Crystal structure of sodium thio­sulfate dihydrate and comparison to the penta­hydrate

Na₂S₂O₃·2H₂O has been known for more than a hundred years but no structural data were known to date. Now, crystals of this compound have been grown at the surface of an aqueous solution of Na₂S₂O₃. The sodium cations are five- to seven-coordinate by thio­sulfate anions and water mol­ecules with the anions acting as mono- and bidentate ligands. The thio­sulfate anions and water mol­ecules are connected by O—H⋯O and O—H⋯S hydrogen bonds of medium strength to form corrugated layers, which are linked by sodium cations.

Abstract

Na₂S₂O₃·2H₂O has been mentioned in the literature for more than a hundred years and pure samples were prepared and investigated, however, no structural data except for a set of lattice parameters were known to date. Now crystals of this compound have been grown at the surface of an aqueous solution of Na₂S₂O₃ and the structure has been determined at 200 and 100 K. Na₂S₂O₃·2H₂O crystallizes in the space group P2₁/n with two formula units in the asymmetric unit and all atoms occupying general positions. The sodium cations are five- to seven-coordinate by thio­sulfate anions and water mol­ecules and the anions act as mono- and bidentate ligands. In the extended structure, the thio­sulfate anions and water mol­ecules are connected by O—H⋯O and O—H⋯S hydrogen bonds of medium strength to form corrugated layers, which are linked by sodium cations. For comparison, the crystal structure of Na₂S₂O₃·5H₂O has been determined at the same conditions, i.e. for the first time below room temperature.

1. Chemical context

Thio­sulfates containing the S₂O₃ ^2– anion have been studied for more than 150 years (Bunte, 1874 ▸). Nowadays, Na₂S₂O₃ and (NH₄)₂S₂O₃ are produced on an industrial scale (Barberá et al., 2012 ▸), and the applications of thio­sulfates are growing (Kumar Paul et al., 2009 ▸). One of the most characteristic features of the thio­sulfate anion is the enhanced reactivity including changes of the sulfur oxidation state, which hampered the preparation of pure compounds. For example, the synthesis of pure thio­sulfuric acid succeeded just lately via the reaction of Na₂S₂O₃ and anhydrous HF (Hopfinger et al., 2018 ▸), and the first pure thio­sulfate complexes of lanthanides were characterized very recently (Dalton et al., 2021 ▸).

The reactivity also might hinder the preparation of pure anhydrous compounds suitable for structural investigation, and thus, only a few anhydrous thio­sulfate structures are known so far: Na₂S₂O₃ (Sándor & Csordás, 1961 ▸; Teng et al., 1984 ▸), K₂S₂O₃ (Lehner et al., 2013 ▸) and PbS₂O₃ (Christensen et al., 1991 ▸). In contrast, numerous hydrates of thio­sulfate compounds have been structurally characterized, and in some classes such as the alkaline-earth metal thio­sulfates, some water mol­ecules of crystallization seem to be crucial for the formation of crystalline matter, indicated by the so far exclusive appearance of hydrated structures AES₂O₃·nH₂O with AE = Mg (n = 6: Elerman et al., 1983 ▸), Ca (n = 6: Held & Bohatý, 2004 ▸), Sr (n = 5: Held & Bohatý, 2004 ▸; n = 1: Klein, 2020 ▸), and Ba (n = 1: Manojlović-Muir, 1975 ▸).

The nature of the hydrates in the Na₂S₂O₃ system was intensively studied by Young & Burke (1906 ▸) and by Picon (1924 ▸), who identified either twelve or even fourteen different crystalline hydrates of Na₂S₂O₃, respectively, among them two different dihydrates, by means of their crystalline appearance and by thio­sulfate analysis. The penta­hydrate is by far the most stable compound at ambient conditions, and all other hydrates were found to convert into this phase more or less rapidly. Extended studies of its full dehydration including thermal analyses, Raman spectroscopy and optical microscopy revealed the dihydrate as an inter­mediate phase (Nirsha et al., 1982 ▸; Edwards & Woolf, 1985 ▸; Guarini & Piccini, 1988 ▸). Finally, Edwards and Woolf (1985 ▸) synthesized dihydrate samples with an analytical water content of 1.999 eq. via shaking the penta­hydrate in MeOH at room temperature and presented lattice parameters for a monoclinic cell (a = 11.431, b = 4.452, c = 20.368 Å, b = 93.79°, V = 1034.4 ų), but no further structural information was given. A different, but unindexed XRD powder pattern was reported for a sample without given composition, which was prepared through dehydration of the penta­hydrate between 338 and 378 K (Nirsha et al., 1982 ▸). Besides these results, the large amount of defined hydrates of Na₂S₂O₃, as implied by the early works, is supported by the structure determinations on single crystals of Na₂S₂O₃·2/3H₂O (Hesse et al., 1993 ▸), Na₂S₂O₃·5/4H₂O (Chan et al., 2008 ▸) and Na₂S₂O₃·5H₂O (Taylor & Beevers, 1952 ▸; Padmanabhan et al., 1971 ▸; Uraz & Armaǧan, 1977 ▸; Lisensky & Levy, 1978 ▸; Prasad & Rani, 2001 ▸). Nevertheless, despite the evidence for its existence, for the dihydrate no structure information is available to date.

For the present paper, the crystal structure of the dihydrate was characterized at 100 and 200 K. For comparison, the structure of the penta­hydrate was determined at the same conditions, i.e., for the first time below ambient temperature.

2. Structural commentary

The crystal structure of the dihydrate of Na₂S₂O₃ has been determined for the first time. Although this phase has been mentioned in the respective literature for many decades and some sophisticated experiments to synthesize pure samples, usually via controlled dehydration of the penta­hydrate, are described, no structural information besides a set of monoclinic lattice parameters is known to date. In the present case, the dihydrate was formed by crystallization at room temperature at the surface of a concentrated aqueous solution, and all dihydrate crystals that have been identified by indexing were isolated from this region. After disturbing the surface tension, most of these crystals subsided immediately to the bottom of the vessel, adding to the bulky crystalline precipitate, which has been identified from X-ray powder patterns as the penta­hydrate without visible impurities. After indexing at room temperature, the crystals were cooled down and datasets were recorded at 200 K and 100 K. Besides slight thermal contraction of lattice parameters and a decrease of displacement parameters (see Fig. 1 ▸ a), no structural change has been observed down to 100 K. The same is true for the crystal structure of the penta­hydrate, Na₂S₂O₃·5H₂O (Fig. 1 ▸ b), which has been published formerly and is not discussed here in detail, but was used for comparison. All values mentioned in the structure description below are taken from the structure determinations at 100 K.

Figure 1.

The asymmetric units (a) of Na₂S₂O₃·2 H₂O, and (b) of Na₂S₂O₃·5 H₂O, with a comparison of relative positions and displacement ellipsoids of the non-hydrogen atoms obtained from structure determinations at 100 K (filled atoms) and at 200 K (contours of ellipsoids drawn around filled atoms). Ellipsoids are drawn at the 80% probability level, hydrogen bonds as dashed lines.

Na₂S₂O₃·2H₂O (Fig. 2 ▸) crystallizes in space group P2₁/n with two formula units in the asymmetric unit and all atoms (4 Na, 4 S, 10 O, and 8 H) lying on general positions. The two independent thio­sulfate anions adopt slightly distorted tetra­hedral shapes with average O—S—O angles (110.30°) above and S—S—O angles (108.63°) below the mean bond angle of 109.46°. The S—S bond lengths of 2.0047 (2) Å and 2.0078 (2) Å are similar to that found in the penta­hydrate [2.0266 (1) Å], and, thus, are shorter than the single bond of 2.055 Å in crystalline S₈ (Rettig & Trotter, 1987 ▸), but substanti­ally longer than the double bond of 1.883 Å in S₂O (Tiemann et al., 1974 ▸) or 1.889 Å in S₂ (Pyykkö & Atsumi, 2009 ▸). Also, the S—O bond lengths, which lie between 1.4722 (4) and 1.4841 (4) Å are in the same range as those of the penta­hydrate [1.4665 (4)–1.4867 (4) Å]. The bond-valence sums (Brown & Altermatt, 1985 ▸) for the central sulfur atoms, as calculated with the parameters of Brese & O’Keeffe (1991 ▸), are 5.87 and 5.88 valence units (v.u.) for S1 and S3, respectively, and are in good agreement with a formal charge of +VI as well as with the value of 5.86 v.u. obtained for the corres­ponding S atom in the penta­hydrate. The anions coordinate to the Na⁺ cations and form hydrogen bonds with the water mol­ecules of crystallization: in detail the terminal S and O atoms are surrounded by one Na⁺ and one H₂O (O1, O4, O6), two Na⁺ and one H₂O (O2, O3), three Na⁺ (O5), three Na⁺ and two H₂O (S2), or four Na⁺ and one H₂O (S4).

Figure 2.

Crystal structure of Na₂S₂O₃·2H₂O: (a) extended unit cell, view along [ 00]; (b) section of two layers of S₂O₃ ²⁻ anions and H₂O mol­ecules connected by hydrogen bonds, view along [ 01], differently coloured tetra­hedra belong to different layers. Anisotropic displacement ellipsoids of non-H atoms are drawn with 80% probability, S₂O₃ ²⁻ ions as tetra­hedra, and hydrogen bonds as dashed lines.

The four independent Na⁺ cations are coordinated irregularly by the S₂O₃ ²⁻ dianions in mono- or bidentate manner and by H₂O, as illustrated in Fig. 3 ▸ a–d. The shortest Na—O distances are in the range between 2.3169 (5) Å and 2.4884 (4) Å, with Na—S between 2.9296 (3) and 2.9695 Å. If these environments are considered exclusively, the resulting coordination polyhedra can be inter­preted as an octa­hedron for Na3, mainly distorted due to two S₂O₃ ^2– ions coordinating as bidentate ligands, a trigonal prism with one missing corner for Na2 or an octa­hedron with one (Na1) or two (Na4) missing corners. This construction starting from six-vertex polyhedra seems to be justified due to the clearly favoured sixfold coordination for Na⁺ in an environment of oxygen atoms (Gagné & Hawthorne, 2016 ▸). However, for the latter cases of open octa­hedra, S₂O₃ ^2– ions as additional ligands with longer bond distances of about 2.5 Å for Na—O and 3.2 Å for Na—S are found, resulting in seven-coordinate polyhedra around Na1 and Na4. For Na2, the H₂O mol­ecule located above the open side of the polyhedron can be excluded from the coord­ination sphere due to the too large Na—O distance of 3.52 Å and the orientation of the H atoms. The bond-valence sums for the Na cations are 1.08, 1.05, 1.15, and 1.06 v.u. with the highest value for the most conventionally coordinated Na3 ion while reduced values indicate weaker bonds in the coordination spheres of Na1 and Na4 or even an apparently incomplete coordination of Na2. This generally ‘overbonded’ situation for the Na cations as well as the trend to higher values for regular coordination polyhedra is similarly found in the penta­hydrate, the respective values are 1.14 and 1.18 v.u. for the two independent cations in relatively regular octa­hedral coordinations, shown in Fig. 3 ▸ e,f.

Figure 3.

Coordination polyhedra around the Na⁺ cations in Na₂S₂O₃·2H₂O (a–d) and in Na₂S₂O₃·5H₂O (e–f). Anisotropic displacement ellipsoids of non-H atoms are drawn with 80% probability, weakly or non-coordinating distances above 2.55 Å for Na—O and 3.18 Å for Na—S as dashed lines.

The four independent water mol­ecules show quite similar, roughly tetra­hedral surroundings, as shown in Fig. 4 ▸. Each H₂O mol­ecule coordinates to two Na⁺ ions, i.e., as a common vertex of neighbouring coordination polyhedra. All the H atoms form one hydrogen bond of moderate strength with O—H⋯O or O—H⋯S angles above 164°, see Table 1 ▸. This is another similarity to observations in the penta­hydrate, where each H atom is part of one almost linear hydrogen bond (Table 2 ▸).

Figure 4.

Environments of the crystal water mol­ecules in Na₂S₂O₃·2H₂O. Anisotropic displacement ellipsoids of non-H atoms are drawn with a probability of 80%, hydrogen bonds as dashed lines, and short contacts to coordinating Na⁺ ions as thin lines.

