Structures of Na9[SO4]4X·2H2O2, where X = Cl or Br, in which the halide anions orchestrate extended orientation sequences of H2O2 solvate molecules

Pritchard, R.G.; Begum, Z.; Lau, Y.F.; Austin, J.

doi:10.1107/S010876810503212X

research papers

STRUCTURAL SCIENCE
CRYSTAL ENGINEERING
MATERIALS

ISSN: 2052-5206

Volume 61| Part 6| December 2005| Pages 663-668

doi:10.1107/S010876810503212X

Structures of Na₉[SO₄]₄X·2H₂O₂, where X = Cl or Br, in which the halide anions orchestrate extended orientation sequences of H₂O₂ solvate molecules

Robin Gavin Pritchard,^a ^* Zubeda Begum,^a Yuf Fai Lau ^a and Jonothan Austin ^a

^aSchool of Chemistry, University of Manchester, Manchester M60 1QD, England
^*Correspondence e-mail: robin.pritchard@manchester.ac.uk

(Received 10 August 2005; accepted 9 October 2005)

Detailed structures of nonasodium tetrakis(sulfate) chloride diperhydrate, Na₉[SO₄]₄Cl·2H₂O₂, and its novel bromide analogue are compared. Hydrogen peroxide could not be resolved in a previously reported Na₉[SO₄]₄Cl·2H₂O₂ substructure [tetragonal, P4/mnc; Adams et al. (1978 ), J. Chem. Soc. Chem. Commun. p. 288; Adams & Pritchard (1978 ), Acta Cryst. B34, 1428–1432]. However, on lowering the symmetry to P4/n, and using reflection data based on full unit-cells, the H₂O₂ solvate can be clearly seen. Although H₂O₂ molecules are not directly bonded to the halide anions, they exert considerable influence on the eight sodium cations that constitute each halide's coordination shell so that H₂O₂ ordering can be linked to halide dimensions.

Keywords: sodium bromide; orientation sequences; perhydrate; sodium sulfate; hydrogen peroxide.

1. Introduction

The title compounds belong to a class of solids in which hydrogen peroxide simultaneously coordinates to alkali metal cations and hydrogen bonds to oxy-acid anions. These include commercially important sodium percarbonate, Na₂(CO₃)·1.5H₂O₂ (Pritchard & Islam, 2003 ), and the extensively studied alkali metal oxalates M₂(C₂O₄)·H₂O₂ (M = Li, Na, K and Rb; Pedersen, 1969 ; Pedersen & Pedersen, 1964 ; Pedersen & Kvick, 1989 , 1990 ; Adams et al., 1980a ,b ). A previous crystallographic investigation of Na₉[SO₄]₄Cl·2H₂O₂ yielded a subcell structure (Adams et al., 1978; Adams & Pritchard, 1978) in which the Na⁺, Cl⁻ and SO₄^2- ions can be seen, but in which the H₂O₂ site is obscured by disorder. This led to continued speculation (Adams et al., 1981 ; Cosgrove & Jones, 1998a ,b ,c ) about the role of H₂O₂ in the architecture of this exceptionally stable compound (Kao Soap Co. Ltd & Nippon Peroxide Co. Ltd, 1975 ).

The current investigation was initiated in order to address this last point and extended to include the bromide analogue, which was discovered during preliminary crystallization studies.

2. Experimental

2.1. Synthesis

The title compounds were prepared by dissolving sodium sulfate and sodium halide in 4:1 molar ratios in 30% w/w hydrogen peroxide and leaving the solution to evaporate over 48 h.

2.2. Data collection, structure solution and refinement

All measurements were carried out using a Nonius Kappa-CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Details of cell parameters, data collection and refinement are summarized in Table 1,¹ together with a listing of the software employed.

Table 1
Experimental details

	Cl	Br
Crystal data
Chemical formula	H₄ClNa₉O₂₀S₄	H₄BrNa₉O₂₀S₄
M_r	694.63	739.09
Cell setting, space group	Tetragonal, P4/n	Tetragonal, P4/n
a, c (Å)	29.6829 (3), 8.40180 (10)	14.9126 (5), 8.4052 (2)
V (Å³)	7402.61 (14)	1869.20 (10)
Z	16	4
D_x (Mg m⁻³)	2.493	2.626
Radiation type	Mo Kα	Mo Kα
No. of reflections for cell parameters	87 529	5097
θ range (°)	1.0–27.5	1.0–32.0
μ (mm⁻¹)	0.97	2.96
Temperature (K)	150 (2)	150 (2)
Crystal form, colour	Plate, colourless	Prism, colourless
Crystal size (mm)	0.1 × 0.1 × 0.05	0.18 × 0.18 × 0.07

Data collection
Diffractometer	KappaCCD	KappaCCD
Data collection method	CCD rotation images, thick slices	CCD rotation images, thick slices
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)
T_min	0.909	0.618
T_max	0.953	0.820
No. of measured, independent and observed reflections	65 291, 8402, 4855	8459, 3226, 2368
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)
R_int	0.090	0.049
θ_max (°)	27.5	32.0
Range of h, k, l	−38 → h → 37	−18 → h → 21
	−38 → k → 38	−22 → k → 12
	−10 → l → 10	−12 → l → 8

Refinement
Refinement on	F²	F²
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.147, 1.24	0.040, 0.093, 1.07
No. of reflections	8402	3226
No. of parameters	649	164
H-atom treatment	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement
Weighting scheme	w = 1/[σ²(F_o²) + (0.0244P)² + 19.2938P], where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0204P)² + 1.5967P], where P = (F_o² + 2F_c²)/3
(Δ/σ)_max	0.011	0.001
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.53	0.59, −0.64
Extinction method	None	SHELXL
Extinction coefficient		0.0047 (5)
Computer programs used: Kappa-CCD server software (Nonius, 1997 ), COLLECT (Nonius, 1998 ), DENZO-SMN (Otwinowski & Minor, 1997 ), SHELXS97 (Sheldrick, 1997 ), SHELXL97 (Sheldrick, 1997), Wingx (Farrugia, 1999 ), ORTEP (Farrugia, 1997 ), SORTAV (Blessing, 1995 , 1997 ).

Systematic absences and statistical tests clearly indicate the space group P4/n for both the chloride and bromide structures, even though the diffraction patterns have very low intensity in regions that are not governed by the subcell.

The structures were solved by direct methods and refined with all data on F². A weighting scheme based on P = [F₂^o + 2F²_c]/3 was employed in order to reduce statistical bias (Wilson, 1976 ).

It did not prove necessary to restrain or constrain the refinements in any way, despite the pseudo-symmetric appearance of the structures.

3. Results and discussion

3.1. Crystallization characteristics

Na₉[SO₄]₄X·2H₂O₂, where X = Cl or Br, crystallize as colourless squares when sodium sulfate and the appropriate sodium halide are dissolved in 30% w/w aqueous hydrogen peroxide and allowed to evaporate to dryness. Once formed the crystals are stable under ambient conditions.

3.2. Supramolecular structures

Fig. 1 shows the asymmetric units of the title chloride and bromide structures as well as the previously reported chloride substructure. It clearly illustrates how the resolution of the H₂O₂ molecules has dramatically increased the number of parameters that are needed to describe the structures. Interestingly, on application of the space-group symmetry the resulting packing diagrams, shown in Fig. 2, are almost identical except for the H₂O₂ sites. The H₂O₂ orientation sequence leads to the chloride a and b axes being double those of the bromide and 8^1/2 those of the chloride substructure.

Figure 1
Asymmetric unit of Na₉[SO₄]₄Cl·2H₂O₂ (top), its bromide analogue (bottom left) and subcell structure (bottom right)

Figure 2
Perspective view of half a unit cell of Na₉[SO₄]₄Cl·2H₂O₂ (c/2) on to the ab plane (top), bromide analogue (bottom left) and subcell structure (bottom right). The sublattice, defined by distorted Na⁺ cubes, has been highlighted in each case. Na⁺ ions are represented by filled ellipses and the X⁻ ions by empty ellipses.

In order to answer the question of why the chloride and bromide structures have different H₂O₂ orientation sequences, it is useful to focus on the distorted cubes with corners defined by six-coordinate Na⁺ that form a sublattice (4 × 4 × 2 cubes for the bromide and 8 × 8 × 2 for the chloride). Each cube houses an SO₄^2-, X⁻, or Na⁺ ion, or an H₂O₂ molecule. Sulfate anions form adjacent cubes from an eight-coordinate shell around each central Na⁺ ion (Fig. 5). The SO₄^2- and H₂O₂ cubes each form stacks, generated by non-crystallographic glides down c. Those cubes containing central Na⁺ and X⁻ ions also stack down c, alternating their Na⁺ and X⁻ contents. Importantly, the halide and hydrogen peroxide cubes share edges parallel to c (Fig. 2). Also, each hydrogen peroxide molecule is not located centrally within its cube, but straddles the top (i.e. perpendicular to the c axis) square face where it coordinates to four sodium cations and hydrogen bonds to two sulfate anions (Fig. 3, Table 2). The side of the Na⁺ square over which the hydrogen bonding is directed distends and impinges on the corners of two neighbouring halide-containing cubes, distorting the halide environments. Travelling along an H₂O₂ stack, i.e. along c, the direction of the hydrogen bonding is reversed at each level and hence the side of the square that is elongated, and is also reversed (Fig. 3). This has two repercussions on the shape of the halide-bearing sodium cubes: firstly, if a top corner is pushed in, the corner directly below is not; secondly, only half the corners of any cube can be pushed in. The four unique chloride ions and their surrounding sodium cubes are shown in Fig. 4 and, given the above conditions, represent all the possible distortions. In contrast, only distortions of the type seen around Cl2, which has C₄ symmetry, and Cl4 with S₄ symmetry, are seen in the bromide structure. A comparison of the Na—X bond lengths from these two sites, presented in Table 3, show that the larger bromide anion is able to interact more effectively with all eight Na⁺ cations than the smaller chloride anion in the C₄ site. The difference between the bromide and chloride structure seems to hinge on the larger halide's tendency to promote C₄ coordination, which would, however, destroy the crystal's tetragonal symmetry if used exclusively. The combination of C₄ and S₄ sites seen in the bromide enable it to retain tetragonal symmetry, whilst doubling the occurrence of what is, presumably, a favourable halide environment for the larger bromide anion.

Table 2
(a) Hydrogen bonds (Å, °) and Na—O coordination bonds (Å) involving H₂O₂; (b) H₂O₂ geometry (Å, °)

(a)

D—H⋯A	d(D—H)	d(H⋯A)	d(D⋯A)	∠(DHA)	Na—O
Cl
O33—H33⋯O10ⁱ	1.00 (6)	1.70 (6)	2.676 (4)	164 (5)	2.413 (3), 2.364 (3)
O34—H34⋯O14ⁱⁱ	0.97 (6)	1.81 (5)	2.706 (4)	152 (5)	2.408 (3), 2.408 (3)
O35—H35⋯O3	0.85 (4)	1.83 (4)	2.677 (4)	169 (4)	2.353 (3), 2.403 (3)
O36—H36⋯O5	0.82 (5)	1.92 (5)	2.711 (4)	162 (5)	2.399 (3), 2.413 (3)
O37—H37⋯O17	0.95 (6)	1.77 (6)	2.700 (4)	167 (5)	2.410 (3), 2.406 (3)
O38—H38⋯O21	0.98 (7)	1.71 (7)	2.677 (4)	171 (5)	2.420 (3), 2.363 (3)
O39—H39⋯O26ⁱⁱⁱ	0.89 (5)	1.84 (5)	2.696 (4)	159 (5)	2.407 (3), 2.394 (3)
O40—H40⋯O30^iv	1.03 (7)	1.71 (6)	2.687 (4)	157 (6)	2.374 (3), 2.414 (3)

Br
O5—H5⋯O3	0.85 (2)	1.86 (3)	2.695 (2)	166 (3)	2.399 (2), 2.391 (2)
O15—H15⋯O13	0.86 (4)	1.86 (4)	2.688 (2)	161 (4)	2.380 (2), 2.379 (2)

(b)

	O—O	O—O—H	H—O—O—H (°)
Cl
O33, O34	1.465 (3)	98 (3), 105 (3)	−114 (3)
O35, O36	1.466 (3)	97 (3), 101 (3)	−107 (3)
O37, O38	1.465 (3)	100 (3), 100 (4)	−98 (4)
O39, O40	1.459 (3)	101 (3), 105 (3)	−112 (3)

Br
O5, O15	1.458 (2)	102 (2), 102 (3)	106 (3)
Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 1-x, 1-y, -z; (iii) $[{1\over 2}+y, 1-x, 1-z]$ ; (iv) $[{1\over 2}+y, 1-x, -z]$ .

