Crystal structure of sodium thio­sulfate dihydrate and comparison to the penta­hydrate

Klein, W.

doi:10.1107/S2056989022011975

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Volume 79| Part 1| January 2023| Pages 44-49

https://doi.org/10.1107/S2056989022011975

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Crystal structure of sodium thiosulfate dihydrate and comparison to the pentahydrate

Wilhelm Klein ^a ^*

^aTechnische Universität München, School of Natural Sciences, Lichtenbergstrasse 4, 85747 Garching, Germany
^*Correspondence e-mail: wilhelm.klein@tum.de

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 7 December 2022; accepted 18 December 2022; online 1 January 2023)

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.

Keywords: crystal structure; thiosulfate; sodium; hydrate; hydrogen bonding.

CCDC references: 2227273; 2227272; 2227271; 2227270

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 Å³), 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. 1a), no structural change has been observed down to 100 K. The same is true for the crystal structure of the pentahydrate, Na₂S₂O₃·5H₂O (Fig. 1b), 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 [ $[\overline{1}]$ 00]; (b) section of two layers of S₂O₃²⁻ anions and H₂O molecules connected by hydrogen bonds, view along [ $[\overline{1}]$ 01], differently coloured tetrahedra belong to different layers. Anisotropic displacement ellipsoids of non-H atoms are drawn with 80% probability, S₂O₃²⁻ ions as tetrahedra, and hydrogen bonds as dashed lines.

The four independent Na⁺ cations are coordinated irregularly by the S₂O₃²⁻ dianions in mono- or bidentate manner and by H₂O, as illustrated in Fig. 3a–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. 3e,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).

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) ; (iii) x+1, y, z.

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⋯S2^iv	0.824 (13)	2.527 (13)	3.3356 (4)	167.5 (11)
O7—H8⋯O8^v	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) x+1, y, z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

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. 5a. These dimeric units (e.g. blue S₂O₃ tetrahedra and H₂O molecules in Fig. 5b) are connected via two further H₂O molecules (pink in Fig. 5b) with a second dimer (green in Fig. 5b). The resulting tetramers are again interlinked with neighbouring tetramers (yellow and red tetrahedra in Fig. 5b) by water molecules, thereby forming corrugated layers lying parallel to (101), also shown in Fig. 2b. 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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC references: 2227273; 2227272; 2227271; 2227270

Crystal structure: contains datablocks global, Na2S2O3H2O2_100K, Na2S2O3H2O2_200K, Na2S2O3H2O5_100K, Na2S2O3H2O5_200K. DOI: https://doi.org/10.1107/S2056989022011975/hb8046sup1.cif

Structure factors: contains datablock Na2S2O3H2O2_100K. DOI: https://doi.org/10.1107/S2056989022011975/hb8046Na2S2O3H2O2_100Ksup2.hkl

Structure factors: contains datablock Na2S2O3H2O2_200K. DOI: https://doi.org/10.1107/S2056989022011975/hb8046Na2S2O3H2O2_200Ksup3.hkl

Structure factors: contains datablock Na2S2O3H2O5_100K. DOI: https://doi.org/10.1107/S2056989022011975/hb8046Na2S2O3H2O5_100Ksup4.hkl

Structure factors: contains datablock Na2S2O3H2O5_200K. DOI: https://doi.org/10.1107/S2056989022011975/hb8046Na2S2O3H2O5_200Ksup5.hkl

checkCIF report

Computing details top

For all structures, data collection: X-AREA (Stoe & Cie, 2015); cell refinement: X-AREA (Stoe & Cie, 2015); data reduction: X-AREA (Stoe & Cie, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2012).

Sodium thiosulfate dihydrate (Na2S2O3H2O2_100K) top

Crystal data top

Na₂S₂O₃·2H₂O	F(000) = 784
M_r = 194.13	D_x = 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