Table 1. Hydrogen-bond geometry (Å, °) for Na₂S₂O₃·2H₂O at 100 K.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H1⋯O2i	0.844 (11)	2.090 (11)	2.9246 (5)	170.1 (11)
O7—H2⋯O3	0.782 (12)	2.190 (12)	2.9498 (6)	164.3 (12)
O8—H3⋯O6ii	0.827 (12)	2.211 (12)	3.0282 (6)	170.1 (11)
O8—H4⋯S2	0.772 (14)	2.545 (14)	3.3142 (4)	174.5 (13)
O9—H5⋯O1	0.851 (15)	1.966 (15)	2.8142 (6)	174.7 (15)
O9—H6⋯S4ii	0.825 (13)	2.471 (13)	3.2959 (4)	177.9 (12)
O10—H7⋯O4iii	0.828 (13)	1.936 (13)	2.7585 (5)	172.4 (12)
O10—H8⋯S2iii	0.810 (13)	2.421 (13)	3.2183 (4)	168.3 (12)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °) for Na₂S₂O₃·5H₂O at 100 K.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1⋯O3	0.808 (12)	2.001 (12)	2.8067 (5)	176.1 (13)
O4—H2⋯O2i	0.812 (12)	2.017 (12)	2.8175 (5)	168.6 (12)
O5—H3⋯O3	0.820 (13)	1.973 (13)	2.7912 (5)	174.9 (12)
O5—H4⋯O3ii	0.809 (13)	2.074 (13)	2.8736 (5)	169.2 (12)
O6—H5⋯O4ii	0.847 (14)	1.993 (14)	2.8365 (6)	173.8 (13)
O6—H6⋯S2iii	0.850 (13)	2.495 (13)	3.3404 (4)	173.6 (12)
O7—H7⋯S2iv	0.824 (13)	2.527 (13)	3.3356 (4)	167.5 (11)
O7—H8⋯O8v	0.812 (13)	2.017 (13)	2.8280 (6)	177.2 (12)
O8—H9⋯S2i	0.792 (13)	2.554 (13)	3.3147 (4)	161.6 (12)
O8—H10⋯S2	0.785 (14)	2.558 (14)	3.3381 (4)	173.0 (13)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

The highly irregular coordination of the Na⁺ cations in the dihydrate is conspicuous with respect to other more conventional structural features, like the usual bond lengths in the anions or the near-linear hydrogen bonds. Obviously, the structure directing effect of the Na⁺ cations is the weakest among the present building units, although more regular coordination polyhedra, particularly octa­hedra, would have been possible as found in the penta­hydrate as well as in the related structures of Na₆(S₂O₃)₃·2H₂O (Hesse et al., 1993 ▸) and Na₈(S₂O₃)₄·5H₂O (Chan et al., 2008 ▸). Such open, or at least higher coordinated, polyhedra including weaker bonded ligands as observed in Na₂S₂O₃·2H₂O should represent an easy possibility to incorporate further water mol­ecules into the structure and, therefore, a hint for the low stability relative to higher hydrates and the retardation of this structure determination.

3. Supra­molecular features

In Na₂S₂O₃·2 H₂O the thio­sulfate anions and water mol­ecules are connected via hydrogen bonds of medium strength, see Table 1 ▸, with all H atoms forming one almost linear bond. Two S₂O₃ ^2– ions are connected by two H₂O mol­ecules to form the building units shown in Fig. 5 ▸ a. These dimeric units (e.g. blue S₂O₃ tetra­hedra and H₂O mol­ecules in Fig. 5 ▸ b) are connected via two further H₂O mol­ecules (pink in Fig. 5 ▸ b) with a second dimer (green in Fig. 5 ▸ b). The resulting tetra­mers are again inter­linked with neighbouring tetra­mers (yellow and red tetra­hedra in Fig. 5 ▸ b) by water mol­ecules, thereby forming corrugated layers lying parallel to (101), also shown in Fig. 2 ▸ b. The number of H atoms nicely matches the number of corners of the S₂O₃ ^2– tetra­hedra; however, by realizing this connection pattern, six of the eight possible corners of the tetra­hedra dimers accept one hydrogen bond, but one corner (S2) accepts two while one corner (O5) is exclusively surrounded by Na⁺ cations. The layers are not inter­connected by hydrogen bonds but only by Na⁺ cations. This is another difference to the penta­hydrate where the S₂O₃ ^2– ions and H₂O mol­ecules form a three-dimensional framework including hydrogen bonds between water mol­ecules, obviously due to the higher number of H₂O mol­ecules and, thus, possible hydrogen bonds.

Figure 5.

(a) A pair of S₂O₃ ^2– anions in Na₂S₂O₃·2H₂O connected by two H₂O mol­ecules via hydrogen bonds. (b) Illustration of the hydrogen-bond network between thio­sulfate anions, drawn as tetra­hedra, and water mol­ecules in Na₂S₂O₃·2H₂O: two S₂O₃ tetra­hedra (e.g., the blue ones) are bonded by two H₂O (blue) to form dimers, which are connected by two H₂O (pink) with another dimer (green). These tetra­meric units are inter­connected by H₂O with neighbouring tetra­mers (yellow and red tetra­hedra).

4. Database survey

Na₂S₂O₃ and its hydrates have been structurally investigated several times within the second half of the last century. Besides the anhydrous phase (Sándor & Csordás, 1961 ▸; Teng et al., 1984 ▸), including a thorough examination of its temperature dependent polymorphism (von Benda & von Benda, 1979 ▸), some structure determinations of hydrates are reported, namely Na₂S₂O₃·2/3H₂O (Hesse et al., 1993 ▸), Na₂S₂O₃·5/4H₂O (Chan et al., 2008 ▸) and Na₂S₂O₃·5H₂O (Taylor & Beevers, 1952 ▸; Padmanabhan et al., 1971 ▸; Uraz & Armaǧan, 1977 ▸; Lisensky & Levy, 1978 ▸; Prasad & Rani, 2001 ▸), with the sheer number of references obviously illustrating the high stability of the latter phase. For other alkali metal thio­sulfates, the structures of anhydrous K₂S₂O₃ (Lehner et al., 2013 ▸) and K₂S₂O₃·1/3H₂O (Csordás, 1969 ▸; Chan et al., 2008 ▸; Lehner et al., 2013 ▸) as well as of the monohydrates of Rb₂S₂O₃ (Lehner et al., 2013 ▸) and Cs₂S₂O₃ (Winkler et al., 2016 ▸) have been reported.

5. Synthesis and crystallization

Colourless crystals of Na₂S₂O₃·2H₂O were grown at ambient conditions from an aqueous solution of Na₂S₂O₃. The crystals were found floating at the surface of the mother liquor, but sank down to the bottom of the crystallization vessel immediately after disturbing the surface tension. A batch of crystals was immersed into perfluoro­ether, and the crystals were found to be unscathed and stable at room temperature for days. In contrast, no crystals of the dihydrate could be found from the crystal bulk at the bottom of the vessel, but all crystals isolated later from there were penta­hydrate crystals. In addition, an X-ray powder pattern of a sample prepared from this bulk did not contain any other reflections than those of the penta­hydrate.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3 ▸. In all presented structure refinements, all hydrogen atoms could be located from the difference-Fourier map and were refined with free atomic coordinates and isotropic displacement parameters.

Table 3. Experimental details.

	Na2S2O3·2H2O at 100 K	Na2S2O3·2H2O at 200 K	Na2S2O3·5H2O at 100 K	Na2S2O3·5H2O at 200 K
Crystal data
Chemical formula	Na2S2O3·2H2O	Na2S2O3·2H2O	Na2S2O3·5H2O	Na2S2O3·5H2O
M r	194.13	194.13	248.18	248.18
Crystal system, space group	Monoclinic, P21/n	Monoclinic, P21/n	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	100	200	100	200
a, b, c (Å)	5.7719 (1), 19.3257 (3), 11.5162 (3)	5.8003 (1), 19.3713 (4), 11.5520 (3)	5.9187 (1), 21.5173 (4), 7.4979 (1)	5.9357 (1), 21.5424 (7), 7.5026 (2)
β (°)	102.388 (2)	102.331 (2)	103.722 (1)	103.722 (2)
V (Å3)	1254.68 (4)	1268.03 (5)	927.64 (3)	931.97 (4)
Z	8	8	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.93	0.92	0.67	0.67
Crystal size (mm)	0.25 × 0.2 × 0.15	0.25 × 0.2 × 0.15	0.6 × 0.3 × 0.15	0.6 × 0.3 × 0.15
Data collection
Diffractometer	Stoe StadiVari	Stoe StadiVari	Stoe StadiVari	Stoe StadiVari
Absorption correction	Empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015 ▸)	Empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015 ▸)	Empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015 ▸)	Empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015 ▸)
T min, T max	0.919, 1.000	0.920, 1.000	0.868, 1.000	0.869, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	52592, 8735, 7524	55208, 8848, 7181	64240, 6486, 5525	56700, 5006, 4212
R int	0.019	0.024	0.026	0.023
(sin θ/λ)max (Å−1)	0.946	0.948	0.948	0.869
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.017, 0.047, 1.02	0.022, 0.057, 1.01	0.020, 0.047, 1.06	0.019, 0.052, 1.08
No. of reflections	8735	8848	6486	5006
No. of parameters	195	195	149	149
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined	All H-atom parameters refined	All H-atom parameters refined
Δρmax, Δρmin (e Å−3)	0.55, −0.41	0.58, −0.34	0.54, −0.27	0.42, −0.28

Computer programs: X-AREA (Stoe & Cie, 2015 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸) and DIAMOND (Brandenburg & Putz, 2012 ▸).

Supplementary Material

CCDC references: 2227273, 2227272, 2227271, 2227270

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Crystal data

Na2S2O3·2H2O	F(000) = 784
Mr = 194.13	Dx = 2.055 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.7719 (1) Å	Cell parameters from 74172 reflections
b = 19.3257 (3) Å	θ = 3.6–42.6°
c = 11.5162 (3) Å	µ = 0.93 mm−1
β = 102.388 (2)°	T = 100 K
V = 1254.68 (4) Å3	Block, colourless
Z = 8	0.25 × 0.2 × 0.15 mm

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Data collection

Stoe StadiVari diffractometer	8735 independent reflections
Radiation source: Genix 3D HF Mo	7524 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.019
Detector resolution: 5.81 pixels mm-1	θmax = 42.3°, θmin = 3.6°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −24→36
Tmin = 0.919, Tmax = 1.000	l = −21→21
52592 measured reflections

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Refinement

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)] = 0.017	Hydrogen site location: difference Fourier map
wR(F2) = 0.047	All H-atom parameters refined
S = 1.02	w = 1/[σ2(Fo2) + (0.0285P)2 + 0.0499P] where P = (Fo2 + 2Fc2)/3
8735 reflections	(Δ/σ)max = 0.002
195 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Special details

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

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.76421 (4)	0.06060 (2)	0.07970 (2)	0.01045 (4)
Na2	0.77035 (4)	0.05630 (2)	0.42885 (2)	0.01123 (4)
Na3	0.69690 (4)	0.18045 (2)	0.68402 (2)	0.00931 (4)
Na4	0.25074 (4)	0.16699 (2)	0.96445 (2)	0.01068 (4)
S1	0.40448 (2)	0.21188 (2)	0.40032 (2)	0.00580 (2)
S2	0.05139 (2)	0.22163 (2)	0.34974 (2)	0.00789 (2)
O1	0.46625 (7)	0.13787 (2)	0.40401 (4)	0.01077 (6)
O2	0.48663 (6)	0.24383 (2)	0.51923 (3)	0.00914 (5)
O3	0.51216 (6)	0.24942 (2)	0.31289 (3)	0.00948 (5)
S3	0.50073 (2)	0.04913 (2)	0.80268 (2)	0.00634 (2)
S4	0.85520 (2)	0.05914 (2)	0.83904 (2)	0.00764 (2)
O4	0.40222 (7)	0.09813 (2)	0.70691 (4)	0.01385 (7)
O5	0.41409 (7)	0.06361 (2)	0.91219 (3)	0.01001 (6)
O6	0.43732 (7)	−0.02303 (2)	0.76485 (3)	0.01022 (6)
O7	0.62228 (7)	0.17816 (2)	0.10472 (4)	0.01099 (6)
H1	0.721 (2)	0.2050 (6)	0.0833 (10)	0.020 (2)*
H2	0.610 (2)	0.1913 (6)	0.1672 (11)	0.024 (3)*
O8	0.14212 (7)	0.11545 (2)	0.13791 (4)	0.01073 (6)
H3	0.250 (2)	0.0899 (6)	0.1722 (10)	0.022 (3)*
H4	0.117 (2)	0.1420 (8)	0.1836 (12)	0.036 (3)*
O9	0.16296 (7)	0.02476 (2)	0.41193 (4)	0.01152 (6)
H5	0.249 (3)	0.0597 (8)	0.4053 (13)	0.040 (4)*
H6	0.162 (2)	0.0032 (7)	0.3500 (11)	0.028 (3)*
O10	0.96285 (7)	0.13736 (2)	0.57734 (4)	0.01076 (6)
H7	1.090 (2)	0.1261 (7)	0.6218 (11)	0.028 (3)*
H8	0.987 (2)	0.1637 (7)	0.5266 (11)	0.030 (3)*

