Coordination behaviour and two-dimensional-network formation in poly[[[mu]-aqua-diaqua­([mu]₅-propane-1,3-diyldinitrilo­tetra­acetato)­dilithium(I)­cobalt(II)] dihydrate]: the first example of an M^II-1,3-pdta complex with a monovalent metal counter-ion

The title compound, {[CoLi₂(C₁₁H₁₄N₂O₈)(H₂O)₃]·2H₂O}_n, constitutes the first example of a salt of the [M^II(1,3-pdta)]^2- complex (1,3-pdta is propane-1,3-diyldinitrilo­tetra­acetate) with a monopositive cation as counter-ion. Insertion of the Li⁺ cation could only be achieved through application of the ion-exchange column technique which, however, appeared unsuccessful with other alkali metals and the ammonium cation. The structure contains two tetra­hedrally coordinated Li⁺ cations, an octa­hedral [Co(1,3-pdta)]^2- anion and five water mol­ecules, two of which are uncoordinated, and is built of two-dimensional layers extending parallel to the (010) lattice plane, the constituents of which are connected by the coordinate bonds. O-H_water...O hydrogen bonds operate both within and between these layers. The crystal investigated belongs to the enanti­omeric space group P2₁ with only one ([Lambda]) of two possible optical isomers of the [Co(1,3-pdta)]^2- complex. A possible cause of enanti­omer separation during crystallization might be the rigidification and polarization of the [M(1,3-pdta)]^2- core, resulting from direct coordination of Li⁺ cations to three out of four carboxyl­ate groups constituting the 1,3-pdta ligand. The structure of (I) differs considerably from those of the other [M^II(1,3-pdta)]^2- complexes, in which the charge compensation is realized by means of divalent hexa­aqua complex cations. This finding demonstrates a significant structure-determining role of the counter-ions.

S1. Comment

This work is a continuation of our study concerning the structural characteristics of 1,3-pdta complexes containing different metal(II) ions. The title compound, (I), constitutes the first example of a metal(II) complex of 1,3-propanediaminetetraacetate (1,3-pdta) with a monovalent metal as the charge-compensating ion. Our previous attempts to obtain M₂[Co^II(1,3-pdta)] complexes (where M is a alkali metal ion) using the same synthetic method as that used for the preparation of the series [M(H₂O)₆][M'(1,3-pdta)].2H₂O (M = Co^II, Mg^II or Zn^II; M'= Co^II, Zn^II, Cu^II, Ni^II or Mg^II) (Rychlewska et al., 2000, 2005; Radanović et al., 2001, 2003, 2004) were unsuccessful. More specifically, from a reaction mixture containing equivalent amounts of Ba[Co^II(1,3-pdta)].8H₂O and Li₂SO₄ or Na₂SO₄, only the homometallic complex salt [Co^II(H₂O)₆][Co^II(1,3-pdta)].2H₂O crystallized. Therefore, in order to obtain Li₂[Co^II(1,3-pdta)].5H₂O, the ion-exchange column technique was applied. However, attempts to use the same technique for the preparation of the analogous M₂[Co^II(1,3-pdta)] salts with M = Na⁺, K⁺, NH₄⁺ or Cs⁺ always yielded the corresponding [Co^III(1,3-pdta)]^- complex.

As expected, the solution that was eluted from the lithium-exchange column did not show any properties of rotation of polarisation, which indicates that the sample obtained is a racemate containing both right-handed (Δ) and left-handed (Λ) enantiomers. Upon crystallization, however, the compound underwent spontaneous resolution. This phenomenon has recently been reviewed by Perez-Garcia & Amabilino (2007). The solution obtained by dissolving a randomly selected group of crystals was optically active and did not undergo racemization for a period of several days. This points to the significant stability of the Li₂[Co(1,3 pdta)] complex and indicates that, at the macroscopic level, groups of crystals are formed which have predominantly one enantiomer, hence leading to chiral colonies. The chiral crystal of which the structure is reported in this paper contains molecules that display the Λ helicity.

The structure is built of two tetrahedrally coordinated Li⁺ cations, an octahedral [Co(1,3-pdta)]^2- anion and five water molecules, two of which are solvent water molecules. The coordination around the Co^II cation is octahedral and the 1,3-pdta acts as a hexadentate ligand (Fig. 1). The in-plane cis bond angles are in a wide range, 79.60 (9)–103.88 (8)°, and the in-plane trans bonds are bent by ca 1 and 6°, respectively (Table 1). The conformations of the glycinate rings are envelope for the more puckered G rings and half-chair for the less puckered R rings (see Fig. 1 for ring definitions). The six-membered diamine ring (T) approaches a half-chair form; the Cremer & Pople (1975) parameters (PARST; Nardelli, 1983) are Q_T = 0.596 (3) Å, ϕ = -24.0 (2)° and θ = 124.2 (2)°.

