensional citrate cubane polymers to have crystallized without serious cation and hydrate disorder.

The structure of (I) is a stack of square two-dimensional polymeric layers (Fig. 1). Each layer is a regular array of cubanes located on sites of symmetry, bridged by six-coordinate Co^II centres which sit on twofold axes. The basic unit of the polymer consists of one cubane and two bridges, viz. {[Co₄(citr)₄][μ-Co(H₂O)₄]₂}⁴⁻; the crystallographic a and b axes are the propagation vectors. In chemical terms, it is perhaps better to view the cubane as sharing bridges with each of four neighbours, with the negative charge of one unit of the polymer arising from [Co₄(citr)₄]⁸⁻ and one-half of each of the four [μ-Co(H₂O)₄]²⁺ bridges, giving a charge of 4− per node of the polymer; there are two nodes per unit cell. Charge is balanced by one [Co(H₂O)₆]²⁺ and two Cs⁺ cations per cubane; these cations are not part of the polymer. The octa­hedral cation is centred at Co3, which resides on , giving two per unit cell. Cs1 resides on a set of general positions but is half-occupied, as determined both by the need for charge balance and by the refinement of the displacement parameters to values in line with those of the rest of the structure. There are thus four Cs⁺ cations per cell. One-quarter of the polymer repeat unit, and its associated cations and solvent water mol­ecules, comprise the crystallographic asymmetric unit.

The geometries of cubanes containing Co and Ni have been reviewed by Isele et al. (2007). The Co₄O₄ core in (I) (Fig. 2 and Table 1) has inter­nal geometry comparable with that observed in previously reported structures based on this unit. The Co⋯Co and O⋯O distances are well within the ranges found by Isele et al. (2007), and the acute and obtuse bond angles at Co1 and O1, respectively, have commonly observed values that can be related to the magnetic properties of the cubanes. The Co₄O₄ fragment in (I) is sufficiently distorted from a regular cubic shape that, for the purposes of describing its geometry, it is best viewed as a stellated octa­hedron (a distortion of the stella octa­ngula) formed by the inter­leaved Co₄ and O₄ tetra­hedra (Fig. 3). The unique Cg1—Co1 and Cg1—O1 distances are 1.9387 (5) and 1.687 (3) Å, respectively (Cg1 represents the centre of the cubane, located at the unweighted average position of the eight constituent atoms). If the two tetra­hedra were considered to be distorted, the Co₄ unit would be taken as very slightly compressed, with two Co—Cg1—Co angles greater than, and four less than, the ideal tetra­hedral value. The O₄ tetra­hedron might similarly be considered as slightly elongated, although quanti­tatively the tetra­hedral distortion is essentially negligible in both cases, with a Robinson tetra­hedral angular variance σ_θ(tet)² of 5.72°² for Co₄ and 2.51°² for O₄ (Robinson et al., 1971). Because of the symmetry, the quadratic elongation 〈λ_tet〉 is 1.00. For the purposes of comparison, we have surveyed the geometries of 40 previously published Co₄^IIO₄ cubane fragments using the Cambridge Structural Database (Version 5.31; Allen, 2002). Structures that we considered to be chemically unrepresentative, such as fused cubanes, were excluded from this study. Eight of these published cubane structures displayed a slightly compressed Co₄ tetra­hedron together with a slightly elongated O₄ unit, and three showed the opposite. None had both tetra­hedra elongated. The calculated angular variances σ_θ(tet)² for the cubanes surveyed varied in the range 0.01–52.9°² for Co₄ and 0.05–63.9°² for O₄. In no case did 〈λ_tet〉 vary by more than 0.02 from the symmetrical value of 1.00 for either of the tetra­hedra.

The four citrate ligands of the cubane in (I) are related by symmetry. Each citrate has its ionized hy­droxy O atom as one corner of the cubane. The three terminal carboxylate groups bind through one O atom each to a Co of the cube, thus forming one five- and two six-membered chelates (Figs. 2a and 2b). The five-membered Co1ⁱⁱ/O1/C1/C2/O2 ring has an envelope conformation with the fold at Co1ⁱⁱ [symmetry code: (ii) −y + 1, x, −z + 1]. Numbering from Co1ⁱⁱ as the 1 position, this would be rendered as E₁. The six-membered rings Co1ⁱ/O1/C1/C3/C4/O4 [symmetry code: (i) −x + 1, −y + 1, z] and Co1/O1/C1/C5/C6/O6 have ring-puckering parameters (Cremer & Pople, 1975) of Q = 0.780 (3) and 0.867 (3) Å, θ = 87.9 (3) and 87.8 (2)°, and φ = 112.0 (3) and 343.7 (2)°, respectively. Thus, the former has a boat conformation, ^1,4B using the given atom sequence, while the latter is a slightly twisted boat based on ^1,4B.

An important topological feature of the [Co₄(citr)₄]⁸⁻ building block is its periphery, at which 12 partially charged O atoms, namely the carboxyl­ate O atoms not involved in chelation to Co of the cube, offer as many reactive nucleophilic sites, which serve as potential linkage points for forming an ample variety of extended structures in one, two and three dimensions. A number of the citrate cubanes characterized to date have transition metals coordinated by one or more of these peripheral O atoms. The 12 O atoms form an irregular icosa­hedron (Fig. 4), with Cg1-to-vertex distances of 5.061 (3), 5.428 (3) and 5.535 (3) Å for atoms O3, O5 and O7, respectively. The crystallographic symmetry relates the vertices in groups of four. Each such group forms a distorted tetra­hedron. That formed by atom O5 and its congeners is elongated along c, with a tetra­hedral angular variance of 889°²; this shape, when it appears as a crystal form, is called a tetra­gonal disphenoid. The tetra­hedron containing atom O3 is compressed, with a similar variance of 828°². The O7 tetra­hedron is nearly regular, with an angular variance of 6.7°². Atom O7 and its equivalents are the linkage points for the extended structure, binding the `satellite' atom Co2 and its congeners, which sit on crystallographic twofold axes and bridge successive cubanes. In this way, the cubane/icosa­hedron and bridging atom Co2 form an unbounded two-dimensional net parallel to the crystallographic ab plane (Fig. 1). The O7 equivalents from neighbouring cubanes are trans to each other at Co2, the coordination of which is completed by four aqua ligands.

Similarities between (I) and previously reported structures with the same cubane building block end at the periphery of the cubane unit. In a previously reported structure of a one-dimensional polymer of Co citrate cubanes (Campo et al., 2008), the analogous icosa­hedron has similar geometry to that found for (I), with elongated, compressed and regular oxygen tetra­hedra having angular variances of 467, 805 and 38.1°², respectively. In that structure, the cubane sits on a general position and five of its peripheral O atoms bind Co, namely those that are analogous to sites O3, O7, O5ⁱⁱⁱ, O3ⁱⁱ and O5ⁱ in Fig. 4. The extended structure in that case does not have the symmetry shown by (I) and the chemical unit formed is a serrated one-dimensional polymer of cubanes. That structure undergoes a chemical reaction in the solid state to form a crosslinked two-dimensional polymer whose icosa­hedra of peripheral O atoms bind Co at the sites analogous to O3, O7, O5ⁱⁱⁱ, O3ⁱⁱ and O7ⁱ, having lost the link to Co at the site analogous to O5ⁱ.