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.01049 (8)	0.01158 (9)	0.00939 (9)	−0.00200 (7)	0.00237 (7)	0.00018 (7)
Na2	0.01055 (9)	0.01247 (9)	0.00991 (9)	0.00314 (7)	0.00051 (7)	−0.00119 (7)
Na3	0.00991 (8)	0.00920 (8)	0.00892 (8)	0.00016 (6)	0.00226 (6)	0.00054 (6)
Na4	0.01100 (8)	0.00982 (9)	0.01091 (9)	0.00286 (7)	0.00168 (7)	−0.00021 (7)
S1	0.00541 (4)	0.00571 (4)	0.00618 (4)	0.00005 (3)	0.00100 (3)	−0.00008 (3)
S2	0.00558 (4)	0.01003 (4)	0.00789 (4)	0.00030 (3)	0.00106 (3)	0.00014 (3)
O1	0.00952 (13)	0.00573 (13)	0.01647 (16)	0.00125 (10)	0.00145 (11)	−0.00059 (11)
O2	0.00966 (13)	0.01030 (14)	0.00666 (12)	−0.00023 (10)	−0.00002 (10)	−0.00154 (10)
O3	0.00852 (12)	0.01143 (14)	0.00930 (13)	−0.00052 (10)	0.00372 (10)	0.00192 (10)
S3	0.00611 (4)	0.00644 (4)	0.00640 (4)	−0.00036 (3)	0.00113 (3)	0.00010 (3)
S4	0.00626 (4)	0.00816 (4)	0.00842 (4)	−0.00021 (3)	0.00138 (3)	0.00005 (3)
O4	0.00915 (13)	0.01576 (16)	0.01486 (16)	−0.00036 (12)	−0.00138 (12)	0.00848 (13)
O5	0.00940 (13)	0.01171 (14)	0.00994 (14)	0.00015 (11)	0.00431 (11)	−0.00291 (11)
O6	0.01128 (13)	0.00868 (13)	0.01099 (14)	−0.00318 (10)	0.00305 (11)	−0.00345 (10)
O7	0.01116 (14)	0.01221 (15)	0.00987 (14)	−0.00230 (11)	0.00287 (11)	−0.00060 (11)
O8	0.01084 (14)	0.00978 (14)	0.01119 (14)	0.00123 (11)	0.00152 (11)	−0.00083 (11)
O9	0.01357 (15)	0.01038 (14)	0.01172 (15)	−0.00148 (11)	0.00516 (12)	−0.00135 (11)
O10	0.00916 (13)	0.01293 (15)	0.01009 (14)	0.00096 (11)	0.00183 (11)	0.00219 (11)

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Geometric parameters (Å, º)