Data collection top

Stoe StadiVari diffractometer	8735 independent reflections
Radiation source: Genix 3D HF Mo	7524 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.019
Detector resolution: 5.81 pixels mm^-1	θ_max = 42.3°, θ_min = 3.6°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −24→36
T_min = 0.919, T_max = 1.000	l = −21→21
52592 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)] = 0.017	Hydrogen site location: difference Fourier map
wR(F²) = 0.047	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0285P)² + 0.0499P] where P = (F_o² + 2F_c²)/3
8735 reflections	(Δ/σ)_max = 0.002
195 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Na1—O8ⁱ	2.3882 (5)	Na4—Na3^x	3.9395 (3)
Na1—O6ⁱⁱ	2.4451 (5)	Na4—Na3^xi	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—Na4^viii	3.0636 (3)
Na1—S4^iv	3.1898 (3)	S1—Na3^xiii	3.2694 (3)
Na1—S3ⁱⁱⁱ	3.2338 (3)	S2—Na3^xiii	2.9354 (3)
Na1—Na4ⁱⁱⁱ	3.6173 (3)	S2—Na4^xiii	3.2208 (3)
Na1—Na4^v	3.9337 (3)	O2—Na4^viii	2.4708 (4)
Na1—Na1^vi	3.9694 (5)	O3—Na3^xiii	2.4883 (4)
Na2—O1	2.3307 (4)	O3—Na4^viii	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—Na2^iv	3.5475 (5)	S3—Na1ⁱⁱ	3.0917 (3)
Na2—Na3	3.8866 (3)	S3—Na1^ix	3.2338 (3)
Na2—H8	2.557 (12)	S4—Na1^ix	2.9295 (3)
Na3—O10	2.3169 (5)	S4—Na1^iv	3.1897 (3)
Na3—O2	2.3636 (4)	S4—Na4ⁱ	3.1981 (3)
Na3—O4	2.3845 (5)	O5—Na1^ix	2.4771 (5)
Na3—O3^vii	2.4884 (4)	O5—Na1ⁱⁱ	2.6213 (5)
Na3—S2^vii	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—S1^vii	3.2694 (3)	O7—H1	0.844 (11)
Na3—Na4^viii	3.9395 (3)	O7—H2	0.782 (12)
Na3—Na4ⁱ	4.0357 (3)	O8—Na1^xi	2.3882 (5)
Na4—O5	2.3423 (4)	O8—Na4ⁱⁱⁱ	2.4316 (5)
Na4—O7^ix	2.4017 (5)	O8—H3	0.827 (12)
Na4—O8^ix	2.4317 (5)	O8—H4	0.772 (14)
Na4—O2^x	2.4708 (4)	O9—Na2ⁱⁱ	2.3793 (5)
Na4—O3^x	2.5536 (4)	O9—Na2^xi	2.3947 (5)
Na4—S1^x	3.0636 (2)	O9—H5	0.851 (15)
Na4—S4^xi	3.1981 (3)	O9—H6	0.825 (13)
Na4—S2^vii	3.2208 (3)	O10—H7	0.828 (13)
Na4—Na1^ix	3.6173 (3)	O10—H8	0.810 (13)
Na4—Na1^xii	3.9337 (3)

