Bridging behaviour of the 2-thio­barbiturate anion in its complexes with Li^I and Na^I

The structures of the Li^I and Na^I salts of 2-thio­barbituric acid (2-sulfanyl­idene-1-3-diazinane-4,6-dione, H₂TBA) have been studied. μ-Aqua-octa­aqua­bis­(μ-2-thio­barbiturato-κ²O:O′)bis(2-thio­barbiturato-κO)tetra­lithium(I) dihydrate, [Li₄(C₄H₃N₂O₂S)₄(H₂O)₉]·2H₂O, (I), crystallizes with four symmetry-independent four-coordinated Li^I cations and four independent HTBA⁻ anions. The structure contains two structurally non-equivalent Li^I cations and two non-equivalent HTBA⁻ anions (bridging and terminal). Eight of the coordinated water ligands are terminal and the ninth acts as a bridge between Li^I cations. Discrete [Li₄(HTBA)₄(H₂O)₉]·2H₂O complexes form two-dimensional layers. Neighbouring layers are connected via hydrogen-bonding inter­actions, resulting in a three-dimensional network. Poly[μ₂-aqua-tetraaqua­(μ₄-2-thio­bar­biturato-κ⁴O:O:S:S)(μ₂-thio­barbiturato-κ²O:S)disodium(I)], [Na₂(C₄H₃N₂O₂S)₂(H₂O)₅]_n, (II), crystallizes with six-coordinated Na^I cations. The octa­hedra are pairwise connected through edge-sharing by a water O atom and an O atom from the μ₄-HTBA⁻ ligand, and these pairs are further top-shared by the S atoms to form continuous chains along the a direction. Two independent HTBA⁻ ligands integrate the chains to give a three-dimensional network.

S1. Comment

Alkali metal cations play an important role in nature, for instance, Li⁺, Na⁺ and K⁺ regulate the ionic equilibrium of living cells in the human body (Birch, 1999). In addition, they find numerous applications in man-made materials (Kennedy et al., 2006; Yin et al., 2011). These cations are known for their mainly ionic chemistry in aqueous media and their coordination number varies depending on the size of the binding partners, and on the electrostatic interaction between ligands and metal ions. Thus, the synthesis of coordination polymer networks with these metal ions is of crucial importance (Fromm, 2008). The properties of heterocyclic thioamides, which have potential as antitumour reagents, are of great interest (Raper, 1997). In particular, 2-thiobarbituric acid (H₂TBA, 2-sulfanylidene-1-3-diazinane-4,6-dione) is important in pharmaceutical products and analytical chemistry (Bondock et al., 2007; Karthikeyan et al., 2008). It is a substituted mercaptopyrimidine with three mobile H atoms and ten possible tautomeric forms (Chierotti et al., 2010; Mendez et al., 2007). The methylene H atoms are very acidic and, in fact, methylene is the most acidic group in 2-thiobarbituric acid (Mendez et al., 2007; Refat et al., 2008). The characterization of alkaline thiobarbiturates is an area of continuous interest because the compounds are promising for their pharmaceutical properties (Masoud et al., 2004). The principle interest of the present study is to investigate the variation of the solid-state structures of thiobarbiturate complexes induced by alkali metal substitution. To date, the structures of 2-thiobarbiturate complexes with such metal ions as Mn^II and Zn^II (Pan et al., 2008), Co^III (Yamanari et al., 2002), Au^I (Hunks et al., 2002) and Sn^IV (Balas et al., 2008) have been determined, but structural information on similar compounds with alkali metals is scarce. As to alkali metal compounds with H₂TBA, only the structures of the sodium complex [Na₂Cl(HTBA)(H₂O)₂]_n (Li et al., 2010) and two potassium complexes, [KHTBA]_n and [K(HTBA)(H₂TBA)(H₂O)]_n (Kubicki et al., 2012), have been characterized so far. In order to clarify the coordination modes of the thiobarbiturate ligand with alkali metals, the structural investigation of new lithium(I) and sodium(I) salts with thiobarbituric acid, namely µ-aqua-octaaquabis(µ-2-thiobarbiturato-κ²O:O)bis(2-thiobarbiturato-κO)tetralithium(I) dihydrate, (I), and poly[µ₂-aqua-tetraaqua(µ₄-2-thiobarbiturato-κ⁴O:O:S:S)(µ₂-thiobarbiturato-κ²O:S)]disodium(I)], (II), has been carried out and the results are presented here.

X-ray single-crystal structure analysis of (I) shows it to be a discrete molecular [Li₄(HTBA)₄(H₂O)₉] complex with two solvent water molecules (Fig. 1). The Li⁺ cation is bonded to four O atoms and this group forms a distorted tetrahedron. Eight coordinated water ligands are terminal but the ninth (O4) acts as a bridge between metal centres. Two Li⁺ cations are linked by a water Li1—O4—Li2 bridge and each of the atoms Li1 and Li2 is coordinated by one O atom (O2 or O1) from one coordinated water molecule, one O atom (O2B or O2D) from a terminal HTBA^- ligand and one O atom (O2C or O2A) from a bridging HTBA^- ligand. The Li1—O and Li2—O bond lengths are in the ranges 1.959 (6)–2.109 (6) and 1.980 (6)–2.112 (6) Å, respectively (Table 1). The bond lengths are similar to those in related Li^I compounds [Cambridge Structural Database (CSD), Version 5.34; Allen, 2002 [How many hits?]]. As is evident from Table 1, the Li1—O4 and Li2—O4 bonds are ~0.12 Å longer than the other Li—O bonds.

The geometry observed for the 2-thiobarbiturate ligand is similar to that of the free ligand (Chierotti et al., 2010). The O1A—C4A bond length of 1.273 (4) Å and O1C—C4C bond length of 1.266 (4) Å observed for the bridging HTBA^- ligand are significantly longer than the conventional C═O double-bond length of 1.20 Å. The other C—O bond lengths are in the range 1.253 (4)–1.258 (4) Å. The O—Li—O bond angles are similar to those commonly observed in Li^I complexes.

Each of the atoms Li3 and Li4 is connected to atoms Li1 and Li2, respectively, through a bridging HTBA^- ligand. In addition, each of them is also bonded to three water O atoms. This arrangement generates a discrete [Li₄(HTBA)₄(H₂O)₉].2H₂O molecular unit which is extended via hydrogen bonding to form a two-dimensional layer (Fig. 2); further hydrogen bonds form connections between the layers.

The crystal structure of (I) is stabilized by a network of N—H···O, O—H···O, O—H···S and N—H···S hydrogen bonds (Table 2). All resolved water H atoms are involved in hydrogen bonding to carbonyl O and S atoms of the HTBA^- ligands. Within the two-dimensional layer (Fig. 2), intramolecular (intra-polymer) N—H···O, O—H···O and N—H···S hydrogen-bond interactions form rings with S(6) and S(8) graph-set motifs (Bernstein et al., 1995).

The π–π stacking synthon plays an important role in the molecular arrangement of (I) and the extended structural architecture. The perpendicular distances between the rings of neighbouring HTBA^- ligands are in the range 3.456 (1)–3.546 (1) Å (Table 5) and are comparable with those in potassium thiobarbiturate (Golovnev & Molokeev, 2013). Rings A and D are approximately coplanar, similar to rings B and C (rings defined in Fig. 1). However, there is a twist of ca 26° about the Li1···Li2 vector between the two two-ring planes. The powder diffraction pattern for (I) simulated from the single-crystal result agrees well with the recorded pattern. This indicates that the measured crystals were representative of the bulk structure.

X-ray single-crystal analysis of (II) indicates that it is a polymeric structure. As shown in Fig. 3, the asymmetric unit of (II) consists of two Na⁺ cations, two HTBA^- ligands and five coordinated water molecules. One HTBA^- ligand (denoted B-type) is connected to four Na⁺ cations in a µ₄-κ⁴O:O:S:S mode, while the second HTBA^- ligand (denoted A-type) is µ₂-bridging. Each Na⁺ cation is six-coordinated by three HTBA^- anions and three water molecules. Atom Na1 is coordinated by water atoms O1, O4 and O5, and by atoms O2B and S2ⁱ [symmetry code: (i) -x + 1, -y + 1, -z + 1] from two HTBA^- (B) ligands and atom O2A from a µ₂-HTBA^- (A) ligand (Fig. 4). Atom Na2 is coordinated by water atoms O1, O2 and O3, atom O2 from an HTBA^- ligand and atoms S1ⁱ and S2ⁱⁱ [symmetry code: (ii) -x, -y + 1, -z + 1] from two different HTBA^- (A and B) ligands. The Na1—O distances are in the range 2.3860 (19)–2.521 (2) Å and the Na2—O distances are in the range 2.325 (2)–2.443 (2) Å (Table 3), and these values are comparable with those reported previously for related Na^I complexes (Li et al., 2010). The Na1···S2ⁱ, Na2···S1ⁱ and Na2···S2ⁱⁱ [Please check added symops] bond lengths are 3.0372 (12), 2.8360 (11) and 3.0322 (13) Å, respectively. The resulting octahedra are pairwise connected through edge-sharing with water atom O1 and atom O2B from the B-type HTBA^- ligand, and these pairs are further connected by top-sharing of atom S2ⁱⁱ to form continuous chains along the a direction (Fig. 4). Two arbitrary HTBA^- ligands connect these chains into a three-dimensional network. The µ₂-bridging type-A HTBA^- ligand coordinates to atom Na1 through atom O2A and to atom Na2ⁱ through atom S1. Combined with the µ₄-κ⁴O:O:S:S coordination of the type-B HTBA^- ligand, this means that atom Na1 is connected to atom S2 [S2ⁱ?] only, while atom Na2 is connected to atoms S2ⁱⁱ and S1ⁱ. Two independent bridging ligands (A and Bⁱ) combine with atoms Na1 and Na2ⁱ to form a 12-membered loop. Such a loop is also formed by ligands B and Bⁱ and atoms Na1 and Na1ⁱ around the centre of inversion, and by ligands B and Bⁱⁱ and atoms Na2 and Na2ⁱⁱ.