In (I), the gaps in the polymer mesh of one layer are covered by the cubanes of the two neighbouring layers. The …ABAB… stacking of the layers is propagated by [111], but alternate layers are actually related by n[110] and are thus mirror images of each other.

The stacking of the two-dimensional polymeric layers leaves channels in the structure parallel to the a and b axes. These are occupied by the Cs⁺ cations (two per polymer repeat unit) along with [Co(H₂O)₆]²⁺ cations, located on , and the solvent water mol­ecules.

The hydrogen bonding in (I), although extensive, is not a structure-determining factor; rather, hydrogen bonds are formed within the channels left by the stacking of the anionic polymers, and also between water mol­ecules within the channels and O atoms of the citrate and aqua ligands attached to the Co atoms of the polymer. The seven independent water fragments present (three of them unligated), along with atoms Co2 and Co3 (to which four of the unique water mol­ecules are bound) and their congeners, form a cyclic structure mediated by coordination and hydrogen bonds and which girds the periphery of the icosa­hedral [Co₄(citr)₄]⁸⁻ unit. The water mol­ecules donate hydrogen bonds to the inner carboxyl­ate O atoms, i.e. those that are bound to cubane Co, as well as to the peripheral carboxyl­ate O atoms (Table 2).

This extensive ordered hydrogen-bonding arrangement is not necessary, however, for the stability of the structure. In other systems based on a closely related two-dimensional polymer but crystallized with other cations (Rb⁺, Cs⁺ or K⁺), we have observed an isomorphous crystal structure: the two-dimensional layer is stacked in the same arrangement as in (I), but the inter­layer space is very different in all cases. Compound (I) is the first case we have observed in which there is no disorder in the non-H atoms of the inter­stitial residues. In the Rb⁺ and Cs⁺ salts (Burzurí et al., 2011), which are stable in the crystalline state, the cations are disordered over two and three independent sites, respectively, and the inter­layer water mol­ecules are severely disordered in the channels. In those structures, the channels account for 39% of the volume of the unit cell, while in (I) 42% of the volume is in the channels. We can speculate that the presence of a larger cation, i.e. [Co(H₂O)₆]²⁺, with its hydrogen-bonding capability, obviates the disordering of the channel contents in (I).

In conclusion, the structure of (I) presents a variety of geometric forms, from the central cubane formed by inter­leaved tetra­hedra to the icosa­hedron composed of 12 O atoms at the periphery of the basic structural building block, to which are ligated four bridging octa­hedral Co^II centres to form a square two-dimensional polymer. These anionic layers are stacked along the c axis, with independent octa­hedral [Co(H₂O)₆]²⁺, Cs⁺ and H₂O in the inter­layer spaces. The fact that the inter­layer space is ordered in (I) and disordered in two previously reported structures of the same type indicates that the hydrogen-bonding pattern in (I) is not a structure-directing feature.

Figure 1 The square polymer that forms one layer of the structure of (I).

Figure 2 (a) The core of the cubane unit, which sits on a site of symmetry. Only the unique citrate ligand is shown. Displacement ellipsoids are drawn at the 50% probability level. (b) The full [Co4(citrate)4]^8− `cubane', showing the five- and six-membered chelates (in the electronic version of the paper, these are in pink and aqua­marine, respectively). H atoms have been omitted for clarity. [Symmetry codes: (i) −x + 1, −y + 1, z; (ii) −y + 1, x, −z + 1; (iii) y, −x + 1, −z + 1.]

Figure 3 The distorted stellated octa­hedron composed of inter­leaved O- and Co-based tetra­hedra.

Figure 4 The icosa­hedron formed by the peripheral O atoms of four citrate ligands. [Symmetry codes: (i) −x + 1, −y + 1, z; (ii) −y + 1, x, −z + 1; (iii) y, −x + 1, −z + 1.]

Experimental

All reagents were commercially available and were used as received. The title compound, (I), was prepared by adding an aqueous solution of CsOH (1.2 M) to an aqueous solution of {[Co(H₂O)₄][Co₂(C₆H₅O₇)₂(H₂O)₄]·6H₂O}_n (Zhou et al., 2005) (0.81 g, 1.00 mmol) until the pH reached 7–8. The resulting mixture was stirred for 30 min and filtered. The addition of 3,3′-sulfanediyl­dipropanol (98%) to the solution produced small quanti­ties of pink crystals of (I) with cubic morphology after several months at room temperature.

Crystal data

• Cs₂[Co(H₂O)₆][Co₆(C₆H₄O₇)₄(H₂O)₈]·12H₂O

• M_r = 1899.11

• Tetragonal,

• a = 12.5738 (1) Å

• c = 19.5895 (3) Å

• V = 3097.11 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 3.11 mm⁻¹

• T = 100 K

• 0.16 × 0.14 × 0.10 mm

Data collection

• Oxford Xcalibur Sapphire3 diffractometer

• Absorption correction: multi-scan [using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm; Oxford Diffraction, 2010] T_min = 0.790, T_max = 1.000

• 14807 measured reflections

• 3677 independent reflections

• 3128 reflections with I > 2σ(I)

• R_int = 0.038

Refinement

• R[F² > 2σ(F²)] = 0.037

• wR(F²) = 0.094

• S = 1.02

• 3677 reflections

• 202 parameters

• H-atom parameters constrained

• Δρ_max = 1.58 e Å⁻³

• Δρ_min = −0.45 e Å⁻³

• Absolute structure: Flack (1983), with 1567 Friedel pairs

• Flack parameter: 0.04 (2)

Table 1
Selected geometric parameters (Å, °)