Na1—O8i	2.3882 (5)	Na4—Na3x	3.9395 (3)
Na1—O6ii	2.4451 (5)	Na4—Na3xi	4.0357 (3)
Na1—O7	2.4529 (5)	S1—O1	1.4725 (4)
Na1—O5iii	2.4771 (5)	S1—O3	1.4815 (4)
Na1—O5ii	2.6214 (5)	S1—O2	1.4841 (4)
Na1—S4iii	2.9296 (3)	S1—S2	2.0047 (2)
Na1—S3ii	3.0917 (3)	S1—Na4viii	3.0636 (3)
Na1—S4iv	3.1898 (3)	S1—Na3xiii	3.2694 (3)
Na1—S3iii	3.2338 (3)	S2—Na3xiii	2.9354 (3)
Na1—Na4iii	3.6173 (3)	S2—Na4xiii	3.2208 (3)
Na1—Na4v	3.9337 (3)	O2—Na4viii	2.4708 (4)
Na1—Na1vi	3.9694 (5)	O3—Na3xiii	2.4883 (4)
Na2—O1	2.3307 (4)	O3—Na4viii	2.5536 (4)
Na2—O9ii	2.3794 (5)	S3—O4	1.4722 (4)
Na2—O6ii	2.3831 (4)	S3—O5	1.4797 (4)
Na2—O9i	2.3947 (5)	S3—O6	1.4832 (4)
Na2—O10	2.4078 (5)	S3—S4	2.0078 (2)
Na2—Na2iv	3.5475 (5)	S3—Na1ii	3.0917 (3)
Na2—Na3	3.8866 (3)	S3—Na1ix	3.2338 (3)
Na2—H8	2.557 (12)	S4—Na1ix	2.9295 (3)
Na3—O10	2.3169 (5)	S4—Na1iv	3.1897 (3)
Na3—O2	2.3636 (4)	S4—Na4i	3.1981 (3)
Na3—O4	2.3845 (5)	O5—Na1ix	2.4771 (5)
Na3—O3vii	2.4884 (4)	O5—Na1ii	2.6213 (5)
Na3—S2vii	2.9354 (3)	O6—Na2ii	2.3831 (4)
Na3—S4	2.9695 (3)	O6—Na1ii	2.4451 (5)
Na3—S3	3.2022 (3)	O7—Na4iii	2.4018 (5)
Na3—S1vii	3.2694 (3)	O7—H1	0.844 (11)
Na3—Na4viii	3.9395 (3)	O7—H2	0.782 (12)
Na3—Na4i	4.0357 (3)	O8—Na1xi	2.3882 (5)
Na4—O5	2.3423 (4)	O8—Na4iii	2.4316 (5)
Na4—O7ix	2.4017 (5)	O8—H3	0.827 (12)
Na4—O8ix	2.4317 (5)	O8—H4	0.772 (14)
Na4—O2x	2.4708 (4)	O9—Na2ii	2.3793 (5)
Na4—O3x	2.5536 (4)	O9—Na2xi	2.3947 (5)
Na4—S1x	3.0636 (2)	O9—H5	0.851 (15)
Na4—S4xi	3.1981 (3)	O9—H6	0.825 (13)
Na4—S2vii	3.2208 (3)	O10—H7	0.828 (13)
Na4—Na1ix	3.6173 (3)	O10—H8	0.810 (13)
Na4—Na1xii	3.9337 (3)
O8i—Na1—O6ii	118.400 (16)	O5—Na4—O7ix	84.197 (15)
O8i—Na1—O7	82.178 (15)	O5—Na4—O8ix	92.899 (16)
O6ii—Na1—O7	88.032 (15)	O7ix—Na4—O8ix	80.483 (15)
O8i—Na1—O5iii	138.729 (17)	O5—Na4—O2x	164.794 (17)
O6ii—Na1—O5iii	98.068 (15)	O7ix—Na4—O2x	106.048 (16)
O7—Na1—O5iii	80.357 (15)	O8ix—Na4—O2x	78.118 (14)
O8i—Na1—O5ii	137.591 (16)	O5—Na4—O3x	123.483 (16)
O6ii—Na1—O5ii	56.628 (13)	O7ix—Na4—O3x	132.507 (17)
O7—Na1—O5ii	134.460 (16)	O8ix—Na4—O3x	128.636 (15)
O5iii—Na1—O5ii	77.780 (15)	O2x—Na4—O3x	57.417 (12)
O8i—Na1—S4iii	86.073 (12)	O5—Na4—S1x	150.169 (14)
O6ii—Na1—S4iii	154.130 (13)	O7ix—Na4—S1x	122.393 (13)
O7—Na1—S4iii	104.610 (12)	O8ix—Na4—S1x	103.959 (12)
O5iii—Na1—S4iii	62.959 (10)	O2x—Na4—S1x	28.631 (9)
O5ii—Na1—S4iii	100.155 (11)	O3x—Na4—S1x	28.794 (9)
O8i—Na1—S3ii	133.571 (13)	O5—Na4—S4xi	67.401 (11)
O6ii—Na1—S3ii	28.098 (9)	O7ix—Na4—S4xi	144.113 (14)
O7—Na1—S3ii	112.008 (13)	O8ix—Na4—S4xi	79.579 (12)
O5iii—Na1—S3ii	87.693 (11)	O2x—Na4—S4xi	98.634 (12)
O5ii—Na1—S3ii	28.531 (9)	O3x—Na4—S4xi	82.850 (11)
S4iii—Na1—S3ii	127.864 (9)	S1x—Na4—S4xi	91.346 (7)
O8i—Na1—S4iv	73.118 (12)	O5—Na4—S2vii	100.525 (12)
O6ii—Na1—S4iv	88.603 (12)	O7ix—Na4—S2vii	74.571 (12)
O7—Na1—S4iv	149.747 (13)	O8ix—Na4—S2vii	150.145 (13)
O5iii—Na1—S4iv	129.865 (13)	O2x—Na4—S2vii	93.140 (11)
O5ii—Na1—S4iv	64.918 (10)	O3x—Na4—S2vii	63.633 (10)
S4iii—Na1—S4iv	91.068 (7)	S1x—Na4—S2vii	76.791 (6)
S3ii—Na1—S4iv	75.409 (6)	S4xi—Na4—S2vii	130.207 (8)
O8i—Na1—S3iii	121.015 (13)	O5—Na4—Na1ix	42.791 (11)
O6ii—Na1—S3iii	120.330 (12)	O7ix—Na4—Na1ix	42.373 (11)
O7—Na1—S3iii	94.657 (12)	O8ix—Na4—Na1ix	78.527 (12)
O5iii—Na1—S3iii	25.963 (9)	O2x—Na4—Na1ix	143.576 (12)
O5ii—Na1—S3iii	82.368 (11)	O3x—Na4—Na1ix	152.820 (13)
S4iii—Na1—S3iii	37.616 (4)	S1x—Na4—Na1ix	164.477 (9)
S3ii—Na1—S3iii	102.300 (7)	S4xi—Na4—Na1ix	104.156 (8)
S4iv—Na1—S3iii	112.843 (8)	S2vii—Na4—Na1ix	93.397 (7)
O8i—Na1—Na4iii	118.543 (13)	O5—Na4—Na1xii	89.810 (12)
O6ii—Na1—Na4iii	87.500 (12)	O7ix—Na4—Na1xii	114.775 (13)
O7—Na1—Na4iii	41.293 (11)	O8ix—Na4—Na1xii	34.934 (10)
O5iii—Na1—Na4iii	39.967 (10)	O2x—Na4—Na1xii	75.773 (11)
O5ii—Na1—Na4iii	103.685 (11)	O3x—Na4—Na1xii	104.000 (11)
S4iii—Na1—Na4iii	87.559 (7)	S1x—Na4—Na1xii	90.270 (7)
S3ii—Na1—Na4iii	96.159 (8)	S4xi—Na4—Na1xii	47.125 (5)
S4iv—Na1—Na4iii	168.094 (9)	S2vii—Na4—Na1xii	166.945 (8)
S3iii—Na1—Na4iii	60.141 (6)	Na1ix—Na4—Na1xii	99.620 (8)
O8i—Na1—Na4v	35.666 (11)	O5—Na4—Na3x	153.485 (13)
O6ii—Na1—Na4v	152.675 (13)	O7ix—Na4—Na3x	71.525 (12)
O7—Na1—Na4v	80.568 (11)	O8ix—Na4—Na3x	73.117 (12)
O5iii—Na1—Na4v	104.310 (12)	O2x—Na4—Na3x	34.529 (10)
O5ii—Na1—Na4v	143.591 (12)	O3x—Na4—Na3x	81.957 (11)
S4iii—Na1—Na4v	53.130 (5)	S1x—Na4—Na3x	56.340 (6)
S3ii—Na1—Na4v	164.219 (9)	S4xi—Na4—Na3x	129.098 (8)
S4iv—Na1—Na4v	88.948 (7)	S2vii—Na4—Na3x	83.498 (7)
S3iii—Na1—Na4v	85.509 (7)	Na1ix—Na4—Na3x	111.170 (8)
Na4iii—Na1—Na4v	99.621 (8)	Na1xii—Na4—Na3x	90.819 (7)
O8i—Na1—Na1vi	163.063 (16)	O5—Na4—Na3xi	98.206 (12)
O6ii—Na1—Na1vi	73.997 (11)	O7ix—Na4—Na3xi	166.439 (14)
O7—Na1—Na1vi	110.978 (14)	O8ix—Na4—Na3xi	112.594 (12)
O5iii—Na1—Na1vi	40.198 (10)	O2x—Na4—Na3xi	74.523 (10)
O5ii—Na1—Na1vi	37.582 (9)	O3x—Na4—Na3xi	36.277 (10)
S4iii—Na1—Na1vi	80.371 (8)	S1x—Na4—Na3xi	52.703 (5)
S3ii—Na1—Na1vi	52.748 (6)	S4xi—Na4—Na3xi	46.719 (5)
S4iv—Na1—Na1vi	96.895 (9)	S2vii—Na4—Na3xi	91.873 (7)
S3iii—Na1—Na1vi	49.552 (6)	Na1ix—Na4—Na3xi	140.915 (8)
Na4iii—Na1—Na1vi	71.213 (8)	Na1xii—Na4—Na3xi	78.663 (6)
Na4v—Na1—Na1vi	133.293 (10)	Na3x—Na4—Na3xi	107.902 (7)
O1—Na2—O9ii	122.205 (18)	O1—S1—O3	111.16 (2)
O1—Na2—O6ii	81.562 (16)	O1—S1—O2	110.48 (2)
O9ii—Na2—O6ii	120.629 (17)	O3—S1—O2	109.02 (2)
O1—Na2—O9i	149.663 (18)	O1—S1—S2	108.927 (16)
O9ii—Na2—O9i	84.012 (16)	O3—S1—S2	107.764 (16)
O6ii—Na2—O9i	98.619 (16)	O2—S1—S2	109.430 (16)
O1—Na2—O10	82.399 (15)	O1—S1—Na4viii	126.430 (16)
O9ii—Na2—O10	84.685 (15)	O3—S1—Na4viii	56.126 (16)
O6ii—Na2—O10	154.570 (17)	O2—S1—Na4viii	52.913 (16)
O9i—Na2—O10	85.577 (16)	S2—S1—Na4viii	124.628 (7)
O1—Na2—Na2iv	160.062 (17)	O1—S1—Na3xiii	133.400 (18)
O9ii—Na2—Na2iv	42.172 (11)	O3—S1—Na3xiii	46.304 (15)
O6ii—Na2—Na2iv	116.288 (15)	O2—S1—Na3xiii	115.505 (16)
O9i—Na2—Na2iv	41.840 (11)	S2—S1—Na3xiii	62.309 (6)
O10—Na2—Na2iv	83.443 (13)	Na4viii—S1—Na3xiii	79.101 (7)
O1—Na2—Na3	58.255 (12)	S1—S2—Na3xiii	80.481 (7)
O9ii—Na2—Na3	81.351 (12)	S1—S2—Na4xiii	123.174 (7)
O6ii—Na2—Na3	139.441 (13)	Na3xiii—S2—Na4xiii	95.180 (7)
O9i—Na2—Na3	118.510 (13)	S1—O1—Na2	146.29 (2)
O10—Na2—Na3	33.899 (10)	S1—O2—Na3	122.18 (2)
Na2iv—Na2—Na3	102.788 (10)	S1—O2—Na4viii	98.46 (2)
O1—Na2—Na1	91.058 (13)	Na3—O2—Na4viii	109.136 (16)
O9ii—Na2—Na1	138.654 (13)	S1—O3—Na3xiii	108.20 (2)
O6ii—Na2—Na1	34.248 (10)	S1—O3—Na4viii	95.079 (19)
O9i—Na2—Na1	74.270 (12)	Na3xiii—O3—Na4viii	106.335 (16)
O10—Na2—Na1	126.973 (13)	O4—S3—O5	111.71 (2)
Na2iv—Na2—Na1	108.694 (10)	O4—S3—O6	110.70 (2)
Na3—Na2—Na1	139.958 (8)	O5—S3—O6	108.72 (2)
O1—Na2—H8	77.9 (3)	O4—S3—S4	107.862 (17)
O9ii—Na2—H8	102.3 (3)	O5—S3—S4	108.640 (16)
O6ii—Na2—H8	137.0 (3)	O6—S3—S4	109.151 (17)
O9i—Na2—H8	82.0 (3)	O4—S3—Na1ii	128.431 (17)
O10—Na2—H8	18.5 (3)	O5—S3—Na1ii	57.791 (16)
Na2iv—Na2—H8	92.7 (3)	O6—S3—Na1ii	50.932 (16)
Na3—Na2—H8	44.6 (3)	S4—S3—Na1ii	123.533 (7)
Na1—Na2—H8	108.8 (3)	O4—S3—Na3	44.406 (17)
O10—Na3—O2	92.578 (16)	O5—S3—Na3	115.395 (17)
O10—Na3—O4	112.849 (18)	O6—S3—Na3	135.020 (17)
O2—Na3—O4	100.309 (15)	S4—S3—Na3	64.837 (6)
O10—Na3—O3vii	91.667 (15)	Na1ii—S3—Na3	169.724 (7)
O2—Na3—O3vii	112.361 (16)	O4—S3—Na1ix	135.99 (2)
O4—Na3—O3vii	138.171 (17)	O5—S3—Na1ix	47.128 (16)
O10—Na3—S2vii	152.992 (14)	O6—S3—Na1ix	112.854 (17)
O2—Na3—S2vii	91.069 (12)	S4—S3—Na1ix	62.944 (6)
O4—Na3—S2vii	92.745 (14)	Na1ii—S3—Na1ix	77.699 (7)
O3vii—Na3—S2vii	62.335 (10)	Na3—S3—Na1ix	103.422 (7)
O10—Na3—S4	83.204 (12)	S3—S4—Na1ix	79.440 (7)
O2—Na3—S4	158.528 (13)	S3—S4—Na3	77.431 (6)
O4—Na3—S4	62.715 (11)	Na1ix—S4—Na3	117.818 (8)
O3vii—Na3—S4	88.861 (11)	S3—S4—Na1iv	126.733 (7)
S2vii—Na3—S4	102.249 (8)	Na1ix—S4—Na1iv	88.932 (7)
O10—Na3—S3	106.058 (13)	Na3—S4—Na1iv	148.524 (7)
O2—Na3—S3	125.851 (13)	S3—S4—Na4i	138.919 (7)
O4—Na3—S3	25.595 (10)	Na1ix—S4—Na4i	79.744 (7)
O3vii—Na3—S3	117.222 (12)	Na3—S4—Na4i	81.648 (7)
S2vii—Na3—S3	93.258 (7)	Na1iv—S4—Na4i	87.727 (7)
S4—Na3—S3	37.733 (4)	S3—O4—Na3	110.00 (2)
O10—Na3—S1vii	117.162 (13)	S3—O5—Na4	127.49 (2)
O2—Na3—S1vii	108.846 (12)	S3—O5—Na1ix	106.91 (2)
O4—Na3—S1vii	119.596 (14)	Na4—O5—Na1ix	97.241 (16)
O3vii—Na3—S1vii	25.496 (9)	S3—O5—Na1ii	93.680 (19)
S2vii—Na3—S1vii	37.209 (4)	Na4—O5—Na1ii	126.101 (17)
S4—Na3—S1vii	91.674 (7)	Na1ix—O5—Na1ii	102.221 (15)
S3—Na3—S1vii	106.535 (7)	S3—O6—Na2ii	124.85 (2)
O10—Na3—Na2	35.423 (11)	S3—O6—Na1ii	100.97 (2)
O2—Na3—Na2	80.408 (11)	Na2ii—O6—Na1ii	112.489 (17)
O4—Na3—Na2	82.405 (14)	Na4iii—O7—Na1	96.333 (16)
O3vii—Na3—Na2	127.067 (12)	Na4iii—O7—H1	114.7 (8)
S2vii—Na3—Na2	169.225 (9)	Na1—O7—H1	105.9 (8)
S4—Na3—Na2	84.133 (7)	Na4iii—O7—H2	113.7 (9)
S3—Na3—Na2	86.521 (7)	Na1—O7—H2	120.6 (9)
S1vii—Na3—Na2	152.539 (8)	H1—O7—H2	105.7 (11)
O10—Na3—Na4viii	77.064 (12)	Na1xi—O8—Na4iii	109.400 (17)
O2—Na3—Na4viii	36.336 (10)	Na1xi—O8—H3	114.8 (8)
O4—Na3—Na4viii	136.606 (12)	Na4iii—O8—H3	109.6 (8)
O3vii—Na3—Na4viii	80.031 (11)	Na1xi—O8—H4	100.9 (10)
S2vii—Na3—Na4viii	90.445 (7)	Na4iii—O8—H4	114.1 (10)
S4—Na3—Na4viii	156.961 (8)	H3—O8—H4	107.9 (13)
S3—Na3—Na4viii	161.959 (8)	Na2ii—O9—Na2xi	95.988 (16)
S1vii—Na3—Na4viii	86.918 (7)	Na2ii—O9—H5	126.2 (10)
Na2—Na3—Na4viii	86.578 (7)	Na2xi—O9—H5	112.6 (10)
O10—Na3—Na4i	84.262 (12)	Na2ii—O9—H6	107.7 (9)
O2—Na3—Na4i	149.099 (13)	Na2xi—O9—H6	111.6 (9)
O4—Na3—Na4i	109.260 (12)	H5—O9—H6	102.7 (12)
O3vii—Na3—Na4i	37.389 (10)	Na3—O10—Na2	110.678 (17)
S2vii—Na3—Na4i	79.004 (6)	Na3—O10—H7	111.4 (8)
S4—Na3—Na4i	51.632 (5)	Na2—O10—H7	118.7 (9)
S3—Na3—Na4i	84.222 (6)	Na3—O10—H8	113.2 (9)
S1vii—Na3—Na4i	48.197 (5)	Na2—O10—H8	91.3 (9)
Na2—Na3—Na4i	111.661 (7)	H7—O10—H8	110.2 (12)
Na4viii—Na3—Na4i	113.819 (7)

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

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O2viii	0.844 (11)	2.090 (11)	2.9246 (5)	170.1 (11)
O7—H2···O3	0.782 (12)	2.190 (12)	2.9498 (6)	164.3 (12)
O8—H3···O6ii	0.827 (12)	2.211 (12)	3.0282 (6)	170.1 (11)
O8—H4···S2	0.772 (14)	2.545 (14)	3.3142 (4)	174.5 (13)
O9—H5···O1	0.851 (15)	1.966 (15)	2.8142 (6)	174.7 (15)
O9—H6···S4ii	0.825 (13)	2.471 (13)	3.2959 (4)	177.9 (12)
O10—H7···O4i	0.828 (13)	1.936 (13)	2.7585 (5)	172.4 (12)
O10—H8···S2i	0.810 (13)	2.421 (13)	3.2183 (4)	168.3 (12)

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

(Na2S2O3H2O2_200K). Crystal data

O3S2·2(H2O)·2(Na)	F(000) = 784
Mr = 194.13	Dx = 2.034 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.8003 (1) Å	Cell parameters from 63400 reflections
b = 19.3713 (4) Å	θ = 3.2–42.5°
c = 11.5520 (3) Å	µ = 0.92 mm−1
β = 102.331 (2)°	T = 200 K
V = 1268.03 (5) Å3	Block, colourless
Z = 8	0.25 × 0.2 × 0.15 mm

(Na2S2O3H2O2_200K). Data collection

Stoe StadiVari diffractometer	8848 independent reflections
Radiation source: Genix 3D HF Mo	7181 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.024
Detector resolution: 5.81 pixels mm-1	θmax = 42.3°, θmin = 3.6°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −24→36
Tmin = 0.920, Tmax = 1.000	l = −21→21
55208 measured reflections

(Na2S2O3H2O2_200K). Refinement

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F2) = 0.057	All H-atom parameters refined
S = 1.01	w = 1/[σ2(Fo2) + (0.0343P)2] where P = (Fo2 + 2Fc2)/3
8848 reflections	(Δ/σ)max = 0.002
195 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