The crystal structure of (II) is stabilized by numerous hydrogen bonds of N—H···O, O—H···O and N—H···S types (Table 4). As observed in (I), (II) also has N—H···S hydrogen-bond interactions, resulting in rings of graph set R₂²(8). All resolved water H atoms are involved in hydrogen bonding to carbonyl O atoms of HTBA^- ligands and O atoms of other water molecules. It is noted that all water O atoms, except for O4, are hydrogen-bond acceptors.

Two intermolecular N—H···O contacts form an eight-membered ring with graph-set descriptor R₂²(8) (Fig. 5). No stacking interactions are observed between the HTBA^- ligands. Self-associated hydrogen bonds between HTBA^- anions were also previously described in the thiobarbiturate complexes of potassium (Kubicki et al., 2012).

Comparison with structurally characterized salts reveals that the title compounds of Li^I and Na^I have novel structure types for alkali metal complexes. Thus, a tetranuclear complex of Li has a discrete structure [Reference?]. However, all the previously determined structures of 2-thiobarbiturate complexes are polymers. In (I), the coordination of HTBA^- occurs through the µ₂-O:O' ligands, as in the polymers {[M(µ₂-HTBA-O,O')₂(H₂O)].2(OC₃H₆)}_n (M = Zn and Mn; Pan et al., 2008). As well as the µ-type ligands, (I) has also terminal O-coordinated HTBA^- ligands, as observed in [(n-Bu)₃Sn(HTBA-O)].H₂O (Balas et al., 2008). Only bridging ligands are present in (II), as in the two potassium complexes [K(µ₃-S,O-HTBA)]_n and [K(µ₂-S,O-HTBA)(µ₂-S,O-H₂TBA)(µ-H₂O)]_n (Kubicki et al., 2012). As observed in (II), in the coordination polymer [Na₂(µ₄-HTBA-O,O,O',O')(µ₄-Cl)(µ₂-H₂O)₂]_n, the Na^I cation is six-coordinated and connected by µ₄-HTBA^- bridging ligands (Li et al., 2010). In this compound, the µ₄-HTBA^- ligand exhibits a µ₄-κ⁴O:O:O':O' coordination mode. However, in (II), one of the two HTBA^- anions is a µ₄-κ⁴O:O:S:S-coordinated ligand and the second is a µ₂-κ²O:S ligand. The crystal structures of three Co^III complexes revealed that coordination occurs through the S- and N-atom donors of TBA^2- (Yamanari et al., 2002). There are also reports of S-coordinated HTBA^- and N,S-coordinated TBA^2- ligands in polynuclear gold(I) complexes (Hunks et al., 2002). Thus, in (I) and (II), new coordination modes of the thiobarbiturate ligand with alkali metals are presented. One of the coordinated water ligands in each of (I) and (II) acts as a bridge between the two metal centres. It is evident that the presence of water significantly affects the crystal packing.

Related literature

For related literature, see: Allen (2002); Balas et al. (2008); Bernstein et al. (1995); Birch (1999); Bondock et al. (2007); Chierotti et al. (2010); Fromm (2008); Golovnev & Molokeev (2013); Hunks et al. (2002); Karthikeyan et al. (2008); Kennedy et al. (2006); Kubicki et al. (2012); Li et al. (2010); Masoud et al. (2004); Mendez et al. (2007); Pan et al. (2008); Raper (1997); Refat et al. (2008); Yamanari et al. (2002); Yin et al. (2011).

S2. Experimental

LiOH.H₂O and NaOH of reagent-grade purity were used as starting materials without additional purification. 2-Thiobarbituric acid (CAS 504-17-6) was supplied by Fluka. The ligand (0.002 mol) was mixed with the corresponding metal hydroxide (0.002 mol) in distilled water (5 ml). After dissolution, the reaction mixture was filtered and left undisturbed for crystallization. Crystals of [Li₄(HTBA)₄(H₂O)₉].2H₂O, (I), and [Na₂(HTBA)₂(H₂O)₅]_n, (II), precipitated from the solutions at room temperature as a result of water evaporation.

S3. Refinement

In both structures, all H atoms of the HTBA^- ions were positioned geometrically as riding on their parent atoms, with C—H = 0.93 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N). Some water H atoms in (I) and all water atoms in (II) were refined with distance restraints of O—H = 0.90 (3) Å. Not all the water H atoms were found via Fourier difference maps in (I); the missing water H-atom positions were calculated on the basis of potential hydrogen bonds and then refined with restraints of O—H = 0.90 (1) Å. Additional H···(S, O) distance restraints and in some cases H···H = 1.44 (3) Å in one molecule of water were used for the missing H atoms. All the water H atoms have U_iso(H) = 1.2U_eq(O). The crystal structure (II) reveals one strong peak on the difference map near water atom O5 that could not be refined as an H atom with reasonable geometry. This water molecule was thus considered as disordered over the O5A and O5B positions. The occupancies were refined with the constraint that the sum of p(O5A) and p(O5B) was equal to 1. The final refined values were p(O5A) = 0.847 (8) and p(O5B) = 0.153 (8). These disordered water O atoms were refined isotropically. Two H atoms in (II) were not resolved due to disordered water atom O5A/O5B.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The structure of (I), showing a layer in the ac plane. The four-coordination of the Li^I cations is shown by distorted tetrahedra. Dashed lines indicate hydrogen bonds and the hydrogen-bonded rings are marked.
	Fig. 3. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the major component of the disordered water atom, O5A, is shown for clarity. The hydrogen bond is indicated by a dashed line.
	Fig. 4. The chains in (II), formed by the Na1 (O5S) and Na2 (O4S2) octahedra, along the crystallographic a direction. A and B are the two independent HTBA^- anions. Only the major component of the disordered water atom, O5A, is shown for clarity.
	Fig. 5. The hydrogen-bonding interactions (dashed lines) in (II). A and B are the two independent HTBA^- anions. Only the major component of the disordered water atom, O5A, is shown for clarity.

(I) µ-Aqua-octaaquabis(µ-2-thiobarbiturato-κ²O:O')bis(2-thiobarbiturato-κO)tetralithium(I) dihydrate

Crystal data

[Li4(C4H3N2O2S)4(H2O)9]·2H2O	F(000) = 1656
Mr = 798.51	Dx = 1.532 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 9969 reflections
a = 18.1669 (16) Å	θ = 2.2–29.0°
b = 7.2059 (6) Å	µ = 0.36 mm^−1
c = 26.435 (2) Å	T = 296 K
V = 3460.6 (5) Å^3	Needle, colourless
Z = 4	0.5 × 0.1 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	9173 independent reflections
Radiation source: fine-focus sealed tube	7512 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 29.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −25→24
Tmin = 0.628, Tmax = 0.746	k = −9→9
31550 measured reflections	l = −36→35

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0909P)^2 + 0.7869P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
9173 reflections	Δρmax = 1.12 e Å^−3
526 parameters	Δρmin = −0.42 e Å^−3
38 restraints	Absolute structure: Flack (1983), with 4988 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (6)