The octahedral coordination of the Co^II ion by 1,3-pdta has previously been observed in two isostructural crystals with either hexaaquamagnesium(II) [Cambridge Structural Database (CSD; Allen, 2002) refcode IMAFOR] or hexaaquacobalt(II) (CSD refcode IMAFIL) complexes as counter-ions (Radanović et al., 2003). Comparison of these two crystal structures (determined at 120 K) with that of (I) (determined at room temperature) reveals significant differences at both the molecular and supramolecular levels. While the former [Co(1,3-pdta)]^2- complexes display C₂ molecular symmetry, the complex in (I) is asymmetric. The asymmetry is introduced to the system by Li⁺ cations which are coordinated to three out of four carboxylate groups (one equatorial and two axial). This asymmetry is particularly well reflected in the variation in the values of the Co—O_equatorial bond lengths which represent, respectively, the longest [2.128 (2) Å] and shortest [2.063 (2) Å] Co—O bonds in this complex. The longest Co—O bond is formed to the O atom that is simultaneously coordinated to the Li⁺ cation, while the shortest involves the only carboxylate O atom that is exclusively coordinated to the Co^II cation. The analogous Co—O_equatorial bond length observed in the C₂ symmetrical [Co(1,3-pdta)]^2- complexes, in which the carboxylate groups are only coordinated to the central Co^II, is 2.055 (2) Å (average of two independent measurements).

The Li⁺ cations each display a tetrahedral environment but the coordination form differs (Fig. 1). Atom Li1 is surrounded by two water molecules (O1W and O2W) and two carboxylate O atoms [O2 and O8ⁱⁱⁱ; symmetry code: (iii) x, y, z + 1] that are not directly coordinated to the Co atom, while atom Li2 is bonded to two water molecules (O1W and O3W) and to two carboxylate O atoms [O6^iv and O1; symmetry code: (iv) x - 1, y, z], of which the former is not coordinated to Co while the latter is. The Li—O bond lengths and angles in the two LiO₄ tetrahedra display rather wide ranges of 1.857 (6)–2.014 (6) Å and 99.1 (3)–120.2 (3)°, respectively. The two Li⁺ cations are joined via the mediating water molecule O1W; the distance between the water-bridged Li⁺ cations is only 3.085 (8) Å and the angle at the O atom is 102.2 (2)°. The two Li⁺ cations are additionally bridged by one of the two equatorial carboxylate groups (O1—C5—O2). This leads to the formation of the puckered six-membered ring shown in Fig. 1. Simultaneous bridging of Li⁺ ions by a carboxylate group and a water molecule has also been observed in crystalline phases of other lithium complexes, including the simplest one, i.e. lithium fumarate (Kansikas & Hermansson, 1989). A search of the CSD yielded 20 such structures, displaying a significant variation of the ring puckering.

The ions connected by coordinate bonds form uncharged two-dimensional layers parallel to (010) (Fig. 2). The layer construction is further supported by a system of O—H···O hydrogen bonds, in which water molecules act as the proton donors and the acceptors are either carboxylate O atoms or uncoordinated water molecules (Table 2). The layers are both chiral and polar. There are two such layers per unit cell, related by the twofold screw axis along the b direction (Fig. 3). Neighbouring layers are anti-parallel, as required by the twofold symmetry, and are joined by hydrogen bonds. This supramolecular arrangement differs dramatically from the packing observed in the analogous [M(H₂O)₆][Co^II(1,3-pdta)].2H₂O complexes mentioned above [M = Mg^II (CSD refcode IMAFOR) or Co^II (CSD refcode IMAFIL); Radanović et al., 2003], which form centrosymmetric crystal structures containing distinct octahedral cationic and anionic species. A somewhat similar layered arrangement of complex anions to that present in (I) has been observed in those [M^III(1,3-pdta)]^- complexes which also underwent enantiomer separation during the crystallization process, i.e. those with M = Cr^III (CSD refcode BACRUS; Herak et al., 1984), Fe^III (CSD refcode JEPKEU; Okamoto et al., 1990) and V^III (CSD refcode PATZIT; Robles et al., 1993), all containing Na⁺ as the counter-ion. As in (I), the Na⁺ ions in these crystals are coordinated to three out of four carboxylate groups of the 1,3-pdta ligand but are situated in between rather than within the anionic layers. A somewhat similar, though more symmetrical, mode of cation/anion bonding is observed in the K[Co(1,3-pdta)] complex (CSD refcode TMACOK; Nagao et al., 1972), which also forms chiral crystals. This analogy in packing prompts us to propose that a possible cause of enantiomer separation during the crystallization process might be the rigidification and polarization of the M(1,3-pdta) core, resulting from the direct coordination of the alkali metal counter-ions to the carboxylate groups constituting the 1,3-pdta ligand. This rigidification may account for the occurrence of one particular orientation and chirality of the constituent complex anions in a layer and cause the non-centrosymmetric packing of neighbouring layers to be energetically preferable.