Co1—O4^i	2.037 (3)	O1⋯O1^i	2.719 (5)
Co1—O1	2.087 (3)	O1⋯O1^iii	2.772 (5)
Co1—O1^iii	2.090 (3)	O7—Co2	2.078 (3)
Co1—O6	2.096 (3)	Co2—O2W	2.082 (4)
Co1—O2^iii	2.124 (3)	Co2—O1W	2.109 (4)
Co1—O1^i	2.134 (3)	Co3—O3W	2.078 (3)
Co1⋯Co1^i	3.2252 (11)	Co3—O4W	2.106 (5)
Co1⋯Co1^iii	3.1357 (9)
O4^i—Co1—O1	115.75 (12)	O6—Co1—O2^iii	83.95 (12)
O4^i—Co1—O1^iii	155.97 (11)	O4^i—Co1—O1^i	86.63 (11)
O1—Co1—O1^iii	83.14 (12)	O1—Co1—O1^i	80.19 (11)
O4^i—Co1—O6	88.35 (11)	O1^iii—Co1—O1^i	82.01 (11)
O1—Co1—O6	86.86 (11)	O6—Co1—O1^i	162.42 (11)
O1^iii—Co1—O6	108.35 (11)	O2^iii—Co1—O1^i	112.64 (11)
O4^i—Co1—O2^iii	87.66 (12)	Co1—O1—Co1^ii	97.31 (11)
O1—Co1—O2^iii	154.59 (11)	Co1—O1—Co1^i	99.65 (11)
O1^iii—Co1—O2^iii	77.41 (11)	Co1^ii—O1—Co1^i	95.87 (11)
Symmetry codes: (i) −x + 1, −y + 1, z; (ii) −y + 1, x, −z + 1; (iii) y, −x + 1, −z + 1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O6	0.95	1.82	2.628 (5)	141
O1W—H1WB⋯O5W	0.96	1.91	2.829 (5)	160
O2W⋯O5^iv			2.604 (5)
O2W⋯O7			2.782 (5)
O3W—H3WA⋯O3^iii	0.83	1.84	2.662 (4)	168
O3W—H3WB⋯O5W	0.84	1.98	2.778 (4)	159
O4W—H4WA⋯O7W^iii	1.00	1.75	2.736 (5)	167
O5W—H5WA⋯O6W^vi	0.91	1.99	2.859 (5)	161
O5W—H5WB⋯O2^v	0.93	1.99	2.905 (5)	167
O6W—H6WA⋯O7W^iv	0.85	1.94	2.785 (7)	180
O6W⋯O2W			2.882 (5)
O7W—H7WA⋯O3	0.98	1.83	2.708 (5)	148
O7W—H7WB⋯O5^vii	0.91	1.90	2.749 (6)	153
Symmetry codes: (iii) y, −x + 1, −z + 1; (iv) x − , −y + , −z + ; (v) 1 − x, −y, z; (vi)  − y,  − x, − + z; (vii) −x + , y − , −z + .

The Cs1 site was refined with an occupancy of 0.5, which gives charge balance for the structure as a whole and results in displacement parameters of Cs1 in line with those of the rest of the structure. Citrate methyl­ene H atoms were added at calculated positions (C—H = 0.99 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C). For the seven water sites present in the asymmetric unit, of which four are bound to Co, a total of ten H atoms were located in difference maps and included as riding, with U_iso(H) = 1.2U_eq(O). There was no attempt to force or otherwise idealize the O—H distances. Atom O4W is located on a twofold axis and its unique H atom was located. Three H atoms were omitted, namely the two on O2W and one on O6W. The two H atoms attached to O6W were initially placed at positions calculated for donor H atoms in the two inter­actions in which O6W must be donor. Specifically, O6W must be the donor in hydrogen bonds to O2W [D⋯A = 2.882 (5) Å] and O7W^iv [D⋯A = 2.785 (7) Å; symmetry code: (iv) x − , −y + , −z + ], because O2W and O7W have two clear hydrogen-bonding contacts each to unprotonated O atoms, and so O2W and O7W^iv must be the acceptors in their inter­actions with O6W. Nevertheless, the position of the H atom involved in a putative hydrogen bond from O6W to O2W could not be verified in an omit map, and so this H atom was removed from the model. One H atom attached to O2W, and which is likely the donor in an inter­action with O7 [D⋯A = 2.782 (5) Å], was neither observed in a difference map nor placed at a calculated position, because there exists the possibility of minor disorder components in which the second H atom on O2W donates to O1W [2.991 (5) Å] or to O2W^v [D⋯A = 2.919 (8) Å; symmetry code: (v) −x + 1, −y, z]. Following refinement, two difference peaks with densities of 1.58 and 1.15 e Å⁻³ were found at 0.79 and 1.06 Å, respectively, from Cs1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, (2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Polynuclear transition metal complexes with cube-shaped cores, generically called cubanes, have been studied for a variety of metals and in a variety of contexts. In recent years, the magnetic properties of cubane complexes of first-row transition elements have been studied, not in small part because the seminal single-molecule magnet (SMM), [Mn₁₂O₁₂(CH₃CO₂)₁₆(H₂O)₄], has a cubane Mn₄O₄ centre (Lis, 1980; Sessoli, Gatteschi et al., 1993; Sessoli, Tsai et al., 1993). The first cobalt-based SMM (Yang et al., 2002) was a cubane, with deprotonated hydroxymethylpyridine ligands. Murrie et al. (2003a,b) described a Co-based SMM with citrate ligands. Citrate cubanes of six different transition metals were described by Hudson et al. (2006) and by Moubaraki et al. (2008) [Galloway et al. (2008) here too?]. The citrate cubanes in these studies were discrete molecules, either with the basic [Co₄(citr)₄]^8- structure (where citr denotes quadruply deprotonated citric acid, C₆H₄O₇^4-), or with two additional Co^II centres covalently bound at the periphery of the [Co₄(citr)₄]^8- unit to give a tetra-anion. We have reported a serrated one-dimensional polymer whose structural building block is the [Co₄(citr)₄]^8- cubane, and which undergoes an unprecedented reversible crosslinking in the crystal structure to form a rhombic two-dimensional cubane polymer (Campo et al., 2008). In the resulting two-dimensional polymer, a Co^II centre within the crosslink fragment possesses an uncommon CoO₇ coordination environment. The first three-dimensional network based on the same building block was reported recently (Galloway et al., 2010).

We have prepared a square anionic two-dimensional polymer, octaaqua-tetra-µ-citrato-hexacobalt(II), the structure of which is related to that of a previously reported two-dimensional polymer containing ethylene glycol, (II). The Rb⁺ and Cs⁺ salts of (II) suffer severe structural disorder but have interesting magnetic properties; these are the subject of another report (Burzurí et al., 2011). In what follows, we report the structure of the title hydrated double salt of this polymer, (I), {Cs₂[Co(H₂O)₆]{[Co₄(C₆H₄O₇)₄][µ-Co(H₂O)₄]₂}.12H₂O}_n, which is the first of the square two-dimensional citrate cubane polymers to have crystallized without serious cation and hydrate disorder.

The structure of (I) is a stack of square two-dimensional polymeric layers (Fig. 1). Each layer is a regular array of cubanes located on sites of 4 symmetry, bridged by six-coordinate Co^II centres which sit on twofold axes. The basic unit of the polymer consists of one cubane and two bridges, {[Co₄(citr)₄][µ-Co(H₂O)₄]₂}^4-; the crystallographic a and b axes are the propagation vectors. In chemical terms, it is perhaps better to view the cubane as sharing bridges with each of four neighbours, with the negative charge of one unit of the polymer arising from [Co₄(citr)₄]^8- and one-half of each of the four [µ-Co(H₂O)₄]²⁺ bridges, giving a charge of 4- per node of the polymer; there are two nodes per unit cell. Charge is balanced by one [Co(H₂O)₆]²⁺ and two Cs⁺ cations per cubane; these cations are not part of the polymer. The octahedral cation is centred at Co3, which resides on 4, giving two per unit cell. Atom Cs1 resides on a set of general positions but is half-occupied, as determined both by the need for charge balance and by the refinement of the displacement parameters to values in line with those of the rest of the structure. There are thus four Cs⁺ cations per cell. One-quarter of the polymer repeat unit, and its associated cations and solvent water molecules, comprises the crystallographic asymmetric unit.