Table 3
Na—X bond lengths (Å) in the C₄ and S₄ sites of Na₉[SO₄]₄X·2H₂O₂

C₄ site		S₄ site
Cl2—Na10	2.845 (2)	Cl4—Na13	2.747 (2)
C12—Na3	3.186 (2)	Cl4—Na16	3.309 (2)

Br11—Na11	2.942 (1)	Br1—Na1	2.847 (1)
Br11—Na13	3.177 (1)	Br1—Na3	3.287 (1)

Figure 3
H₂O₂ environment in Na₉[SO₄]₄X·2H₂O₂. Projections down (a) a and (b) c. The c axis is directed up the page in the top view.

Figure 4
The four Cl⁻ environments in Na₉[SO₄]₄Cl·2H₂O₂ viewed down c. Referring to how many Na⁺ are pushed in on the top and bottom faces of the cube, the four configurations are 2–2, 0–4, 1–3 and diagonal 2–2.

Unlike sodium percarbonate (Pritchard & Islam, 2003), the current structures show no evidence of disordered H₂O₂. In sodium percarbonate dynamic H₂O₂ disorder becomes complete above 240 K, however, no disorder is observed in Na₉[SO₄]₄Cl·2H₂O₂, even when the temperature is raised to 300 K.

3.3. Molecular conformations and dimensions

Although the sulfate anions in both structures conform to the expected tetrahedral geometry they all display minor systematic deviations, which are related to crystal packing interactions.

In the chloride the 32 crystallographically unique S—O bonds can be divided into two groups with those involved in hydrogen bonding to H₂O₂ being longer [1.488 (3)–1.492 (3) Å] than the remainder [1.456 (3)–1.484 (3) Å]. A similar picture is seen in the bromide where the hydrogen-bonding S—O bonds of 1.492 (2) and 1.494 (2) Å are clearly distinguished from the shorter non-hydrogen bonding variety of 1.467 (2)–1.479 (2) Å.

The O—S—O angles do not deviate substantially from the expected tetrahedral value, falling in the range 108.1 (2)–110.6 (2)°, however, there is a demarcation within this group with sulfate O atoms that participate in the eight-fold coordination of sodium cations (Fig. 5) subtending the smaller O—S—O bond angles [108.1 (2)–108.7 (2)°]. An identical situation arises in the bromide, where the O—S—O angles range from 108.5 (1) to 110.1 (1)°, but those involved in the eightfold coordination of sodium are both 108.5 (1)°.

Figure 5
Eight-fold coordination shell of central sodium cation involving four SO₄^2- anions.

The peroxide O—O bond lengths are presented in Table 2 and show that the chloride values of 1.459 (3)–1.466 (3) Å, average 1.464 Å, are in good agreement with the single bromide O—O bond of 1.458 (2) Å. All these bonds are slightly shorter than an equivalent bond in sodium percarbonate, which was determined to be 1.4785 (8) Å at 150 K, but are well within the range, 1.439 (15)–1.509 (7) Å, defined by alkali-metal oxalate monoperhydrates.

HOOH torsion angles vary from −98 (4) to −114 (3)° in the chloride, but their average, −108°, is a good match for the bromide value of 106 (3)°. All these values coincide with the staggered minimum energy conformation that was identified from gas-phase spectroscopic measurements (Hunt et al., 1965 ).

The O—H bonds fall in the range 0.82 (5)–1.03 (7) Å in the chloride and 0.85 (2), 0.86 (4) Å in the bromide, showing good agreement with the analogous bonds in the oxalate perhydrates [0.83 (10)–1.0117 (5) Å].² Also at 97 (3)–105 (3)° in the chloride and 102 (3)° in the bromide the OOH angles show excellent agreement with the oxalate values of 97 (3)–104 (5)°.

4. Conclusions

Despite the rather elaborate pattern of H₂O₂ orientations within the above structures, each H₂O₂ site is identical (or nearly identical) as well as optimal in terms of H₂O₂ conformation, coordination and hydrogen bonding. In contrast to the alkali metal oxalate perhydrates, the title perhydrates do not form analogous hydrates. H₂O₂ must template these structures in a very specific way as crystallization from water yields a mixture of sodium halide and sodium sulfate. This is somewhat surprising, given that both sodium sulfate fluoride [Kogarkoite, Na₃(SO₄)F]; Fanfani et al., 1980 ] and sodium sulfate fluoride chloride [Na₆(SO₄)₂FCl, sulphohalite; Sakamoto, 1968 ] are known. In these structures the halide is octahedrally coordinated by sodium cations, matching its geometry in NaF or NaCl. Also, as each sulfate coordinates to 12 sodium cations (three per oxygen), an octahedral geometry is maintained around each cation. The sodium octahedra that surround each halide share faces with the 12-pointed polyhedra that encase the sulfate anions, a truncated trigonal bipyramid for Kogarkoite and truncated cube for sulphohalite. In sulphohalite the halide octahedra share corners to form a three-dimensional orthogonal grid with alternating F and Cl anions so that the unit-cell dimension in this cubic structure corresponds directly to the sum of the bond distances in the Na–Cl–Na–F–Na sequence. If fluoride is replaced with chloride the unit cell and, consequently, the sodium polyhedra around the sulfate would expand, making it harder for the sulfate to span all 12 cations. This does not happen and, given the scenario of a system where full coordination of the cations becomes difficult due to steric effects, it is not surprising that hydrogen peroxide, with its excess of lone pairs, is able to create a niche for itself.

Initially, interest in perhydrates centred on their commercial application as bleaches, but more recent research has employed them as a convenient and safe method of introducing anhydrous hydrogen peroxide to chemical reactions (Jones, 1999 ). This work included extensive studies on their use in the presence of bromide ions to oxidize and brominate substituted toluenes (Jones et al., 1996 ) and suggests that it would be worthwhile to test Na₉[SO₄]₄Br·2H₂O₂ as a combined H₂O₂/Br⁻ source.

Supporting information

Crystal structure: contains datablocks kc, rgp29c. DOI: 10.1107/S010876810503212X/de5022sup1.cif

Structure factors: contains datablock kc. DOI: 10.1107/S010876810503212X/de5022kcsup2.hkl

Structure factors: contains datablock rgp29c. DOI: 10.1107/S010876810503212X/de5022rgp29csup3.hkl

Computing details top

For both compounds, data collection: Collect (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997). Program(s) used to solve structure: SIR92 (Giacovazzo et al., 1993) for kc; SHELXS86 (Sheldrick, 1986) for rgp29c. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

(kc) top

Crystal data top

H₄ClNa₉O₂₀S₄	D_x = 2.493 Mg m⁻³
M_r = 694.63	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 87529 reflections
Hall symbol: -P 4a	θ = 1.0–27.5°
a = 29.6829 (3) Å	µ = 0.97 mm⁻¹
c = 8.4018 (1) Å	T = 150 K
V = 7402.61 (14) Å³	Plate, colourless
Z = 16	0.1 × 0.1 × 0.05 mm
F(000) = 5504

Data collection top

KappaCCD diffractometer	8402 independent reflections
Radiation source: Enraf Nonius FR590	4855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 1.4°
CCD rotation images, thick slices scans	h = −38→37
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	k = −38→38
T_min = 0.909, T_max = 0.953	l = −10→10
65291 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	w = 1/[σ²(F_o²) + (0.0244P)² + 19.2938P] where P = (F_o² + 2F_c²)/3
8402 reflections	(Δ/σ)_max = 0.011
649 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

H₄ClNa₉O₂₀S₄	Z = 16
M_r = 694.63	Mo Kα radiation
Tetragonal, P4/n	µ = 0.97 mm⁻¹
a = 29.6829 (3) Å	T = 150 K
c = 8.4018 (1) Å	0.1 × 0.1 × 0.05 mm
V = 7402.61 (14) Å³