S2. Experimental

All commercially obtained reagent-grade chemicals were used without further purification. An aqueous solution (10 ml) of [Mg(H₂O)₆][Co^II(1,3-pdta)].2H₂O (1.50 g, 2.83 mmol), prepared as described by Radanović et al. (2003), was passed through a column packed with Merck I cation exchanger in the Li⁺ form. The eluate was evaporated at room temperature to a volume of 2 ml and the Li₂[Co^II(1,3-pdta)].5H₂O complex was crystallized after addition of ethanol and cooling in a refrigerator for 2 d. The red–violet crystals were removed by filtration and air-dried (0.92 g). The complex was checked by UV–Vis spectroscopy and its spectrum compared with that obtained for the [Mg(H₂O)₆][Co^II(1,3-pdta)].2H₂O complex (Radanović et al., 2003). Analysis, calculated for Li₂[Co^II(1,3-pdta)].5H₂O, C₁₁H₂₄O₁₃N₂Li₂Co (FW = 465.13): C 28.40, H 5.20, N 6.02%; found: C 28.44, H 5.10, N 6.00%.

S3. Refinement

H atoms attached to C atoms were placed in calculated positions and refined using a riding model, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). H atoms attached to hydroxyl groups and water molecules were located in subsequent difference Fourier maps, their O—H distances were standardized to 0.85 Å and they were thereafter refined using a riding model with U_iso(H) = 1.2U_eq(O). The absolute configuration of the complex was established as Λ on the basis of the Flack absolute structure parameter (Flack, 1983), which refined to a value of -0.017 (12).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2008).

Figures

	Fig. 1. A portion of the structure of (I), showing one [Co(1,3-pdta)]^2- complex and several attached Li^+ counter-ions. Displacement ellipsoids are drawn at the 40% probability level. The configuration around the Co^II cation is Λ. G, R and T indicate rings discussed in the text. [Primes and double primes indicate what?]. [Symmetry codes: (i) x + 1, y, z; (ii) x, y, z - 1; (iii) x, y, z + 1; (iv) x - 1, y, z; (v) x + 1, y, z + 1; (vi) x - 1, y, z - 1].
	Fig. 2. A view down the monoclinic [010] direction. illustrating the structure of the two-dimensional layer. Dashed lines represent hydrogen bonds.
	Fig. 3. A side view of the (010) layers. Successive layers along b are related by the 21 axis.

poly[[µ-aqua-diaqua(µ₅-propane-1,3- diyldinitrilotetraacetato)dilithium(I)cobalt(II)] dihydrate]

Crystal data

[CoLi2(C11H14N2O8)(H2O)3]·2H2O	F(000) = 482
Mr = 465.13	Dx = 1.648 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4043 reflections
a = 7.8767 (4) Å	θ = 2.2–28.1°
b = 12.7381 (6) Å	µ = 0.99 mm^−1
c = 9.3440 (4) Å	T = 293 K
β = 90.756 (4)°	Plate, light-violet
V = 937.44 (8) Å^3	0.20 × 0.15 × 0.08 mm
Z = 2

Data collection

Kuma KM4 CCD κ-geometry diffractometer	3069 independent reflections
Radiation source: fine-focus sealed tube	2487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and ϕ scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	h = −9→9
Tmin = 0.846, Tmax = 0.924	k = −15→14
7554 measured reflections	l = −10→11