The geometries of cubanes containing Co and Ni have been reviewed by Isele et al. (2007). The Co₄O₄ core in (I) (Fig. 2 and Table 1) has internal geometry comparable with that observed in previously reported structures based on this unit. The Co···Co and O···O distances are well within the ranges found by Isele et al. (2007), and the acute and obtuse bond angles at Co1 and O1, respectively, have commonly observed values that can be related to the magnetic properties of the cubanes. The Co₄O₄ fragment in (I) is sufficiently distorted from a regular cubic shape that, for the purposes of describing its geometry, it is best viewed as a stellated octahedron (a distortion of the stella octangula) formed by the interleaved Co₄ and O₄ tetrahedra (Fig. 3). The unique Cg1—Co1 and Cg1—O1 distances are 1.9387 (5) and 1.687 (3) Å, respectively (Cg1 represents the centre of the cubane, located at the unweighted average position of the eight constituent atoms). If the two tetrahedra were considered to be distorted, the Co₄ unit would be taken as very slightly compressed, with two Co—Cg1—Co angles greater than, and four less than, the ideal tetrahedral value. The O₄ tetrahedron might similarly be considered as slightly elongated, although quantitatively the tetrahedral distortion is essentially negligible in both cases, with a Robinson tetrahedral angular variance σ_θ(tet)² of 5.72°² for Co₄ and 2.51°² for O₄ (Robinson et al., 1971). Because of the 4 symmetry, the quadratic elongation <λ_tet> is 1.00. For the purposes of comparison, we have surveyed the geometries of 40 previously published Co^II₄O₄ cubane fragments using the Cambridge Structural Database (Version 5.31; Allen, 2002). Structures that we considered to be chemically unrepresentative, such as fused cubanes, were excluded from this study. Eight of these published cubane structures displayed a slightly compressed Co₄ tetrahedron together with a slightly elongated O₄ unit, and three showed the opposite. None had both tetrahedra elongated. The calculated angular variances σ_θ(tet)² for the cubanes surveyed varied in the ranges 0.01–52.9°² for atom Co₄ and 0.05–63.9°² for atom O₄. In no case did <λ_tet> vary by more than 0.02 from the symmetrical value of 1.00 for either of the tetrahedra.

The four citrate ligands of the cubane in (I) are related by 4 symmetry. Each citrate has its hydroxy O atom at one corner of the cubane. The three terminal carboxyl groups bind through one O atom each to a Co atom of the cube, thus forming one five-membered and two six-membered chelates (Figs. 2a and 2b). The five-membered ring Co1ⁱⁱ/O1/C1/C2/O2 has an envelope conformation with the fold at Co1ⁱⁱ [symmetry code: (ii) -y + 1, x, -z + 1]. Numbering from Co1ⁱⁱ as the 1 position, this would be rendered as E₁. The six-membered rings Co1ⁱ/O1/C1/C3/C4/O4 [symmetry code: (i) -x + 1, -y + 1, z] and Co1/O1/C1/C5/C6/O6 have ring-puckering parameters (Cremer & Pople, 1975) of Q = 0.780 (3) and 0.867 (3) Å, θ = 87.9 (3) and 87.8 (2)°, and ϕ = 112.0 (3) and 343.7 (2)°, respectively. Thus, the former has a boat conformation, ^1,4B using the given atom sequence, while the latter is a slightly twisted boat, based on ^1,4B.

An important topological feature of the [Co₄(citr)₄]^8- building block is its periphery, at which 12 partially charged O atoms, namely the carboxylate O atoms not involved in chelation to Co of the cube, offer as many reactive nucleophilic sites, which serve as potential linkage points for forming an ample variety of extended structures in one, two and three dimensions. A number of the citrate cubanes characterized to date have transition metals coordinated by one or more of these peripheral O atoms. The 12 O atoms form an irregular icosahedron (Fig. 4), with Cg1-to-vertex distances of 5.061 (3), 5.428 (3) and 5.535 (3) Å for atoms O3, O5 and O7, respectively. The crystallographic 4 symmetry relates the vertices in groups of four. Each such group forms a distorted tetrahedron. That formed by atom O5 and its congeners is elongated along c, with a tetrahedral angular variance of 889°²; this shape, when it appears as a crystal form, is called a tetragonal disphenoid. The tetrahedron containing atom O3 is compressed, with a similar variance of 828°². The O7 tetrahedron is nearly regular, with an angular variance of 6.7°². Atom O7 and its equivalents are the linkage points for the extended structure, binding the `satellite' atom Co2 and its congeners, which sit on crystallographic twofold axes and bridge successive cubanes. In this way, the cubane/icosahedron and bridging atom Co2 form an unbounded two-dimensional net parallel to the crystallographic ab plane (Fig. 1). The O7 equivalents from neighbouring cubanes are trans to each other at Co2, the coordination of which is completed by four aqua ligands.

Similarities between (I) and previously reported structures with the same cubane building block end at the periphery of the cubane unit. In a previously reported structure of a one-dimensional polymer of Co citrate cubanes (Campo et al., 2008), the analogous icosahedron has similar geometry to that found for (I), with elongated, compressed and regular oxygen tetrahedra having angular variances of 467, 805 and 38.1°², respectively. In that structure the cubane sits on a general position. Five of its peripheral O atoms bind Co, namely those that are analogous to atoms O3, O7, O5ⁱⁱⁱ, O3ⁱⁱ and O5ⁱ in Fig. 4. The extended structure in that case does not have the symmetry shown by (I) and the chemical unit formed is a serrated one-dimensional polymer of cubanes. That structure undergoes a chemical reaction in the solid state to form a cross-linked two-dimensional polymer whose icosahedra of peripheral O atoms bind Co at the sites analogous to O3, O7, O5ⁱⁱⁱ, O3ⁱⁱ and O7ⁱ, having lost the link to Co at the site analogous to O5ⁱ.

In (I), the gaps in the polymer mesh of one layer are covered by the cubanes of the two neighbouring layers. The ABAB stacking of the layers is propagated by 1/2[111], but alternate layers are actually related by n[110] and are thus mirror images of each other.

The stacking of the two-dimensional polymeric layers leaves channels in the structure parallel to the a and b axes. These are occupied by the Cs⁺ cations (two per polymer repeat unit) along with [Co(H₂O)₆]²⁺ cations, located on 4, and the solvent water molecules.