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
S1	−0.32975 (4)	0.44593 (15)	0.93058 (3)	0.0460 (2)
O1A	−0.12710 (12)	0.3412 (4)	1.05048 (8)	0.0473 (6)
O2A	−0.07137 (11)	0.4253 (3)	0.87691 (9)	0.0380 (5)
N1A	−0.18758 (13)	0.4289 (4)	0.90675 (10)	0.0319 (5)
H1A	−0.2022	0.4481	0.8763	0.038*
N3A	−0.21451 (13)	0.3896 (4)	0.99082 (9)	0.0314 (5)
H3A	−0.2464	0.3845	1.0148	0.038*
C2A	−0.23944 (15)	0.4194 (4)	0.94365 (11)	0.0297 (6)
C4A	−0.14014 (16)	0.3663 (5)	1.00368 (11)	0.0336 (6)
C5A	−0.08962 (15)	0.3764 (5)	0.96457 (11)	0.0345 (6)
H5A	−0.0398	0.3606	0.9716	0.041*
C6A	−0.11185 (15)	0.4097 (4)	0.91498 (11)	0.0295 (6)
S2	0.49863 (4)	0.55297 (14)	0.86972 (3)	0.0448 (2)
O1B	0.36100 (13)	0.6751 (5)	1.02641 (9)	0.0566 (7)
O2B	0.23001 (11)	0.5247 (4)	0.87771 (9)	0.0401 (5)
N1B	0.35362 (13)	0.5480 (4)	0.88002 (10)	0.0341 (6)
H1B	0.3534	0.5227	0.8482	0.041*
N3B	0.41753 (13)	0.6201 (4)	0.95187 (10)	0.0334 (5)
H3B	0.4588	0.6412	0.9668	0.040*
C2B	0.41924 (15)	0.5754 (4)	0.90225 (11)	0.0294 (6)
C4B	0.35339 (17)	0.6342 (5)	0.98044 (12)	0.0358 (6)
C5B	0.28675 (16)	0.6015 (5)	0.95577 (11)	0.0347 (6)
H5B	0.2428	0.6092	0.9736	0.042*
C6B	0.28583 (15)	0.5575 (4)	0.90452 (12)	0.0305 (6)
S3	0.57893 (4)	0.43620 (13)	0.72718 (3)	0.0408 (2)
O1C	0.37188 (11)	0.2871 (4)	0.61372 (8)	0.0405 (5)
O2C	0.32159 (11)	0.4328 (3)	0.78450 (9)	0.0401 (5)
N1C	0.43759 (13)	0.4275 (4)	0.75270 (9)	0.0306 (5)
H1C	0.4532	0.4560	0.7824	0.037*
N3C	0.46209 (13)	0.3618 (4)	0.66988 (9)	0.0332 (5)
H3C	0.4933	0.3493	0.6457	0.040*
C2C	0.48802 (15)	0.4072 (4)	0.71578 (10)	0.0278 (5)
C4C	0.38743 (14)	0.3331 (4)	0.65870 (11)	0.0315 (6)
C5C	0.33775 (16)	0.3561 (5)	0.69784 (11)	0.0332 (6)
H5C	0.2878	0.3382	0.6918	0.040*
C6C	0.36125 (15)	0.4055 (4)	0.74614 (11)	0.0282 (5)
S4	−0.24740 (4)	0.54046 (15)	0.78840 (3)	0.0472 (2)
O1D	−0.10559 (13)	0.6778 (5)	0.63364 (10)	0.0557 (8)
O2D	0.02093 (11)	0.5294 (3)	0.78496 (8)	0.0378 (5)
N1D	−0.10247 (13)	0.5468 (4)	0.78017 (10)	0.0336 (6)
H1D	−0.1031	0.5188	0.8118	0.040*
N3D	−0.16421 (14)	0.6223 (4)	0.70818 (10)	0.0360 (6)
H3D	−0.2051	0.6462	0.6931	0.043*
C2D	−0.16756 (16)	0.5720 (4)	0.75731 (11)	0.0320 (6)
C4D	−0.09904 (17)	0.6389 (4)	0.67961 (12)	0.0335 (6)
C5D	−0.03335 (15)	0.6116 (4)	0.70584 (12)	0.0333 (6)
H5D	0.0112	0.6265	0.6890	0.040*
C6D	−0.03340 (15)	0.5623 (4)	0.75687 (11)	0.0277 (6)
O1	0.08980 (13)	0.5727 (4)	0.90701 (10)	0.0423 (6)
H11	0.1376 (15)	0.586 (6)	0.9027 (17)	0.051*
H12	0.071 (2)	0.684 (4)	0.9062 (15)	0.051*
O2	0.16179 (14)	0.5818 (4)	0.75851 (10)	0.0453 (6)
H21	0.1167 (16)	0.588 (6)	0.7681 (17)	0.054*
H22	0.175 (2)	0.694 (4)	0.7663 (16)	0.054*
O3	−0.29199 (13)	0.3821 (4)	1.08541 (9)	0.0460 (6)
H31	−0.321 (2)	0.292 (5)	1.1011 (15)	0.055*
H32	−0.317 (2)	0.485 (4)	1.0900 (17)	0.055*
O4	0.12485 (15)	0.2775 (3)	0.83031 (10)	0.0348 (4)
H41	0.1060 (19)	0.209 (5)	0.8041 (12)	0.042*
H42	0.128 (2)	0.193 (5)	0.8536 (13)	0.042*
O5	0.44684 (14)	0.3967 (4)	0.51176 (9)	0.0477 (6)
H51	0.414 (2)	0.459 (5)	0.4903 (14)	0.057*
H52	0.450 (2)	0.484 (5)	0.5362 (13)	0.057*
O6	0.39648 (18)	−0.0065 (5)	0.51317 (12)	0.0603 (7)
H61	0.409 (3)	0.013 (6)	0.4814 (11)	0.072*
H62	0.412 (2)	−0.119 (5)	0.5227 (16)	0.072*
O7	0.53252 (12)	0.1768 (4)	0.58381 (10)	0.0455 (6)
H71	0.5580 (17)	0.253 (4)	0.5647 (14)	0.055*
H72	0.555 (2)	0.080 (4)	0.5941 (15)	0.055*
O8	−0.19522 (16)	0.1320 (5)	1.15046 (11)	0.0628 (8)
H81	−0.204 (3)	0.041 (3)	1.1268 (11)	0.075*
H82	−0.1514 (13)	0.092 (6)	1.1636 (16)	0.075*
O9	0.2722 (2)	0.6782 (8)	1.10410 (13)	0.0980 (14)
H91	0.2223 (8)	0.680 (8)	1.097 (2)	0.118*
H92	0.294 (2)	0.697 (5)	1.0722 (10)	0.118*
O10	−0.14991 (19)	0.5288 (5)	1.15617 (14)	0.0697 (9)
H101	−0.149 (3)	0.527 (6)	1.1906 (4)	0.084*
H102	−0.184 (2)	0.617 (5)	1.1487 (16)	0.084*
O11	−0.0041 (2)	0.8412 (7)	0.57324 (18)	0.1108 (18)
H111	−0.023 (3)	0.777 (9)	0.6000 (19)	0.133*
H112	0.038 (2)	0.783 (8)	0.565 (2)	0.133*
Li1	0.2175 (3)	0.4343 (9)	0.8083 (2)	0.0415 (13)
Li2	0.0329 (3)	0.4320 (9)	0.8551 (2)	0.0433 (13)
Li3	0.4323 (3)	0.1872 (12)	0.5582 (2)	0.0563 (17)
Li4	−0.1885 (3)	0.3472 (11)	1.1095 (2)	0.0532 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0190 (3)	0.0832 (6)	0.0357 (4)	0.0056 (3)	−0.0016 (3)	−0.0170 (4)
O1A	0.0290 (11)	0.0831 (18)	0.0298 (11)	0.0125 (11)	0.0029 (9)	0.0164 (11)
O2A	0.0210 (10)	0.0623 (14)	0.0307 (11)	0.0014 (9)	0.0056 (8)	0.0039 (10)
N1A	0.0214 (11)	0.0495 (15)	0.0248 (12)	0.0015 (10)	−0.0005 (9)	−0.0023 (10)
N3A	0.0198 (10)	0.0501 (14)	0.0243 (11)	−0.0006 (9)	0.0032 (9)	0.0000 (10)
C2A	0.0227 (13)	0.0387 (15)	0.0279 (14)	0.0008 (10)	0.0005 (10)	−0.0052 (11)
C4A	0.0219 (12)	0.0503 (17)	0.0284 (14)	0.0040 (11)	0.0001 (10)	0.0054 (12)
C5A	0.0195 (12)	0.0538 (18)	0.0300 (14)	0.0051 (12)	0.0013 (11)	0.0067 (13)
C6A	0.0193 (12)	0.0373 (15)	0.0318 (14)	−0.0001 (10)	0.0023 (10)	−0.0023 (11)
S2	0.0194 (3)	0.0754 (6)	0.0396 (4)	−0.0053 (3)	0.0028 (3)	−0.0126 (4)
O1B	0.0340 (12)	0.109 (2)	0.0264 (12)	−0.0122 (13)	−0.0011 (9)	−0.0115 (14)
O2B	0.0209 (9)	0.0663 (15)	0.0330 (11)	−0.0044 (9)	−0.0033 (8)	−0.0078 (10)
N1B	0.0192 (11)	0.0565 (16)	0.0266 (12)	−0.0008 (10)	−0.0017 (9)	−0.0046 (11)
N3B	0.0212 (11)	0.0474 (14)	0.0315 (13)	−0.0021 (10)	−0.0029 (10)	−0.0058 (11)
C2B	0.0204 (12)	0.0378 (15)	0.0302 (14)	−0.0012 (10)	−0.0008 (11)	−0.0021 (11)
C4B	0.0260 (13)	0.0509 (18)	0.0305 (15)	−0.0012 (12)	−0.0014 (11)	−0.0045 (13)
C5B	0.0219 (13)	0.0538 (19)	0.0285 (14)	−0.0025 (12)	0.0020 (11)	−0.0052 (13)
C6B	0.0194 (12)	0.0399 (15)	0.0324 (14)	−0.0013 (10)	−0.0033 (11)	0.0004 (11)
S3	0.0191 (3)	0.0698 (5)	0.0335 (4)	−0.0054 (3)	−0.0020 (3)	0.0111 (4)
O1C	0.0259 (10)	0.0700 (15)	0.0257 (10)	0.0028 (10)	−0.0011 (8)	−0.0076 (10)
O2C	0.0235 (10)	0.0671 (15)	0.0296 (11)	−0.0033 (9)	0.0020 (8)	−0.0116 (10)
N1C	0.0201 (11)	0.0488 (14)	0.0228 (11)	−0.0030 (9)	−0.0021 (9)	−0.0001 (10)
N3C	0.0229 (11)	0.0510 (15)	0.0257 (11)	0.0007 (10)	0.0012 (9)	0.0014 (10)
C2C	0.0187 (11)	0.0373 (14)	0.0273 (13)	−0.0020 (10)	−0.0004 (10)	0.0067 (10)
C4C	0.0227 (12)	0.0407 (16)	0.0309 (14)	0.0024 (11)	−0.0022 (11)	−0.0001 (11)
C5C	0.0204 (12)	0.0490 (17)	0.0301 (14)	−0.0015 (11)	−0.0018 (10)	−0.0060 (12)
C6C	0.0197 (12)	0.0386 (15)	0.0263 (12)	−0.0006 (10)	0.0002 (10)	−0.0014 (11)
S4	0.0189 (3)	0.0792 (6)	0.0436 (5)	0.0043 (3)	0.0035 (3)	0.0183 (4)
O1D	0.0329 (12)	0.096 (2)	0.0377 (13)	0.0021 (13)	−0.0029 (10)	0.0297 (15)
O2D	0.0175 (9)	0.0670 (14)	0.0288 (10)	0.0026 (9)	−0.0009 (8)	0.0042 (10)
N1D	0.0203 (11)	0.0519 (15)	0.0287 (13)	0.0038 (9)	−0.0013 (9)	0.0052 (11)
N3D	0.0200 (11)	0.0519 (15)	0.0361 (13)	0.0012 (10)	−0.0066 (10)	0.0122 (11)
C2D	0.0208 (13)	0.0421 (15)	0.0330 (16)	0.0031 (11)	0.0012 (11)	0.0047 (12)
C4D	0.0272 (13)	0.0420 (16)	0.0315 (15)	0.0013 (11)	0.0017 (11)	0.0090 (12)
C5D	0.0201 (12)	0.0463 (17)	0.0333 (15)	0.0001 (11)	0.0026 (11)	0.0024 (13)
C6D	0.0184 (12)	0.0359 (14)	0.0286 (14)	0.0014 (10)	0.0008 (10)	−0.0010 (10)
O1	0.0271 (11)	0.0612 (16)	0.0385 (13)	0.0068 (10)	0.0003 (9)	−0.0095 (11)
O2	0.0265 (11)	0.0647 (16)	0.0447 (15)	−0.0076 (11)	0.0036 (10)	0.0116 (11)
O3	0.0359 (12)	0.0667 (16)	0.0354 (12)	0.0076 (11)	0.0090 (10)	0.0116 (11)
O4	0.0311 (8)	0.0478 (11)	0.0255 (8)	−0.0013 (11)	−0.0064 (6)	0.0002 (10)
O5	0.0364 (13)	0.0755 (18)	0.0312 (12)	0.0118 (12)	−0.0012 (10)	0.0028 (11)
O6	0.0624 (18)	0.0688 (18)	0.0496 (16)	−0.0036 (15)	−0.0056 (14)	−0.0053 (14)
O7	0.0293 (10)	0.0604 (15)	0.0467 (13)	0.0074 (10)	0.0020 (10)	0.0088 (12)
O8	0.0480 (15)	0.090 (2)	0.0505 (17)	0.0045 (15)	−0.0043 (13)	0.0252 (15)
O9	0.0595 (19)	0.182 (4)	0.0524 (18)	0.010 (3)	0.0085 (16)	−0.003 (2)
O10	0.0504 (17)	0.095 (2)	0.064 (2)	−0.0057 (16)	0.0016 (15)	0.0105 (18)
O11	0.082 (2)	0.128 (3)	0.122 (3)	0.063 (2)	0.070 (2)	0.072 (3)
Li1	0.024 (2)	0.077 (4)	0.023 (2)	−0.008 (2)	0.000 (2)	−0.001 (2)
Li2	0.020 (2)	0.077 (4)	0.033 (3)	0.003 (2)	0.001 (2)	−0.004 (2)
Li3	0.038 (3)	0.092 (5)	0.039 (3)	0.019 (3)	−0.007 (2)	−0.021 (3)
Li4	0.036 (3)	0.089 (5)	0.035 (3)	−0.006 (3)	0.006 (2)	0.023 (3)