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)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0239P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
3069 reflections	Δρmax = 0.28 e Å^−3
262 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.017 (12)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Co1	0.90239 (5)	0.37587 (3)	0.31058 (4)	0.02235 (10)
O1	0.7179 (3)	0.33828 (14)	0.4668 (2)	0.0292 (5)
O2	0.6791 (3)	0.21375 (16)	0.6339 (2)	0.0401 (6)
O3	0.8794 (3)	0.53616 (18)	0.2858 (3)	0.0320 (7)
O4	0.9508 (3)	0.66371 (15)	0.1365 (2)	0.0344 (6)
O5	1.0681 (2)	0.3811 (2)	0.48744 (17)	0.0284 (4)
O6	1.3315 (3)	0.41722 (16)	0.5574 (2)	0.0363 (6)
O7	0.7634 (3)	0.35384 (16)	0.1212 (2)	0.0396 (7)
O8	0.6293 (3)	0.23161 (19)	−0.0096 (3)	0.0439 (7)
N1	1.1343 (3)	0.41023 (16)	0.2050 (2)	0.0210 (6)
N2	0.8974 (4)	0.2090 (2)	0.2996 (3)	0.0250 (8)
C1	1.1960 (4)	0.3173 (2)	0.1281 (3)	0.0298 (8)
H1A	1.3074	0.3325	0.0900	0.036*
H1B	1.1201	0.3030	0.0478	0.036*
C2	1.2080 (4)	0.2190 (2)	0.2232 (3)	0.0319 (8)
H2A	1.2966	0.1737	0.1869	0.038*
H2B	1.2411	0.2402	0.3192	0.038*
C3	1.0448 (5)	0.1569 (3)	0.2307 (4)	0.0433 (10)
H3A	1.0112	0.1378	0.1339	0.052*
H3B	1.0684	0.0922	0.2820	0.052*
C4	0.8731 (4)	0.1781 (2)	0.4495 (3)	0.0284 (8)
H4A	0.9811	0.1816	0.5003	0.034*
H4B	0.8333	0.1061	0.4530	0.034*
C5	0.7475 (4)	0.2480 (3)	0.5221 (3)	0.0284 (8)
C6	0.9641 (4)	0.5724 (3)	0.1808 (4)	0.0255 (8)
C7	1.0870 (4)	0.4984 (2)	0.1086 (3)	0.0247 (7)
H7A	1.0350	0.4708	0.0218	0.030*
H7B	1.1884	0.5366	0.0823	0.030*
C8	1.2591 (4)	0.4457 (2)	0.3139 (3)	0.0264 (7)
H8A	1.2645	0.5218	0.3119	0.032*
H8B	1.3702	0.4192	0.2888	0.032*
C9	1.2188 (4)	0.4107 (2)	0.4643 (3)	0.0257 (7)
C10	0.7101 (4)	0.2610 (3)	0.0979 (3)	0.0326 (8)
C11	0.7419 (5)	0.1813 (2)	0.2160 (3)	0.0389 (9)
H11A	0.6451	0.1795	0.2791	0.047*
H11B	0.7550	0.1120	0.1745	0.047*
O1W	0.6351 (3)	0.43034 (17)	0.7634 (2)	0.0342 (6)
H1WA	0.7415	0.4352	0.7783	0.041*
H1WB	0.5917	0.4781	0.8147	0.041*
O2W	0.3424 (3)	0.26157 (19)	0.7674 (3)	0.0539 (7)
H2WA	0.2555	0.2242	0.7844	0.065*
H2WB	0.2925	0.3140	0.7294	0.065*
O3W	0.6155 (3)	0.57686 (18)	0.4663 (2)	0.0456 (7)
H3WA	0.6978	0.5780	0.4083	0.055*
H3WB	0.5726	0.6380	0.4605	0.055*
O4W	0.9672 (2)	0.3774 (2)	0.77715 (18)	0.0404 (5)
H4WA	1.0186	0.3803	0.6978	0.048*
H4WB	0.9695	0.3155	0.8111	0.048*
O5W	0.5433 (3)	0.5277 (2)	1.0095 (3)	0.0672 (9)