The hydrogen bonding in (I), although extensive, is not a structure-determining factor; rather, hydrogen bonds are formed within the channels left by the stacking of the anionic polymers, and also between water molecules within the channels and O atoms of the citrate and aqua ligands attached to the Co atoms of the polymer. The seven independent water fragments present (three of them unligated), along with atoms Co2 and Co3 (to which four of the unique water molecules are bound) and their congeners, form a cyclic structure mediated by coordination and hydrogen bonds and which girds the periphery of the icosahedral [Co₄(citr)₄]^8- unit. The water molecules donate hydrogen bonds to the inner carboxylate O atoms, i.e. those that are bound to cubane Co, as well as to the peripheral carboxylate O atoms (Table 2).

This extensive ordered hydrogen-bonding arrangement is not necessary, however, for the stability of the structure. In other systems based on a closely related two-dimensional polymer but crystallized with other cations (Rb⁺, Cs⁺ or K⁺), we have observed an isomorphous crystal structure – the two-dimensional layer is stacked in the same arrangement as in (I), but the interlayer space is very different in all cases. Compound (I) is the first case we have observed in which there is no disorder in the non-H atoms of the interstitial residues. In the Rb⁺ and Cs⁺ salts (Burzurí et al., 2011), which are stable in the crystalline state, the cations are disordered over two and three independent sites, respectively, and the interlayer water molecules are severely disordered in the channels. In those structures, the channels account for 39% of the volume of the unit cell, while in (I) 42% of the volume is in the channels. We can speculate that the presence of a larger cation, [Co(H₂O)₆]²⁺, with its hydrogen-bonding capability, obviates the disordering of the channel contents in (I).

In conclusion, the structure of (I) presents a variety of geometric forms, from the central cubane formed by interleaved tetrahedra to the icosahedron composed of 12 O atoms at the periphery of the basic structural building block, to which are ligated four bridging octahedral Co^II centres to form a square two-dimensional polymer. These anionic layers are stacked along the c axis, with independent octahedral [Co(H₂O)₆]²⁺, Cs⁺ and H₂O in the interlayer spaces. The fact that the interlayer space is ordered in (I) and disordered in two previously reported structures of the same type indicates that the hydrogen-bonding pattern in (I) is not a structure-directing feature.

Related literature

For related literature, see: Allen (2002); Burzurí et al. (2011); Campo et al. (2008); Cremer & Pople (1975); Galloway et al. (2008, 2010); Hudson et al. (2006); Isele et al. (2007); Lis (1980); Moubaraki et al. (2008); Murrie et al. (2003a, 2003b); Robinson et al. (1971); Sessoli, Gatteschi, Caneschi & Novak (1993); Sessoli, Tsai, Schake, Wang, Vincent, Folting, Gatteschi, Christou & Hendrickson (1993); Yang et al. (2002); Zhou et al. (2005).

S2. Experimental

All reagents were commercial and were used as received. The title compound, (I), was prepared by adding an aqueous solution of CsOH (1.2 M) to an aqueous solution of {[Co(H₂O)₄][Co₂(C₆H₅O₇)₂(H₂O)₄].6H₂O}_n (Zhou et al., 2005) (0.81 g, 1.00 mmol) until the pH reached 7–8. The resulting mixture was stirred for 30 min and filtered. The addition of 3,3'-thiodipropanol (98%) to the solution produced small quantities of red [Please clarify - pink given in CIF tables] crystals of (I) with cubic morphology after several months at room temperature.

S3. Refinement

The caesium site, Cs1, was refined with an occupancy of 0.5, which gives charge balance for the structure as a whole and results in displacement parameters for Cs1 in line with those of the rest of the structure. Citrate methylene H atoms were added at calculated positions (C—H = 0.99 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C). For the seven water sites present in the asymmetric unit, of which four are bound to Co, a total of ten H atoms were located in difference maps and included as riding, with U_iso(H) = 1.2U_eq(O). We did not force or otherwise attempt to idealize the O—H distances. Atom O4W is located on a twofold axis and its unique H atom was located. Three H atoms were omitted, namely the two on O2W and one on O6W. The two H atoms attached to O6W were initially placed at positions calculated for donor H atoms in the two interactions in which O6W must be donor. Specifically, O6W must be the donor in hydrogen bonds to O2W [D···A = 2.882 (5) Å] and O7W^iv [symmetry code: (iv) x - 1/3, -y + 1/2, -z + 3/2; D···A = 2.785 (7) Å], because O2W and O7W have two clear hydrogen-bonding contacts each to unprotonated O atoms, and so O2W and O7W^iv must be the acceptors in their interactions with O6W. Nevertheless, the position of the H atom involved in a putative hydrogen bond from O6W to O2W could not be verified in an omit map, and so this H atom was removed from the model. One H atom attached to O2W, and which is likely the donor in an interaction with O7 [D···A = 2.782 (5) Å], was neither observed in a difference map nor placed at a calculated position, because there exists the possibility of minor disorder components in which the second H atom on O2W donates to O1W [2.991 (5) Å] or to O2W^v [symmetry code: (v) -x + 1, -y, z; D···A = 2.919 (8) Å]. Following refinement, two difference peaks with densities of 1.58 and 1.15 e Å^-3 were found at 0.79 and 1.06 Å, respectively, from Cs1.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, (2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The square polymer that forms one layer of the structure of (I).
	Fig. 2. (a) The core of the cubane unit, which sits on a site of 4 symmetry. Only the unique citrate ligand is shown. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. (b) The full [Co4(citrate)4]^8- `cubane', showing the five- and six-membered chelates [in the electronic version of the journal, these are in pink and aquamarine, respectively]. [Symmetry codes: (i) -x + 1, -y + 1, z; (ii) -y + 1, x, -z + 1; (iii) y, -x + 1, -z + 1.]
	Fig. 3. The distorted stellated octahedron composed of interleaved O- and Co-based tetrahedra.
	Fig. 4. The icosahedron formed by the peripheral O atoms of four citrate ligands. [Symmetry codes: (i) -x + 1, -y + 1, z; (ii) -y + 1, x, -z + 1; (iii) y, -x + 1, -z + 1.]

poly[dicaesium(I) hexaaquacobalt(II) [octaaqua-tetra-µ-citrato-hexacobalt(II)] dodecahydrate]

Crystal data

Cs2[Co(H2O)6][Co6(C6H4O7)4(H2O)8]·12H2O	Dx = 2.036 Mg m^−3
Mr = 1899.11	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 8136 reflections
a = 12.5738 (1) Å	θ = 4.2–28.8°
c = 19.5895 (3) Å	µ = 3.11 mm^−1
V = 3097.11 (6) Å^3	T = 100 K
Z = 2	Block, pink
F(000) = 1886	0.16 × 0.14 × 0.10 mm

Data collection

Oxford Xcalibur, Sapphire3 diffractometer	3677 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3128 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 16.0655 pixels mm^-1	θmax = 28.8°, θmin = 4.2°
ω scans	h = −13→16
Absorption correction: multi-scan (multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm; Oxford Diffraction, 2010)	k = −15→16
Tmin = 0.790, Tmax = 1.000	l = −25→21
14807 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.059P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3677 reflections	Δρmax = 1.58 e Å^−3
202 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