O8ⁱ—Na1—O6ⁱⁱ	118.400 (16)	O5—Na4—O7^ix	84.197 (15)
O8ⁱ—Na1—O7	82.178 (15)	O5—Na4—O8^ix	92.899 (16)
O6ⁱⁱ—Na1—O7	88.032 (15)	O7^ix—Na4—O8^ix	80.483 (15)
O8ⁱ—Na1—O5ⁱⁱⁱ	138.729 (17)	O5—Na4—O2^x	164.794 (17)
O6ⁱⁱ—Na1—O5ⁱⁱⁱ	98.068 (15)	O7^ix—Na4—O2^x	106.048 (16)
O7—Na1—O5ⁱⁱⁱ	80.357 (15)	O8^ix—Na4—O2^x	78.118 (14)
O8ⁱ—Na1—O5ⁱⁱ	137.591 (16)	O5—Na4—O3^x	123.483 (16)
O6ⁱⁱ—Na1—O5ⁱⁱ	56.628 (13)	O7^ix—Na4—O3^x	132.507 (17)
O7—Na1—O5ⁱⁱ	134.460 (16)	O8^ix—Na4—O3^x	128.636 (15)
O5ⁱⁱⁱ—Na1—O5ⁱⁱ	77.780 (15)	O2^x—Na4—O3^x	57.417 (12)
O8ⁱ—Na1—S4ⁱⁱⁱ	86.073 (12)	O5—Na4—S1^x	150.169 (14)
O6ⁱⁱ—Na1—S4ⁱⁱⁱ	154.130 (13)	O7^ix—Na4—S1^x	122.393 (13)
O7—Na1—S4ⁱⁱⁱ	104.610 (12)	O8^ix—Na4—S1^x	103.959 (12)
O5ⁱⁱⁱ—Na1—S4ⁱⁱⁱ	62.959 (10)	O2^x—Na4—S1^x	28.631 (9)
O5ⁱⁱ—Na1—S4ⁱⁱⁱ	100.155 (11)	O3^x—Na4—S1^x	28.794 (9)
O8ⁱ—Na1—S3ⁱⁱ	133.571 (13)	O5—Na4—S4^xi	67.401 (11)
O6ⁱⁱ—Na1—S3ⁱⁱ	28.098 (9)	O7^ix—Na4—S4^xi	144.113 (14)
O7—Na1—S3ⁱⁱ	112.008 (13)	O8^ix—Na4—S4^xi	79.579 (12)
O5ⁱⁱⁱ—Na1—S3ⁱⁱ	87.693 (11)	O2^x—Na4—S4^xi	98.634 (12)
O5ⁱⁱ—Na1—S3ⁱⁱ	28.531 (9)	O3^x—Na4—S4^xi	82.850 (11)
S4ⁱⁱⁱ—Na1—S3ⁱⁱ	127.864 (9)	S1^x—Na4—S4^xi	91.346 (7)
O8ⁱ—Na1—S4^iv	73.118 (12)	O5—Na4—S2^vii	100.525 (12)
O6ⁱⁱ—Na1—S4^iv	88.603 (12)	O7^ix—Na4—S2^vii	74.571 (12)
O7—Na1—S4^iv	149.747 (13)	O8^ix—Na4—S2^vii	150.145 (13)
O5ⁱⁱⁱ—Na1—S4^iv	129.865 (13)	O2^x—Na4—S2^vii	93.140 (11)
O5ⁱⁱ—Na1—S4^iv	64.918 (10)	O3^x—Na4—S2^vii	63.633 (10)
S4ⁱⁱⁱ—Na1—S4^iv	91.068 (7)	S1^x—Na4—S2^vii	76.791 (6)
S3ⁱⁱ—Na1—S4^iv	75.409 (6)	S4^xi—Na4—S2^vii	130.207 (8)
O8ⁱ—Na1—S3ⁱⁱⁱ	121.015 (13)	O5—Na4—Na1^ix	42.791 (11)
O6ⁱⁱ—Na1—S3ⁱⁱⁱ	120.330 (12)	O7^ix—Na4—Na1^ix	42.373 (11)
O7—Na1—S3ⁱⁱⁱ	94.657 (12)	O8^ix—Na4—Na1^ix	78.527 (12)
O5ⁱⁱⁱ—Na1—S3ⁱⁱⁱ	25.963 (9)	O2^x—Na4—Na1^ix	143.576 (12)
O5ⁱⁱ—Na1—S3ⁱⁱⁱ	82.368 (11)	O3^x—Na4—Na1^ix	152.820 (13)
S4ⁱⁱⁱ—Na1—S3ⁱⁱⁱ	37.616 (4)	S1^x—Na4—Na1^ix	164.477 (9)
S3ⁱⁱ—Na1—S3ⁱⁱⁱ	102.300 (7)	S4^xi—Na4—Na1^ix	104.156 (8)
S4^iv—Na1—S3ⁱⁱⁱ	112.843 (8)	S2^vii—Na4—Na1^ix	93.397 (7)
O8ⁱ—Na1—Na4ⁱⁱⁱ	118.543 (13)	O5—Na4—Na1^xii	89.810 (12)
O6ⁱⁱ—Na1—Na4ⁱⁱⁱ	87.500 (12)	O7^ix—Na4—Na1^xii	114.775 (13)
O7—Na1—Na4ⁱⁱⁱ	41.293 (11)	O8^ix—Na4—Na1^xii	34.934 (10)
O5ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	39.967 (10)	O2^x—Na4—Na1^xii	75.773 (11)
O5ⁱⁱ—Na1—Na4ⁱⁱⁱ	103.685 (11)	O3^x—Na4—Na1^xii	104.000 (11)
S4ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	87.559 (7)	S1^x—Na4—Na1^xii	90.270 (7)
S3ⁱⁱ—Na1—Na4ⁱⁱⁱ	96.159 (8)	S4^xi—Na4—Na1^xii	47.125 (5)
S4^iv—Na1—Na4ⁱⁱⁱ	168.094 (9)	S2^vii—Na4—Na1^xii	166.945 (8)