(Na2S2O3H2O2_200K). Special details

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

(Na2S2O3H2O2_200K). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.76083 (5)	0.06118 (2)	0.07884 (3)	0.01992 (5)
Na2	0.77256 (5)	0.05700 (2)	0.42842 (3)	0.02061 (5)
Na3	0.69341 (5)	0.18066 (2)	0.68350 (2)	0.01663 (5)
Na4	0.24774 (5)	0.16710 (2)	0.96288 (3)	0.01997 (5)
S1	0.40321 (2)	0.21139 (2)	0.39998 (2)	0.01053 (2)
S2	0.05175 (2)	0.22031 (2)	0.34932 (2)	0.01460 (3)
O1	0.46682 (8)	0.13784 (2)	0.40371 (5)	0.01990 (8)
O2	0.48340 (8)	0.24334 (2)	0.51827 (4)	0.01645 (7)
O3	0.50946 (8)	0.24916 (3)	0.31300 (4)	0.01705 (7)
S3	0.49533 (2)	0.04958 (2)	0.80242 (2)	0.01214 (3)
S4	0.84805 (2)	0.05883 (2)	0.83802 (2)	0.01430 (3)
O4	0.39836 (9)	0.09907 (3)	0.70831 (5)	0.02776 (11)
O5	0.41052 (8)	0.06351 (3)	0.91195 (4)	0.01854 (8)
O6	0.43089 (9)	−0.02198 (3)	0.76389 (4)	0.02031 (8)
O7	0.61781 (9)	0.17868 (3)	0.10362 (4)	0.01977 (8)
H1	0.714 (2)	0.2063 (6)	0.0822 (12)	0.032 (3)*
H2	0.603 (2)	0.1921 (7)	0.1666 (12)	0.034 (3)*
O8	0.13817 (9)	0.11508 (3)	0.13587 (5)	0.01947 (8)
H3	0.242 (2)	0.0895 (7)	0.1678 (11)	0.032 (3)*
H4	0.116 (3)	0.1393 (9)	0.1796 (14)	0.055 (4)*
O9	0.16529 (10)	0.02449 (3)	0.41317 (5)	0.02058 (8)
H5	0.248 (3)	0.0584 (9)	0.4037 (16)	0.059 (5)*
H6	0.165 (2)	0.0039 (7)	0.3523 (12)	0.033 (3)*
O10	0.96144 (8)	0.13779 (3)	0.57813 (4)	0.01861 (8)
H7	1.088 (2)	0.1259 (7)	0.6229 (12)	0.038 (3)*
H8	0.990 (2)	0.1628 (7)	0.5310 (12)	0.037 (3)*

(Na2S2O3H2O2_200K). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.02111 (12)	0.02219 (13)	0.01677 (11)	−0.00539 (9)	0.00473 (9)	−0.00005 (9)
Na2	0.01952 (12)	0.02307 (13)	0.01777 (12)	0.00628 (9)	0.00067 (9)	−0.00274 (9)
Na3	0.01804 (11)	0.01634 (11)	0.01560 (11)	0.00029 (8)	0.00381 (8)	0.00127 (8)
Na4	0.02085 (12)	0.01800 (12)	0.02026 (12)	0.00594 (9)	0.00261 (9)	−0.00061 (9)
S1	0.01007 (4)	0.01019 (5)	0.01107 (5)	0.00009 (3)	0.00164 (3)	−0.00023 (3)
S2	0.01013 (5)	0.01901 (6)	0.01424 (5)	0.00055 (4)	0.00167 (4)	0.00046 (4)
O1	0.01663 (17)	0.01085 (17)	0.0309 (2)	0.00213 (13)	0.00209 (16)	−0.00127 (15)
O2	0.01729 (17)	0.01861 (18)	0.01175 (16)	−0.00063 (14)	−0.00069 (13)	−0.00254 (13)
O3	0.01504 (16)	0.02101 (19)	0.01647 (18)	−0.00113 (14)	0.00641 (13)	0.00321 (14)
S3	0.01239 (5)	0.01208 (5)	0.01166 (5)	−0.00133 (4)	0.00192 (4)	0.00020 (4)
S4	0.01222 (5)	0.01537 (6)	0.01526 (6)	0.00022 (4)	0.00283 (4)	0.00047 (4)
O4	0.01646 (19)	0.0326 (3)	0.0303 (3)	−0.00209 (18)	−0.00376 (17)	0.0184 (2)
O5	0.01686 (17)	0.0215 (2)	0.01898 (19)	0.00002 (14)	0.00763 (15)	−0.00642 (15)
O6	0.0240 (2)	0.01761 (19)	0.0204 (2)	−0.00826 (16)	0.00714 (16)	−0.00775 (15)
O7	0.02038 (19)	0.0217 (2)	0.01769 (19)	−0.00475 (16)	0.00510 (15)	−0.00113 (15)
O8	0.02040 (19)	0.01723 (19)	0.0201 (2)	0.00224 (15)	0.00281 (16)	−0.00136 (15)
O9	0.0244 (2)	0.0185 (2)	0.0211 (2)	−0.00272 (16)	0.00981 (17)	−0.00309 (16)
O10	0.01630 (18)	0.0226 (2)	0.01676 (18)	0.00175 (15)	0.00311 (14)	0.00375 (15)

(Na2S2O3H2O2_200K). Geometric parameters (Å, º)