Geometric parameters (Å, º)

Li1—O2B	1.959 (6)	N1C—C2C	1.347 (4)
Li1—O2	1.972 (6)	N1C—C6C	1.407 (3)
Li1—O2C	1.993 (6)	N1C—H1C	0.8600
Li1—O4	2.109 (6)	N3C—C2C	1.342 (4)
Li2—O2A	1.980 (6)	N3C—C4C	1.403 (4)
Li2—O1	1.995 (6)	N3C—H3C	0.8600
Li2—O2D	1.995 (7)	C4C—C5C	1.383 (4)
Li2—O4	2.112 (6)	C5C—C6C	1.393 (4)
Li3—O7	1.944 (6)	C5C—H5C	0.9300
Li3—O6	1.947 (8)	S4—C2D	1.682 (3)
Li3—O5	1.964 (9)	O1D—C4D	1.253 (4)
Li3—O1C	1.969 (6)	O2D—C6D	1.258 (3)
Li4—O8	1.895 (7)	N1D—C2D	1.340 (4)
Li4—O1A	1.919 (6)	N1D—C6D	1.402 (4)
Li4—O10	1.930 (9)	N1D—H1D	0.8600
Li4—O3	2.001 (7)	N3D—C2D	1.350 (4)
S1—C2A	1.688 (3)	N3D—C4D	1.409 (4)
O1A—C4A	1.273 (4)	N3D—H3D	0.8600
O2A—C6A	1.251 (4)	C4D—C5D	1.394 (4)
N1A—C2A	1.358 (4)	C5D—C6D	1.395 (4)
N1A—C6A	1.400 (4)	C5D—H5D	0.9300
N1A—H1A	0.8600	O1—H11	0.88 (3)
N3A—C2A	1.344 (4)	O1—H12	0.87 (3)
N3A—C4A	1.403 (4)	O2—H21	0.86 (3)
N3A—H3A	0.8600	O2—H22	0.87 (3)
C4A—C5A	1.384 (4)	O3—H31	0.94 (3)
C5A—C6A	1.393 (4)	O3—H32	0.88 (3)
C5A—H5A	0.9300	O4—H41	0.92 (2)
S2—C2B	1.687 (3)	O4—H42	0.87 (2)
O1B—C4B	1.258 (4)	O5—H51	0.93 (2)
O2B—C6B	1.260 (4)	O5—H52	0.90 (2)
N1B—C2B	1.344 (4)	O6—H61	0.88 (3)
N1B—C6B	1.393 (4)	O6—H62	0.89 (2)
N1B—H1B	0.8600	O7—H71	0.878 (19)
N3B—C2B	1.351 (4)	O7—H72	0.85 (2)
N3B—C4B	1.392 (4)	O8—H81	0.922 (9)
N3B—H3B	0.8600	O8—H82	0.913 (10)
C4B—C5B	1.395 (4)	O9—H91	0.923 (10)
C5B—C6B	1.391 (4)	O9—H92	0.940 (8)
C5B—H5B	0.9300	O10—H101	0.910 (10)
S3—C2C	1.692 (3)	O10—H102	0.904 (10)
O1C—C4C	1.266 (4)	O11—H111	0.91 (3)
O2C—C6C	1.259 (4)	O11—H112	0.901 (10)
C4A—O1A—Li4	132.8 (3)	Li2—O1—H11	118 (3)
C6A—O2A—Li2	143.0 (3)	Li2—O1—H12	104 (3)
C2A—N1A—C6A	124.4 (3)	H11—O1—H12	107 (4)
C2A—N1A—H1A	117.8	Li1—O2—H21	109 (3)
C6A—N1A—H1A	117.8	Li1—O2—H22	102 (3)
C2A—N3A—C4A	124.6 (2)	H21—O2—H22	98 (4)
C2A—N3A—H3A	117.7	Li4—O3—H31	108 (3)
C4A—N3A—H3A	117.7	Li4—O3—H32	123 (3)
N3A—C2A—N1A	116.2 (2)	H31—O3—H32	104 (4)
N3A—C2A—S1	122.4 (2)	Li1—O4—Li2	115.8 (2)
N1A—C2A—S1	121.4 (2)	Li1—O4—H41	112 (2)
O1A—C4A—C5A	127.6 (3)	Li2—O4—H41	103 (2)
O1A—C4A—N3A	115.6 (3)	Li1—O4—H42	121 (3)
C5A—C4A—N3A	116.8 (3)	Li2—O4—H42	102 (3)
C4A—C5A—C6A	121.3 (3)	H41—O4—H42	101 (3)
C4A—C5A—H5A	119.3	Li3—O5—H51	131 (3)
C6A—C5A—H5A	119.3	Li3—O5—H52	96 (3)
O2A—C6A—C5A	127.0 (3)	H51—O5—H52	98 (3)
O2A—C6A—N1A	116.3 (3)	Li3—O6—H61	112 (3)
C5A—C6A—N1A	116.6 (3)	Li3—O6—H62	112 (3)
C6B—O2B—Li1	133.0 (3)	H61—O6—H62	109 (3)
C2B—N1B—C6B	125.0 (3)	Li3—O7—H71	106 (2)
C2B—N1B—H1B	117.5	Li3—O7—H72	126 (3)
C6B—N1B—H1B	117.5	H71—O7—H72	116 (3)
C2B—N3B—C4B	124.3 (3)	Li4—O8—H81	102 (2)
C2B—N3B—H3B	117.9	Li4—O8—H82	115 (3)
C4B—N3B—H3B	117.9	H81—O8—H82	101 (5)
N1B—C2B—N3B	116.0 (3)	H91—O9—H92	104 (4)
N1B—C2B—S2	121.4 (2)	Li4—O10—H101	129 (3)
N3B—C2B—S2	122.5 (2)	Li4—O10—H102	95 (3)
O1B—C4B—N3B	116.7 (3)	H101—O10—H102	104 (3)
O1B—C4B—C5B	125.9 (3)	H111—O11—H112	106 (3)
N3B—C4B—C5B	117.4 (3)	O2B—Li1—O2	120.3 (3)
C6B—C5B—C4B	120.3 (3)	O2B—Li1—O2C	100.8 (3)
C6B—C5B—H5B	119.9	O2—Li1—O2C	106.2 (3)
C4B—C5B—H5B	119.9	O2B—Li1—O4	90.7 (2)
O2B—C6B—C5B	126.9 (3)	O2—Li1—O4	93.6 (2)
O2B—C6B—N1B	116.2 (3)	O2C—Li1—O4	147.3 (4)
C5B—C6B—N1B	116.9 (3)	O2B—Li1—H22	102.6 (9)
C4C—O1C—Li3	132.2 (3)	O2—Li1—H22	21.7 (8)
C6C—O2C—Li1	143.0 (3)	O2C—Li1—H22	99.7 (11)
C2C—N1C—C6C	124.7 (2)	O4—Li1—H22	107.5 (10)
C2C—N1C—H1C	117.7	O2A—Li2—O2D	100.1 (3)
C6C—N1C—H1C	117.7	O2A—Li2—O1	108.0 (3)
C2C—N3C—C4C	124.4 (2)	O2D—Li2—O1	121.1 (3)
C2C—N3C—H3C	117.8	O2A—Li2—O4	146.5 (4)
C4C—N3C—H3C	117.8	O2D—Li2—O4	89.0 (2)
N3C—C2C—N1C	116.3 (2)	O1—Li2—O4	94.1 (2)
N3C—C2C—S3	122.3 (2)	O7—Li3—O6	119.9 (4)
N1C—C2C—S3	121.4 (2)	O7—Li3—O5	97.0 (4)
O1C—C4C—C5C	126.0 (3)	O6—Li3—O5	102.4 (3)
O1C—C4C—N3C	116.9 (2)	O7—Li3—O1C	106.1 (3)
C5C—C4C—N3C	117.1 (3)	O6—Li3—O1C	122.1 (4)
C4C—C5C—C6C	121.1 (3)	O5—Li3—O1C	105.1 (4)
C4C—C5C—H5C	119.5	O7—Li3—H52	89.4 (11)
C6C—C5C—H5C	119.5	O6—Li3—H52	125.1 (8)
O2C—C6C—C5C	127.1 (3)	O5—Li3—H52	23.7 (8)
O2C—C6C—N1C	116.6 (3)	O1C—Li3—H52	85.8 (10)
C5C—C6C—N1C	116.4 (2)	O7—Li3—H71	21.2 (7)
C6D—O2D—Li2	134.5 (2)	O6—Li3—H71	121.1 (10)
C2D—N1D—C6D	125.5 (3)	O5—Li3—H71	76.0 (7)
C2D—N1D—H1D	117.2	O1C—Li3—H71	114.5 (10)
C6D—N1D—H1D	117.2	H52—Li3—H71	71.5 (13)
C2D—N3D—C4D	125.2 (3)	O8—Li4—O1A	118.9 (4)