Data collection top

KappaCCD diffractometer	8402 independent reflections
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	4855 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.953	R_int = 0.090
65291 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	w = 1/[σ²(F_o²) + (0.0244P)² + 19.2938P] where P = (F_o² + 2F_c²)/3
8402 reflections	Δρ_max = 0.59 e Å⁻³
649 parameters	Δρ_min = −0.53 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.5	0.5	0.5	0.0199 (4)
Cl2	0.25	0.25	0.4967 (2)	0.0221 (5)
Cl3	0.50129 (4)	0.24869 (4)	−0.00132 (10)	0.01858 (19)
Cl4	0.75	0.25	0.5	0.0171 (5)
Na1	0.44071 (5)	0.69788 (5)	0.18103 (18)	0.0174 (3)
Na2	0.56244 (5)	0.67803 (5)	0.21408 (18)	0.0188 (3)
Na3	0.68905 (5)	0.68139 (5)	0.3066 (2)	0.0193 (4)
Na4	0.43877 (5)	0.55061 (5)	0.32099 (19)	0.0167 (3)
Na5	0.55257 (5)	0.55940 (5)	0.32492 (19)	0.0178 (3)
Na6	0.69977 (5)	0.56102 (5)	0.18434 (18)	0.0169 (3)
Na7	0.43867 (5)	0.42897 (5)	0.2925 (2)	0.0201 (4)
Na8	0.56912 (5)	0.43795 (5)	0.2956 (2)	0.0215 (4)
Na9	0.68833 (5)	0.44778 (5)	0.18338 (19)	0.0179 (3)
Na10	0.30152 (5)	0.31147 (5)	0.31134 (19)	0.0178 (3)
Na11	0.44919 (5)	0.30913 (5)	0.17069 (17)	0.0158 (3)
Na12	0.57066 (5)	0.31119 (5)	0.20173 (19)	0.0205 (4)
Na13	0.69097 (5)	0.30080 (5)	0.32344 (18)	0.0158 (3)
Na14	0.43117 (5)	0.18784 (5)	0.1989 (2)	0.0199 (4)
Na15	0.56092 (5)	0.18157 (5)	0.19786 (19)	0.0195 (3)
Na16	0.68755 (5)	0.17876 (5)	0.29231 (19)	0.0190 (3)
Na17	0.5	0.5	0	0.0168 (6)
Na18	0.25	0.25	−0.0227 (4)	0.0168 (7)
Na19	0.50038 (5)	0.24998 (5)	0.48907 (16)	0.0173 (3)
Na20	0.75	0.25	0	0.0169 (8)
O1	0.57626 (9)	0.50738 (9)	−0.1411 (3)	0.0168 (6)
O2	0.57508 (9)	0.50595 (9)	0.1443 (3)	0.0164 (6)
O3	0.63396 (10)	0.54737 (10)	0.0057 (3)	0.0167 (7)
O4	0.63297 (11)	0.46536 (10)	0.0031 (3)	0.0194 (7)
O5	0.61719 (10)	0.54852 (10)	0.5058 (3)	0.0174 (7)
O6	0.61645 (10)	0.46682 (10)	0.4978 (3)	0.0176 (7)
O7	0.67484 (9)	0.50791 (9)	0.3611 (3)	0.0172 (6)
O8	0.67405 (9)	0.50580 (9)	0.6461 (3)	0.0181 (6)
O9	0.46628 (10)	0.38335 (11)	0.5001 (3)	0.0180 (7)
O10	0.54772 (10)	0.38354 (10)	0.4994 (3)	0.0174 (7)
O11	0.50646 (9)	0.32504 (9)	0.6376 (3)	0.0167 (6)
O12	0.50694 (9)	0.32678 (9)	0.3522 (3)	0.0163 (6)
O13	0.46711 (10)	0.36584 (10)	−0.0050 (3)	0.0163 (7)
O14	0.54846 (10)	0.36687 (10)	−0.0006 (3)	0.0169 (7)
O15	0.50595 (9)	0.42416 (9)	0.1387 (3)	0.0169 (6)
O16	0.50710 (9)	0.42446 (9)	−0.1450 (3)	0.0161 (6)
O17	0.38332 (10)	0.29828 (10)	−0.0111 (3)	0.0174 (7)
O18	0.38381 (10)	0.21691 (10)	−0.0027 (3)	0.0167 (7)
O19	0.32545 (8)	0.25809 (9)	0.1334 (3)	0.0157 (6)
O20	0.32640 (9)	0.25577 (9)	−0.1516 (3)	0.0159 (6)
O21	0.36625 (10)	0.29802 (10)	0.4889 (3)	0.0164 (7)
O22	0.36655 (10)	0.21632 (10)	0.4923 (3)	0.0142 (7)
O23	0.42375 (9)	0.25776 (8)	0.6362 (3)	0.0157 (6)
O24	0.42485 (9)	0.25628 (9)	0.3501 (3)	0.0152 (6)
O25	0.63388 (11)	0.28343 (11)	0.5002 (3)	0.0186 (7)
O26	0.63342 (10)	0.20204 (10)	0.4957 (3)	0.0165 (7)
O27	0.57612 (9)	0.24391 (8)	0.3556 (3)	0.0156 (6)
O28	0.57583 (9)	0.24263 (8)	0.6402 (3)	0.0149 (6)
O29	0.61650 (11)	0.28337 (10)	−0.0048 (3)	0.0160 (7)
O30	0.61665 (10)	0.20203 (10)	−0.0040 (3)	0.0156 (7)
O31	0.67499 (9)	0.24349 (9)	−0.1431 (3)	0.0158 (6)
O32	0.67322 (9)	0.24285 (9)	0.1428 (3)	0.0158 (6)
O33	0.38864 (9)	0.64518 (8)	0.2992 (3)	0.0181 (6)
O34	0.38725 (9)	0.60382 (8)	0.2042 (3)	0.0193 (6)
O35	0.60498 (8)	0.61115 (9)	0.2063 (3)	0.0186 (6)
O36	0.64643 (8)	0.61274 (9)	0.3010 (3)	0.0190 (6)
O37	0.35516 (8)	0.36249 (8)	0.1936 (3)	0.0165 (6)
O38	0.39644 (8)	0.36147 (9)	0.2892 (3)	0.0177 (6)
O39	0.63763 (9)	0.39457 (8)	0.3008 (3)	0.0189 (6)
O40	0.63859 (9)	0.35339 (8)	0.2061 (3)	0.0196 (6)
S1	0.60498 (4)	0.50632 (4)	0.00275 (9)	0.0114 (2)
S2	0.64521 (4)	0.50688 (4)	0.50257 (9)	0.0113 (2)
S3	0.50636 (4)	0.35506 (4)	0.49707 (10)	0.0126 (2)
S4	0.50693 (4)	0.39517 (4)	−0.00308 (10)	0.0122 (2)
S5	0.35487 (4)	0.25691 (4)	−0.00769 (10)	0.0114 (2)
S6	0.39513 (4)	0.25690 (4)	0.49202 (10)	0.0113 (2)
S7	0.60486 (4)	0.24334 (4)	0.49809 (9)	0.0122 (2)
S8	0.64508 (4)	0.24332 (4)	−0.00216 (9)	0.0121 (2)
H33	0.4078 (19)	0.6337 (18)	0.388 (7)	0.060 (18)*
H34	0.4035 (17)	0.6108 (18)	0.107 (7)	0.052 (16)*
H35	0.6148 (14)	0.5935 (14)	0.134 (5)	0.023 (12)*
H36	0.6391 (16)	0.5975 (17)	0.378 (6)	0.038 (15)*
H37	0.3635 (18)	0.3428 (18)	0.110 (7)	0.053 (17)*
H38	0.388 (2)	0.339 (2)	0.369 (10)	0.11 (3)*
H39	0.6535 (17)	0.3861 (16)	0.386 (6)	0.042 (15)*
H40	0.658 (2)	0.361 (2)	0.108 (9)	0.09 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0108 (7)	0.0246 (9)	0.0241 (9)	−0.0006 (6)	−0.0003 (4)	0.0077 (5)
Cl2	0.0211 (8)	0.0211 (8)	0.0241 (12)	0	0	0
Cl3	0.0157 (6)	0.0173 (7)	0.0227 (5)	−0.0015 (7)	0.0040 (3)	−0.0042 (3)
Cl4	0.0159 (7)	0.0159 (7)	0.0194 (11)	0	0	0
Na1	0.0166 (7)	0.0169 (7)	0.0188 (8)	0.0004 (6)	−0.0028 (6)	−0.0012 (6)
Na2	0.0217 (8)	0.0164 (7)	0.0184 (8)	−0.0023 (6)	0.0014 (6)	−0.0027 (6)
Na3	0.0178 (7)	0.0197 (8)	0.0203 (9)	0.0030 (6)	0.0036 (6)	0.0047 (7)
Na4	0.0161 (7)	0.0143 (7)	0.0195 (8)	−0.0015 (6)	0.0036 (6)	−0.0002 (6)
Na5	0.0180 (7)	0.0171 (7)	0.0184 (8)	0.0026 (6)	−0.0025 (6)	−0.0029 (6)
Na6	0.0162 (7)	0.0158 (7)	0.0188 (8)	−0.0023 (6)	−0.0020 (6)	0.0040 (6)
Na7	0.0204 (8)	0.0177 (8)	0.0224 (9)	0.0032 (6)	0.0028 (7)	0.0060 (6)
Na8	0.0233 (8)	0.0170 (8)	0.0242 (9)	−0.0036 (6)	−0.0086 (7)	0.0044 (7)
Na9	0.0169 (7)	0.0154 (7)	0.0213 (8)	0.0016 (6)	−0.0039 (6)	−0.0003 (6)
Na10	0.0159 (7)	0.0199 (8)	0.0177 (8)	0.0021 (6)	−0.0011 (6)	−0.0042 (6)
Na11	0.0166 (7)	0.0159 (7)	0.0148 (7)	−0.0005 (6)	0.0023 (6)	0.0002 (6)
Na12	0.0197 (8)	0.0211 (8)	0.0208 (8)	0.0046 (6)	0.0064 (7)	0.0043 (7)
Na13	0.0141 (7)	0.0163 (7)	0.0171 (8)	0.0002 (6)	0.0016 (6)	0.0001 (6)
Na14	0.0207 (8)	0.0155 (7)	0.0236 (9)	0.0031 (6)	−0.0061 (7)	−0.0036 (7)
Na15	0.0169 (7)	0.0171 (8)	0.0245 (8)	−0.0018 (6)	0.0046 (7)	−0.0055 (7)
Na16	0.0173 (8)	0.0179 (8)	0.0219 (9)	0.0034 (6)	0.0034 (6)	0.0045 (6)
Na17	0.0097 (12)	0.0113 (12)	0.0293 (15)	−0.0004 (9)	−0.0015 (8)	−0.0005 (8)
Na18	0.0176 (11)	0.0176 (11)	0.0151 (15)	0	0	0
Na19	0.0140 (10)	0.0139 (10)	0.0239 (8)	0.0004 (10)	0.0003 (6)	−0.0004 (6)
Na20	0.0182 (12)	0.0182 (12)	0.0144 (18)	0	0	0
O1	0.0184 (14)	0.0143 (13)	0.0177 (14)	−0.0014 (11)	−0.0024 (11)	0.0014 (11)
O2	0.0188 (14)	0.0140 (13)	0.0165 (14)	−0.0031 (11)	0.0035 (11)	−0.0007 (11)
O3	0.0162 (16)	0.0155 (16)	0.0183 (16)	−0.0066 (14)	0.0021 (9)	−0.0015 (9)
O4	0.0204 (17)	0.0143 (17)	0.0236 (18)	0.0052 (14)	−0.0016 (10)	−0.0011 (10)
O5	0.0187 (17)	0.0152 (16)	0.0183 (16)	0.0040 (13)	0.0019 (10)	0.0015 (9)
O6	0.0147 (16)	0.0142 (16)	0.0240 (18)	−0.0036 (13)	0.0021 (10)	−0.0022 (10)
O7	0.0163 (14)	0.0174 (14)	0.0177 (14)	−0.0004 (11)	0.0049 (11)	0.0013 (11)
O8	0.0174 (14)	0.0199 (14)	0.0170 (14)	0.0001 (11)	−0.0033 (11)	−0.0008 (11)
O9	0.0155 (17)	0.0193 (17)	0.0191 (17)	0.0058 (13)	−0.0028 (9)	−0.0028 (10)
O10	0.0156 (16)	0.0160 (16)	0.0207 (17)	−0.0048 (13)	−0.0017 (9)	0.0024 (9)
O11	0.0168 (14)	0.0152 (13)	0.0181 (14)	−0.0010 (11)	−0.0019 (11)	0.0049 (11)
O12	0.0157 (13)	0.0164 (14)	0.0168 (14)	0.0013 (11)	0.0006 (11)	−0.0039 (11)
O13	0.0160 (16)	0.0145 (16)	0.0183 (16)	−0.0043 (13)	−0.0002 (9)	0.0017 (9)
O14	0.0115 (16)	0.0186 (17)	0.0205 (17)	0.0041 (14)	0.0015 (9)	0.0027 (9)
O15	0.0166 (14)	0.0166 (14)	0.0175 (14)	0.0001 (11)	−0.0014 (11)	−0.0033 (11)
O16	0.0143 (13)	0.0175 (14)	0.0165 (14)	−0.0002 (11)	0.0014 (11)	0.0022 (11)
O17	0.0164 (16)	0.0157 (16)	0.0200 (16)	−0.0049 (13)	0.0024 (10)	−0.0018 (10)
O18	0.0132 (16)	0.0129 (16)	0.0238 (18)	0.0043 (13)	0.0018 (9)	0.0012 (9)
O19	0.0126 (13)	0.0157 (13)	0.0188 (14)	0.0008 (11)	0.0044 (11)	−0.0001 (11)
O20	0.0122 (13)	0.0174 (14)	0.0181 (15)	0.0009 (11)	−0.0022 (11)	−0.0001 (11)
O21	0.0156 (16)	0.0134 (16)	0.0202 (16)	0.0032 (13)	0.0015 (10)	0.0015 (10)
O22	0.0135 (16)	0.0135 (16)	0.0157 (15)	−0.0041 (13)	−0.0018 (9)	0.0002 (9)
O23	0.0143 (13)	0.0145 (13)	0.0183 (14)	0.0000 (11)	−0.0037 (11)	0.0009 (11)
O24	0.0133 (13)	0.0154 (13)	0.0168 (14)	0.0014 (11)	0.0036 (11)	−0.0012 (11)
O25	0.0184 (17)	0.0183 (18)	0.0190 (17)	−0.0055 (14)	0.0030 (10)	−0.0023 (10)
O26	0.0165 (17)	0.0158 (17)	0.0173 (17)	0.0038 (13)	0.0036 (9)	0.0022 (9)
O27	0.0185 (14)	0.0133 (13)	0.0152 (14)	−0.0010 (11)	−0.0028 (11)	−0.0017 (11)
O28	0.0179 (14)	0.0117 (13)	0.0152 (14)	−0.0016 (11)	0.0034 (11)	0.0021 (11)
O29	0.0193 (17)	0.0167 (17)	0.0120 (15)	0.0034 (14)	−0.0018 (9)	−0.0024 (9)
O30	0.0164 (16)	0.0108 (16)	0.0196 (17)	−0.0017 (13)	0.0018 (9)	−0.0014 (9)
O31	0.0143 (13)	0.0166 (14)	0.0163 (14)	0.0000 (11)	0.0043 (11)	−0.0006 (11)
O32	0.0145 (13)	0.0172 (14)	0.0156 (14)	0.0019 (11)	−0.0049 (11)	−0.0002 (11)
O33	0.0179 (13)	0.0165 (13)	0.0199 (14)	−0.0005 (10)	−0.0004 (11)	−0.0044 (11)
O34	0.0233 (14)	0.0161 (13)	0.0184 (15)	−0.0011 (11)	0.0015 (12)	−0.0051 (11)
O35	0.0158 (13)	0.0202 (13)	0.0197 (15)	0.0021 (11)	−0.0039 (11)	−0.0023 (12)
O36	0.0148 (13)	0.0211 (14)	0.0210 (15)	−0.0023 (11)	−0.0050 (11)	0.0003 (12)
O37	0.0137 (12)	0.0170 (13)	0.0189 (14)	0.0032 (10)	−0.0046 (11)	0.0010 (11)
O38	0.0146 (13)	0.0204 (13)	0.0182 (14)	−0.0002 (11)	−0.0032 (11)	−0.0012 (11)
O39	0.0187 (13)	0.0161 (13)	0.0219 (15)	−0.0005 (11)	−0.0026 (12)	−0.0044 (11)
O40	0.0205 (14)	0.0164 (13)	0.0221 (15)	0.0018 (11)	−0.0006 (12)	−0.0034 (11)
S1	0.0114 (5)	0.0109 (5)	0.0120 (5)	−0.0012 (4)	−0.0002 (3)	0.0003 (3)
S2	0.0119 (5)	0.0093 (5)	0.0127 (5)	0.0002 (4)	0.0004 (3)	−0.0001 (3)
S3	0.0123 (6)	0.0091 (5)	0.0165 (6)	−0.0013 (4)	−0.0009 (3)	−0.0001 (3)
S4	0.0125 (5)	0.0090 (5)	0.0152 (5)	−0.0010 (4)	0.0003 (3)	0.0007 (3)
S5	0.0113 (5)	0.0083 (5)	0.0146 (5)	−0.0013 (4)	0.0003 (3)	−0.0001 (3)
S6	0.0103 (5)	0.0092 (5)	0.0144 (5)	−0.0005 (4)	−0.0002 (3)	0.0001 (3)
S7	0.0120 (5)	0.0126 (6)	0.0121 (5)	−0.0011 (4)	0.0008 (3)	0.0005 (3)
S8	0.0116 (5)	0.0110 (5)	0.0137 (5)	0.0017 (4)	0.0001 (3)	−0.0001 (3)