Na1—O8i	2.3873 (6)	Na4—Na3x	3.9539 (4)
Na1—O6ii	2.4447 (6)	Na4—Na3xi	4.0486 (4)
Na1—O7	2.4602 (6)	S1—O1	1.4702 (5)
Na1—O5iii	2.4848 (6)	S1—O3	1.4795 (5)
Na1—O5ii	2.6227 (6)	S1—O2	1.4816 (4)
Na1—S4iii	2.9323 (3)	S1—S2	2.0047 (2)
Na1—S3ii	3.0924 (3)	S1—Na4viii	3.0727 (3)
Na1—S3iii	3.2433 (3)	S1—Na3xiii	3.2875 (3)
Na1—S4iv	3.2470 (3)	S2—Na3xiii	2.9490 (3)
Na1—Na4iii	3.6275 (4)	S2—Na4xiii	3.2520 (3)
Na1—Na4v	3.9492 (4)	O2—Na4viii	2.4878 (5)
Na1—Na1vi	3.9670 (6)	O3—Na3xiii	2.5051 (5)
Na2—O1	2.3372 (5)	O3—Na4viii	2.5529 (6)
Na2—O6ii	2.3808 (6)	S3—O4	1.4684 (5)
Na2—O9ii	2.3851 (6)	S3—O5	1.4770 (5)
Na2—O9i	2.4058 (6)	S3—O6	1.4793 (5)
Na2—O10	2.4148 (6)	S3—S4	2.0068 (2)
Na2—Na2iv	3.5650 (6)	S3—Na1ii	3.0924 (3)
Na2—Na3	3.9000 (4)	S3—Na1ix	3.2432 (3)
Na2—H8	2.560 (13)	S4—Na1ix	2.9323 (3)
Na3—O10	2.3231 (6)	S4—Na4i	3.2288 (3)
Na3—O2	2.3681 (5)	S4—Na1iv	3.2470 (3)
Na3—O4	2.3914 (6)	O5—Na1ix	2.4848 (6)
Na3—O3vii	2.5051 (5)	O5—Na1ii	2.6227 (6)
Na3—S2vii	2.9491 (3)	O6—Na2ii	2.3808 (6)
Na3—S4	2.9794 (3)	O6—Na1ii	2.4447 (6)
Na3—S3	3.2139 (3)	O7—Na4iii	2.4106 (6)
Na3—S1vii	3.2874 (3)	O7—H1	0.847 (13)
Na3—Na4viii	3.9540 (4)	O7—H2	0.795 (13)
Na3—Na4i	4.0486 (4)	O8—Na1xi	2.3872 (6)
Na4—O5	2.3456 (5)	O8—Na4iii	2.4403 (6)
Na4—O7ix	2.4105 (6)	O8—H3	0.804 (13)
Na4—O8ix	2.4403 (6)	O8—H4	0.721 (17)
Na4—O2x	2.4877 (5)	O9—Na2ii	2.3851 (6)
Na4—O3x	2.5529 (6)	O9—Na2xi	2.4059 (6)
Na4—S1x	3.0726 (3)	O9—H5	0.835 (17)
Na4—S4xi	3.2289 (3)	O9—H6	0.808 (14)
Na4—S2vii	3.2520 (3)	O10—H7	0.835 (14)
Na4—Na1ix	3.6275 (4)	O10—H8	0.772 (14)
Na4—Na1xii	3.9493 (4)
O8i—Na1—O6ii	117.81 (2)	O5—Na4—O7ix	84.30 (2)
O8i—Na1—O7	82.834 (19)	O5—Na4—O8ix	92.37 (2)
O6ii—Na1—O7	89.01 (2)	O7ix—Na4—O8ix	80.573 (19)
O8i—Na1—O5iii	139.09 (2)	O5—Na4—O2x	164.65 (2)
O6ii—Na1—O5iii	98.969 (19)	O7ix—Na4—O2x	105.701 (19)
O7—Na1—O5iii	80.403 (18)	O8ix—Na4—O2x	78.158 (18)
O8i—Na1—O5ii	136.44 (2)	O5—Na4—O3x	124.20 (2)
O6ii—Na1—O5ii	56.453 (16)	O7ix—Na4—O3x	132.33 (2)
O7—Na1—O5ii	135.01 (2)	O8ix—Na4—O3x	128.304 (19)
O5iii—Na1—O5ii	78.12 (2)	O2x—Na4—O3x	57.124 (15)
O8i—Na1—S4iii	86.263 (16)	O5—Na4—S1x	150.730 (17)
O6ii—Na1—S4iii	153.927 (16)	O7ix—Na4—S1x	121.920 (17)
O7—Na1—S4iii	104.804 (16)	O8ix—Na4—S1x	103.888 (16)
O5iii—Na1—S4iii	62.763 (12)	O2x—Na4—S1x	28.502 (10)
O5ii—Na1—S4iii	99.662 (14)	O3x—Na4—S1x	28.635 (10)
O8i—Na1—S3ii	132.852 (17)	O5—Na4—S4xi	67.748 (14)
O6ii—Na1—S3ii	27.992 (11)	O7ix—Na4—S4xi	144.363 (17)
O7—Na1—S3ii	112.607 (16)	O8ix—Na4—S4xi	79.041 (15)
O5iii—Na1—S3ii	88.056 (14)	O2x—Na4—S4xi	98.321 (14)
O5ii—Na1—S3ii	28.468 (11)	O3x—Na4—S4xi	82.917 (13)
S4iii—Na1—S3ii	127.348 (11)	S1x—Na4—S4xi	91.333 (8)
O8i—Na1—S3iii	121.104 (16)	O5—Na4—S2vii	100.986 (16)
O6ii—Na1—S3iii	120.962 (16)	O7ix—Na4—S2vii	74.230 (15)
O7—Na1—S3iii	94.456 (15)	O8ix—Na4—S2vii	149.970 (17)
O5iii—Na1—S3iii	25.800 (11)	O2x—Na4—S2vii	93.044 (14)
O5ii—Na1—S3iii	82.631 (13)	O3x—Na4—S2vii	64.017 (12)
S4iii—Na1—S3iii	37.501 (5)	S1x—Na4—S2vii	76.829 (8)
S3ii—Na1—S3iii	102.508 (9)	S4xi—Na4—S2vii	130.911 (10)
O8i—Na1—S4iv	71.943 (15)	O5—Na4—Na1ix	42.800 (14)
O6ii—Na1—S4iv	87.582 (16)	O7ix—Na4—Na1ix	42.386 (14)
O7—Na1—S4iv	149.277 (16)	O8ix—Na4—Na1ix	78.499 (15)
O5iii—Na1—S4iv	130.273 (16)	O2x—Na4—Na1ix	143.281 (15)
O5ii—Na1—S4iv	64.881 (13)	O3x—Na4—Na1ix	153.189 (16)
S4iii—Na1—S4iv	91.048 (9)	S1x—Na4—Na1ix	164.044 (11)
S3ii—Na1—S4iv	75.144 (8)	S4xi—Na4—Na1ix	104.579 (10)
S3iii—Na1—S4iv	113.356 (10)	S2vii—Na4—Na1ix	93.185 (9)
O8i—Na1—Na4iii	119.081 (17)	O5—Na4—Na1xii	89.768 (15)
O6ii—Na1—Na4iii	89.002 (17)	O7ix—Na4—Na1xii	114.701 (16)
O7—Na1—Na4iii	41.342 (13)	O8ix—Na4—Na1xii	34.668 (13)
O5iii—Na1—Na4iii	39.891 (12)	O2x—Na4—Na1xii	75.547 (14)
O5ii—Na1—Na4iii	104.346 (15)	O3x—Na4—Na1xii	103.732 (14)
S4iii—Na1—Na4iii	87.283 (9)	S1x—Na4—Na1xii	90.121 (9)
S3ii—Na1—Na4iii	97.020 (10)	S4xi—Na4—Na1xii	46.906 (7)
S3iii—Na1—Na4iii	59.736 (7)	S2vii—Na4—Na1xii	166.892 (10)
S4iv—Na1—Na4iii	168.666 (11)	Na1ix—Na4—Na1xii	99.823 (10)
O8i—Na1—Na4v	35.554 (14)	O5—Na4—Na3x	153.064 (17)
O6ii—Na1—Na4v	152.272 (16)	O7ix—Na4—Na3x	71.212 (15)
O7—Na1—Na4v	80.915 (15)	O8ix—Na4—Na3x	73.120 (14)
O5iii—Na1—Na4v	104.647 (15)	O2x—Na4—Na3x	34.492 (11)
O5ii—Na1—Na4v	142.833 (15)	O3x—Na4—Na3x	81.785 (13)
S4iii—Na1—Na4v	53.522 (7)	S1x—Na4—Na3x	56.206 (7)
S3ii—Na1—Na4v	163.151 (11)	S4xi—Na4—Na3x	128.605 (10)
S3iii—Na1—Na4v	85.734 (8)	S2vii—Na4—Na3x	83.368 (8)
S4iv—Na1—Na4v	88.121 (8)	Na1ix—Na4—Na3x	110.847 (10)
Na4iii—Na1—Na4v	99.823 (10)	Na1xii—Na4—Na3x	90.440 (9)
O8i—Na1—Na1vi	162.27 (2)	O5—Na4—Na3xi	98.583 (15)
O6ii—Na1—Na1vi	74.472 (14)	O7ix—Na4—Na3xi	166.615 (18)
O7—Na1—Na1vi	111.295 (17)	O8ix—Na4—Na3xi	112.225 (16)
O5iii—Na1—Na1vi	40.314 (13)	O2x—Na4—Na3xi	74.432 (12)
O5ii—Na1—Na1vi	37.803 (12)	O3x—Na4—Na3xi	36.423 (12)
S4iii—Na1—Na1vi	79.880 (10)	S1x—Na4—Na3xi	52.850 (6)
S3ii—Na1—Na1vi	52.954 (7)	S4xi—Na4—Na3xi	46.673 (6)
S3iii—Na1—Na1vi	49.554 (7)	S2vii—Na4—Na3xi	92.385 (8)
S4iv—Na1—Na1vi	97.138 (11)	Na1ix—Na4—Na3xi	141.291 (10)
Na4iii—Na1—Na1vi	71.532 (10)	Na1xii—Na4—Na3xi	78.487 (8)
Na4v—Na1—Na1vi	133.254 (12)	Na3x—Na4—Na3xi	107.842 (8)
O1—Na2—O6ii	82.24 (2)	O1—S1—O3	111.15 (3)
O1—Na2—O9ii	121.57 (2)	O1—S1—O2	110.51 (3)
O6ii—Na2—O9ii	119.40 (2)	O3—S1—O2	109.00 (3)
O1—Na2—O9i	150.70 (2)	O1—S1—S2	108.98 (2)
O6ii—Na2—O9i	98.37 (2)	O3—S1—S2	107.713 (19)
O9ii—Na2—O9i	83.83 (2)	O2—S1—S2	109.43 (2)
O1—Na2—O10	82.508 (19)	O1—S1—Na4viii	126.09 (2)
O6ii—Na2—O10	155.73 (2)	O3—S1—Na4viii	55.78 (2)
O9ii—Na2—O10	84.74 (2)	O2—S1—Na4viii	53.25 (2)
O9i—Na2—O10	85.998 (19)	S2—S1—Na4viii	124.926 (9)
O1—Na2—Na2iv	159.85 (2)	O1—S1—Na3xiii	133.51 (2)
O6ii—Na2—Na2iv	115.254 (19)	O3—S1—Na3xiii	46.299 (19)
O9ii—Na2—Na2iv	42.140 (14)	O2—S1—Na3xiii	115.357 (19)
O9i—Na2—Na2iv	41.695 (14)	S2—S1—Na3xiii	62.288 (7)
O10—Na2—Na2iv	83.775 (16)	Na4viii—S1—Na3xiii	78.992 (8)
O1—Na2—Na3	58.132 (15)	S1—S2—Na3xiii	80.713 (8)
O6ii—Na2—Na3	139.920 (17)	S1—S2—Na4xiii	123.039 (9)
O9ii—Na2—Na3	81.357 (15)	Na3xiii—S2—Na4xiii	94.364 (8)
O9i—Na2—Na3	118.828 (17)	S1—O1—Na2	146.31 (3)
O10—Na2—Na3	33.841 (13)	S1—O2—Na3	122.37 (3)
Na2iv—Na2—Na3	102.995 (12)	S1—O2—Na4viii	98.24 (2)
O1—Na2—Na1	90.813 (17)	Na3—O2—Na4viii	109.004 (19)
O6ii—Na2—Na1	33.978 (14)	S1—O3—Na3xiii	108.43 (2)
O9ii—Na2—Na1	138.631 (17)	S1—O3—Na4viii	95.58 (2)
O9i—Na2—Na1	75.239 (16)	Na3xiii—O3—Na4viii	106.34 (2)
O10—Na2—Na1	127.834 (17)	O4—S3—O5	111.71 (3)
Na2iv—Na2—Na1	109.277 (12)	O4—S3—O6	110.90 (3)
Na3—Na2—Na1	140.011 (10)	O5—S3—O6	108.66 (3)
O1—Na2—H8	78.8 (3)	O4—S3—S4	107.82 (2)
O6ii—Na2—H8	139.2 (3)	O5—S3—S4	108.64 (2)
O9ii—Na2—H8	101.3 (3)	O6—S3—S4	109.05 (2)
O9i—Na2—H8	82.1 (3)	O4—S3—Na1ii	129.57 (2)
O10—Na2—H8	17.5 (3)	O5—S3—Na1ii	57.81 (2)
Na2iv—Na2—H8	92.2 (3)	O6—S3—Na1ii	50.86 (2)
Na3—Na2—H8	44.3 (3)	S4—S3—Na1ii	122.440 (9)
Na1—Na2—H8	110.5 (3)	O4—S3—Na3	44.20 (2)
O10—Na3—O2	92.728 (19)	O5—S3—Na3	115.89 (2)
O10—Na3—O4	113.74 (2)	O6—S3—Na3	134.61 (2)
O2—Na3—O4	100.217 (19)	S4—S3—Na3	64.862 (7)
O10—Na3—O3vii	91.184 (18)	Na1ii—S3—Na3	170.840 (9)
O2—Na3—O3vii	112.831 (19)	O4—S3—Na1ix	135.24 (3)
O4—Na3—O3vii	137.58 (2)	O5—S3—Na1ix	47.07 (2)
O10—Na3—S2vii	152.055 (17)	O6—S3—Na1ix	113.42 (2)
O2—Na3—S2vii	91.337 (14)	S4—S3—Na1ix	62.814 (7)
O4—Na3—S2vii	92.654 (19)	Na1ii—S3—Na1ix	77.492 (9)
O3vii—Na3—S2vii	61.898 (12)	Na3—S3—Na1ix	103.191 (8)
O10—Na3—S4	83.176 (15)	S3—S4—Na1ix	79.685 (8)
O2—Na3—S4	157.854 (16)	S3—S4—Na3	77.566 (8)
O4—Na3—S4	62.368 (14)	Na1ix—S4—Na3	117.727 (9)
O3vii—Na3—S4	89.069 (14)	S3—S4—Na4i	138.838 (9)
S2vii—Na3—S4	102.479 (9)	Na1ix—S4—Na4i	79.571 (9)
O10—Na3—S3	106.368 (16)	Na3—S4—Na4i	81.298 (8)
O2—Na3—S3	125.470 (15)	S3—S4—Na1iv	127.876 (9)
O4—Na3—S3	25.345 (12)	Na1ix—S4—Na1iv	88.951 (9)
O3vii—Na3—S3	117.147 (15)	Na3—S4—Na1iv	147.809 (9)
S2vii—Na3—S3	93.535 (8)	Na4i—S4—Na1iv	86.748 (8)
S4—Na3—S3	37.573 (5)	S3—O4—Na3	110.46 (3)
O10—Na3—S1vii	116.459 (16)	S3—O5—Na4	126.64 (3)
O2—Na3—S1vii	109.280 (14)	S3—O5—Na1ix	107.13 (2)
O4—Na3—S1vii	119.167 (19)	Na4—O5—Na1ix	97.307 (19)
O3vii—Na3—S1vii	25.276 (10)	S3—O5—Na1ii	93.72 (2)
S2vii—Na3—S1vii	36.999 (5)	Na4—O5—Na1ii	126.97 (2)
S4—Na3—S1vii	91.884 (8)	Na1ix—O5—Na1ii	101.88 (2)
S3—Na3—S1vii	106.583 (9)	S3—O6—Na2ii	126.21 (3)
O10—Na3—Na2	35.370 (14)	S3—O6—Na1ii	101.14 (3)
O2—Na3—Na2	80.167 (14)	Na2ii—O6—Na1ii	113.05 (2)
O4—Na3—Na2	83.528 (19)	Na4iii—O7—Na1	96.27 (2)
O3vii—Na3—Na2	126.537 (14)	Na4iii—O7—H1	114.1 (9)
S2vii—Na3—Na2	169.873 (10)	Na1—O7—H1	106.9 (9)
S4—Na3—Na2	84.098 (8)	Na4iii—O7—H2	113.1 (9)
S3—Na3—Na2	87.028 (8)	Na1—O7—H2	121.0 (9)
S1vii—Na3—Na2	151.796 (10)	H1—O7—H2	105.6 (12)
O10—Na3—Na4viii	76.972 (15)	Na1xi—O8—Na4iii	109.78 (2)
O2—Na3—Na4viii	36.505 (13)	Na1xi—O8—H3	114.0 (9)
O4—Na3—Na4viii	136.702 (15)	Na4iii—O8—H3	109.3 (9)
O3vii—Na3—Na4viii	80.289 (14)	Na1xi—O8—H4	100.8 (13)
S2vii—Na3—Na4viii	90.294 (9)	Na4iii—O8—H4	114.9 (13)
S4—Na3—Na4viii	157.179 (10)	H3—O8—H4	107.9 (15)
S3—Na3—Na4viii	161.760 (10)	Na2ii—O9—Na2xi	96.16 (2)
S1vii—Na3—Na4viii	87.044 (8)	Na2ii—O9—H5	128.6 (13)
Na2—Na3—Na4viii	86.141 (8)	Na2xi—O9—H5	112.6 (12)
O10—Na3—Na4i	83.574 (15)	Na2ii—O9—H6	108.2 (10)
O2—Na3—Na4i	149.322 (16)	Na2xi—O9—H6	111.5 (9)
O4—Na3—Na4i	109.170 (15)	H5—O9—H6	99.8 (14)
O3vii—Na3—Na4i	37.235 (13)	Na3—O10—Na2	110.79 (2)
S2vii—Na3—Na4i	78.954 (8)	Na3—O10—H7	111.9 (9)
S4—Na3—Na4i	52.030 (6)	Na2—O10—H7	118.0 (9)
S3—Na3—Na4i	84.462 (8)	Na3—O10—H8	114.5 (10)
S1vii—Na3—Na4i	48.157 (6)	Na2—O10—H8	92.0 (10)
Na2—Na3—Na4i	111.153 (9)	H7—O10—H8	108.4 (13)
Na4viii—Na3—Na4i	113.778 (9)

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

(Na2S2O3H2O2_200K). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O2viii	0.847 (13)	2.105 (13)	2.9400 (7)	168.4 (12)
O7—H2···O3	0.795 (13)	2.183 (13)	2.9595 (7)	165.6 (13)
O8—H3···O6ii	0.804 (13)	2.303 (14)	3.0991 (7)	170.8 (12)
O8—H4···S2	0.721 (17)	2.600 (17)	3.3188 (5)	175.7 (17)
O9—H5···O1	0.835 (17)	1.994 (18)	2.8237 (7)	172.4 (18)
O9—H6···S4ii	0.808 (14)	2.499 (14)	3.3069 (5)	178.4 (12)
O10—H7···O4i	0.835 (14)	1.930 (14)	2.7602 (7)	172.5 (13)
O10—H8···S2i	0.772 (14)	2.469 (14)	3.2261 (5)	166.9 (13)

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

(Na2S2O3H2O5_100K). Crystal data

O3S2·5(H2O)·2(Na)	F(000) = 512
Mr = 248.18	Dx = 1.777 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.9187 (1) Å	Cell parameters from 69507 reflections
b = 21.5173 (4) Å	θ = 3.0–42.4°
c = 7.4979 (1) Å	µ = 0.67 mm−1
β = 103.722 (1)°	T = 100 K
V = 927.64 (3) Å3	Block, colourless
Z = 4	0.6 × 0.3 × 0.15 mm

(Na2S2O3H2O5_100K). Data collection

Stoe StadiVari diffractometer	6486 independent reflections
Radiation source: Genix 3D HF Mo	5525 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.026
Detector resolution: 5.81 pixels mm-1	θmax = 42.3°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −40→40
Tmin = 0.868, Tmax = 1.000	l = −14→9
64240 measured reflections