C2D—N3D—H3D	117.4	O8—Li4—O10	102.3 (3)
C4D—N3D—H3D	117.4	O1A—Li4—O10	108.9 (3)
N1D—C2D—N3D	115.5 (3)	O8—Li4—O3	103.0 (3)
N1D—C2D—S4	121.5 (2)	O1A—Li4—O3	106.9 (3)
N3D—C2D—S4	123.0 (2)	O10—Li4—O3	117.4 (4)
O1D—C4D—C5D	126.5 (3)	O8—Li4—H81	23.4 (6)
O1D—C4D—N3D	117.3 (3)	O1A—Li4—H81	102.4 (10)
C5D—C4D—N3D	116.1 (3)	O10—Li4—H81	125.1 (8)
C4D—C5D—C6D	121.1 (3)	O3—Li4—H81	94.0 (14)
C4D—C5D—H5D	119.5	O8—Li4—H102	117.2 (10)
C6D—C5D—H5D	119.5	O1A—Li4—H102	112.2 (12)
O2D—C6D—C5D	128.2 (3)	O10—Li4—H102	24.1 (7)
O2D—C6D—N1D	115.3 (3)	O3—Li4—H102	94.4 (9)
C5D—C6D—N1D	116.5 (2)	H81—Li4—H102	140.1 (12)
C4A—N3A—C2A—N1A	−0.8 (4)	C4C—C5C—C6C—O2C	179.0 (3)
C4A—N3A—C2A—S1	179.8 (2)	C4C—C5C—C6C—N1C	−0.9 (5)
C6A—N1A—C2A—N3A	0.1 (4)	C2C—N1C—C6C—O2C	−178.8 (3)
C6A—N1A—C2A—S1	179.5 (2)	C2C—N1C—C6C—C5C	1.2 (4)
Li4—O1A—C4A—C5A	173.0 (4)	C6D—N1D—C2D—N3D	−2.3 (5)
Li4—O1A—C4A—N3A	−5.7 (6)	C6D—N1D—C2D—S4	177.2 (2)
C2A—N3A—C4A—O1A	179.3 (3)	C4D—N3D—C2D—N1D	3.8 (5)
C2A—N3A—C4A—C5A	0.5 (5)	C4D—N3D—C2D—S4	−175.7 (2)
O1A—C4A—C5A—C6A	−178.2 (4)	C2D—N3D—C4D—O1D	176.4 (3)
N3A—C4A—C5A—C6A	0.5 (5)	C2D—N3D—C4D—C5D	−4.1 (5)
Li2—O2A—C6A—C5A	−4.0 (7)	O1D—C4D—C5D—C6D	−177.7 (4)
Li2—O2A—C6A—N1A	175.6 (4)	N3D—C4D—C5D—C6D	2.8 (5)
C4A—C5A—C6A—O2A	178.5 (3)	Li2—O2D—C6D—C5D	−172.0 (4)
C4A—C5A—C6A—N1A	−1.1 (5)	Li2—O2D—C6D—N1D	7.8 (5)
C2A—N1A—C6A—O2A	−178.8 (3)	C4D—C5D—C6D—O2D	178.3 (3)
C2A—N1A—C6A—C5A	0.8 (5)	C4D—C5D—C6D—N1D	−1.6 (4)
C6B—N1B—C2B—N3B	−1.8 (5)	C2D—N1D—C6D—O2D	−178.6 (3)
C6B—N1B—C2B—S2	177.7 (2)	C2D—N1D—C6D—C5D	1.3 (5)
C4B—N3B—C2B—N1B	1.6 (5)	C6B—O2B—Li1—O2	−122.9 (4)
C4B—N3B—C2B—S2	−177.9 (2)	C6B—O2B—Li1—O2C	−6.8 (5)
C2B—N3B—C4B—O1B	179.2 (3)	C6B—O2B—Li1—O4	142.5 (3)
C2B—N3B—C4B—C5B	−0.6 (5)	C6C—O2C—Li1—O2B	−174.8 (4)
O1B—C4B—C5B—C6B	179.9 (4)	C6C—O2C—Li1—O2	−48.6 (6)
N3B—C4B—C5B—C6B	−0.3 (5)	C6C—O2C—Li1—O4	76.4 (8)
Li1—O2B—C6B—C5B	−171.9 (4)	Li2—O4—Li1—O2B	65.1 (3)
Li1—O2B—C6B—N1B	7.9 (5)	Li2—O4—Li1—O2	−55.4 (3)
C4B—C5B—C6B—O2B	179.9 (3)	Li2—O4—Li1—O2C	176.6 (4)
C4B—C5B—C6B—N1B	0.1 (5)	C6A—O2A—Li2—O2D	−166.0 (4)
C2B—N1B—C6B—O2B	−178.8 (3)	C6A—O2A—Li2—O1	−38.5 (6)
C2B—N1B—C6B—C5B	1.0 (5)	C6A—O2A—Li2—O4	90.2 (7)
C4C—N3C—C2C—N1C	−0.7 (4)	C6D—O2D—Li2—O2A	−7.3 (5)
C4C—N3C—C2C—S3	178.9 (2)	C6D—O2D—Li2—O1	−125.5 (4)
C6C—N1C—C2C—N3C	−0.4 (4)	C6D—O2D—Li2—O4	140.3 (3)
C6C—N1C—C2C—S3	−179.9 (2)	Li1—O4—Li2—O2A	174.1 (5)
Li3—O1C—C4C—C5C	−162.1 (4)	Li1—O4—Li2—O2D	67.1 (3)
Li3—O1C—C4C—N3C	17.3 (6)	Li1—O4—Li2—O1	−54.0 (4)
C2C—N3C—C4C—O1C	−178.6 (3)	C4C—O1C—Li3—O7	−2.6 (7)
C2C—N3C—C4C—C5C	0.8 (4)	C4C—O1C—Li3—O6	139.8 (4)
O1C—C4C—C5C—C6C	179.4 (3)	C4C—O1C—Li3—O5	−104.6 (4)
N3C—C4C—C5C—C6C	0.0 (5)	C4A—O1A—Li4—O8	121.0 (4)
Li1—O2C—C6C—C5C	−0.3 (7)	C4A—O1A—Li4—O10	−122.4 (4)
Li1—O2C—C6C—N1C	179.6 (4)	C4A—O1A—Li4—O3	5.2 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S4	0.86	2.55	3.408 (3)	174
N3A—H3A···O3	0.86	2.04	2.870 (4)	162
N1B—H1B···O2C	0.86	1.90	2.721 (4)	160
N3B—H3B···O5^i	0.86	2.11	2.931 (4)	161
N1C—H1C···S2	0.86	2.55	3.408 (3)	178
N3C—H3C···O7	0.86	2.17	2.931 (4)	147
N1D—H1D···O2A	0.86	1.94	2.762 (4)	160
N3D—H3D···O8^ii	0.86	2.14	2.976 (4)	165
O1—H11···O2B	0.88 (1)	1.86 (1)	2.685 (3)	156 (5)
O1—H12···S2^iii	0.87 (3)	2.50 (3)	3.315 (3)	156 (4)
O2—H21···O2D	0.86 (2)	1.85 (2)	2.680 (3)	164 (5)
O2—H22···S4^iv	0.87 (3)	2.44 (3)	3.280 (3)	161 (3)
O3—H31···O1D^v	0.94 (3)	1.78 (3)	2.693 (4)	163 (3)
O3—H32···O1C^vi	0.88 (3)	2.02 (3)	2.890 (4)	170 (4)
O4—H41···S3^vii	0.92 (4)	2.34 (3)	3.240 (3)	168 (3)
O4—H42···S1^viii	0.87 (4)	2.39 (3)	3.209 (3)	157 (3)
O5—H51···S1^ix	0.93 (4)	2.31 (4)	3.227 (3)	169 (3)
O5—H52···O11^iv	0.90 (3)	1.80 (4)	2.646 (5)	155 (5)
O6—H61···O1^x	0.88 (2)	2.01 (2)	2.875 (4)	165 (4)
O7—H71···O1B^xi	0.88 (2)	1.86 (3)	2.680 (4)	155 (4)
O8—H81···O9^vii	0.92 (3)	1.74 (3)	2.617 (6)	158 (4)
O8—H82···S3^xii	0.91 (3)	2.41 (3)	3.251 (4)	152 (4)
O9—H91···O1C^xiii	0.92 (3)	1.93 (3)	2.744 (4)	147 (4)
O9—H92···O1B	0.94 (3)	1.72 (3)	2.611 (4)	156 (4)
O10—H101···O2^vi	0.91 (3)	1.97 (3)	2.829 (4)	156 (4)
O10—H102···O9^iii	0.90 (3)	2.05 (3)	2.890 (4)	154 (4)
O11—H111···O1D	0.91 (3)	1.88 (3)	2.708 (6)	149 (4)
O11—H112···O1A^ix	0.90 (3)	1.89 (3)	2.788 (6)	177 (4)