Bond lengths (Å) top

Cl1—Na5ⁱ	2.7764 (16)	Na14—O24	2.404 (3)
Cl1—Na5	2.7764 (16)	Na14—O37^iv	2.406 (3)
Cl1—Na4ⁱ	2.7967 (15)	Na14—O3^ix	2.433 (3)
Cl1—Na4	2.7967 (15)	Na14—Na6^ix	3.247 (2)
Cl1—Na8ⁱ	3.2484 (17)	Na14—S2^vi	3.3579 (18)
Cl1—Na8	3.2484 (17)	Na14—S6	3.3782 (18)
Cl1—Na7	3.2863 (16)	Na14—Na19	3.683 (2)
Cl1—Na7ⁱ	3.2863 (16)	Na14—Na10^iv	3.690 (2)
Cl2—Na10ⁱⁱ	2.8448 (18)	Na15—O27	2.321 (3)
Cl2—Na10ⁱⁱⁱ	2.8448 (18)	Na15—O4^ix	2.354 (3)
Cl2—Na10^iv	2.8448 (18)	Na15—O8^vi	2.385 (3)
Cl2—Na10	2.8448 (19)	Na15—O34^iv	2.408 (3)
Cl2—Na3ⁱ	3.1860 (19)	Na15—O30	2.446 (3)
Cl2—Na3^v	3.1860 (19)	Na15—Na9^ix	3.220 (2)
Cl2—Na3^vi	3.1860 (19)	Na15—S7	3.3804 (18)
Cl2—Na3^vii	3.1860 (19)	Na15—Na19	3.652 (2)
Cl3—Na11	2.7746 (18)	Na15—Na4^iv	3.731 (2)
Cl3—Na1^viii	2.7856 (19)	Na15—Na16	3.843 (2)
Cl3—Na9^ix	2.7990 (19)	Na16—O32	2.319 (3)
Cl3—Na6^ix	2.8095 (19)	Na16—O25^vi	2.357 (3)
Cl3—Na15	3.1469 (19)	Na16—O33^iv	2.364 (3)
Cl3—Na14	3.2285 (19)	Na16—O31^ix	2.403 (3)
Cl3—Na12	3.2546 (19)	Na16—O26	2.446 (3)
Cl4—Na13^x	2.7466 (15)	Na16—Na13^vi	3.267 (2)
Cl4—Na13^vi	2.7466 (15)	Na16—S8^ix	3.3395 (18)
Cl4—Na13^xi	2.7466 (15)	Na16—S8	3.3739 (18)
Cl4—Na13	2.7466 (15)	Na16—Na13^xi	3.6658 (19)
Cl4—Na16	3.3096 (16)	Na16—Na1^iv	3.680 (2)
Cl4—Na16^vi	3.3096 (16)	Na17—O15	2.541 (3)
Cl4—Na16^xi	3.3096 (16)	Na17—O15^viii	2.541 (3)
Cl4—Na16^x	3.3096 (16)	Na17—O2	2.543 (3)
Na1—O11ⁱ	2.290 (3)	Na17—O2^viii	2.543 (3)
Na1—O29^viii	2.321 (3)	Na17—O16	2.561 (3)
Na1—O28ⁱ	2.370 (3)	Na17—O16^viii	2.561 (3)
Na1—O33	2.413 (3)	Na17—O1^viii	2.565 (3)
Na1—O14^viii	2.469 (3)	Na17—O1	2.565 (3)
Na1—Cl3^viii	2.7856 (19)	Na17—S4^viii	3.1186 (11)
Na1—Na12^viii	3.245 (2)	Na17—S4	3.1186 (11)
Na1—Na9^xii	3.384 (2)	Na17—S1^viii	3.1218 (11)
Na1—Na19ⁱ	3.624 (2)	Na17—S1	3.1218 (11)
Na1—Na2	3.672 (2)	Na18—O20ⁱⁱ	2.519 (3)
Na1—Na16ⁱⁱⁱ	3.680 (2)	Na18—O20^iv	2.519 (3)
Na2—O23ⁱ	2.320 (3)	Na18—O20ⁱⁱⁱ	2.519 (3)
Na2—O35	2.353 (3)	Na18—O20	2.519 (3)
Na2—O13^viii	2.356 (3)	Na18—O19ⁱⁱⁱ	2.606 (3)
Na2—O11ⁱ	2.397 (3)	Na18—O19	2.607 (3)
Na2—O17^viii	2.448 (3)	Na18—O19ⁱⁱ	2.607 (3)
Na2—Na11^viii	3.273 (2)	Na18—O19^iv	2.607 (3)
Na2—S3ⁱ	3.3203 (18)	Na18—S5ⁱⁱⁱ	3.1223 (11)
Na2—S6ⁱ	3.3785 (17)	Na18—S5ⁱⁱ	3.1223 (11)
Na2—Na6^xii	3.636 (2)	Na18—S5^iv	3.1223 (11)
Na2—Na5	3.654 (2)	Na18—S5	3.1223 (11)
Na2—Na19ⁱ	3.777 (2)	Na19—O27	2.519 (3)
Na3—O20^viii	2.321 (3)	Na19—O8^vi	2.531 (3)
Na3—O22^x	2.352 (3)	Na19—O24	2.534 (3)
Na3—O20^xiii	2.382 (3)	Na19—O11	2.560 (3)
Na3—O36	2.399 (3)	Na19—O12	2.561 (3)
Na3—O21ⁱ	2.453 (3)	Na19—O7^vi	2.573 (3)
Na3—Cl2ⁱ	3.1860 (19)	Na19—O28	2.584 (3)
Na3—Na10ⁱ	3.229 (3)	Na19—O23	2.599 (3)
Na3—S5^viii	3.3709 (18)	Na19—S7	3.1086 (19)
Na3—Na18^viii	3.621 (3)	Na19—S2^vi	3.1181 (19)
Na3—Na6	3.731 (2)	Na19—S3	3.1249 (19)
Na3—Na3^xiv	3.852 (2)	Na19—S6	3.1308 (19)
Na4—O6ⁱ	2.296 (3)	Na20—O31	2.538 (3)
Na4—O16^viii	2.306 (3)	Na20—O31^xiii	2.538 (3)
Na4—O1^viii	2.334 (3)	Na20—O31^xi	2.538 (3)
Na4—O34	2.408 (3)	Na20—O31^ix	2.538 (3)
Na4—O10ⁱ	2.502 (3)	Na20—O32^xi	2.584 (3)
Na4—Na8ⁱ	3.248 (2)	Na20—O32^ix	2.584 (3)
Na4—S2ⁱ	3.3652 (17)	Na20—O32	2.584 (3)
Na4—Na5	3.388 (2)	Na20—O32^xiii	2.584 (3)
Na4—Na17	3.5822 (15)	Na20—S8	3.1206 (11)
Na4—Na7	3.618 (2)	Na20—S8^xi	3.1206 (11)
Na4—Na15ⁱⁱⁱ	3.731 (2)	Na20—S8^ix	3.1206 (11)
Na5—O2	2.295 (3)	Na20—S8^xiii	3.1206 (11)
Na5—O9ⁱ	2.315 (3)	O1—S1	1.479 (3)
Na5—O16^viii	2.378 (3)	O1—Na7^viii	2.320 (3)
Na5—O35	2.403 (3)	O1—Na4^viii	2.334 (3)
Na5—O5	2.468 (3)	O2—S1	1.484 (3)
Na5—Na7ⁱ	3.243 (2)	O3—S1	1.492 (3)
Na5—Na17	3.6051 (15)	O3—Na14^xiii	2.433 (3)
Na5—Na8	3.647 (2)	O4—S1	1.473 (3)
Na5—H35	2.64 (4)	O4—Na15^xiii	2.354 (3)
Na6—O7	2.289 (3)	O5—S2	1.490 (3)
Na6—O18^xiii	2.295 (3)	O5—Na7ⁱ	2.463 (3)
Na6—O23^x	2.333 (3)	O6—S2	1.465 (3)
Na6—O36	2.413 (3)	O6—Na4ⁱ	2.296 (3)
Na6—O3	2.496 (3)	O7—S2	1.479 (3)
Na6—Cl3^xiii	2.8095 (19)	O7—Na19^x	2.573 (3)
Na6—Na14^xiii	3.247 (2)	O8—S2	1.479 (3)
Na6—S5^xiii	3.3632 (17)	O8—Na14^x	2.316 (3)
Na6—Na9	3.378 (2)	O8—Na15^x	2.385 (3)
Na6—Na19^x	3.615 (2)	O8—Na19^x	2.531 (3)
Na6—Na2^xiv	3.636 (2)	O9—S3	1.456 (3)
Na6—H36	2.66 (5)	O9—Na5ⁱ	2.315 (3)
Na7—O1^viii	2.320 (3)	O10—S3	1.491 (3)
Na7—O9	2.355 (3)	O10—Na4ⁱ	2.502 (3)
Na7—O38	2.363 (3)	O11—S3	1.479 (3)
Na7—O15	2.383 (3)	O11—Na1ⁱ	2.290 (3)
Na7—O5ⁱ	2.463 (3)	O11—Na2ⁱ	2.397 (3)
Na7—Na5ⁱ	3.243 (2)	O12—S3	1.479 (3)
Na7—S4	3.3584 (19)	O13—S4	1.468 (3)
Na7—Na17	3.7147 (15)	O13—Na2^viii	2.356 (3)
Na7—Na11	3.715 (2)	O14—S4	1.492 (3)
Na7—Na14ⁱⁱⁱ	3.837 (2)	O14—Na1^viii	2.469 (3)
Na8—O15	2.328 (3)	O15—S4	1.470 (3)
Na8—O6	2.365 (3)	O16—S4	1.475 (3)
Na8—O2	2.392 (3)	O16—Na4^viii	2.306 (3)
Na8—O39	2.407 (3)	O16—Na5^viii	2.378 (3)
Na8—O10	2.438 (3)	O17—S5	1.491 (3)
Na8—Na4ⁱ	3.248 (2)	O17—Na2^viii	2.448 (3)
Na8—S1	3.3620 (18)	O18—S5	1.466 (3)
Na8—S4	3.3639 (18)	O18—Na6^ix	2.295 (3)
Na8—Na9	3.674 (2)	O19—S5	1.473 (3)
Na8—Na17	3.7104 (15)	O19—Na10^iv	2.353 (3)
Na9—O4	2.295 (3)	O20—S5	1.476 (3)
Na9—O28^x	2.299 (3)	O20—Na3^viii	2.321 (3)
Na9—O7	2.361 (3)	O20—Na3^ix	2.382 (3)
Na9—O39	2.394 (3)	O21—S6	1.492 (3)
Na9—O30^xiii	2.469 (3)	O21—Na3ⁱ	2.453 (3)
Na9—Cl3^xiii	2.7990 (19)	O22—S6	1.473 (3)
Na9—Na15^xiii	3.220 (2)	O22—Na10^iv	2.295 (3)
Na9—S1	3.3829 (18)	O22—Na3^vi	2.352 (3)
Na9—Na1^xiv	3.384 (2)	O23—S6	1.480 (3)
Na9—Na19^x	3.645 (2)	O23—Na2ⁱ	2.320 (3)
Na10—O19	2.291 (3)	O23—Na6^vi	2.333 (3)
Na10—O22ⁱⁱⁱ	2.295 (3)	O24—S6	1.483 (3)
Na10—O19ⁱⁱⁱ	2.353 (3)	O25—S7	1.469 (3)
Na10—O37	2.410 (3)	O25—Na16^x	2.357 (3)
Na10—O21	2.465 (3)	O26—S7	1.491 (3)
Na10—Na3ⁱ	3.229 (3)	O26—Na13^vi	2.496 (3)
Na10—Na10ⁱⁱⁱ	3.367 (2)	O27—S7	1.470 (3)
Na10—Na10^iv	3.367 (2)	O28—S7	1.473 (3)
Na10—S6ⁱⁱⁱ	3.3881 (18)	O28—Na9^vi	2.299 (3)
Na10—Na18	3.680 (3)	O28—Na1ⁱ	2.370 (3)
Na10—Na14ⁱⁱⁱ	3.690 (2)	O29—S8	1.460 (3)
Na10—H37	2.67 (6)	O29—Na1^viii	2.321 (3)
Na11—O24	2.293 (3)	O30—S8	1.488 (3)
Na11—O13	2.301 (3)	O30—Na9^ix	2.469 (3)
Na11—O12	2.354 (3)	O31—S8	1.480 (3)
Na11—O38	2.420 (3)	O31—Na13^ix	2.290 (3)
Na11—O17	2.502 (3)	O31—Na16^xiii	2.403 (3)
Na11—Na2^viii	3.273 (2)	O32—S8	1.477 (3)
Na11—Na19	3.542 (2)	O33—O34	1.465 (3)
Na11—Na12	3.615 (2)	O33—Na16ⁱⁱⁱ	2.364 (3)
Na11—Na14	3.647 (2)	O33—H33	1.00 (6)
Na11—H38	2.63 (8)	O34—Na15ⁱⁱⁱ	2.408 (3)
Na12—O12	2.321 (3)	O34—H34	0.97 (6)
Na12—O29	2.355 (3)	O35—O36	1.466 (4)
Na12—O40	2.374 (3)	O35—H35	0.85 (5)
Na12—O27	2.384 (3)	O36—H36	0.82 (5)
Na12—O14	2.461 (3)	O37—O38	1.465 (3)
Na12—Na1^viii	3.245 (2)	O37—Na14ⁱⁱⁱ	2.406 (3)
Na12—S7	3.3595 (18)	O37—H37	0.95 (6)
Na12—Na19	3.672 (2)	O38—H38	0.98 (8)
Na12—Na13	3.728 (2)	O39—O40	1.459 (4)
Na13—O31^xiii	2.290 (3)	O39—H39	0.89 (5)
Na13—O25	2.312 (3)	O40—H40	1.03 (7)
Na13—O32	2.354 (3)	S2—Na19^x	3.1181 (19)
Na13—O40	2.414 (3)	S2—Na14^x	3.3579 (18)
Na13—O26^x	2.496 (3)	S2—Na4ⁱ	3.3652 (18)
Na13—Na16^x	3.267 (2)	S3—Na2ⁱ	3.3203 (18)
Na13—Na20	3.5676 (15)	S5—Na6^ix	3.3632 (17)
Na13—Na16	3.633 (2)	S5—Na3^viii	3.3709 (18)
Na13—Na16^xi	3.6658 (19)	S6—Na2ⁱ	3.3785 (17)
Na14—O8^vi	2.316 (3)	S6—Na10^iv	3.3881 (18)
Na14—O18	2.364 (3)	S8—Na16^xiii	3.3395 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O33—H33···O10ⁱ	1.00 (6)	1.70 (6)	2.675 (4)	164 (5)
O34—H34···O14^viii	0.97 (6)	1.81 (6)	2.706 (4)	152 (5)
O35—H35···O3	0.85 (4)	1.83 (4)	2.677 (4)	169 (4)
O36—H36···O5	0.82 (5)	1.92 (5)	2.711 (4)	162 (5)
O37—H37···O17	0.95 (6)	1.77 (6)	2.700 (4)	167 (5)
O38—H38···O21	0.98 (7)	1.71 (6)	2.677 (4)	171 (6)
O39—H39···O26^x	0.89 (5)	1.84 (5)	2.696 (4)	159 (5)
O40—H40···O30^xiii	1.02 (7)	1.71 (6)	2.687 (4)	158 (6)