(Na2S2O3H2O5_100K). Refinement

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)] = 0.020	Hydrogen site location: difference Fourier map
wR(F2) = 0.047	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0269P)2 + 0.0151P] where P = (Fo2 + 2Fc2)/3
6486 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

(Na2S2O3H2O5_100K). Special details

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

(Na2S2O3H2O5_100K). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.72487 (4)	0.34133 (2)	0.07542 (3)	0.01006 (3)
Na2	0.25504 (4)	0.40853 (2)	0.21568 (3)	0.01143 (4)
S1	0.14781 (2)	0.14166 (2)	0.27653 (2)	0.00683 (2)
S2	0.10308 (2)	0.06742 (2)	0.10544 (2)	0.00895 (2)
O1	0.33884 (6)	0.12823 (2)	0.43602 (5)	0.01248 (6)
O2	−0.07043 (6)	0.15368 (2)	0.33255 (5)	0.01157 (5)
O3	0.20340 (6)	0.19572 (2)	0.17106 (5)	0.01064 (5)
O4	0.62384 (6)	0.23471 (2)	0.09598 (6)	0.01306 (6)
H1	0.505 (2)	0.2244 (6)	0.1222 (17)	0.029 (3)*
H2	0.7229 (19)	0.2157 (6)	0.1692 (16)	0.021 (2)*
O5	0.09097 (6)	0.31382 (2)	0.27759 (5)	0.01099 (5)
H3	0.132 (2)	0.2794 (6)	0.2504 (17)	0.029 (3)*
H4	0.104 (2)	0.3116 (6)	0.3873 (18)	0.026 (3)*
O6	0.61660 (6)	0.36783 (2)	0.35694 (5)	0.01218 (6)
H5	0.620 (2)	0.3354 (7)	0.4218 (18)	0.032 (3)*
H6	0.736 (2)	0.3872 (6)	0.4162 (17)	0.029 (3)*
O7	0.86492 (7)	0.44750 (2)	0.10769 (5)	0.01232 (5)
H7	0.849 (2)	0.4768 (6)	0.1746 (18)	0.028 (3)*
H8	0.806 (2)	0.4592 (6)	0.0042 (17)	0.026 (3)*
O8	0.64754 (6)	0.01526 (2)	0.24596 (6)	0.01309 (6)
H9	0.733 (2)	0.0319 (6)	0.1941 (18)	0.032 (3)*
H10	0.524 (2)	0.0297 (6)	0.2069 (18)	0.033 (3)*

(Na2S2O3H2O5_100K). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.00909 (7)	0.01107 (8)	0.00987 (8)	−0.00034 (6)	0.00196 (6)	−0.00033 (6)
Na2	0.00991 (8)	0.01013 (8)	0.01364 (9)	0.00026 (6)	0.00160 (6)	0.00022 (6)
S1	0.00648 (3)	0.00759 (4)	0.00631 (4)	−0.00005 (3)	0.00127 (3)	0.00026 (3)
S2	0.01010 (4)	0.00757 (4)	0.00881 (4)	−0.00018 (3)	0.00151 (3)	−0.00055 (3)
O1	0.00991 (12)	0.01622 (14)	0.00904 (13)	0.00008 (10)	−0.00225 (9)	0.00048 (10)
O2	0.00971 (12)	0.01476 (14)	0.01171 (13)	0.00181 (10)	0.00544 (10)	0.00062 (10)
O3	0.01410 (13)	0.00786 (12)	0.01111 (13)	−0.00165 (10)	0.00524 (10)	0.00061 (9)
O4	0.01005 (12)	0.01317 (14)	0.01548 (15)	−0.00037 (10)	0.00204 (10)	0.00128 (11)
O5	0.01314 (13)	0.00956 (12)	0.00996 (13)	0.00146 (10)	0.00211 (10)	−0.00052 (9)
O6	0.00987 (12)	0.01442 (14)	0.01149 (14)	−0.00074 (10)	0.00105 (10)	0.00104 (10)
O7	0.01419 (13)	0.01036 (13)	0.01148 (14)	0.00069 (10)	0.00118 (10)	−0.00052 (10)
O8	0.01060 (13)	0.01258 (14)	0.01597 (15)	0.00096 (10)	0.00292 (11)	0.00182 (11)

(Na2S2O3H2O5_100K). Geometric parameters (Å, º)

Na1—O1i	2.3682 (4)	S1—S2	2.0266 (1)
Na1—O4	2.3850 (4)	S1—Na2vi	3.3793 (2)
Na1—O5ii	2.4052 (4)	S2—Na2i	3.2961 (3)
Na1—O6	2.4152 (4)	O1—Na1vi	2.3683 (4)
Na1—O2iii	2.4170 (4)	O1—Na2vi	2.4004 (4)
Na1—O7	2.4227 (4)	O2—Na1vii	2.4170 (4)
Na1—Na2ii	3.3879 (3)	O4—H1	0.808 (12)
Na1—Na2	3.5095 (3)	O4—H2	0.812 (12)
Na1—H8	2.658 (12)	O5—Na1v	2.4052 (4)
Na2—O6	2.3223 (4)	O5—H3	0.820 (13)
Na2—O5	2.3506 (4)	O5—H4	0.809 (13)
Na2—O8iv	2.3686 (4)	O6—H5	0.847 (14)
Na2—O1i	2.4004 (4)	O6—H6	0.850 (13)
Na2—O7v	2.4090 (4)	O7—Na2ii	2.4090 (4)
Na2—S2vi	3.2960 (3)	O7—H7	0.824 (13)
Na2—S1i	3.3793 (2)	O7—H8	0.812 (13)
Na2—Na1v	3.3879 (3)	O8—Na2viii	2.3687 (4)
S1—O1	1.4665 (4)	O8—H9	0.792 (13)
S1—O2	1.4728 (3)	O8—H10	0.785 (14)
S1—O3	1.4867 (4)
O1i—Na1—O4	93.674 (15)	S2vi—Na2—S1i	152.425 (7)
O1i—Na1—O5ii	167.632 (16)	O6—Na2—Na1v	131.763 (13)
O4—Na1—O5ii	85.687 (14)	O5—Na2—Na1v	45.224 (10)
O1i—Na1—O6	83.813 (14)	O8iv—Na2—Na1v	129.225 (13)
O4—Na1—O6	92.752 (15)	O1i—Na2—Na1v	87.492 (11)
O5ii—Na1—O6	83.881 (14)	O7v—Na2—Na1v	45.643 (10)
O1i—Na1—O2iii	104.997 (15)	S2vi—Na2—Na1v	85.113 (6)
O4—Na1—O2iii	105.640 (15)	S1i—Na2—Na1v	67.361 (6)
O5ii—Na1—O2iii	87.024 (14)	O6—Na2—Na1	43.228 (11)
O6—Na1—O2iii	158.798 (16)	O5—Na2—Na1	95.497 (12)
O1i—Na1—O7	93.139 (15)	O8iv—Na2—Na1	104.388 (12)
O4—Na1—O7	170.292 (17)	O1i—Na2—Na1	42.257 (10)
O5ii—Na1—O7	86.177 (14)	O7v—Na2—Na1	143.813 (13)
O6—Na1—O7	81.115 (14)	S2vi—Na2—Na1	137.109 (8)
O2iii—Na1—O7	79.197 (14)	S1i—Na2—Na1	63.600 (6)
O1i—Na1—Na2ii	138.122 (13)	Na1v—Na2—Na1	118.197 (9)
O4—Na1—Na2ii	128.202 (12)	O1—S1—O2	111.14 (2)
O5ii—Na1—Na2ii	43.924 (10)	O1—S1—O3	111.28 (2)
O6—Na1—Na2ii	92.647 (11)	O2—S1—O3	109.52 (2)
O2iii—Na1—Na2ii	67.791 (11)	O1—S1—S2	108.693 (17)
O7—Na1—Na2ii	45.314 (10)	O2—S1—S2	109.098 (16)
O1i—Na1—Na2	42.968 (10)	O3—S1—S2	106.994 (15)
O4—Na1—Na2	98.530 (12)	O1—S1—Na2vi	38.016 (16)
O5ii—Na1—Na2	124.885 (12)	O2—S1—Na2vi	75.695 (16)
O6—Na1—Na2	41.191 (10)	O3—S1—Na2vi	138.961 (15)
O2iii—Na1—Na2	141.432 (13)	S2—S1—Na2vi	109.327 (6)
O7—Na1—Na2	81.849 (11)	S1—S2—Na2i	114.539 (6)
Na2ii—Na1—Na2	118.197 (9)	S1—O1—Na1vi	141.43 (2)
O1i—Na1—H8	81.3 (3)	S1—O1—Na2vi	119.88 (2)
O4—Na1—H8	172.1 (3)	Na1vi—O1—Na2vi	94.775 (14)
O5ii—Na1—H8	100.6 (3)	S1—O2—Na1vii	148.53 (2)
O6—Na1—H8	92.8 (3)	Na1—O4—H1	121.7 (9)
O2iii—Na1—H8	70.1 (3)	Na1—O4—H2	112.1 (8)
O7—Na1—H8	17.6 (3)	H1—O4—H2	103.3 (12)
Na2ii—Na1—H8	57.2 (3)	Na2—O5—Na1v	90.850 (14)
Na2—Na1—H8	82.0 (3)	Na2—O5—H3	124.9 (9)
O6—Na2—O5	87.830 (15)	Na1v—O5—H3	110.0 (9)
O6—Na2—O8iv	97.981 (16)	Na2—O5—H4	108.0 (9)
O5—Na2—O8iv	156.443 (17)	Na1v—O5—H4	120.6 (9)
O6—Na2—O1i	85.131 (15)	H3—O5—H4	103.7 (12)
O5—Na2—O1i	93.865 (15)	Na2—O6—Na1	95.581 (15)
O8iv—Na2—O1i	109.318 (16)	Na2—O6—H5	117.9 (9)
O6—Na2—O7v	172.157 (17)	Na1—O6—H5	109.3 (9)
O5—Na2—O7v	87.719 (15)	Na2—O6—H6	128.0 (9)
O8iv—Na2—O7v	83.664 (14)	Na1—O6—H6	102.3 (8)
O1i—Na2—O7v	101.611 (15)	H5—O6—H6	101.4 (12)
O6—Na2—S2vi	94.048 (12)	Na2ii—O7—Na1	89.042 (14)
O5—Na2—S2vi	75.443 (11)	Na2ii—O7—H7	107.4 (9)
O8iv—Na2—S2vi	81.366 (12)	Na1—O7—H7	134.1 (9)
O1i—Na2—S2vi	169.304 (13)	Na2ii—O7—H8	126.3 (8)
O7v—Na2—S2vi	78.579 (11)	Na1—O7—H8	97.8 (9)
O6—Na2—S1i	105.285 (12)	H7—O7—H8	105.0 (12)
O5—Na2—S1i	85.665 (11)	Na2viii—O8—H9	109.5 (10)
O8iv—Na2—S1i	114.344 (13)	Na2viii—O8—H10	127.3 (10)
O1i—Na2—S1i	22.102 (9)	H9—O8—H10	106.5 (13)
O7v—Na2—S1i	80.806 (11)

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

(Na2S2O3H2O5_100K). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O3	0.808 (12)	2.001 (12)	2.8067 (5)	176.1 (13)
O4—H2···O2ii	0.812 (12)	2.017 (12)	2.8175 (5)	168.6 (12)
O5—H3···O3	0.820 (13)	1.973 (13)	2.7912 (5)	174.9 (12)
O5—H4···O3vi	0.809 (13)	2.074 (13)	2.8736 (5)	169.2 (12)
O6—H5···O4vi	0.847 (14)	1.993 (14)	2.8365 (6)	173.8 (13)
O6—H6···S2ix	0.850 (13)	2.495 (13)	3.3404 (4)	173.6 (12)
O7—H7···S2iv	0.824 (13)	2.527 (13)	3.3356 (4)	167.5 (11)
O7—H8···O8i	0.812 (13)	2.017 (13)	2.8280 (6)	177.2 (12)
O8—H9···S2ii	0.792 (13)	2.554 (13)	3.3147 (4)	161.6 (12)
O8—H10···S2	0.785 (14)	2.558 (14)	3.3381 (4)	173.0 (13)