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

(II) Poly[µ₂-aqua-tetraaqua(µ₄-2-thiobarbiturato-κ⁴O:O:S:S)(µ₂-thiobarbiturato-κ²O:S)disodium(I)]

Crystal data

[Na2(C4H3N2O2S)2(H2O)5]	Z = 2
Mr = 422.34	F(000) = 434
Triclinic, P1	Dx = 1.652 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4043 (11) Å	Cell parameters from 1956 reflections
b = 10.6987 (16) Å	θ = 2.9–27.2°
c = 11.4837 (17) Å	µ = 0.42 mm^−1
α = 101.175 (2)°	T = 296 K
β = 106.932 (2)°	Plate, pink
γ = 92.527 (2)°	0.4 × 0.35 × 0.05 mm
V = 848.8 (2) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	4405 independent reflections
Radiation source: fine-focus sealed tube	2984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 29.8°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
Tmin = 0.644, Tmax = 0.746	k = −14→14
8317 measured reflections	l = −15→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.2081P] where P = (Fo^2 + 2Fc^2)/3
4405 reflections	(Δ/σ)max = 0.018
260 parameters	Δρmax = 0.37 e Å^−3
8 restraints	Δρmin = −0.39 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.

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	Occ. (<1)
Na1	0.34690 (15)	0.35532 (9)	0.19771 (9)	0.0357 (3)
Na2	−0.02735 (14)	0.16179 (9)	0.22220 (9)	0.0326 (2)
S1	0.82635 (10)	0.96675 (6)	0.59386 (6)	0.03625 (18)
N1A	0.6467 (3)	0.74628 (17)	0.44730 (17)	0.0252 (4)
H1A	0.6988	0.7130	0.5097	0.030*
N3A	0.5996 (3)	0.92165 (18)	0.36094 (17)	0.0283 (5)
H3A	0.6228	1.0026	0.3672	0.034*
O1A	0.4208 (3)	0.91260 (16)	0.16341 (15)	0.0370 (5)
O2A	0.5194 (2)	0.54611 (15)	0.33813 (16)	0.0331 (4)
C2A	0.6835 (3)	0.8730 (2)	0.4609 (2)	0.0247 (5)
C4A	0.4785 (3)	0.8508 (2)	0.2487 (2)	0.0274 (5)
C5A	0.4390 (3)	0.7214 (2)	0.2412 (2)	0.0287 (5)
H5A	0.3508	0.6718	0.1702	0.034*
C6A	0.5298 (3)	0.6646 (2)	0.3389 (2)	0.0248 (5)
S2	0.33107 (9)	0.77119 (6)	0.65418 (6)	0.03047 (16)
N1B	0.2163 (3)	0.55448 (17)	0.48373 (17)	0.0247 (4)
H1B	0.2826	0.5193	0.5410	0.030*
N3B	0.0941 (3)	0.73217 (18)	0.42298 (17)	0.0273 (4)
H3B	0.0826	0.8127	0.4410	0.033*
O1B	−0.0971 (3)	0.72596 (16)	0.22671 (16)	0.0389 (5)
O2B	0.1603 (2)	0.35972 (15)	0.35012 (15)	0.0305 (4)
C2B	0.2063 (3)	0.6813 (2)	0.5129 (2)	0.0237 (5)
C4B	−0.0052 (3)	0.6640 (2)	0.3024 (2)	0.0269 (5)
C5B	0.0097 (4)	0.5326 (2)	0.2783 (2)	0.0287 (5)
H5B	−0.0601	0.4820	0.2014	0.034*
C6B	0.1262 (3)	0.4759 (2)	0.3666 (2)	0.0244 (5)
O1	0.2255 (3)	0.13259 (18)	0.12583 (17)	0.0372 (4)
H11	0.299 (4)	0.077 (3)	0.157 (3)	0.045*
H12	0.212 (4)	0.105 (3)	0.048 (2)	0.045*
O2	−0.1963 (3)	−0.05273 (18)	0.13340 (18)	0.0386 (5)
H21	−0.150 (4)	−0.114 (2)	0.168 (3)	0.046*
H22	−0.316 (3)	−0.052 (3)	0.135 (3)	0.046*
O3	−0.2038 (3)	0.23857 (19)	0.05265 (17)	0.0406 (5)
H31	−0.270 (4)	0.187 (3)	−0.017 (2)	0.049*
H32	−0.285 (4)	0.296 (3)	0.070 (3)	0.049*
O4	0.0861 (3)	0.3834 (2)	0.01292 (18)	0.0437 (5)
H41	0.111 (4)	0.353 (3)	−0.058 (2)	0.052*
H42	−0.018 (4)	0.336 (3)	0.015 (3)	0.052*
O5A	0.5598 (5)	0.4295 (3)	0.0927 (3)	0.0498 (10)	0.847 (8)
O5B	0.467 (2)	0.3760 (14)	0.0216 (14)	0.036 (5)	0.153 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0396 (6)	0.0312 (5)	0.0324 (6)	−0.0003 (4)	0.0080 (5)	0.0032 (4)
Na2	0.0390 (6)	0.0282 (5)	0.0266 (5)	0.0011 (4)	0.0031 (4)	0.0073 (4)
S1	0.0508 (4)	0.0218 (3)	0.0236 (3)	−0.0037 (3)	−0.0061 (3)	0.0041 (2)
N1A	0.0328 (11)	0.0192 (9)	0.0198 (10)	0.0002 (8)	0.0014 (8)	0.0061 (8)
N3A	0.0392 (12)	0.0167 (9)	0.0218 (10)	0.0008 (8)	−0.0014 (9)	0.0044 (8)
O1A	0.0511 (12)	0.0257 (9)	0.0249 (9)	0.0038 (8)	−0.0047 (8)	0.0089 (7)
O2A	0.0399 (10)	0.0187 (8)	0.0329 (10)	−0.0009 (7)	−0.0001 (8)	0.0056 (7)
C2A	0.0275 (12)	0.0225 (11)	0.0220 (11)	0.0030 (9)	0.0046 (9)	0.0046 (9)
C4A	0.0296 (13)	0.0251 (12)	0.0236 (12)	0.0043 (10)	0.0012 (10)	0.0066 (10)
C5A	0.0342 (13)	0.0209 (11)	0.0225 (12)	−0.0013 (10)	−0.0027 (10)	0.0034 (9)
C6A	0.0258 (12)	0.0217 (11)	0.0244 (12)	0.0011 (9)	0.0049 (9)	0.0036 (9)
S2	0.0388 (4)	0.0215 (3)	0.0236 (3)	0.0031 (2)	0.0008 (3)	0.0007 (2)
N1B	0.0313 (11)	0.0188 (9)	0.0208 (10)	0.0025 (8)	0.0025 (8)	0.0054 (7)
N3B	0.0350 (12)	0.0187 (10)	0.0245 (10)	0.0065 (8)	0.0032 (9)	0.0039 (8)
O1B	0.0515 (12)	0.0298 (10)	0.0278 (10)	0.0133 (9)	−0.0015 (8)	0.0072 (8)
O2B	0.0418 (10)	0.0178 (8)	0.0268 (9)	0.0035 (7)	0.0032 (8)	0.0038 (7)
C2B	0.0280 (12)	0.0197 (11)	0.0228 (11)	0.0014 (9)	0.0073 (9)	0.0038 (9)
C4B	0.0312 (13)	0.0251 (12)	0.0218 (12)	0.0045 (10)	0.0042 (10)	0.0046 (9)
C5B	0.0355 (14)	0.0232 (12)	0.0212 (12)	0.0020 (10)	0.0016 (10)	0.0016 (9)
C6B	0.0299 (13)	0.0199 (11)	0.0230 (12)	0.0005 (9)	0.0087 (10)	0.0030 (9)
O1	0.0483 (12)	0.0322 (10)	0.0288 (10)	0.0134 (9)	0.0068 (9)	0.0065 (8)
O2	0.0446 (12)	0.0334 (10)	0.0350 (10)	0.0040 (9)	0.0054 (9)	0.0108 (8)
O3	0.0468 (12)	0.0368 (11)	0.0268 (10)	0.0068 (9)	−0.0037 (9)	0.0027 (8)
O4	0.0532 (13)	0.0445 (12)	0.0330 (11)	0.0073 (10)	0.0119 (10)	0.0088 (9)
O5A	0.0484 (19)	0.0579 (19)	0.043 (2)	0.0058 (15)	0.0159 (16)	0.0085 (15)
O5B	0.026 (8)	0.051 (9)	0.028 (9)	−0.012 (6)	0.012 (6)	−0.004 (7)