S3ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	60.141 (6)	Na1^ix—Na4—Na1^xii	99.620 (8)
O8ⁱ—Na1—Na4^v	35.666 (11)	O5—Na4—Na3^x	153.485 (13)
O6ⁱⁱ—Na1—Na4^v	152.675 (13)	O7^ix—Na4—Na3^x	71.525 (12)
O7—Na1—Na4^v	80.568 (11)	O8^ix—Na4—Na3^x	73.117 (12)
O5ⁱⁱⁱ—Na1—Na4^v	104.310 (12)	O2^x—Na4—Na3^x	34.529 (10)
O5ⁱⁱ—Na1—Na4^v	143.591 (12)	O3^x—Na4—Na3^x	81.957 (11)
S4ⁱⁱⁱ—Na1—Na4^v	53.130 (5)	S1^x—Na4—Na3^x	56.340 (6)
S3ⁱⁱ—Na1—Na4^v	164.219 (9)	S4^xi—Na4—Na3^x	129.098 (8)
S4^iv—Na1—Na4^v	88.948 (7)	S2^vii—Na4—Na3^x	83.498 (7)
S3ⁱⁱⁱ—Na1—Na4^v	85.509 (7)	Na1^ix—Na4—Na3^x	111.170 (8)
Na4ⁱⁱⁱ—Na1—Na4^v	99.621 (8)	Na1^xii—Na4—Na3^x	90.819 (7)
O8ⁱ—Na1—Na1^vi	163.063 (16)	O5—Na4—Na3^xi	98.206 (12)
O6ⁱⁱ—Na1—Na1^vi	73.997 (11)	O7^ix—Na4—Na3^xi	166.439 (14)
O7—Na1—Na1^vi	110.978 (14)	O8^ix—Na4—Na3^xi	112.594 (12)
O5ⁱⁱⁱ—Na1—Na1^vi	40.198 (10)	O2^x—Na4—Na3^xi	74.523 (10)
O5ⁱⁱ—Na1—Na1^vi	37.582 (9)	O3^x—Na4—Na3^xi	36.277 (10)
S4ⁱⁱⁱ—Na1—Na1^vi	80.371 (8)	S1^x—Na4—Na3^xi	52.703 (5)
S3ⁱⁱ—Na1—Na1^vi	52.748 (6)	S4^xi—Na4—Na3^xi	46.719 (5)
S4^iv—Na1—Na1^vi	96.895 (9)	S2^vii—Na4—Na3^xi	91.873 (7)
S3ⁱⁱⁱ—Na1—Na1^vi	49.552 (6)	Na1^ix—Na4—Na3^xi	140.915 (8)
Na4ⁱⁱⁱ—Na1—Na1^vi	71.213 (8)	Na1^xii—Na4—Na3^xi	78.663 (6)
Na4^v—Na1—Na1^vi	133.293 (10)	Na3^x—Na4—Na3^xi	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—Na4^viii	126.430 (16)
O9ⁱⁱ—Na2—O10	84.685 (15)	O3—S1—Na4^viii	56.126 (16)
O6ⁱⁱ—Na2—O10	154.570 (17)	O2—S1—Na4^viii	52.913 (16)
O9ⁱ—Na2—O10	85.577 (16)	S2—S1—Na4^viii	124.628 (7)
O1—Na2—Na2^iv	160.062 (17)	O1—S1—Na3^xiii	133.400 (18)
O9ⁱⁱ—Na2—Na2^iv	42.172 (11)	O3—S1—Na3^xiii	46.304 (15)
O6ⁱⁱ—Na2—Na2^iv	116.288 (15)	O2—S1—Na3^xiii	115.505 (16)
O9ⁱ—Na2—Na2^iv	41.840 (11)	S2—S1—Na3^xiii	62.309 (6)
O10—Na2—Na2^iv	83.443 (13)	Na4^viii—S1—Na3^xiii	79.101 (7)
O1—Na2—Na3	58.255 (12)	S1—S2—Na3^xiii	80.481 (7)
O9ⁱⁱ—Na2—Na3	81.351 (12)	S1—S2—Na4^xiii	123.174 (7)
O6ⁱⁱ—Na2—Na3	139.441 (13)	Na3^xiii—S2—Na4^xiii	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)
Na2^iv—Na2—Na3	102.788 (10)	S1—O2—Na4^viii	98.46 (2)
O1—Na2—Na1	91.058 (13)	Na3—O2—Na4^viii	109.136 (16)
O9ⁱⁱ—Na2—Na1	138.654 (13)	S1—O3—Na3^xiii	108.20 (2)
O6ⁱⁱ—Na2—Na1	34.248 (10)	S1—O3—Na4^viii	95.079 (19)
O9ⁱ—Na2—Na1	74.270 (12)	Na3^xiii—O3—Na4^viii	106.335 (16)
O10—Na2—Na1	126.973 (13)	O4—S3—O5	111.71 (2)
Na2^iv—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)
Na2^iv—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—O3^vii	91.667 (15)	Na1ⁱⁱ—S3—Na3	169.724 (7)