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

(Na2S2O3H2O5_200K). Crystal data

O3S2·5(H2O)·2(Na)	F(000) = 512
Mr = 248.18	Dx = 1.769 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.9357 (1) Å	Cell parameters from 72911 reflections
b = 21.5424 (7) Å	θ = 3.4–38.4°
c = 7.5026 (2) Å	µ = 0.67 mm−1
β = 103.722 (2)°	T = 200 K
V = 931.97 (4) Å3	Block, colourless
Z = 4	0.6 × 0.3 × 0.15 mm

(Na2S2O3H2O5_200K). Data collection

Stoe StadiVari diffractometer	5006 independent reflections
Radiation source: Genix 3D HF Mo	4212 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.023
Detector resolution: 5.81 pixels mm-1	θmax = 38.1°, θmin = 3.4°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −37→37
Tmin = 0.869, Tmax = 1.000	l = −12→12
56700 measured reflections

(Na2S2O3H2O5_200K). Refinement

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)] = 0.019	Hydrogen site location: difference Fourier map
wR(F2) = 0.052	All H-atom parameters refined
S = 1.08	w = 1/[σ2(Fo2) + (0.0284P)2 + 0.0519P] where P = (Fo2 + 2Fc2)/3
5006 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

(Na2S2O3H2O5_200K). Special details

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

(Na2S2O3H2O5_200K). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.72432 (4)	0.34120 (2)	0.07497 (3)	0.01737 (5)
Na2	0.25469 (5)	0.40844 (2)	0.21534 (4)	0.02015 (5)
S1	0.14796 (2)	0.14165 (2)	0.27688 (2)	0.01199 (3)
S2	0.10261 (3)	0.06772 (2)	0.10611 (2)	0.01584 (3)
O1	0.33851 (8)	0.12808 (3)	0.43550 (6)	0.02186 (9)
O2	−0.06889 (8)	0.15357 (2)	0.33334 (7)	0.02022 (9)
O3	0.20282 (8)	0.19559 (2)	0.17211 (6)	0.01850 (8)
O4	0.62336 (9)	0.23466 (2)	0.09666 (7)	0.02250 (9)
H1	0.510 (3)	0.2256 (6)	0.1234 (19)	0.050 (4)*
H2	0.722 (2)	0.2159 (5)	0.1725 (16)	0.029 (3)*
O5	0.09082 (9)	0.31379 (2)	0.27781 (7)	0.01859 (8)
H3	0.135 (2)	0.2789 (6)	0.2509 (17)	0.041 (3)*
H4	0.100 (2)	0.3107 (6)	0.3837 (18)	0.037 (3)*
O6	0.61589 (8)	0.36779 (3)	0.35662 (7)	0.02082 (9)
H5	0.616 (2)	0.3358 (6)	0.4249 (18)	0.042 (3)*
H6	0.734 (2)	0.3882 (6)	0.4170 (17)	0.046 (3)*
O7	0.86448 (9)	0.44752 (2)	0.10841 (7)	0.02104 (9)
H7	0.851 (2)	0.4775 (6)	0.1719 (18)	0.042 (3)*
H8	0.801 (2)	0.4599 (6)	−0.0005 (19)	0.042 (3)*
O8	0.64707 (9)	0.01512 (2)	0.24637 (8)	0.02268 (9)
H9	0.734 (3)	0.0327 (7)	0.194 (2)	0.053 (4)*
H10	0.528 (3)	0.0308 (6)	0.2099 (19)	0.049 (4)*

(Na2S2O3H2O5_200K). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.01558 (11)	0.01926 (12)	0.01702 (11)	−0.00067 (9)	0.00338 (9)	−0.00062 (8)
Na2	0.01729 (12)	0.01729 (12)	0.02491 (13)	0.00058 (9)	0.00308 (9)	0.00077 (9)
S1	0.01134 (5)	0.01321 (6)	0.01121 (5)	−0.00010 (4)	0.00228 (4)	0.00042 (4)
S2	0.01840 (6)	0.01296 (6)	0.01544 (6)	−0.00045 (4)	0.00258 (5)	−0.00103 (4)
O1	0.01746 (19)	0.0281 (2)	0.01595 (18)	0.00009 (17)	−0.00416 (15)	0.00017 (16)
O2	0.01731 (19)	0.0257 (2)	0.02027 (19)	0.00338 (16)	0.00971 (16)	0.00130 (16)
O3	0.0247 (2)	0.01328 (18)	0.01982 (19)	−0.00270 (15)	0.00978 (16)	0.00071 (14)
O4	0.0169 (2)	0.0227 (2)	0.0272 (2)	−0.00065 (17)	0.00376 (18)	0.00230 (18)
O5	0.0227 (2)	0.01597 (19)	0.01668 (18)	0.00263 (16)	0.00376 (15)	−0.00085 (14)
O6	0.01690 (19)	0.0251 (2)	0.0192 (2)	−0.00092 (17)	0.00170 (16)	0.00212 (16)
O7	0.0241 (2)	0.0170 (2)	0.0204 (2)	0.00113 (17)	0.00206 (17)	−0.00118 (16)
O8	0.0185 (2)	0.0208 (2)	0.0287 (2)	0.00186 (17)	0.00558 (18)	0.00340 (17)

(Na2S2O3H2O5_200K). Geometric parameters (Å, º)

Na1—O1i	2.3750 (5)	S1—S2	2.0216 (2)
Na1—O4	2.3872 (6)	S1—Na2vi	3.3761 (3)
Na1—O5ii	2.4138 (6)	S2—Na2i	3.3060 (3)
Na1—O6	2.4193 (6)	O1—Na1vi	2.3750 (5)
Na1—O2iii	2.4210 (5)	O1—Na2vi	2.4020 (6)
Na1—O7	2.4294 (6)	O2—Na1vii	2.4211 (5)
Na1—Na2ii	3.3978 (4)	O4—H1	0.774 (15)
Na1—Na2	3.5172 (4)	O4—H2	0.820 (12)
Na2—O6	2.3256 (6)	O5—Na1v	2.4138 (6)
Na2—O5	2.3536 (6)	O5—H3	0.836 (13)
Na2—O8iv	2.3717 (6)	O5—H4	0.786 (13)
Na2—O1i	2.4021 (6)	O6—H5	0.859 (14)
Na2—O7v	2.4157 (6)	O6—H6	0.860 (14)
Na2—S2vi	3.3060 (3)	O7—Na2ii	2.4157 (6)
Na2—S1i	3.3761 (3)	O7—H7	0.818 (14)
Na2—Na1v	3.3978 (4)	O7—H8	0.857 (14)
S1—O1	1.4637 (5)	O8—Na2viii	2.3718 (6)
S1—O2	1.4700 (5)	O8—H9	0.813 (15)
S1—O3	1.4818 (5)	O8—H10	0.775 (15)
O1i—Na1—O4	93.81 (2)	O1i—Na2—Na1v	87.607 (15)
O1i—Na1—O5ii	167.57 (2)	O7v—Na2—Na1v	45.635 (14)
O4—Na1—O5ii	85.708 (19)	S2vi—Na2—Na1v	85.025 (8)
O1i—Na1—O6	83.704 (19)	S1i—Na2—Na1v	67.409 (7)
O4—Na1—O6	92.58 (2)	O6—Na2—Na1	43.196 (14)
O5ii—Na1—O6	83.912 (18)	O5—Na2—Na1	95.577 (15)
O1i—Na1—O2iii	105.32 (2)	O8iv—Na2—Na1	104.229 (16)
O4—Na1—O2iii	106.02 (2)	O1i—Na2—Na1	42.288 (13)
O5ii—Na1—O2iii	86.693 (19)	O7v—Na2—Na1	144.062 (17)
O6—Na1—O2iii	158.46 (2)	S2vi—Na2—Na1	137.059 (10)
O1i—Na1—O7	93.07 (2)	S1i—Na2—Na1	63.609 (7)
O4—Na1—O7	169.96 (2)	Na1v—Na2—Na1	118.260 (11)
O5ii—Na1—O7	85.995 (19)	O1—S1—O2	111.17 (3)
O6—Na1—O7	80.912 (19)	O1—S1—O3	111.30 (3)
O2iii—Na1—O7	79.125 (19)	O2—S1—O3	109.48 (3)
O1i—Na1—Na2ii	138.025 (17)	O1—S1—S2	108.60 (2)
O4—Na1—Na2ii	128.156 (17)	O2—S1—S2	109.04 (2)
O5ii—Na1—Na2ii	43.834 (13)	O3—S1—S2	107.13 (2)
O6—Na1—Na2ii	92.705 (15)	O1—S1—Na2vi	38.16 (2)
O2iii—Na1—Na2ii	67.367 (14)	O2—S1—Na2vi	75.51 (2)
O7—Na1—Na2ii	45.307 (14)	O3—S1—Na2vi	138.89 (2)
O1i—Na1—Na2	42.885 (14)	S2—S1—Na2vi	109.377 (8)
O4—Na1—Na2	98.391 (16)	S1—S2—Na2i	114.600 (8)
O5ii—Na1—Na2	124.870 (16)	S1—O1—Na1vi	141.35 (3)
O6—Na1—Na2	41.148 (13)	S1—O1—Na2vi	119.72 (3)
O2iii—Na1—Na2	141.592 (17)	Na1vi—O1—Na2vi	94.828 (18)
O7—Na1—Na2	81.785 (15)	S1—O2—Na1vii	149.10 (3)
Na2ii—Na1—Na2	118.261 (11)	Na1—O4—H1	120.6 (10)
O6—Na2—O5	87.88 (2)	Na1—O4—H2	111.8 (8)
O6—Na2—O8iv	97.82 (2)	H1—O4—H2	102.6 (12)
O5—Na2—O8iv	156.45 (2)	Na2—O5—Na1v	90.905 (19)
O6—Na2—O1i	85.146 (19)	Na2—O5—H3	124.4 (9)
O5—Na2—O1i	94.10 (2)	Na1v—O5—H3	110.7 (8)
O8iv—Na2—O1i	109.10 (2)	Na2—O5—H4	110.0 (9)
O6—Na2—O7v	171.97 (2)	Na1v—O5—H4	119.5 (9)
O5—Na2—O7v	87.654 (19)	H3—O5—H4	102.6 (12)
O8iv—Na2—O7v	83.76 (2)	Na2—O6—Na1	95.66 (2)
O1i—Na2—O7v	101.82 (2)	Na2—O6—H5	116.3 (9)
O6—Na2—S2vi	94.040 (15)	Na1—O6—H5	111.7 (9)
O5—Na2—S2vi	75.245 (14)	Na2—O6—H6	126.7 (9)
O8iv—Na2—S2vi	81.549 (16)	Na1—O6—H6	103.2 (9)
O1i—Na2—S2vi	169.337 (17)	H5—O6—H6	102.2 (12)
O7v—Na2—S2vi	78.368 (15)	Na2ii—O7—Na1	89.058 (19)
O6—Na2—S1i	105.273 (16)	Na2ii—O7—H7	107.5 (9)
O5—Na2—S1i	85.774 (14)	Na1—O7—H7	136.6 (9)
O8iv—Na2—S1i	114.306 (17)	Na2ii—O7—H8	126.5 (9)
O1i—Na2—S1i	22.118 (12)	Na1—O7—H8	97.7 (9)
O7v—Na2—S1i	81.039 (15)	H7—O7—H8	103.1 (12)
S2vi—Na2—S1i	152.391 (10)	Na2viii—O8—H9	110.1 (10)
O6—Na2—Na1v	131.833 (17)	Na2viii—O8—H10	130.1 (10)
O5—Na2—Na1v	45.260 (14)	H9—O8—H10	105.0 (13)
O8iv—Na2—Na1v	129.328 (17)

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

(Na2S2O3H2O5_200K). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O3	0.774 (15)	2.045 (15)	2.8161 (7)	174.2 (14)
O4—H2···O2ii	0.820 (12)	2.022 (12)	2.8290 (7)	168.0 (11)
O5—H3···O3	0.836 (13)	1.961 (13)	2.7937 (7)	173.8 (12)
O5—H4···O3vi	0.786 (13)	2.109 (13)	2.8811 (7)	167.3 (12)
O6—H5···O4vi	0.859 (14)	1.984 (14)	2.8423 (8)	176.3 (13)
O6—H6···S2ix	0.860 (14)	2.495 (14)	3.3488 (5)	171.7 (12)
O7—H7···S2iv	0.818 (14)	2.531 (14)	3.3365 (5)	168.3 (12)
O7—H8···O8i	0.857 (14)	1.977 (14)	2.8334 (8)	177.3 (13)
O8—H9···S2ii	0.813 (15)	2.544 (15)	3.3245 (6)	161.3 (13)
O8—H10···S2	0.775 (15)	2.583 (15)	3.3499 (5)	171.0 (14)

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