Geometric parameters (Å, º)

Na1—O2A	2.3860 (19)	C5A—C6A	1.393 (3)
Na1—O1	2.405 (2)	C5A—H5A	0.9300
Na1—O5A	2.437 (3)	S2—C2B	1.690 (2)
Na1—O5B	2.477 (12)	S2—Na2^ii	3.0322 (13)
Na1—O4	2.497 (2)	S2—Na1^i	3.0373 (12)
Na1—O2B	2.521 (2)	N1B—C2B	1.343 (3)
Na1—S2^i	3.0372 (12)	N1B—C6B	1.396 (3)
Na2—O3	2.325 (2)	N1B—H1B	0.8600
Na2—O2B	2.4327 (18)	N3B—C2B	1.345 (3)
Na2—O1	2.440 (2)	N3B—C4B	1.400 (3)
Na2—O2	2.443 (2)	N3B—H3B	0.8600
Na2—S1^i	2.8360 (11)	O1B—C4B	1.255 (3)
Na2—S2^ii	3.0322 (13)	O2B—C6B	1.269 (3)
Na1—C6B	3.026 (2)	C4B—C5B	1.395 (3)
Na1—Na2	3.4955 (15)	C5B—C6B	1.383 (3)
S1—C2A	1.682 (2)	C5B—H5B	0.9300
S1—Na2^i	2.8361 (11)	O1—H11	0.88 (2)
N1A—C2A	1.340 (3)	O1—H12	0.86 (2)
N1A—C6A	1.395 (3)	O2—H21	0.86 (2)
N1A—H1A	0.8600	O2—H22	0.89 (2)
N3A—C2A	1.349 (3)	O3—H31	0.87 (2)
N3A—C4A	1.388 (3)	O3—H32	0.91 (2)
N3A—H3A	0.8600	O4—H41	0.90 (2)
O1A—C4A	1.269 (3)	O4—H42	0.91 (2)
O2A—C6A	1.265 (3)	O5A—O5B	0.960 (14)
C4A—C5A	1.383 (3)
O2A—Na1—O1	158.19 (7)	C2A—N3A—C4A	124.9 (2)
O2A—Na1—O5A	75.67 (10)	C2A—N3A—H3A	117.6
O1—Na1—O5A	115.06 (10)	C4A—N3A—H3A	117.6
O2A—Na1—O5B	96.8 (4)	C6A—O2A—Na1	136.34 (15)
O1—Na1—O5B	97.4 (4)	N1A—C2A—N3A	116.0 (2)
O5A—Na1—O5B	22.5 (3)	N1A—C2A—S1	122.50 (17)
O2A—Na1—O4	116.69 (7)	N3A—C2A—S1	121.49 (17)
O1—Na1—O4	83.99 (7)	O1A—C4A—C5A	127.5 (2)
O5A—Na1—O4	85.36 (10)	O1A—C4A—N3A	115.6 (2)
O5B—Na1—O4	68.5 (3)	C5A—C4A—N3A	116.8 (2)
O2A—Na1—O2B	84.60 (6)	C4A—C5A—C6A	120.7 (2)
O1—Na1—O2B	85.42 (7)	C4A—C5A—H5A	119.6
O5A—Na1—O2B	159.48 (10)	C6A—C5A—H5A	119.6
O5B—Na1—O2B	166.4 (3)	O2A—C6A—C5A	126.4 (2)
O4—Na1—O2B	98.78 (7)	O2A—C6A—N1A	116.8 (2)
O2A—Na1—C6B	68.69 (7)	C5A—C6A—N1A	116.8 (2)
O1—Na1—C6B	106.86 (7)	C2B—S2—Na2^ii	103.23 (9)
O5A—Na1—C6B	136.90 (9)	C2B—S2—Na1^i	114.63 (8)
O5B—Na1—C6B	145.4 (3)	Na2^ii—S2—Na1^i	114.80 (3)
O4—Na1—C6B	89.55 (7)	C2B—N1B—C6B	124.38 (19)
O2B—Na1—C6B	24.33 (5)	C2B—N1B—H1B	117.8
O2A—Na1—S2^i	82.99 (5)	C6B—N1B—H1B	117.8
O1—Na1—S2^i	78.46 (5)	C2B—N3B—C4B	124.9 (2)
O5A—Na1—S2^i	89.05 (8)	C2B—N3B—H3B	117.5
O5B—Na1—S2^i	99.4 (3)	C4B—N3B—H3B	117.5
O4—Na1—S2^i	157.25 (6)	C6B—O2B—Na2	133.06 (15)
O2B—Na1—S2^i	94.17 (5)	C6B—O2B—Na1	100.74 (14)
C6B—Na1—S2^i	109.26 (6)	Na2—O2B—Na1	89.73 (6)
O2A—Na1—Na2	128.69 (6)	N1B—C2B—N3B	116.3 (2)
O1—Na1—Na2	44.21 (5)	N1B—C2B—S2	121.42 (17)
O5A—Na1—Na2	155.32 (10)	N3B—C2B—S2	122.27 (17)
O5B—Na1—Na2	133.1 (4)	O1B—C4B—C5B	126.5 (2)
O4—Na1—Na2	79.64 (6)	O1B—C4B—N3B	117.6 (2)
O2B—Na1—Na2	44.10 (4)	C5B—C4B—N3B	115.9 (2)
C6B—Na1—Na2	62.91 (5)	C6B—C5B—C4B	121.4 (2)
S2^i—Na1—Na2	97.25 (3)	C6B—C5B—H5B	119.3
O3—Na2—O2B	99.69 (7)	C4B—C5B—H5B	119.3
O3—Na2—O1	89.34 (8)	O2B—C6B—C5B	125.9 (2)
O2B—Na2—O1	86.64 (7)	O2B—C6B—N1B	117.2 (2)
O3—Na2—O2	91.54 (7)	C5B—C6B—N1B	116.9 (2)
O2B—Na2—O2	168.25 (7)	O2B—C6B—Na1	54.94 (12)
O1—Na2—O2	96.99 (8)	C5B—C6B—Na1	94.78 (15)
O3—Na2—S1^i	171.86 (7)	N1B—C6B—Na1	121.96 (15)
O2B—Na2—S1^i	88.03 (5)	Na1—O1—Na2	92.36 (7)
O1—Na2—S1^i	88.57 (5)	Na1—O1—H11	117.0 (19)
O2—Na2—S1^i	80.91 (5)	Na2—O1—H11	110.0 (19)
O3—Na2—S2^ii	88.41 (6)	Na1—O1—H12	112 (2)
O2B—Na2—S2^ii	88.09 (5)	Na2—O1—H12	127 (2)
O1—Na2—S2^ii	173.84 (6)	H11—O1—H12	100 (3)
O2—Na2—S2^ii	88.80 (6)	Na2—O2—H21	117 (2)
S1^i—Na2—S2^ii	94.44 (3)	Na2—O2—H22	110 (2)
O3—Na2—Na1	83.38 (6)	H21—O2—H22	107 (3)
O2B—Na2—Na1	46.16 (5)	Na2—O3—H31	121 (2)
O1—Na2—Na1	43.43 (5)	Na2—O3—H32	114.6 (19)
O2—Na2—Na1	139.90 (6)	H31—O3—H32	105 (3)
S1^i—Na2—Na1	100.41 (4)	Na1—O4—H41	112 (2)
S2^ii—Na2—Na1	130.54 (4)	Na1—O4—H42	105.1 (19)
C2A—S1—Na2^i	116.14 (8)	H41—O4—H42	109 (3)
C2A—N1A—C6A	124.57 (19)	O5B—O5A—Na1	81.1 (7)
C2A—N1A—H1A	117.7	O5A—O5B—Na1	76.4 (8)
C6A—N1A—H1A	117.7
O2A—Na1—Na2—O3	111.97 (8)	O5B—Na1—O2B—C6B	−49.2 (16)
O1—Na1—Na2—O3	−96.07 (9)	O4—Na1—O2B—C6B	−68.85 (15)
O5A—Na1—Na2—O3	−57.53 (19)	S2^i—Na1—O2B—C6B	129.92 (13)
O5B—Na1—Na2—O3	−51.1 (4)	Na2—Na1—O2B—C6B	−133.96 (16)
O4—Na1—Na2—O3	−4.04 (7)	O2A—Na1—O2B—Na2	−178.67 (6)
O2B—Na1—Na2—O3	110.27 (8)	O1—Na1—O2B—Na2	−18.08 (6)
C6B—Na1—Na2—O3	90.81 (8)	O5A—Na1—O2B—Na2	165.4 (3)
S2^i—Na1—Na2—O3	−161.23 (6)	O5B—Na1—O2B—Na2	84.7 (16)
O2A—Na1—Na2—O2B	1.70 (8)	O4—Na1—O2B—Na2	65.11 (7)
O1—Na1—Na2—O2B	153.66 (9)	C6B—Na1—O2B—Na2	133.96 (16)
O5A—Na1—Na2—O2B	−167.80 (19)	S2^i—Na1—O2B—Na2	−96.13 (5)
O5B—Na1—Na2—O2B	−161.4 (4)	C6B—N1B—C2B—N3B	3.1 (3)
O4—Na1—Na2—O2B	−114.31 (8)	C6B—N1B—C2B—S2	−175.98 (18)
C6B—Na1—Na2—O2B	−19.45 (7)	C4B—N3B—C2B—N1B	−2.4 (3)
S2^i—Na1—Na2—O2B	88.50 (6)	C4B—N3B—C2B—S2	176.70 (19)