H5WA	0.5720	0.5103	1.0943	0.081*
H5WB	0.5100	0.5906	1.0204	0.081*
Li1	0.5734 (7)	0.2796 (5)	0.8018 (6)	0.0368 (15)
Li2	0.5715 (7)	0.4461 (5)	0.5621 (6)	0.0328 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0262 (2)	0.01847 (18)	0.0224 (2)	0.0002 (2)	0.00060 (15)	0.0017 (3)
O1	0.0266 (13)	0.0273 (13)	0.0338 (13)	0.0025 (9)	0.0027 (10)	0.0013 (10)
O2	0.0550 (16)	0.0336 (14)	0.0320 (14)	−0.0061 (11)	0.0141 (12)	0.0031 (11)
O3	0.0435 (16)	0.0230 (15)	0.0299 (15)	0.0082 (11)	0.0176 (13)	0.0077 (11)
O4	0.0452 (15)	0.0228 (12)	0.0355 (14)	0.0059 (10)	0.0087 (11)	0.0124 (10)
O5	0.0270 (11)	0.0385 (11)	0.0197 (10)	−0.0066 (15)	0.0025 (8)	0.0013 (15)
O6	0.0287 (13)	0.0504 (15)	0.0296 (12)	−0.0061 (10)	−0.0082 (11)	0.0082 (10)
O7	0.0498 (15)	0.0303 (18)	0.0384 (13)	−0.0104 (12)	−0.0142 (11)	0.0119 (12)
O8	0.0520 (17)	0.0517 (15)	0.0275 (14)	−0.0056 (13)	−0.0128 (13)	0.0057 (12)
N1	0.0274 (15)	0.0202 (14)	0.0154 (13)	0.0037 (10)	0.0004 (11)	0.0009 (11)
N2	0.0309 (18)	0.0202 (17)	0.0238 (18)	0.0066 (13)	0.0004 (14)	0.0028 (13)
C1	0.039 (2)	0.0275 (19)	0.0233 (19)	0.0028 (16)	0.0053 (16)	−0.0002 (15)
C2	0.032 (2)	0.0257 (17)	0.038 (2)	0.0115 (16)	0.0086 (17)	−0.0015 (16)
C3	0.061 (3)	0.030 (2)	0.040 (2)	0.0037 (19)	0.017 (2)	−0.0021 (17)
C4	0.041 (2)	0.0234 (17)	0.0209 (18)	−0.0019 (16)	0.0062 (16)	0.0010 (14)
C5	0.030 (2)	0.0281 (19)	0.0274 (19)	−0.0063 (16)	−0.0043 (16)	−0.0051 (17)
C6	0.026 (2)	0.0248 (19)	0.026 (2)	−0.0032 (15)	−0.0004 (16)	0.0041 (16)
C7	0.0315 (19)	0.0221 (17)	0.0205 (18)	−0.0025 (16)	0.0045 (15)	0.0069 (14)
C8	0.0255 (18)	0.0262 (17)	0.0274 (18)	−0.0011 (15)	0.0007 (14)	0.0015 (15)
C9	0.0305 (19)	0.0198 (16)	0.0268 (18)	0.0002 (13)	0.0018 (15)	0.0004 (13)
C10	0.035 (2)	0.043 (2)	0.0199 (19)	−0.0004 (17)	0.0013 (16)	0.0055 (17)
C11	0.058 (3)	0.0300 (18)	0.029 (2)	−0.0095 (17)	−0.0082 (18)	−0.0011 (16)
O1W	0.0315 (14)	0.0337 (13)	0.0374 (14)	−0.0006 (10)	−0.0001 (11)	−0.0064 (11)
O2W	0.0330 (15)	0.0658 (18)	0.0629 (17)	−0.0072 (13)	−0.0014 (12)	0.0243 (14)
O3W	0.0453 (16)	0.0386 (13)	0.0535 (16)	0.0115 (11)	0.0177 (13)	0.0149 (12)
O4W	0.0461 (13)	0.0446 (11)	0.0306 (11)	0.0075 (18)	0.0034 (9)	0.0029 (17)
O5W	0.085 (2)	0.0709 (19)	0.0461 (18)	0.0285 (18)	−0.0016 (16)	0.0019 (16)
Li1	0.041 (4)	0.037 (4)	0.033 (3)	−0.001 (3)	0.002 (3)	0.008 (3)
Li2	0.026 (3)	0.041 (3)	0.031 (3)	−0.003 (3)	0.003 (2)	0.003 (3)