O2—Na3—O3^vii	112.361 (16)	O4—S3—Na1^ix	135.99 (2)
O4—Na3—O3^vii	138.171 (17)	O5—S3—Na1^ix	47.128 (16)
O10—Na3—S2^vii	152.992 (14)	O6—S3—Na1^ix	112.854 (17)
O2—Na3—S2^vii	91.069 (12)	S4—S3—Na1^ix	62.944 (6)
O4—Na3—S2^vii	92.745 (14)	Na1ⁱⁱ—S3—Na1^ix	77.699 (7)
O3^vii—Na3—S2^vii	62.335 (10)	Na3—S3—Na1^ix	103.422 (7)
O10—Na3—S4	83.204 (12)	S3—S4—Na1^ix	79.440 (7)
O2—Na3—S4	158.528 (13)	S3—S4—Na3	77.431 (6)
O4—Na3—S4	62.715 (11)	Na1^ix—S4—Na3	117.818 (8)
O3^vii—Na3—S4	88.861 (11)	S3—S4—Na1^iv	126.733 (7)
S2^vii—Na3—S4	102.249 (8)	Na1^ix—S4—Na1^iv	88.932 (7)
O10—Na3—S3	106.058 (13)	Na3—S4—Na1^iv	148.524 (7)
O2—Na3—S3	125.851 (13)	S3—S4—Na4ⁱ	138.919 (7)
O4—Na3—S3	25.595 (10)	Na1^ix—S4—Na4ⁱ	79.744 (7)
O3^vii—Na3—S3	117.222 (12)	Na3—S4—Na4ⁱ	81.648 (7)
S2^vii—Na3—S3	93.258 (7)	Na1^iv—S4—Na4ⁱ	87.727 (7)
S4—Na3—S3	37.733 (4)	S3—O4—Na3	110.00 (2)
O10—Na3—S1^vii	117.162 (13)	S3—O5—Na4	127.49 (2)
O2—Na3—S1^vii	108.846 (12)	S3—O5—Na1^ix	106.91 (2)
O4—Na3—S1^vii	119.596 (14)	Na4—O5—Na1^ix	97.241 (16)
O3^vii—Na3—S1^vii	25.496 (9)	S3—O5—Na1ⁱⁱ	93.680 (19)
S2^vii—Na3—S1^vii	37.209 (4)	Na4—O5—Na1ⁱⁱ	126.101 (17)
S4—Na3—S1^vii	91.674 (7)	Na1^ix—O5—Na1ⁱⁱ	102.221 (15)
S3—Na3—S1^vii	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)
O3^vii—Na3—Na2	127.067 (12)	Na4ⁱⁱⁱ—O7—H1	114.7 (8)
S2^vii—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)
S1^vii—Na3—Na2	152.539 (8)	H1—O7—H2	105.7 (11)
O10—Na3—Na4^viii	77.064 (12)	Na1^xi—O8—Na4ⁱⁱⁱ	109.400 (17)
O2—Na3—Na4^viii	36.336 (10)	Na1^xi—O8—H3	114.8 (8)
O4—Na3—Na4^viii	136.606 (12)	Na4ⁱⁱⁱ—O8—H3	109.6 (8)
O3^vii—Na3—Na4^viii	80.031 (11)	Na1^xi—O8—H4	100.9 (10)
S2^vii—Na3—Na4^viii	90.445 (7)	Na4ⁱⁱⁱ—O8—H4	114.1 (10)
S4—Na3—Na4^viii	156.961 (8)	H3—O8—H4	107.9 (13)
S3—Na3—Na4^viii	161.959 (8)	Na2ⁱⁱ—O9—Na2^xi	95.988 (16)
S1^vii—Na3—Na4^viii	86.918 (7)	Na2ⁱⁱ—O9—H5	126.2 (10)
Na2—Na3—Na4^viii	86.578 (7)	Na2^xi—O9—H5	112.6 (10)
O10—Na3—Na4ⁱ	84.262 (12)	Na2ⁱⁱ—O9—H6	107.7 (9)
O2—Na3—Na4ⁱ	149.099 (13)	Na2^xi—O9—H6	111.6 (9)
O4—Na3—Na4ⁱ	109.260 (12)	H5—O9—H6	102.7 (12)
O3^vii—Na3—Na4ⁱ	37.389 (10)	Na3—O10—Na2	110.678 (17)
S2^vii—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)
S1^vii—Na3—Na4ⁱ	48.197 (5)	Na2—O10—H8	91.3 (9)
Na2—Na3—Na4ⁱ	111.661 (7)	H7—O10—H8	110.2 (12)
Na4^viii—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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O2^viii	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) top