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

(rgp29c) top

Crystal data top

H₄BrNa₉O₂₀S₄	D_x = 2.626 Mg m⁻³
M_r = 739.09	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 5097 reflections
Hall symbol: -P 4a	θ = 1.0–32.0°
a = 14.9126 (5) Å	µ = 2.96 mm⁻¹
c = 8.4052 (2) Å	T = 150 K
V = 1869.20 (10) Å³	Prism, colourless
Z = 4	0.18 × 0.18 × 0.07 mm
F(000) = 1448

Data collection top

KappaCCD diffractometer	3226 independent reflections
Radiation source: Enraf Nonius FR590	2368 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 9 pixels mm^-1	θ_max = 32.0°, θ_min = 1.9°
CCD rotation images, thick slices scans	h = −18→21
Absorption correction: multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]	k = −22→12
T_min = 0.618, T_max = 0.820	l = −12→8
8459 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0204P)² + 1.5967P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3226 reflections	Δρ_max = 0.59 e Å⁻³
164 parameters	Δρ_min = −0.64 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (5)

Crystal data top

H₄BrNa₉O₂₀S₄	Z = 4
M_r = 739.09	Mo Kα radiation
Tetragonal, P4/n	µ = 2.96 mm⁻¹
a = 14.9126 (5) Å	T = 150 K
c = 8.4052 (2) Å	0.18 × 0.18 × 0.07 mm
V = 1869.20 (10) Å³

Data collection top

KappaCCD diffractometer	3226 independent reflections
Absorption correction: multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]	2368 reflections with I > 2σ(I)
T_min = 0.618, T_max = 0.820	R_int = 0.049
8459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.59 e Å⁻³
3226 reflections	Δρ_min = −0.64 e Å⁻³
164 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.75	0.25	1	0.01417 (12)
Br11	0.25	0.25	0.48695 (5)	0.01273 (12)
Na1	0.64723 (7)	0.37337 (6)	0.81685 (12)	0.0146 (2)
Na2	0.75	0.25	0.5	0.0163 (4)
Na3	0.62673 (7)	0.39174 (7)	0.20464 (12)	0.0163 (2)
Na11	0.35448 (6)	0.37461 (7)	0.68522 (11)	0.0142 (2)
Na12	0.25	0.25	1.0196 (2)	0.0161 (4)
Na13	0.37149 (7)	0.38946 (7)	1.29937 (12)	0.0163 (2)
O1	0.48432 (12)	0.18355 (12)	0.50326 (18)	0.0144 (4)
O2	0.59709 (11)	0.26609 (11)	0.3582 (2)	0.0149 (3)
O3	0.48255 (12)	0.34608 (11)	0.50464 (18)	0.0140 (4)
O4	0.59943 (11)	0.26410 (11)	0.6435 (2)	0.0142 (3)
O5	0.54143 (12)	0.47531 (12)	0.7030 (2)	0.0166 (4)
O11	0.51614 (12)	0.18381 (12)	1.00036 (18)	0.0150 (4)
O12	0.40253 (11)	0.26427 (11)	1.1447 (2)	0.0149 (3)
O13	0.51716 (12)	0.34647 (12)	1.00146 (17)	0.0146 (4)
O14	0.40122 (11)	0.26533 (11)	0.8598 (2)	0.0140 (3)
O15	0.46047 (12)	0.47460 (12)	0.8003 (2)	0.0167 (4)
S1	0.54035 (4)	0.26441 (4)	0.50241 (6)	0.01007 (13)
S11	0.45972 (4)	0.26436 (4)	1.00141 (6)	0.01007 (13)
H5	0.527 (2)	0.440 (2)	0.628 (4)	0.032 (9)*
H15	0.477 (3)	0.443 (3)	0.881 (5)	0.055 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01358 (15)	0.01358 (15)	0.0153 (2)	0	0	0
Br11	0.01265 (14)	0.01265 (14)	0.0129 (2)	0	0	0
Na1	0.0153 (5)	0.0151 (5)	0.0134 (5)	−0.0012 (4)	0.0002 (4)	−0.0014 (4)
Na2	0.0133 (6)	0.0133 (6)	0.0223 (11)	0	0	0
Na3	0.0161 (5)	0.0160 (5)	0.0167 (5)	−0.0020 (4)	−0.0017 (4)	0.0030 (4)
Na11	0.0141 (5)	0.0144 (5)	0.0140 (5)	0.0002 (4)	0.0000 (4)	0.0022 (4)
Na12	0.0139 (6)	0.0139 (6)	0.0204 (10)	0	0	0
Na13	0.0164 (5)	0.0167 (5)	0.0158 (5)	0.0013 (4)	−0.0013 (4)	−0.0035 (4)
O1	0.0137 (8)	0.0151 (8)	0.0145 (9)	−0.0051 (6)	0.0018 (6)	0.0000 (6)
O2	0.0157 (8)	0.0147 (8)	0.0145 (8)	−0.0013 (7)	0.0036 (7)	0.0017 (7)
O3	0.0136 (8)	0.0131 (8)	0.0152 (9)	0.0041 (6)	−0.0009 (6)	−0.0008 (6)
O4	0.0158 (8)	0.0140 (8)	0.0130 (8)	0.0015 (7)	−0.0035 (7)	−0.0001 (6)
O5	0.0141 (8)	0.0181 (9)	0.0175 (9)	−0.0010 (7)	0.0032 (7)	−0.0009 (7)
O11	0.0144 (8)	0.0155 (8)	0.0151 (9)	0.0043 (6)	−0.0019 (6)	−0.0015 (6)
O12	0.0149 (8)	0.0164 (8)	0.0135 (8)	−0.0003 (7)	0.0020 (7)	−0.0016 (7)
O13	0.0152 (8)	0.0143 (8)	0.0142 (9)	−0.0034 (6)	−0.0016 (6)	0.0020 (6)
O14	0.0136 (8)	0.0151 (8)	0.0133 (8)	−0.0003 (6)	−0.0039 (6)	0.0008 (6)
O15	0.0150 (8)	0.0181 (9)	0.0169 (9)	0.0005 (7)	0.0028 (7)	0.0022 (7)
S1	0.0105 (2)	0.0102 (2)	0.0095 (3)	0.00005 (19)	−0.00022 (19)	−0.00019 (19)
S11	0.0101 (2)	0.0104 (2)	0.0097 (3)	−0.00001 (19)	−0.00067 (19)	−0.00026 (19)