Geometric parameters (Å, º)

Co1—O3	2.063 (2)	C3—H3B	0.9700
Co1—O7	2.088 (2)	C4—C5	1.500 (4)
Co1—O5	2.0932 (17)	C4—H4A	0.9700
Co1—O1	2.128 (2)	C4—H4B	0.9700
Co1—N2	2.129 (3)	C6—C7	1.515 (4)
Co1—N1	2.133 (2)	C7—H7A	0.9700
O1—C5	1.280 (3)	C7—H7B	0.9700
O1—Li2	2.009 (6)	C8—C9	1.512 (4)
O2—C5	1.260 (4)	C8—H8A	0.9700
O2—Li1	1.973 (6)	C8—H8B	0.9700
O3—C6	1.281 (4)	C10—C11	1.518 (4)
O4—C6	1.238 (3)	C11—H11A	0.9700
O5—C9	1.267 (3)	C11—H11B	0.9700
O6—C9	1.238 (3)	O1W—Li2	1.950 (6)
O6—Li2^i	1.926 (6)	O1W—Li1	2.014 (6)
O7—C10	1.273 (4)	O1W—H1WA	0.8500
O8—C10	1.240 (4)	O1W—H1WB	0.8500
O8—Li1^ii	1.911 (6)	O2W—Li1	1.857 (6)
N1—C1	1.471 (3)	O2W—H2WA	0.8500
N1—C8	1.476 (3)	O2W—H2WB	0.8500
N1—C7	1.484 (3)	O3W—Li2	1.924 (6)
N2—C4	1.469 (4)	O3W—H3WA	0.8500
N2—C11	1.486 (4)	O3W—H3WB	0.8501
N2—C3	1.491 (4)	O4W—H4WA	0.8500
C1—C2	1.538 (4)	O4W—H4WB	0.8500
C1—H1A	0.9700	O5W—H5WA	0.8500
C1—H1B	0.9700	O5W—H5WB	0.8499
C2—C3	1.512 (5)	Li1—O8^iii	1.911 (6)
C2—H2A	0.9700	Li1—Li2	3.085 (7)
C2—H2B	0.9700	Li2—O6^iv	1.926 (6)
C3—H3A	0.9700
O3—Co1—O7	89.64 (9)	O1—C5—C4	117.9 (3)
O3—Co1—O5	96.31 (10)	O4—C6—O3	123.5 (3)
O7—Co1—O5	171.14 (9)	O4—C6—C7	119.2 (3)
O3—Co1—O1	103.88 (8)	O3—C6—C7	117.3 (3)
O7—Co1—O1	101.31 (9)	N1—C7—C6	111.0 (2)
O5—Co1—O1	83.68 (7)	N1—C7—H7A	109.4
O3—Co1—N2	169.01 (8)	C6—C7—H7A	109.4
O7—Co1—N2	79.38 (9)	N1—C7—H7B	109.4
O5—Co1—N2	94.64 (10)	C6—C7—H7B	109.4
O1—Co1—N2	78.23 (9)	H7A—C7—H7B	108.0
O3—Co1—N1	79.60 (9)	N1—C8—C9	113.8 (2)
O7—Co1—N1	94.49 (8)	N1—C8—H8A	108.8
O5—Co1—N1	80.20 (8)	C9—C8—H8A	108.8
O1—Co1—N1	163.80 (8)	N1—C8—H8B	108.8
N2—Co1—N1	101.43 (9)	C9—C8—H8B	108.8
C5—O1—Li2	122.6 (3)	H8A—C8—H8B	107.7
C5—O1—Co1	110.9 (2)	O6—C9—O5	124.4 (3)
Li2—O1—Co1	123.44 (19)	O6—C9—C8	118.4 (3)
C5—O2—Li1	134.6 (3)	O5—C9—C8	117.1 (3)
C6—O3—Co1	113.4 (2)	O8—C10—O7	125.7 (3)
C9—O5—Co1	116.77 (17)	O8—C10—C11	117.7 (3)
C9—O6—Li2^i	136.3 (3)	O7—C10—C11	116.5 (3)
C10—O7—Co1	115.98 (19)	N2—C11—C10	110.5 (3)
C10—O8—Li1^ii	139.4 (3)	N2—C11—H11A	109.5
C1—N1—C8	111.2 (2)	C10—C11—H11A	109.5
C1—N1—C7	113.2 (2)	N2—C11—H11B	109.5
C8—N1—C7	110.2 (2)	C10—C11—H11B	109.5
C1—N1—Co1	110.60 (17)	H11A—C11—H11B	108.1
C8—N1—Co1	108.12 (16)	Li2—O1W—Li1	102.2 (3)
C7—N1—Co1	103.08 (17)	Li2—O1W—H1WA	113.0
C4—N2—C11	108.7 (3)	Li1—O1W—H1WA	106.2
C4—N2—C3	113.9 (3)	Li2—O1W—H1WB	111.7
C11—N2—C3	108.0 (3)	Li1—O1W—H1WB	118.8
C4—N2—Co1	102.91 (19)	H1WA—O1W—H1WB	105.0