Crystal data top

O₃S₂·2(H₂O)·2(Na)	F(000) = 784
M_r = 194.13	D_x = 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

Data collection top

Stoe StadiVari diffractometer	8848 independent reflections
Radiation source: Genix 3D HF Mo	7181 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.024
Detector resolution: 5.81 pixels mm^-1	θ_max = 42.3°, θ_min = 3.6°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −24→36
T_min = 0.920, T_max = 1.000	l = −21→21
55208 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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F²) = 0.057	All H-atom parameters refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0343P)²] where P = (F_o² + 2F_c²)/3
8848 reflections	(Δ/σ)_max = 0.002
195 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Na1—O8ⁱ	2.3873 (6)	Na4—Na3^x	3.9539 (4)
Na1—O6ⁱⁱ	2.4447 (6)	Na4—Na3^xi	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—Na4^viii	3.0727 (3)
Na1—S3ⁱⁱⁱ	3.2433 (3)	S1—Na3^xiii	3.2875 (3)
Na1—S4^iv	3.2470 (3)	S2—Na3^xiii	2.9490 (3)
Na1—Na4ⁱⁱⁱ	3.6275 (4)	S2—Na4^xiii	3.2520 (3)
Na1—Na4^v	3.9492 (4)	O2—Na4^viii	2.4878 (5)
Na1—Na1^vi	3.9670 (6)	O3—Na3^xiii	2.5051 (5)
Na2—O1	2.3372 (5)	O3—Na4^viii	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—Na2^iv	3.5650 (6)	S3—Na1ⁱⁱ	3.0924 (3)
Na2—Na3	3.9000 (4)	S3—Na1^ix	3.2432 (3)
Na2—H8	2.560 (13)	S4—Na1^ix	2.9323 (3)
Na3—O10	2.3231 (6)	S4—Na4ⁱ	3.2288 (3)
Na3—O2	2.3681 (5)	S4—Na1^iv	3.2470 (3)
Na3—O4	2.3914 (6)	O5—Na1^ix	2.4848 (6)
Na3—O3^vii	2.5051 (5)	O5—Na1ⁱⁱ	2.6227 (6)
Na3—S2^vii	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—S1^vii	3.2874 (3)	O7—H1	0.847 (13)
Na3—Na4^viii	3.9540 (4)	O7—H2	0.795 (13)
Na3—Na4ⁱ	4.0486 (4)	O8—Na1^xi	2.3872 (6)
Na4—O5	2.3456 (5)	O8—Na4ⁱⁱⁱ	2.4403 (6)
Na4—O7^ix	2.4105 (6)	O8—H3	0.804 (13)
Na4—O8^ix	2.4403 (6)	O8—H4	0.721 (17)
Na4—O2^x	2.4877 (5)	O9—Na2ⁱⁱ	2.3851 (6)
Na4—O3^x	2.5529 (6)	O9—Na2^xi	2.4059 (6)
Na4—S1^x	3.0726 (3)	O9—H5	0.835 (17)
Na4—S4^xi	3.2289 (3)	O9—H6	0.808 (14)
Na4—S2^vii	3.2520 (3)	O10—H7	0.835 (14)
Na4—Na1^ix	3.6275 (4)	O10—H8	0.772 (14)
Na4—Na1^xii	3.9493 (4)