Geometric parameters (Å, º) top

Br1—Na1ⁱ	2.8466 (10)	Na11—Na13^xii	3.2606 (15)
Br1—Na1ⁱⁱ	2.8466 (10)	Na11—Na11^ix	3.4294 (14)
Br1—Na1ⁱⁱⁱ	2.8466 (10)	Na11—Na11^x	3.4294 (14)
Br1—Na1	2.8466 (10)	Na11—Na3^xvi	3.6161 (14)
Br1—Na3^iv	3.2872 (10)	Na11—Na12	3.7121 (18)
Br1—Na3^v	3.2872 (10)	Na11—H15	2.66 (4)
Br1—Na3^vi	3.2872 (10)	Na12—O12	2.5147 (19)
Br1—Na3^vii	3.2872 (10)	Na12—O12^ix	2.5147 (19)
Br11—Na11	2.9424 (10)	Na12—O12^x	2.5147 (19)
Br11—Na11^viii	2.9424 (10)	Na12—O12^viii	2.5147 (19)
Br11—Na11^ix	2.9424 (10)	Na12—O14^viii	2.635 (2)
Br11—Na11^x	2.9424 (10)	Na12—O14^ix	2.635 (2)
Br11—Na13^xi	3.1770 (11)	Na12—O14^x	2.635 (2)
Br11—Na13^xii	3.1770 (11)	Na12—O14	2.635 (2)
Br11—Na13^xiii	3.1770 (11)	Na12—S11^viii	3.1385 (6)
Br11—Na13^xiv	3.1770 (11)	Na12—S11^ix	3.1385 (6)
Na1—O4	2.2993 (19)	Na12—S11^x	3.1385 (6)
Na1—O11ⁱ	2.3179 (19)	Na12—S11	3.1385 (6)
Na1—O2^vi	2.345 (2)	Na13—O12	2.322 (2)
Na1—O5	2.391 (2)	Na13—O1^xvii	2.3689 (19)
Na1—O13	2.516 (2)	Na13—O5^xv	2.399 (2)
Na1—Na3^v	3.2852 (15)	Na13—O12^x	2.414 (2)
Na1—Na2	3.5813 (10)	Na13—O3^v	2.4777 (19)
Na1—Na3^vi	3.6507 (14)	Na13—Br11^v	3.1770 (11)
Na1—Na13^xv	3.6798 (14)	Na13—Na11^v	3.2606 (15)
Na1—Na3^iv	3.7281 (14)	Na13—S11^x	3.3872 (11)
Na1—H5	2.59 (3)	Na13—S11	3.3888 (11)
Na2—O4^iv	2.5574 (17)	Na13—Na1^xv	3.6798 (14)
Na2—O4ⁱⁱⁱ	2.5574 (17)	Na13—Na3^v	3.8889 (15)
Na2—O4	2.5574 (17)	O1—S1	1.4670 (18)
Na2—O4^vi	2.5574 (17)	O1—Na11^ix	2.3103 (19)
Na2—O2	2.5842 (18)	O1—Na13^xiv	2.3689 (19)
Na2—O2^iv	2.5842 (18)	O2—S1	1.4786 (17)
Na2—O2^vi	2.5842 (18)	O2—Na1^iv	2.3452 (19)
Na2—O2ⁱⁱⁱ	2.5842 (18)	O3—S1	1.4921 (17)
Na2—S1^iv	3.1339 (6)	O3—Na13^xii	2.4777 (19)
Na2—S1	3.1339 (6)	O4—S1	1.4773 (17)
Na2—S1^vi	3.1339 (6)	O4—Na3^iv	2.4173 (19)
Na2—S1ⁱⁱⁱ	3.1339 (6)	O5—O15	1.458 (2)
Na3—O2	2.3178 (19)	O5—Na13^xv	2.399 (2)
Na3—O11^vi	2.3623 (19)	O5—H5	0.85 (3)
Na3—O15^xvi	2.380 (2)	O11—S11	1.4666 (18)
Na3—O4^vi	2.4173 (19)	O11—Na1ⁱⁱ	2.3179 (19)
Na3—O13^xii	2.458 (2)	O11—Na3^iv	2.3623 (19)
Na3—Na1^xii	3.2852 (15)	O12—S11	1.4755 (18)
Na3—Br1^xii	3.2872 (10)	O12—Na13^ix	2.414 (2)
Na3—S1^vi	3.3621 (11)	O13—S11	1.4945 (18)
Na3—Na11^xvi	3.6161 (14)	O13—Na3^v	2.458 (2)
Na3—Na1^iv	3.6507 (14)	O14—S11	1.4759 (17)
Na3—Na1^vi	3.7281 (14)	O14—Na11^ix	2.3457 (19)
Na11—O14	2.3009 (19)	O15—Na3^xvi	2.380 (2)
Na11—O1^x	2.3103 (19)	O15—H15	0.86 (4)
Na11—O14^x	2.3457 (19)	S1—Na3^iv	3.3621 (11)
Na11—O15	2.379 (2)	S11—Na13^ix	3.3872 (11)
Na11—O3	2.4764 (19)