C11—N2—Co1	106.07 (19)	Li1—O2W—H2WA	145.7
C3—N2—Co1	116.8 (2)	Li1—O2W—H2WB	114.9
N1—C1—C2	113.0 (2)	H2WA—O2W—H2WB	98.6
N1—C1—H1A	109.0	Li2—O3W—H3WA	117.0
C2—C1—H1A	109.0	Li2—O3W—H3WB	138.4
N1—C1—H1B	109.0	H3WA—O3W—H3WB	104.5
C2—C1—H1B	109.0	H4WA—O4W—H4WB	110.9
H1A—C1—H1B	107.8	H5WA—O5W—H5WB	102.3
C3—C2—C1	114.0 (3)	O2W—Li1—O8^iii	109.5 (3)
C3—C2—H2A	108.7	O2W—Li1—O2	103.4 (3)
C1—C2—H2A	108.7	O8^iii—Li1—O2	120.2 (3)
C3—C2—H2B	108.7	O2W—Li1—O1W	109.0 (3)
C1—C2—H2B	108.7	O8^iii—Li1—O1W	114.6 (3)
H2A—C2—H2B	107.6	O2—Li1—O1W	99.1 (3)
N2—C3—C2	117.1 (3)	O2W—Li1—Li2	87.9 (2)
N2—C3—H3A	108.0	O8^iii—Li1—Li2	152.7 (3)
C2—C3—H3A	108.0	O2—Li1—Li2	73.3 (2)
N2—C3—H3B	108.0	O1W—Li1—Li2	38.16 (16)
C2—C3—H3B	108.0	O3W—Li2—O6^iv	109.7 (3)
H3A—C3—H3B	107.3	O3W—Li2—O1W	119.5 (3)
N2—C4—C5	111.5 (3)	O6^iv—Li2—O1W	104.0 (3)
N2—C4—H4A	109.3	O3W—Li2—O1	106.1 (3)
C5—C4—H4A	109.3	O6^iv—Li2—O1	115.3 (3)
N2—C4—H4B	109.3	O1W—Li2—O1	102.4 (3)
C5—C4—H4B	109.3	O3W—Li2—Li1	159.0 (3)
H4A—C4—H4B	108.0	O6^iv—Li2—Li1	83.1 (2)
O2—C5—O1	124.6 (3)	O1W—Li2—Li1	39.66 (17)
O2—C5—C4	117.5 (3)	O1—Li2—Li1	81.6 (2)
O3—Co1—O1—C5	−162.22 (19)	Li1—O2—C5—C4	155.7 (3)
O7—Co1—O1—C5	105.33 (19)	Li2—O1—C5—O2	6.0 (4)
O5—Co1—O1—C5	−67.26 (19)	Co1—O1—C5—O2	166.5 (3)
N2—Co1—O1—C5	28.84 (19)	Li2—O1—C5—C4	−173.6 (3)
N1—Co1—O1—C5	−61.6 (4)	Co1—O1—C5—C4	−13.1 (3)
O3—Co1—O1—Li2	−1.9 (2)	N2—C4—C5—O2	160.1 (3)
O7—Co1—O1—Li2	−94.3 (2)	N2—C4—C5—O1	−20.2 (4)
O5—Co1—O1—Li2	93.1 (2)	Co1—O3—C6—O4	170.5 (2)
N2—Co1—O1—Li2	−170.8 (2)	Co1—O3—C6—C7	−9.6 (4)
N1—Co1—O1—Li2	98.7 (3)	C1—N1—C7—C6	157.7 (2)
O7—Co1—O3—C6	−69.2 (2)	C8—N1—C7—C6	−77.0 (3)
O5—Co1—O3—C6	104.2 (2)	Co1—N1—C7—C6	38.2 (3)
O1—Co1—O3—C6	−170.8 (2)	O4—C6—C7—N1	158.5 (3)
N2—Co1—O3—C6	−71.0 (5)	O3—C6—C7—N1	−21.3 (4)
N1—Co1—O3—C6	25.4 (2)	C1—N1—C8—C9	−99.8 (3)
O3—Co1—O5—C9	−71.5 (2)	C7—N1—C8—C9	133.8 (3)
O1—Co1—O5—C9	−174.8 (2)	Co1—N1—C8—C9	21.8 (3)
N2—Co1—O5—C9	107.6 (2)	Li2^i—O6—C9—O5	173.6 (3)
N1—Co1—O5—C9	6.8 (2)	Li2^i—O6—C9—C8	−9.9 (5)
O3—Co1—O7—C10	−166.8 (2)	Co1—O5—C9—O6	−179.5 (2)
O1—Co1—O7—C10	−62.7 (2)	Co1—O5—C9—C8	3.9 (3)
N2—Co1—O7—C10	12.9 (2)	N1—C8—C9—O6	165.2 (2)
N1—Co1—O7—C10	113.7 (2)	N1—C8—C9—O5	−18.1 (4)
O3—Co1—N1—C1	−155.0 (2)	Li1^ii—O8—C10—O7	14.2 (7)
O7—Co1—N1—C1	−66.17 (18)	Li1^ii—O8—C10—C11	−168.9 (4)
O5—Co1—N1—C1	106.68 (19)	Co1—O7—C10—O8	−178.2 (3)
O1—Co1—N1—C1	101.0 (3)	Co1—O7—C10—C11	4.9 (4)