O2A—Na1—Na2—O1	−151.96 (10)	Na2^ii—S2—C2B—N1B	−108.88 (19)
O5A—Na1—Na2—O1	38.54 (19)	Na1^i—S2—C2B—N1B	16.7 (2)
O5B—Na1—Na2—O1	45.0 (4)	Na2^ii—S2—C2B—N3B	72.1 (2)
O4—Na1—Na2—O1	92.03 (9)	Na1^i—S2—C2B—N3B	−162.31 (17)
O2B—Na1—Na2—O1	−153.66 (9)	C2B—N3B—C4B—O1B	−176.6 (2)
C6B—Na1—Na2—O1	−173.12 (9)	C2B—N3B—C4B—C5B	2.9 (4)
S2^i—Na1—Na2—O1	−65.16 (7)	O1B—C4B—C5B—C6B	175.4 (2)
O2A—Na1—Na2—O2	−163.53 (10)	N3B—C4B—C5B—C6B	−4.1 (4)
O1—Na1—Na2—O2	−11.57 (10)	Na2—O2B—C6B—C5B	−32.3 (4)
O5A—Na1—Na2—O2	27.0 (2)	Na1—O2B—C6B—C5B	67.6 (3)
O5B—Na1—Na2—O2	33.4 (4)	Na2—O2B—C6B—N1B	148.69 (16)
O4—Na1—Na2—O2	80.46 (10)	Na1—O2B—C6B—N1B	−111.48 (19)
O2B—Na1—Na2—O2	−165.23 (10)	Na2—O2B—C6B—Na1	−99.83 (18)
C6B—Na1—Na2—O2	175.32 (10)	C4B—C5B—C6B—O2B	−174.2 (2)
S2^i—Na1—Na2—O2	−76.72 (9)	C4B—C5B—C6B—N1B	4.8 (4)
O2A—Na1—Na2—S1^i	−75.31 (7)	C4B—C5B—C6B—Na1	−124.8 (2)
O1—Na1—Na2—S1^i	76.65 (7)	C2B—N1B—C6B—O2B	174.7 (2)
O5A—Na1—Na2—S1^i	115.19 (18)	C2B—N1B—C6B—C5B	−4.4 (3)
O5B—Na1—Na2—S1^i	121.6 (4)	C2B—N1B—C6B—Na1	110.9 (2)
O4—Na1—Na2—S1^i	168.67 (6)	O2A—Na1—C6B—O2B	−128.16 (15)
O2B—Na1—Na2—S1^i	−77.02 (6)	O1—Na1—C6B—O2B	29.23 (15)
C6B—Na1—Na2—S1^i	−96.47 (6)	O5A—Na1—C6B—O2B	−164.47 (17)
S2^i—Na1—Na2—S1^i	11.49 (4)	O5B—Na1—C6B—O2B	161.8 (7)
O2A—Na1—Na2—S2^ii	29.79 (9)	O4—Na1—C6B—O2B	112.82 (14)
O1—Na1—Na2—S2^ii	−178.25 (8)	S2^i—Na1—C6B—O2B	−54.13 (14)
O5A—Na1—Na2—S2^ii	−139.71 (17)	Na2—Na1—C6B—O2B	34.24 (12)
O5B—Na1—Na2—S2^ii	−133.3 (4)	O2A—Na1—C6B—C5B	100.57 (15)
O4—Na1—Na2—S2^ii	−86.22 (7)	O1—Na1—C6B—C5B	−102.04 (15)
O2B—Na1—Na2—S2^ii	28.09 (7)	O5A—Na1—C6B—C5B	64.3 (2)
C6B—Na1—Na2—S2^ii	8.63 (6)	O5B—Na1—C6B—C5B	30.5 (7)
S2^i—Na1—Na2—S2^ii	116.59 (5)	O4—Na1—C6B—C5B	−18.46 (15)
O1—Na1—O2A—C6A	−170.0 (2)	O2B—Na1—C6B—C5B	−131.3 (2)
O5A—Na1—O2A—C6A	67.4 (2)	S2^i—Na1—C6B—C5B	174.60 (13)
O5B—Na1—O2A—C6A	59.6 (4)	Na2—Na1—C6B—C5B	−97.03 (14)
O4—Na1—O2A—C6A	−9.8 (3)	O2A—Na1—C6B—N1B	−25.38 (16)
O2B—Na1—O2A—C6A	−106.9 (2)	O1—Na1—C6B—N1B	132.01 (16)
C6B—Na1—O2A—C6A	−87.9 (2)	O5A—Na1—C6B—N1B	−61.7 (2)
S2^i—Na1—O2A—C6A	158.2 (2)	O5B—Na1—C6B—N1B	−95.4 (7)
Na2—Na1—O2A—C6A	−108.1 (2)	O4—Na1—C6B—N1B	−144.41 (17)
C6A—N1A—C2A—N3A	−0.1 (4)	O2B—Na1—C6B—N1B	102.8 (2)
C6A—N1A—C2A—S1	−179.80 (18)	S2^i—Na1—C6B—N1B	48.65 (17)
C4A—N3A—C2A—N1A	1.1 (4)	Na2—Na1—C6B—N1B	137.02 (17)
C4A—N3A—C2A—S1	−179.25 (19)	O2A—Na1—O1—Na2	81.0 (2)
Na2^i—S1—C2A—N1A	8.2 (2)	O5A—Na1—O1—Na2	−163.31 (9)
Na2^i—S1—C2A—N3A	−171.47 (17)	O5B—Na1—O1—Na2	−148.6 (3)
C2A—N3A—C4A—O1A	−176.7 (2)	O4—Na1—O1—Na2	−81.30 (7)
C2A—N3A—C4A—C5A	1.5 (4)	O2B—Na1—O1—Na2	18.05 (6)
O1A—C4A—C5A—C6A	172.9 (2)	C6B—Na1—O1—Na2	6.40 (8)
N3A—C4A—C5A—C6A	−5.1 (4)	S2^i—Na1—O1—Na2	113.25 (6)
Na1—O2A—C6A—C5A	−4.8 (4)	O3—Na2—O1—Na1	81.05 (8)
Na1—O2A—C6A—N1A	176.60 (15)	O2B—Na2—O1—Na1	−18.70 (7)
C4A—C5A—C6A—O2A	−172.7 (2)	O2—Na2—O1—Na1	172.52 (7)
C4A—C5A—C6A—N1A	5.9 (4)	S1^i—Na2—O1—Na1	−106.81 (6)
C2A—N1A—C6A—O2A	175.5 (2)	S2^ii—Na2—O1—Na1	12.5 (6)
C2A—N1A—C6A—C5A	−3.3 (4)	O2A—Na1—O5A—O5B	−159.2 (8)
O3—Na2—O2B—C6B	33.6 (2)	O1—Na1—O5A—O5B	41.0 (8)
O1—Na2—O2B—C6B	122.3 (2)	O4—Na1—O5A—O5B	−40.1 (8)
O2—Na2—O2B—C6B	−129.2 (4)	O2B—Na1—O5A—O5B	−142.8 (8)
S1^i—Na2—O2B—C6B	−149.0 (2)	C6B—Na1—O5A—O5B	−124.5 (8)
S2^ii—Na2—O2B—C6B	−54.5 (2)	S2^i—Na1—O5A—O5B	117.8 (8)
Na1—Na2—O2B—C6B	104.5 (2)	Na2—Na1—O5A—O5B	12.3 (9)
O3—Na2—O2B—Na1	−70.96 (8)	O2A—Na1—O5B—O5A	20.3 (8)
O1—Na2—O2B—Na1	17.79 (6)	O1—Na1—O5B—O5A	−143.2 (8)
O2—Na2—O2B—Na1	126.2 (4)	O4—Na1—O5B—O5A	136.3 (9)
S1^i—Na2—O2B—Na1	106.47 (5)	O2B—Na1—O5B—O5A	115.4 (14)
S2^ii—Na2—O2B—Na1	−159.02 (5)	C6B—Na1—O5B—O5A	82.1 (10)
O2A—Na1—O2B—C6B	47.38 (14)	S2^i—Na1—O5B—O5A	−63.7 (8)
O1—Na1—O2B—C6B	−152.04 (14)	Na2—Na1—O5B—O5A	−173.0 (5)
O5A—Na1—O2B—C6B	31.5 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2B^i	0.86	1.97	2.823 (3)	175
N1B—H1B···O2A^i	0.86	1.96	2.806 (3)	167
O1—H11···O1A^iii	0.86 (3)	2.03 (3)	2.857 (3)	162 (3)
O1—H12···O2^iv	0.87 (2)	2.01 (2)	2.874 (3)	176 (3)
O2—H21···O1B^iii	0.88 (3)	1.96 (3)	2.822 (3)	165 (4)
O2—H22···O1A^v	0.89 (2)	2.12 (3)	2.970 (3)	166 (3)
O3—H31···O1A^vi	0.89 (2)	1.81 (2)	2.691 (3)	174 (3)
O3—H32···O5A^vii	0.90 (3)	1.91 (3)	2.801 (4)	169 (3)
O4—H41···O1B^vi	0.91 (3)	1.93 (2)	2.798 (3)	168 (3)
O4—H42···O3	0.91 (3)	1.89 (3)	2.784 (4)	165 (3)
N3A—H3A···S2^viii	0.86	2.50	3.349 (2)	170
N3B—H3B···S1^viii	0.86	2.56	3.302 (2)	145

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