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	0.43328 (4)	0.39047 (4)	0.55493 (3)	0.01208 (13)
O1	0.5910 (2)	0.4417 (2)	0.55095 (14)	0.0131 (5)
C1	0.6707 (3)	0.3870 (3)	0.5883 (2)	0.0140 (8)
C2	0.7240 (3)	0.3037 (3)	0.5415 (2)	0.0149 (8)
O2	0.6967 (2)	0.2990 (2)	0.47954 (14)	0.0170 (6)
O3	0.7891 (3)	0.2410 (3)	0.56827 (15)	0.0234 (7)
C3	0.7557 (3)	0.4652 (3)	0.6125 (2)	0.0179 (9)
H3A	0.7840	0.5045	0.5726	0.021*
H3B	0.8152	0.4252	0.6333	0.021*
C4	0.7115 (4)	0.5447 (4)	0.6647 (2)	0.0215 (10)
O4	0.6366 (2)	0.6046 (2)	0.64869 (16)	0.0182 (6)
O5	0.7518 (3)	0.5467 (4)	0.7231 (2)	0.0537 (13)
C5	0.6226 (3)	0.3269 (3)	0.6496 (2)	0.0153 (8)
H5A	0.6805	0.3054	0.6810	0.018*
H5B	0.5744	0.3752	0.6749	0.018*
C6	0.5616 (3)	0.2295 (3)	0.6279 (2)	0.0157 (8)
O6	0.4933 (2)	0.2400 (2)	0.57999 (14)	0.0173 (6)
O7	0.5827 (2)	0.1428 (2)	0.65632 (17)	0.0217 (7)
Co2	0.5000	0.0000	0.65049 (4)	0.02063 (19)
O1W	0.3958 (3)	0.0553 (3)	0.57394 (18)	0.0325 (8)
H1WA	0.4191	0.1212	0.5556	0.039*
H1WB	0.3903	0.0117	0.5339	0.039*
O2W	0.4055 (3)	0.0674 (3)	0.72630 (19)	0.0393 (10)
Co3	0.0000	0.0000	0.5000	0.0159 (2)
O3W	0.1570 (2)	0.0513 (2)	0.50292 (17)	0.0231 (7)
H3WA	0.1912	0.1000	0.4841	0.028*
H3WB	0.2027	0.0033	0.4977	0.028*
O4W	0.0000	0.0000	0.3925 (2)	0.0383 (12)
H4WA	0.0561	0.0371	0.3653	0.046*
Cs1	0.22000 (5)	0.17011 (5)	0.65067 (3)	0.03163 (16)	0.50
O5W	0.3296 (3)	−0.0710 (3)	0.46224 (17)	0.0300 (8)
H5WA	0.3369	−0.0520	0.4178	0.036*
H5WB	0.3294	−0.1432	0.4731	0.036*
O6W	0.5222 (3)	0.1987 (3)	0.82087 (17)	0.0420 (10)
H6WA	0.4767	0.2486	0.8214	0.050*
O7W	0.8722 (4)	0.1384 (3)	0.6775 (2)	0.0514 (12)
H7WA	0.8197	0.1757	0.6493	0.062*
H7WB	0.8353	0.1284	0.7172	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0120 (3)	0.0134 (3)	0.0108 (2)	−0.0008 (2)	−0.0003 (2)	0.0009 (2)
O1	0.0115 (13)	0.0163 (14)	0.0115 (12)	0.0000 (11)	−0.0021 (11)	0.0018 (12)
C1	0.014 (2)	0.0128 (19)	0.0155 (19)	0.0017 (17)	0.0009 (16)	0.0034 (16)
C2	0.0135 (19)	0.015 (2)	0.016 (2)	0.0018 (16)	0.0026 (16)	0.0034 (15)
O2	0.0202 (16)	0.0164 (15)	0.0143 (14)	0.0054 (12)	0.0006 (11)	−0.0001 (11)
O3	0.0242 (16)	0.0291 (17)	0.0167 (16)	0.0117 (14)	0.0021 (12)	0.0027 (13)
C3	0.014 (2)	0.023 (2)	0.016 (2)	−0.0031 (18)	−0.0032 (16)	0.0016 (16)
C4	0.021 (2)	0.022 (2)	0.021 (2)	−0.001 (2)	−0.0058 (18)	−0.0035 (17)
O4	0.0209 (15)	0.0155 (14)	0.0181 (15)	0.0002 (12)	−0.0028 (13)	−0.0017 (13)
O5	0.057 (3)	0.071 (3)	0.033 (2)	0.039 (2)	−0.033 (2)	−0.030 (2)
C5	0.020 (2)	0.0152 (19)	0.0106 (17)	0.0002 (16)	−0.0015 (17)	−0.0016 (17)
C6	0.015 (2)	0.019 (2)	0.0133 (18)	0.0010 (18)	0.0055 (16)	0.0003 (16)
O6	0.0168 (14)	0.0178 (14)	0.0174 (14)	0.0033 (13)	−0.0045 (12)	0.0009 (11)
O7	0.0262 (17)	0.0156 (14)	0.0231 (16)	−0.0028 (13)	−0.0086 (14)	0.0086 (13)
Co2	0.0311 (4)	0.0171 (4)	0.0137 (4)	−0.0077 (4)	0.000	0.000
O1W	0.043 (2)	0.0254 (17)	0.0294 (19)	−0.0150 (17)	−0.0103 (16)	0.0054 (14)
O2W	0.055 (3)	0.0301 (19)	0.033 (2)	−0.0101 (19)	0.0152 (18)	−0.0113 (16)
Co3	0.0145 (3)	0.0145 (3)	0.0185 (5)	0.000	0.000	0.000
O3W	0.0152 (15)	0.0196 (15)	0.0344 (18)	−0.0039 (13)	−0.0005 (14)	0.0032 (15)
O4W	0.052 (3)	0.043 (3)	0.019 (2)	−0.020 (3)	0.000	0.000
Cs1	0.0369 (3)	0.0339 (3)	0.0241 (3)	0.0018 (3)	0.0074 (3)	0.0039 (3)
O5W	0.0390 (19)	0.0255 (17)	0.0257 (19)	0.0083 (16)	0.0026 (15)	0.0013 (14)
O6W	0.064 (3)	0.041 (2)	0.0208 (18)	−0.002 (2)	−0.0087 (17)	−0.0089 (15)
O7W	0.073 (3)	0.054 (3)	0.027 (2)	0.032 (2)	0.011 (2)	0.0128 (18)

Geometric parameters (Å, º)