N2—Co1—N1—C1	13.9 (2)	C4—N2—C11—C10	146.2 (3)
O3—Co1—N1—C8	83.04 (18)	C3—N2—C11—C10	−89.8 (3)
O7—Co1—N1—C8	171.85 (17)	Co1—N2—C11—C10	36.1 (3)
O5—Co1—N1—C8	−15.30 (17)	O8—C10—C11—N2	154.0 (3)
O1—Co1—N1—C8	−21.0 (4)	O7—C10—C11—N2	−28.9 (4)
N2—Co1—N1—C8	−108.10 (18)	C5—O2—Li1—O2W	103.7 (4)
O3—Co1—N1—C7	−33.67 (16)	C5—O2—Li1—O8^iii	−133.9 (4)
O7—Co1—N1—C7	55.14 (17)	C5—O2—Li1—O1W	−8.4 (5)
O5—Co1—N1—C7	−132.01 (18)	C5—O2—Li1—Li2	20.0 (4)
O1—Co1—N1—C7	−137.7 (3)	Li2—O1W—Li1—O2W	−60.1 (3)
N2—Co1—N1—C7	135.19 (16)	Li2—O1W—Li1—O8^iii	176.9 (3)
O3—Co1—N2—C4	−138.8 (4)	Li2—O1W—Li1—O2	47.6 (3)
O7—Co1—N2—C4	−140.6 (2)	Li1—O1W—Li2—O3W	−176.9 (3)
O5—Co1—N2—C4	46.0 (2)	Li1—O1W—Li2—O6^iv	60.4 (3)
O1—Co1—N2—C4	−36.5 (2)	Li1—O1W—Li2—O1	−60.0 (3)
N1—Co1—N2—C4	126.9 (2)	C5—O1—Li2—O3W	165.0 (3)
O3—Co1—N2—C11	−24.6 (6)	Co1—O1—Li2—O3W	6.9 (3)
O7—Co1—N2—C11	−26.4 (2)	C5—O1—Li2—O6^iv	−73.3 (4)
O5—Co1—N2—C11	160.1 (2)	Co1—O1—Li2—O6^iv	128.6 (2)
O1—Co1—N2—C11	77.6 (2)	C5—O1—Li2—O1W	38.9 (4)
N1—Co1—N2—C11	−118.9 (2)	Co1—O1—Li2—O1W	−119.2 (2)
O3—Co1—N2—C3	95.7 (5)	C5—O1—Li2—Li1	4.9 (3)
O7—Co1—N2—C3	93.9 (2)	Co1—O1—Li2—Li1	−153.14 (16)
O5—Co1—N2—C3	−79.5 (2)	O2W—Li1—Li2—O3W	132.6 (8)
O1—Co1—N2—C3	−162.0 (2)	O8^iii—Li1—Li2—O3W	1.5 (12)
N1—Co1—N2—C3	1.4 (2)	O2—Li1—Li2—O3W	−122.7 (8)
C8—N1—C1—C2	67.7 (3)	O1W—Li1—Li2—O3W	7.7 (7)
C7—N1—C1—C2	−167.5 (2)	O2W—Li1—Li2—O6^iv	3.1 (2)
Co1—N1—C1—C2	−52.4 (3)	O8^iii—Li1—Li2—O6^iv	−127.9 (6)
N1—C1—C2—C3	86.7 (3)	O2—Li1—Li2—O6^iv	107.8 (2)
C4—N2—C3—C2	−98.6 (4)	O1W—Li1—Li2—O6^iv	−121.8 (3)
C11—N2—C3—C2	140.6 (3)	O2W—Li1—Li2—O1W	124.9 (3)
Co1—N2—C3—C2	21.3 (4)	O8^iii—Li1—Li2—O1W	−6.1 (6)
C1—C2—C3—N2	−65.3 (4)	O2—Li1—Li2—O1W	−130.4 (3)
C11—N2—C4—C5	−71.2 (3)	O2W—Li1—Li2—O1	−113.8 (3)
C3—N2—C4—C5	168.3 (3)	O8^iii—Li1—Li2—O1	115.1 (6)
Co1—N2—C4—C5	41.0 (3)	O2—Li1—Li2—O1	−9.16 (19)
Li1—O2—C5—O1	−23.9 (5)	O1W—Li1—Li2—O1	121.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4W	0.85	1.92	2.703 (3)	152
O1W—H1WB···O5W	0.85	1.97	2.720 (3)	147
O2W—H2WA···O4^v	0.85	1.95	2.784 (3)	165
O2W—H2WB···O6^iv	0.85	2.10	2.790 (3)	138
O3W—H3WA···O3	0.85	1.92	2.743 (3)	163
O3W—H3WB···O2^vi	0.85	2.37	3.041 (3)	137
O4W—H4WA···O5	0.85	2.01	2.832 (2)	163
O4W—H4WB···O4^vii	0.85	2.09	2.910 (3)	162
O5W—H5WA···O7^iii	0.85	2.51	2.992 (3)	117
O5W—H5WB···O8^vi	0.85	2.11	2.931 (3)	164

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