O8ⁱ—Na1—O6ⁱⁱ	117.81 (2)	O5—Na4—O7^ix	84.30 (2)
O8ⁱ—Na1—O7	82.834 (19)	O5—Na4—O8^ix	92.37 (2)
O6ⁱⁱ—Na1—O7	89.01 (2)	O7^ix—Na4—O8^ix	80.573 (19)
O8ⁱ—Na1—O5ⁱⁱⁱ	139.09 (2)	O5—Na4—O2^x	164.65 (2)
O6ⁱⁱ—Na1—O5ⁱⁱⁱ	98.969 (19)	O7^ix—Na4—O2^x	105.701 (19)
O7—Na1—O5ⁱⁱⁱ	80.403 (18)	O8^ix—Na4—O2^x	78.158 (18)
O8ⁱ—Na1—O5ⁱⁱ	136.44 (2)	O5—Na4—O3^x	124.20 (2)
O6ⁱⁱ—Na1—O5ⁱⁱ	56.453 (16)	O7^ix—Na4—O3^x	132.33 (2)
O7—Na1—O5ⁱⁱ	135.01 (2)	O8^ix—Na4—O3^x	128.304 (19)
O5ⁱⁱⁱ—Na1—O5ⁱⁱ	78.12 (2)	O2^x—Na4—O3^x	57.124 (15)
O8ⁱ—Na1—S4ⁱⁱⁱ	86.263 (16)	O5—Na4—S1^x	150.730 (17)
O6ⁱⁱ—Na1—S4ⁱⁱⁱ	153.927 (16)	O7^ix—Na4—S1^x	121.920 (17)
O7—Na1—S4ⁱⁱⁱ	104.804 (16)	O8^ix—Na4—S1^x	103.888 (16)
O5ⁱⁱⁱ—Na1—S4ⁱⁱⁱ	62.763 (12)	O2^x—Na4—S1^x	28.502 (10)
O5ⁱⁱ—Na1—S4ⁱⁱⁱ	99.662 (14)	O3^x—Na4—S1^x	28.635 (10)
O8ⁱ—Na1—S3ⁱⁱ	132.852 (17)	O5—Na4—S4^xi	67.748 (14)
O6ⁱⁱ—Na1—S3ⁱⁱ	27.992 (11)	O7^ix—Na4—S4^xi	144.363 (17)
O7—Na1—S3ⁱⁱ	112.607 (16)	O8^ix—Na4—S4^xi	79.041 (15)
O5ⁱⁱⁱ—Na1—S3ⁱⁱ	88.056 (14)	O2^x—Na4—S4^xi	98.321 (14)
O5ⁱⁱ—Na1—S3ⁱⁱ	28.468 (11)	O3^x—Na4—S4^xi	82.917 (13)
S4ⁱⁱⁱ—Na1—S3ⁱⁱ	127.348 (11)	S1^x—Na4—S4^xi	91.333 (8)
O8ⁱ—Na1—S3ⁱⁱⁱ	121.104 (16)	O5—Na4—S2^vii	100.986 (16)
O6ⁱⁱ—Na1—S3ⁱⁱⁱ	120.962 (16)	O7^ix—Na4—S2^vii	74.230 (15)
O7—Na1—S3ⁱⁱⁱ	94.456 (15)	O8^ix—Na4—S2^vii	149.970 (17)
O5ⁱⁱⁱ—Na1—S3ⁱⁱⁱ	25.800 (11)	O2^x—Na4—S2^vii	93.044 (14)
O5ⁱⁱ—Na1—S3ⁱⁱⁱ	82.631 (13)	O3^x—Na4—S2^vii	64.017 (12)
S4ⁱⁱⁱ—Na1—S3ⁱⁱⁱ	37.501 (5)	S1^x—Na4—S2^vii	76.829 (8)
S3ⁱⁱ—Na1—S3ⁱⁱⁱ	102.508 (9)	S4^xi—Na4—S2^vii	130.911 (10)
O8ⁱ—Na1—S4^iv	71.943 (15)	O5—Na4—Na1^ix	42.800 (14)
O6ⁱⁱ—Na1—S4^iv	87.582 (16)	O7^ix—Na4—Na1^ix	42.386 (14)
O7—Na1—S4^iv	149.277 (16)	O8^ix—Na4—Na1^ix	78.499 (15)
O5ⁱⁱⁱ—Na1—S4^iv	130.273 (16)	O2^x—Na4—Na1^ix	143.281 (15)
O5ⁱⁱ—Na1—S4^iv	64.881 (13)	O3^x—Na4—Na1^ix	153.189 (16)