Co1—O4^i	2.037 (3)	C6—O7	1.253 (5)
Co1—O1	2.087 (3)	C6—O6	1.279 (5)
Co1—O1^ii	2.090 (3)	O7—Co2	2.078 (3)
Co1—O6	2.096 (3)	Co2—O7^iv	2.078 (3)
Co1—O2^ii	2.124 (3)	Co2—O2W	2.082 (4)
Co1—O1^i	2.134 (3)	Co2—O1W	2.109 (4)
O1—C1	1.419 (5)	O1W—Cs1	3.038 (4)
O1—Co1^iii	2.090 (3)	O1W—H1WA	0.9497
O1—Co1^i	2.134 (3)	O1W—H1WB	0.9600
C1—C3	1.527 (6)	O2W—Cs1	3.050 (4)
C1—C5	1.542 (6)	Co3—O3W	2.078 (3)
C1—C2	1.545 (6)	Co3—O4W	2.106 (5)
C2—O3	1.252 (5)	O3W—Cs1	3.352 (3)
C2—O2	1.262 (5)	O3W—H3WA	0.8339
O2—Co1^iii	2.124 (3)	O3W—H3WB	0.8401
O2—Cs1^iii	3.209 (3)	O4W—H4WA	0.9993
C3—C4	1.534 (6)	Cs1—O6W^v	3.036 (4)
C3—H3A	0.9900	Cs1—O2^ii	3.209 (3)
C3—H3B	0.9900	Cs1—O4^i	3.358 (3)
C4—O4	1.247 (5)	O5W—H5WA	0.9076
C4—O5	1.251 (6)	O5W—H5WB	0.9314
O4—Co1^i	2.037 (3)	O6W—Cs1^vi	3.036 (4)
O4—Cs1^i	3.358 (3)	O6W—H6WA	0.8495
C5—C6	1.506 (6)	O7W—H7WA	0.9800
C5—H5A	0.9900	O7W—H7WB	0.9150
C5—H5B	0.9900
O4^i—Co1—O1	115.75 (12)	O7—C6—C5	118.3 (4)
O4^i—Co1—O1^ii	155.97 (11)	O6—C6—C5	117.7 (4)
O1—Co1—O1^ii	83.14 (12)	C6—O6—Co1	120.4 (3)
O4^i—Co1—O6	88.35 (11)	C6—O6—Cs1	108.4 (2)
O1—Co1—O6	86.86 (11)	Co1—O6—Cs1	88.20 (10)
O1^ii—Co1—O6	108.35 (11)	C6—O7—Co2	128.4 (3)
O4^i—Co1—O2^ii	87.66 (12)	O7—Co2—O7^iv	173.69 (19)
O1—Co1—O2^ii	154.59 (11)	O7—Co2—O2W^iv	91.55 (13)
O1^ii—Co1—O2^ii	77.41 (11)	O7—Co2—O2W	83.94 (14)
O6—Co1—O2^ii	83.95 (12)	O2W^iv—Co2—O2W	89.0 (2)
O4^i—Co1—O1^i	86.63 (11)	O7—Co2—O1W	93.75 (12)
O1—Co1—O1^i	80.19 (11)	O2W—Co2—O1W	91.06 (15)
O1^ii—Co1—O1^i	82.01 (11)	O7—Co2—O1W^iv	90.74 (13)
O6—Co1—O1^i	162.42 (11)	O2W—Co2—O1W^iv	174.68 (14)
O2^ii—Co1—O1^i	112.64 (11)	O1W—Co2—O1W^iv	89.4 (2)
C1—O1—Co1	120.1 (2)	Co2—O1W—Cs1	104.88 (14)
C1—O1—Co1^iii	114.2 (2)	Co2—O1W—H1WA	111.4
Co1—O1—Co1^iii	97.31 (11)	Cs1—O1W—H1WA	89.8
C1—O1—Co1^i	124.2 (2)	Co2—O1W—H1WB	115.9
Co1—O1—Co1^i	99.65 (11)	Cs1—O1W—H1WB	128.6
Co1^iii—O1—Co1^i	95.87 (11)	H1WA—O1W—H1WB	102.2
O1—C1—C3	110.0 (3)	Co2—O2W—Cs1	105.20 (15)
O1—C1—C5	111.2 (3)	O3W—Co3—O3W^vii	176.85 (18)
C3—C1—C5	110.4 (3)	O3W—Co3—O3W^viii	90.043 (5)
O1—C1—C2	109.1 (3)	O3W—Co3—O4W^ix	88.42 (9)
C3—C1—C2	108.5 (3)	O3W—Co3—O4W	91.58 (9)
C5—C1—C2	107.5 (3)	O4W^ix—Co3—O4W	180.0
O3—C2—O2	123.4 (4)	Co3—O3W—Cs1	112.75 (12)
O3—C2—C1	117.5 (4)	Co3—O3W—H3WA	134.9
O2—C2—C1	119.0 (4)	Cs1—O3W—H3WA	86.2
C2—O2—Co1^iii	114.1 (3)	Co3—O3W—H3WB	115.0
C2—O2—Cs1^iii	129.6 (3)	Cs1—O3W—H3WB	105.3
Co1^iii—O2—Cs1^iii	105.23 (10)	H3WA—O3W—H3WB	96.9
C1—C3—C4	111.9 (4)	Co3—O4W—H4WA	122.2
C1—C3—H3A	109.2	O6W^v—Cs1—O1W	160.92 (9)
C4—C3—H3A	109.2	O6W^v—Cs1—O2W	140.11 (10)
C1—C3—H3B	109.2	O1W—Cs1—O2W	58.85 (9)
C4—C3—H3B	109.2	O6W^v—Cs1—O2^ii	96.65 (9)
H3A—C3—H3B	107.9	O1W—Cs1—O2^ii	68.25 (8)
O4—C4—O5	121.5 (4)	O2W—Cs1—O2^ii	111.74 (9)
O4—C4—C3	120.0 (4)	O6W^v—Cs1—O3W	101.96 (9)
O5—C4—C3	118.5 (4)	O1W—Cs1—O3W	62.16 (8)
C4—O4—Co1^i	124.8 (3)	O2W—Cs1—O3W	114.31 (9)
C4—O4—Cs1^i	95.8 (3)	O2^ii—Cs1—O3W	67.62 (8)
Co1^i—O4—Cs1^i	102.51 (11)	O6W^v—Cs1—O4^i	89.05 (10)
C4—O5—Cs1^vi	123.5 (3)	O1W—Cs1—O4^i	90.25 (8)
C6—C5—C1	112.2 (3)	O2W—Cs1—O4^i	87.24 (8)
C6—C5—H5A	109.2	O2^ii—Cs1—O4^i	52.01 (8)
C1—C5—H5A	109.2	O3W—Cs1—O4^i	119.52 (8)
C6—C5—H5B	109.2	H5WA—O5W—H5WB	118.5
C1—C5—H5B	109.2	Cs1^vi—O6W—H6WA	98.5