Na1ⁱ—Br1—Na1ⁱⁱ	114.53 (4)	O1^x—Na11—O14^x	96.16 (7)
Na1ⁱ—Br1—Na1ⁱⁱⁱ	107.005 (19)	O14—Na11—O15	89.05 (7)
Na1ⁱⁱ—Br1—Na1ⁱⁱⁱ	107.005 (19)	O1^x—Na11—O15	89.33 (7)
Na1ⁱ—Br1—Na1	107.005 (19)	O14^x—Na11—O15	98.38 (7)
Na1ⁱⁱ—Br1—Na1	107.005 (19)	O14—Na11—O3	92.04 (7)
Na1ⁱⁱⁱ—Br1—Na1	114.53 (4)	O1^x—Na11—O3	84.56 (6)
Na1ⁱ—Br1—Na3^iv	178.43 (2)	O14^x—Na11—O3	179.08 (7)
Na1ⁱⁱ—Br1—Na3^iv	64.30 (3)	O15—Na11—O3	81.05 (6)
Na1ⁱⁱⁱ—Br1—Na3^iv	72.65 (3)	O14—Na11—Br11	94.26 (5)
Na1—Br1—Na3^iv	74.47 (3)	O1^x—Na11—Br11	86.69 (5)
Na1ⁱ—Br1—Na3^v	74.47 (3)	O14^x—Na11—Br11	93.31 (5)
Na1ⁱⁱ—Br1—Na3^v	72.65 (3)	O15—Na11—Br11	167.99 (6)
Na1ⁱⁱⁱ—Br1—Na3^v	178.43 (2)	O3—Na11—Br11	87.29 (5)
Na1—Br1—Na3^v	64.30 (3)	O14—Na11—Na13^xii	131.21 (6)
Na3^iv—Br1—Na3^v	105.890 (16)	O1^x—Na11—Na13^xii	46.57 (5)
Na1ⁱ—Br1—Na3^vi	64.30 (3)	O14^x—Na11—Na13^xii	132.06 (6)
Na1ⁱⁱ—Br1—Na3^vi	178.43 (3)	O15—Na11—Na13^xii	108.07 (6)
Na1ⁱⁱⁱ—Br1—Na3^vi	74.47 (3)	O3—Na11—Na13^xii	48.86 (4)
Na1—Br1—Na3^vi	72.65 (3)	Br11—Na11—Na13^xii	61.36 (3)
Na3^iv—Br1—Na3^vi	116.90 (3)	O14—Na11—Na11^ix	42.94 (5)
Na3^v—Br1—Na3^vi	105.890 (16)	O1^x—Na11—Na11^ix	136.63 (5)
Na1ⁱ—Br1—Na3^vii	72.65 (3)	O14^x—Na11—Na11^ix	103.60 (5)
Na1ⁱⁱ—Br1—Na3^vii	74.47 (3)	O15—Na11—Na11^ix	124.50 (6)
Na1ⁱⁱⁱ—Br1—Na3^vii	64.30 (3)	O3—Na11—Na11^ix	76.19 (5)
Na1—Br1—Na3^vii	178.43 (3)	Br11—Na11—Na11^ix	54.355 (10)
Na3^iv—Br1—Na3^vii	105.890 (16)	Na13^xii—Na11—Na11^ix	93.49 (2)
Na3^v—Br1—Na3^vii	116.90 (3)	O14—Na11—Na11^x	103.87 (5)
Na3^vi—Br1—Na3^vii	105.890 (16)	O1^x—Na11—Na11^x	79.48 (6)
Na11—Br11—Na11^viii	111.00 (4)	O14^x—Na11—Na11^x	41.93 (5)
Na11—Br11—Na11^ix	71.29 (2)	O15—Na11—Na11^x	135.80 (6)
Na11^viii—Br11—Na11^ix	71.29 (2)	O3—Na11—Na11^x	138.87 (4)
Na11—Br11—Na11^x	71.29 (2)	Br11—Na11—Na11^x	54.355 (10)
Na11^viii—Br11—Na11^x	71.29 (2)	Na13^xii—Na11—Na11^x	94.79 (2)
Na11^ix—Br11—Na11^x	111.00 (4)	Na11^ix—Na11—Na11^x	90
Na11—Br11—Na13^xi	175.17 (3)	O14—Na11—Na3^xvi	119.72 (6)
Na11^viii—Br11—Na13^xi	64.26 (3)	O1^x—Na11—Na3^xvi	60.40 (5)
Na11^ix—Br11—Na13^xi	107.13 (3)	O14^x—Na11—Na3^xvi	74.69 (5)
Na11^x—Br11—Na13^xi	105.52 (3)	O15—Na11—Na3^xvi	40.56 (5)
Na11—Br11—Na13^xii	64.26 (3)	O3—Na11—Na3^xvi	105.23 (5)
Na11^viii—Br11—Na13^xii	175.17 (3)	Br11—Na11—Na3^xvi	142.61 (4)
Na11^ix—Br11—Na13^xii	105.52 (3)	Na13^xii—Na11—Na3^xvi	100.55 (3)
Na11^x—Br11—Na13^xii	107.13 (3)	Na11^ix—Na11—Na3^xvi	162.38 (3)
Na13^xi—Br11—Na13^xii	120.49 (4)	Na11^x—Na11—Na3^xvi	99.30 (4)
Na11—Br11—Na13^xiii	105.52 (3)	O14—Na11—Na12	44.75 (5)
Na11^viii—Br11—Na13^xiii	107.13 (3)	O1^x—Na11—Na12	138.83 (6)
Na11^ix—Br11—Na13^xiii	175.17 (3)	O14^x—Na11—Na12	44.88 (5)
Na11^x—Br11—Na13^xiii	64.26 (3)	O15—Na11—Na12	106.55 (6)
Na13^xi—Br11—Na13^xiii	75.742 (17)	O3—Na11—Na12	134.57 (5)
Na13^xii—Br11—Na13^xiii	75.742 (17)	Br11—Na11—Na12	83.71 (3)
Na11—Br11—Na13^xiv	107.13 (3)	Na13^xii—Na11—Na12	145.06 (4)
Na11^viii—Br11—Na13^xiv	105.52 (3)	Na11^ix—Na11—Na12	62.489 (15)
Na11^ix—Br11—Na13^xiv	64.26 (3)	Na11^x—Na11—Na12	62.489 (15)
Na11^x—Br11—Na13^xiv	175.17 (3)	Na3^xvi—Na11—Na12	108.73 (3)
Na13^xi—Br11—Na13^xiv	75.742 (17)	O14—Na11—H15	70.7 (9)
Na13^xii—Br11—Na13^xiv	75.742 (17)	O1^x—Na11—H15	107.8 (9)
Na13^xiii—Br11—Na13^xiv	120.49 (4)	O14^x—Na11—H15	94.2 (8)
O4—Na1—O11ⁱ	175.40 (8)	O15—Na11—H15	18.6 (9)
O4—Na1—O2^vi	88.27 (7)	O3—Na11—H15	85.1 (8)
O11ⁱ—Na1—O2^vi	96.00 (7)	Br11—Na11—H15	162.8 (8)
O4—Na1—O5	89.57 (7)	Na13^xii—Na11—H15	122.3 (9)
O11ⁱ—Na1—O5	88.20 (7)	Na11^ix—Na11—H15	108.8 (8)
O2^vi—Na1—O5	97.37 (7)	Na11^x—Na11—H15	135.9 (8)
O4—Na1—O13	92.23 (7)	Na3^xvi—Na11—H15	54.5 (8)
O11ⁱ—Na1—O13	83.45 (6)	Na12—Na11—H15	90.7 (9)
O2^vi—Na1—O13	178.06 (7)	O12—Na12—O12^ix	79.94 (4)
O5—Na1—O13	80.76 (6)	O12—Na12—O12^x	79.94 (4)
O4—Na1—Br1	92.96 (5)	O12^ix—Na12—O12^x	130.59 (11)
O11ⁱ—Na1—Br1	88.53 (5)	O12—Na12—O12^viii	130.59 (11)
O2^vi—Na1—Br1	93.08 (5)	O12^ix—Na12—O12^viii	79.94 (4)
O5—Na1—Br1	169.32 (6)	O12^x—Na12—O12^viii	79.94 (4)
O13—Na1—Br1	88.77 (5)	O12—Na12—O14^viii	174.04 (9)
O4—Na1—Na3^v	131.23 (6)	O12^ix—Na12—O14^viii	101.95 (5)
O11ⁱ—Na1—Na3^v	45.97 (5)	O12^x—Na12—O14^viii	102.66 (5)
O2^vi—Na1—Na3^v	132.62 (6)	O12^viii—Na12—O14^viii	55.36 (6)
O5—Na1—Na3^v	106.42 (6)	O12—Na12—O14^ix	101.95 (5)
O13—Na1—Na3^v	47.91 (4)	O12^ix—Na12—O14^ix	55.36 (6)
Br1—Na1—Na3^v	64.37 (3)	O12^x—Na12—O14^ix	174.04 (9)
O4—Na1—Na2	45.36 (5)	O12^viii—Na12—O14^ix	102.66 (5)
O11ⁱ—Na1—Na2	139.23 (6)	O14^viii—Na12—O14^ix	74.93 (5)
O2^vi—Na1—Na2	46.10 (5)	O12—Na12—O14^x	102.66 (5)
O5—Na1—Na2	108.15 (6)	O12^ix—Na12—O14^x	174.04 (9)
O13—Na1—Na2	134.96 (5)	O12^x—Na12—O14^x	55.36 (6)
Br1—Na1—Na2	80.78 (2)	O12^viii—Na12—O14^x	101.95 (5)
Na3^v—Na1—Na2	145.13 (4)	O14^viii—Na12—O14^x	74.93 (5)
O4—Na1—Na3^vi	106.14 (5)	O14^ix—Na12—O14^x	118.69 (11)
O11ⁱ—Na1—Na3^vi	78.35 (5)	O12—Na12—O14	55.36 (6)
O2^vi—Na1—Na3^vi	38.21 (5)	O12^ix—Na12—O14	102.66 (5)
O5—Na1—Na3^vi	129.76 (6)	O12^x—Na12—O14	101.95 (5)
O13—Na1—Na3^vi	143.17 (5)	O12^viii—Na12—O14	174.04 (9)
Br1—Na1—Na3^vi	59.25 (2)	O14^viii—Na12—O14	118.69 (11)
Na3^v—Na1—Na3^vi	98.17 (3)	O14^ix—Na12—O14	74.93 (5)
Na2—Na1—Na3^vi	62.33 (2)	O14^x—Na12—O14	74.93 (5)
O4—Na1—Na13^xv	119.30 (6)	O12—Na12—S11^viii	158.04 (9)
O11ⁱ—Na1—Na13^xv	60.70 (5)	O12^ix—Na12—S11^viii	92.46 (4)
O2^vi—Na1—Na13^xv	73.16 (5)	O12^x—Na12—S11^viii	89.87 (4)
O5—Na1—Na13^xv	39.87 (5)	O12^viii—Na12—S11^viii	27.54 (4)
O13—Na1—Na13^xv	104.98 (5)	O14^viii—Na12—S11^viii	27.92 (4)
Br1—Na1—Na13^xv	143.67 (4)	O14^ix—Na12—S11^viii	90.19 (4)
Na3^v—Na1—Na13^xv	100.15 (3)	O14^x—Na12—S11^viii	86.97 (4)
Na2—Na1—Na13^xv	109.20 (3)	O14—Na12—S11^viii	146.50 (8)
Na3^vi—Na1—Na13^xv	93.61 (3)	O12—Na12—S11^ix	92.46 (4)
O4—Na1—Na3^iv	38.90 (5)	O12^ix—Na12—S11^ix	27.54 (4)
O11ⁱ—Na1—Na3^iv	140.36 (6)	O12^x—Na12—S11^ix	158.04 (9)
O2^vi—Na1—Na3^iv	105.83 (5)	O12^viii—Na12—S11^ix	89.87 (4)
O5—Na1—Na3^iv	120.34 (6)	O14^viii—Na12—S11^ix	86.97 (4)
O13—Na1—Na3^iv	75.67 (5)	O14^ix—Na12—S11^ix	27.92 (4)
Br1—Na1—Na3^iv	58.16 (2)	O14^x—Na12—S11^ix	146.50 (8)
Na3^v—Na1—Na3^iv	96.65 (3)	O14—Na12—S11^ix	90.19 (4)
Na2—Na1—Na3^iv	61.57 (2)	S11^viii—Na12—S11^ix	89.864 (4)
Na3^vi—Na1—Na3^iv	98.80 (3)	O12—Na12—S11^x	89.87 (4)
Na13^xv—Na1—Na3^iv	157.45 (4)	O12^ix—Na12—S11^x	158.04 (9)
O4—Na1—H5	70.6 (7)	O12^x—Na12—S11^x	27.54 (4)
O11ⁱ—Na1—H5	107.3 (8)	O12^viii—Na12—S11^x	92.46 (4)
O2^vi—Na1—H5	94.0 (7)	O14^viii—Na12—S11^x	90.19 (4)
O5—Na1—H5	19.2 (7)	O14^ix—Na12—S11^x	146.50 (8)
O13—Na1—H5	84.4 (7)	O14^x—Na12—S11^x	27.92 (4)
Br1—Na1—H5	161.8 (7)	O14—Na12—S11^x	86.97 (4)
Na3^v—Na1—H5	120.7 (7)	S11^viii—Na12—S11^x	89.864 (4)
Na2—Na1—H5	92.2 (7)	S11^ix—Na12—S11^x	174.41 (7)
Na3^vi—Na1—H5	131.5 (7)	O12—Na12—S11	27.54 (4)
Na13^xv—Na1—H5	54.5 (7)	O12^ix—Na12—S11	89.87 (4)
Na3^iv—Na1—H5	103.8 (7)	O12^x—Na12—S11	92.46 (4)
O4^iv—Na2—O4ⁱⁱⁱ	102.85 (3)	O12^viii—Na12—S11	158.04 (9)
O4^iv—Na2—O4	102.85 (3)	O14^viii—Na12—S11	146.50 (8)
O4ⁱⁱⁱ—Na2—O4	123.73 (7)	O14^ix—Na12—S11	86.97 (4)
O4^iv—Na2—O4^vi	123.73 (7)	O14^x—Na12—S11	90.19 (4)
O4ⁱⁱⁱ—Na2—O4^vi	102.85 (3)	O14—Na12—S11	27.92 (4)
O4—Na2—O4^vi	102.85 (3)	S11^viii—Na12—S11	174.41 (7)
O4^iv—Na2—O2	77.96 (5)	S11^ix—Na12—S11	89.864 (4)
O4ⁱⁱⁱ—Na2—O2	179.11 (5)	S11^x—Na12—S11	89.864 (4)
O4—Na2—O2	55.61 (6)	O12—Na13—O1^xvii	162.63 (8)
O4^vi—Na2—O2	76.91 (5)	O12—Na13—O5^xv	124.29 (7)
O4^iv—Na2—O2^iv	55.61 (6)	O1^xvii—Na13—O5^xv	72.03 (7)
O4ⁱⁱⁱ—Na2—O2^iv	77.96 (5)	O12—Na13—O12^x	86.01 (9)
O4—Na2—O2^iv	76.91 (5)	O1^xvii—Na13—O12^x	92.92 (7)
O4^vi—Na2—O2^iv	179.11 (5)	O5^xv—Na13—O12^x	112.44 (7)
O2—Na2—O2^iv	102.28 (3)	O12—Na13—O3^v	92.68 (7)
O4^iv—Na2—O2^vi	179.11 (5)	O1^xvii—Na13—O3^v	83.32 (6)
O4ⁱⁱⁱ—Na2—O2^vi	76.91 (5)	O5^xv—Na13—O3^v	82.15 (7)
O4—Na2—O2^vi	77.96 (5)	O12^x—Na13—O3^v	163.10 (7)
O4^vi—Na2—O2^vi	55.61 (6)	O12—Na13—Br11^v	82.26 (5)
O2—Na2—O2^vi	102.28 (3)	O1^xvii—Na13—Br11^v	80.46 (5)
O2^iv—Na2—O2^vi	125.06 (7)	O5^xv—Na13—Br11^v	149.68 (6)
O4^iv—Na2—O2ⁱⁱⁱ	76.91 (5)	O12^x—Na13—Br11^v	80.91 (5)
O4ⁱⁱⁱ—Na2—O2ⁱⁱⁱ	55.61 (6)	O3^v—Na13—Br11^v	82.22 (5)
O4—Na2—O2ⁱⁱⁱ	179.11 (5)	O12—Na13—Na11^v	121.20 (6)
O4^vi—Na2—O2ⁱⁱⁱ	77.96 (5)	O1^xvii—Na13—Na11^v	45.09 (5)
O2—Na2—O2ⁱⁱⁱ	125.06 (7)	O5^xv—Na13—Na11^v	96.17 (6)
O2^iv—Na2—O2ⁱⁱⁱ	102.28 (3)	O12^x—Na13—Na11^v	118.43 (6)
O2^vi—Na2—O2ⁱⁱⁱ	102.28 (3)	O3^v—Na13—Na11^v	48.82 (4)
O4^iv—Na2—S1^iv	27.80 (4)	Br11^v—Na13—Na11^v	54.38 (2)
O4ⁱⁱⁱ—Na2—S1^iv	88.92 (4)	O12—Na13—S11^x	87.36 (5)
O4—Na2—S1^iv	91.42 (4)	O1^xvii—Na13—S11^x	98.22 (5)
O4^vi—Na2—S1^iv	151.46 (4)	O5^xv—Na13—S11^x	93.30 (5)
O2—Na2—S1^iv	91.67 (4)	O12^x—Na13—S11^x	22.36 (4)
O2^iv—Na2—S1^iv	27.91 (4)	O3^v—Na13—S11^x	174.52 (6)
O2^vi—Na2—S1^iv	152.83 (4)	Br11^v—Na13—S11^x	103.20 (3)
O2ⁱⁱⁱ—Na2—S1^iv	87.99 (4)	Na11^v—Na13—S11^x	135.23 (4)
O4^iv—Na2—S1	88.92 (4)	O12—Na13—S11	20.93 (4)
O4ⁱⁱⁱ—Na2—S1	151.46 (4)	O1^xvii—Na13—S11	176.30 (6)
O4—Na2—S1	27.80 (4)	O5^xv—Na13—S11	104.27 (6)
O4^vi—Na2—S1	91.42 (4)	O12^x—Na13—S11	88.39 (5)
O2—Na2—S1	27.91 (4)	O3^v—Na13—S11	96.39 (5)
O2^iv—Na2—S1	87.99 (4)	Br11^v—Na13—S11	103.17 (3)
O2^vi—Na2—S1	91.67 (4)	Na11^v—Na13—S11	136.71 (4)
O2ⁱⁱⁱ—Na2—S1	152.83 (4)	S11^x—Na13—S11	81.73 (3)
S1^iv—Na2—S1	90	O12—Na13—Na12	43.52 (5)
O4^iv—Na2—S1^vi	151.46 (4)	O1^xvii—Na13—Na12	129.70 (6)
O4ⁱⁱⁱ—Na2—S1^vi	91.42 (4)	O5^xv—Na13—Na12	138.38 (6)
O4—Na2—S1^vi	88.92 (4)	O12^x—Na13—Na12	43.75 (4)
O4^vi—Na2—S1^vi	27.80 (4)	O3^v—Na13—Na12	129.50 (5)
O2—Na2—S1^vi	87.99 (4)	Br11^v—Na13—Na12	70.20 (3)
O2^iv—Na2—S1^vi	152.83 (4)	Na11^v—Na13—Na12	124.57 (4)
O2^vi—Na2—S1^vi	27.91 (4)	S11^x—Na13—Na12	53.05 (2)
O2ⁱⁱⁱ—Na2—S1^vi	91.67 (4)	S11—Na13—Na12	53.04 (2)
S1^iv—Na2—S1^vi	179.259 (19)	O12—Na13—Na1^xv	129.74 (6)
S1—Na2—S1^vi	90	O1^xvii—Na13—Na1^xv	65.91 (5)
O4^iv—Na2—S1ⁱⁱⁱ	91.42 (4)	O5^xv—Na13—Na1^xv	39.72 (5)
O4ⁱⁱⁱ—Na2—S1ⁱⁱⁱ	27.80 (4)	O12^x—Na13—Na1^xv	73.49 (5)
O4—Na2—S1ⁱⁱⁱ	151.46 (4)	O3^v—Na13—Na1^xv	119.11 (5)
O4^vi—Na2—S1ⁱⁱⁱ	88.92 (4)	Br11^v—Na13—Na1^xv	135.86 (3)
O2—Na2—S1ⁱⁱⁱ	152.83 (4)	Na11^v—Na13—Na1^xv	108.87 (3)
O2^iv—Na2—S1ⁱⁱⁱ	91.67 (4)	S11^x—Na13—Na1^xv	57.39 (2)
O2^vi—Na2—S1ⁱⁱⁱ	87.99 (4)	S11—Na13—Na1^xv	111.25 (3)
O2ⁱⁱⁱ—Na2—S1ⁱⁱⁱ	27.91 (4)	Na12—Na13—Na1^xv	109.96 (3)
S1^iv—Na2—S1ⁱⁱⁱ	90	O12—Na13—Na3^v	72.38 (5)
S1—Na2—S1ⁱⁱⁱ	179.259 (19)	O1^xvii—Na13—Na3^v	118.82 (6)
S1^vi—Na2—S1ⁱⁱⁱ	90	O5^xv—Na13—Na3^v	57.39 (5)
O2—Na3—O11^vi	160.90 (8)	O12^x—Na13—Na3^v	135.22 (6)
O2—Na3—O15^xvi	125.63 (8)	O3^v—Na13—Na3^v	59.37 (5)
O11^vi—Na3—O15^xvi	72.37 (7)	Br11^v—Na13—Na3^v	131.72 (3)
O2—Na3—O4^vi	84.93 (7)	Na11^v—Na13—Na3^v	106.28 (3)
O11^vi—Na3—O4^vi	92.76 (7)	S11^x—Na13—Na3^v	115.55 (3)
O15^xvi—Na3—O4^vi	115.25 (7)	S11—Na13—Na3^v	58.23 (2)
O2—Na3—O13^xii	92.18 (7)	Na12—Na13—Na3^v	111.19 (3)
O11^vi—Na3—O13^xii	83.83 (6)	Na1^xv—Na13—Na3^v	90.66 (3)
O15^xvi—Na3—O13^xii	81.64 (7)	S1—O1—Na11^ix	127.47 (10)
O4^vi—Na3—O13^xii	160.94 (7)	S1—O1—Na13^xiv	128.41 (9)
O2—Na3—Na1^xii	120.18 (6)	Na11^ix—O1—Na13^xiv	88.34 (7)
O11^vi—Na3—Na1^xii	44.87 (5)	S1—O2—Na3	125.40 (10)
O15^xvi—Na3—Na1^xii	95.93 (6)	S1—O2—Na1^iv	127.52 (10)
O4^vi—Na3—Na1^xii	116.72 (6)	Na3—O2—Na1^iv	103.05 (7)
O13^xii—Na3—Na1^xii	49.43 (4)	S1—O2—Na2	97.20 (9)
O2—Na3—Br1^xii	83.00 (5)	Na3—O2—Na2	99.42 (6)
O11^vi—Na3—Br1^xii	77.92 (5)	Na1^iv—O2—Na2	93.06 (6)
O15^xvi—Na3—Br1^xii	146.60 (6)	S1—O3—Na11	126.40 (10)
O4^vi—Na3—Br1^xii	80.64 (5)	S1—O3—Na13^xii	126.19 (9)
O13^xii—Na3—Br1^xii	80.31 (5)	Na11—O3—Na13^xii	82.32 (6)
Na1^xii—Na3—Br1^xii	51.33 (2)	S1—O4—Na1	133.74 (10)
O2—Na3—S1^vi	87.26 (5)	S1—O4—Na3^iv	117.32 (9)
O11^vi—Na3—S1^vi	97.99 (5)	Na1—O4—Na3^iv	104.42 (7)
O15^xvi—Na3—S1^vi	95.40 (6)	S1—O4—Na2	98.36 (9)
O4^vi—Na3—S1^vi	22.98 (4)	Na1—O4—Na2	94.87 (6)
O13^xii—Na3—S1^vi	175.93 (6)	Na3^iv—O4—Na2	97.56 (6)
Na1^xii—Na3—S1^vi	134.02 (4)	O15—O5—Na1	108.50 (12)
Br1^xii—Na3—S1^vi	103.62 (3)	O15—O5—Na13^xv	117.32 (13)
O2—Na3—Na11^xvi	130.63 (6)	Na1—O5—Na13^xv	100.41 (7)
O11^vi—Na3—Na11^xvi	66.33 (5)	O15—O5—H5	101 (2)
O15^xvi—Na3—Na11^xvi	40.53 (5)	Na1—O5—H5	94 (2)
O4^vi—Na3—Na11^xvi	75.32 (5)	Na13^xv—O5—H5	131 (2)
O13^xii—Na3—Na11^xvi	119.60 (6)	S11—O11—Na1ⁱⁱ	126.62 (10)
Na1^xii—Na3—Na11^xvi	109.10 (3)	S11—O11—Na3^iv	129.28 (10)
Br1^xii—Na3—Na11^xvi	135.25 (3)	Na1ⁱⁱ—O11—Na3^iv	89.16 (7)
S1^vi—Na3—Na11^xvi	58.33 (2)	S11—O12—Na13	124.86 (10)
O2—Na3—Na1^iv	38.74 (5)	S11—O12—Na13^ix	119.14 (10)
O11^vi—Na3—Na1^iv	123.02 (6)	Na13—O12—Na13^ix	110.89 (9)
O15^xvi—Na3—Na1^iv	146.64 (6)	S11—O12—Na12	100.48 (10)
O4^vi—Na3—Na1^iv	94.64 (5)	Na13—O12—Na12	96.99 (7)
O13^xii—Na3—Na1^iv	72.00 (5)	Na13^ix—O12—Na12	94.66 (7)
Na1^xii—Na3—Na1^iv	82.40 (3)	S11—O13—Na3^v	127.32 (9)
Br1^xii—Na3—Na1^iv	48.10 (2)	S11—O13—Na1	124.91 (10)
S1^vi—Na3—Na1^iv	109.71 (3)	Na3^v—O13—Na1	82.66 (6)
Na11^xvi—Na3—Na1^iv	167.18 (4)	S11—O14—Na11	134.46 (10)
O2—Na3—Na1^vi	95.11 (5)	S11—O14—Na11^ix	126.65 (10)
O11^vi—Na3—Na1^vi	72.53 (5)	Na11—O14—Na11^ix	95.13 (8)
O15^xvi—Na3—Na1^vi	131.97 (6)	S11—O14—Na12	95.38 (9)
O4^vi—Na3—Na1^vi	36.68 (4)	Na11—O14—Na12	97.31 (7)
O13^xii—Na3—Na1^vi	125.41 (6)	Na11^ix—O14—Na12	96.20 (7)
Na1^xii—Na3—Na1^vi	81.21 (3)	O5—O15—Na11	109.07 (13)
Br1^xii—Na3—Na1^vi	47.37 (2)	O5—O15—Na3^xvi	115.88 (13)
S1^vi—Na3—Na1^vi	58.67 (2)	Na11—O15—Na3^xvi	98.91 (7)
Na11^xvi—Na3—Na1^vi	94.94 (3)	O5—O15—H15	102 (3)
Na1^iv—Na3—Na1^vi	80.93 (3)	Na11—O15—H15	100 (3)
O2—Na3—Na2	42.93 (5)	Na3^xvi—O15—H15	129 (3)
O11^vi—Na3—Na2	129.43 (6)	O1—S1—O4	109.46 (10)
O15^xvi—Na3—Na2	138.83 (6)	O1—S1—O2	110.11 (10)
O4^vi—Na3—Na2	42.63 (4)	O4—S1—O2	108.47 (11)
O13^xii—Na3—Na2	129.21 (5)	O1—S1—O3	109.99 (11)
Na1^xii—Na3—Na2	124.42 (3)	O4—S1—O3	109.69 (9)
Br1^xii—Na3—Na2	73.10 (2)	O2—S1—O3	109.09 (10)
S1^vi—Na3—Na2	52.009 (17)	O11—S11—O12	109.62 (10)
Na11^xvi—Na3—Na2	109.65 (3)	O11—S11—O14	110.02 (10)
Na1^iv—Na3—Na2	57.93 (2)	O12—S11—O14	108.45 (11)
Na1^vi—Na3—Na2	57.29 (2)	O11—S11—O13	110.01 (11)
O14—Na11—O1^x	176.42 (8)	O12—S11—O13	109.38 (10)
O14—Na11—O14^x	87.23 (9)	O14—S11—O13	109.33 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.86 (3)	1.85 (3)	2.695 (2)	166 (3)
O15—H15···O13	0.86 (4)	1.86 (4)	2.688 (2)	161 (4)