H5A—C5—H5B	107.9	H7WA—O7W—H7WB	101.7
O7—C6—O6	123.9 (4)
O4^i—Co1—O1—C1	62.1 (3)	O4^i—Co1—O6—C6	−65.7 (3)
O1^ii—Co1—O1—C1	−133.5 (3)	O1—Co1—O6—C6	50.2 (3)
O6—Co1—O1—C1	−24.5 (3)	O1^ii—Co1—O6—C6	131.9 (3)
O2^ii—Co1—O1—C1	−93.4 (4)	O2^ii—Co1—O6—C6	−153.5 (3)
O1^i—Co1—O1—C1	143.5 (2)	O1^i—Co1—O6—C6	7.7 (6)
O4^i—Co1—O1—Co1^iii	−174.41 (10)	O4^i—Co1—O6—Cs1	44.62 (9)
O1^ii—Co1—O1—Co1^iii	−9.98 (11)	O1—Co1—O6—Cs1	160.52 (9)
O6—Co1—O1—Co1^iii	98.93 (11)	O1^ii—Co1—O6—Cs1	−117.77 (9)
O2^ii—Co1—O1—Co1^iii	30.1 (3)	O2^ii—Co1—O6—Cs1	−43.21 (8)
O1^i—Co1—O1—Co1^iii	−93.01 (10)	O1^i—Co1—O6—Cs1	118.0 (4)
O4^i—Co1—O1—Co1^i	−77.16 (14)	O6—C6—O7—Co2	−12.7 (6)
O1^ii—Co1—O1—Co1^i	87.28 (11)	C5—C6—O7—Co2	169.5 (3)
O6—Co1—O1—Co1^i	−163.81 (12)	C6—O7—Co2—O2W^iv	−171.9 (4)
O2^ii—Co1—O1—Co1^i	127.4 (2)	C6—O7—Co2—O2W	−83.1 (4)
O1^i—Co1—O1—Co1^i	4.24 (16)	C6—O7—Co2—O1W	7.6 (4)
Co1—O1—C1—C3	−146.9 (3)	C6—O7—Co2—O1W^iv	97.0 (4)
Co1^iii—O1—C1—C3	98.2 (3)	O7—Co2—O1W—Cs1	−84.63 (13)
Co1^i—O1—C1—C3	−17.9 (4)	O7^iv—Co2—O1W—Cs1	90.94 (12)
Co1—O1—C1—C5	−24.2 (4)	O2W—Co2—O1W—Cs1	−0.63 (13)
Co1^iii—O1—C1—C5	−139.1 (3)	O1W^iv—Co2—O1W—Cs1	−175.32 (18)
Co1^i—O1—C1—C5	104.7 (3)	O7—Co2—O2W—Cs1	94.28 (13)
Co1—O1—C1—C2	94.3 (3)	O7^iv—Co2—O2W—Cs1	−90.14 (14)
Co1^iii—O1—C1—C2	−20.7 (4)	O2W^iv—Co2—O2W—Cs1	−174.1 (2)
Co1^i—O1—C1—C2	−136.8 (3)	O1W—Co2—O2W—Cs1	0.62 (13)
O1—C1—C2—O3	−173.1 (3)	O3W^viii—Co3—O3W—Cs1	69.27 (10)
C3—C1—C2—O3	67.1 (5)	O3W^ix—Co3—O3W—Cs1	−113.88 (15)
C5—C1—C2—O3	−52.4 (5)	O4W—Co3—O3W—Cs1	157.69 (9)
O1—C1—C2—O2	3.7 (5)	O3W—Co3—O4W—Cs1^viii	−109.61 (9)
C3—C1—C2—O2	−116.0 (4)	O3W^vii—Co3—O4W—Cs1^viii	70.39 (9)
C5—C1—C2—O2	124.5 (4)	O3W^viii—Co3—O4W—Cs1^viii	−19.61 (9)
O3—C2—O2—Co1^iii	−168.6 (3)	O3W^ix—Co3—O4W—Cs1^viii	160.39 (9)
C1—C2—O2—Co1^iii	14.7 (4)	O3W—Co3—O4W—Cs1^ix	70.39 (9)
O3—C2—O2—Cs1^iii	−30.6 (6)	O3W^vii—Co3—O4W—Cs1^ix	−109.61 (9)
C1—C2—O2—Cs1^iii	152.7 (3)	O3W^viii—Co3—O4W—Cs1^ix	160.39 (9)
O1—C1—C3—C4	66.0 (4)	O3W^ix—Co3—O4W—Cs1^ix	−19.61 (9)
C5—C1—C3—C4	−57.1 (5)	Co2—O1W—Cs1—O6W^v	175.0 (3)
C2—C1—C3—C4	−174.7 (3)	Co2—O1W—Cs1—O2W	0.50 (10)
C1—C3—C4—O4	−59.9 (5)	Co2—O1W—Cs1—O2^ii	135.48 (14)
C1—C3—C4—O5	119.5 (5)	Co2—O1W—Cs1—O3W	−149.17 (15)
C1—C3—C4—Cs1^i	−136.0 (3)	Co2—O1W—Cs1—O4^i	87.12 (13)
O5—C4—O4—Co1^i	179.0 (4)	Co2—O1W—Cs1—O5W^viii	164.78 (11)
C3—C4—O4—Co1^i	−1.6 (6)	Co2—O1W—Cs1—O4W^ix	−115.29 (12)
Cs1^i—C4—O4—Co1^i	109.6 (3)	Co2—O2W—Cs1—O6W^v	−177.69 (13)
O5—C4—O4—Cs1^i	69.4 (5)	Co2—O2W—Cs1—O1W	−0.51 (10)
C3—C4—O4—Cs1^i	−111.2 (4)	Co2—O2W—Cs1—O2^ii	−45.52 (15)
O4—C4—O5—Cs1^vi	110.0 (4)	Co2—O2W—Cs1—O3W	28.83 (16)
C3—C4—O5—Cs1^vi	−69.4 (5)	Co2—O2W—Cs1—O4^i	−92.47 (13)
Cs1^i—C4—O5—Cs1^vi	167.8 (2)	Co2—O2W—Cs1—O5W^viii	−56.7 (4)
O1—C1—C5—C6	73.3 (4)	Co2—O2W—Cs1—O4W^ix	84.06 (15)
C3—C1—C5—C6	−164.3 (3)	Co3—O3W—Cs1—O6W^v	−40.66 (14)
C2—C1—C5—C6	−46.2 (4)	Co3—O3W—Cs1—O1W	150.63 (16)
C1—C5—C6—O7	128.7 (4)	Co3—O3W—Cs1—O2W	122.32 (13)
C1—C5—C6—O6	−49.3 (5)	Co3—O3W—Cs1—O2^ii	−133.00 (14)
O7—C6—O6—Co1	162.9 (3)	Co3—O3W—Cs1—O4^i	−136.43 (11)
C5—C6—O6—Co1	−19.3 (5)	Co3—O3W—Cs1—O5W^viii	−77.25 (13)
O7—C6—O6—Cs1	63.9 (4)	Co3—O3W—Cs1—O4W^ix	16.99 (8)
C5—C6—O6—Cs1	−118.3 (3)

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