Experimental details

	(kc)	(rgp29c)
Crystal data
Chemical formula	H₄ClNa₉O₂₀S₄	H₄BrNa₉O₂₀S₄
M_r	694.63	739.09
Crystal system, space group	Tetragonal, P4/n	Tetragonal, P4/n
Temperature (K)	150	150
a, c (Å)	29.6829 (3), 8.4018 (1)	14.9126 (5), 8.4052 (2)
V (Å³)	7402.61 (14)	1869.20 (10)
Z	16	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.97	2.96
Crystal size (mm)	0.1 × 0.1 × 0.05	0.18 × 0.18 × 0.07

Data collection
Diffractometer	KappaCCD diffractometer	KappaCCD diffractometer
Absorption correction	Multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	Multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]
T_min, T_max	0.909, 0.953	0.618, 0.820
No. of measured, independent and observed [I > 2σ(I)] reflections	65291, 8402, 4855	8459, 3226, 2368
R_int	0.090	0.049
(sin θ/λ)_max (Å⁻¹)	0.649	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.147, 1.24	0.040, 0.093, 1.07
No. of reflections	8402	3226
No. of parameters	649	164
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0244P)² + 19.2938P] where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0204P)² + 1.5967P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.53	0.59, −0.64

Computer programs: Collect (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SIR92 (Giacovazzo et al., 1993), SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) for (kc) top

D—H···A	D—H	H···A	D···A	D—H···A
O33—H33···O10ⁱ	1.00 (6)	1.70 (6)	2.675 (4)	164 (5)
O34—H34···O14ⁱⁱ	0.97 (6)	1.81 (6)	2.706 (4)	152 (5)
O35—H35···O3	0.85 (4)	1.83 (4)	2.677 (4)	169 (4)
O36—H36···O5	0.82 (5)	1.92 (5)	2.711 (4)	162 (5)
O37—H37···O17	0.95 (6)	1.77 (6)	2.700 (4)	167 (5)
O38—H38···O21	0.98 (7)	1.71 (6)	2.677 (4)	171 (6)
O39—H39···O26ⁱⁱⁱ	0.89 (5)	1.84 (5)	2.696 (4)	159 (5)
O40—H40···O30^iv	1.02 (7)	1.71 (6)	2.687 (4)	158 (6)

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

Hydrogen-bond geometry (Å, º) for (rgp29c) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.86 (3)	1.85 (3)	2.695 (2)	166 (3)
O15—H15···O13	0.86 (4)	1.86 (4)	2.688 (2)	161 (4)

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: DE5022 ). Services for accessing these data are described at the back of the journal.

²Determined using neutrons.

Acknowledgements

We would like to thank the EPSRC for purchasing the Nonius Kappa CCD diffractometer.

References

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Volume 61| Part 6| December 2005| Pages 663-668

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