S4ⁱⁱⁱ—Na1—S4^iv	91.048 (9)	S1^x—Na4—Na1^ix	164.044 (11)
S3ⁱⁱ—Na1—S4^iv	75.144 (8)	S4^xi—Na4—Na1^ix	104.579 (10)
S3ⁱⁱⁱ—Na1—S4^iv	113.356 (10)	S2^vii—Na4—Na1^ix	93.185 (9)
O8ⁱ—Na1—Na4ⁱⁱⁱ	119.081 (17)	O5—Na4—Na1^xii	89.768 (15)
O6ⁱⁱ—Na1—Na4ⁱⁱⁱ	89.002 (17)	O7^ix—Na4—Na1^xii	114.701 (16)
O7—Na1—Na4ⁱⁱⁱ	41.342 (13)	O8^ix—Na4—Na1^xii	34.668 (13)
O5ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	39.891 (12)	O2^x—Na4—Na1^xii	75.547 (14)
O5ⁱⁱ—Na1—Na4ⁱⁱⁱ	104.346 (15)	O3^x—Na4—Na1^xii	103.732 (14)
S4ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	87.283 (9)	S1^x—Na4—Na1^xii	90.121 (9)
S3ⁱⁱ—Na1—Na4ⁱⁱⁱ	97.020 (10)	S4^xi—Na4—Na1^xii	46.906 (7)
S3ⁱⁱⁱ—Na1—Na4ⁱⁱⁱ	59.736 (7)	S2^vii—Na4—Na1^xii	166.892 (10)
S4^iv—Na1—Na4ⁱⁱⁱ	168.666 (11)	Na1^ix—Na4—Na1^xii	99.823 (10)
O8ⁱ—Na1—Na4^v	35.554 (14)	O5—Na4—Na3^x	153.064 (17)
O6ⁱⁱ—Na1—Na4^v	152.272 (16)	O7^ix—Na4—Na3^x	71.212 (15)
O7—Na1—Na4^v	80.915 (15)	O8^ix—Na4—Na3^x	73.120 (14)
O5ⁱⁱⁱ—Na1—Na4^v	104.647 (15)	O2^x—Na4—Na3^x	34.492 (11)
O5ⁱⁱ—Na1—Na4^v	142.833 (15)	O3^x—Na4—Na3^x	81.785 (13)
S4ⁱⁱⁱ—Na1—Na4^v	53.522 (7)	S1^x—Na4—Na3^x	56.206 (7)
S3ⁱⁱ—Na1—Na4^v	163.151 (11)	S4^xi—Na4—Na3^x	128.605 (10)
S3ⁱⁱⁱ—Na1—Na4^v	85.734 (8)	S2^vii—Na4—Na3^x	83.368 (8)
S4^iv—Na1—Na4^v	88.121 (8)	Na1^ix—Na4—Na3^x	110.847 (10)
Na4ⁱⁱⁱ—Na1—Na4^v	99.823 (10)	Na1^xii—Na4—Na3^x	90.440 (9)
O8ⁱ—Na1—Na1^vi	162.27 (2)	O5—Na4—Na3^xi	98.583 (15)
O6ⁱⁱ—Na1—Na1^vi	74.472 (14)	O7^ix—Na4—Na3^xi	166.615 (18)
O7—Na1—Na1^vi	111.295 (17)	O8^ix—Na4—Na3^xi	112.225 (16)
O5ⁱⁱⁱ—Na1—Na1^vi	40.314 (13)	O2^x—Na4—Na3^xi	74.432 (12)
O5ⁱⁱ—Na1—Na1^vi	37.803 (12)	O3^x—Na4—Na3^xi	36.423 (12)
S4ⁱⁱⁱ—Na1—Na1^vi	79.880 (10)	S1^x—Na4—Na3^xi	52.850 (6)
S3ⁱⁱ—Na1—Na1^vi	52.954 (7)	S4^xi—Na4—Na3^xi	46.673 (6)
S3ⁱⁱⁱ—Na1—Na1^vi	49.554 (7)	S2^vii—Na4—Na3^xi	92.385 (8)
S4^iv—Na1—Na1^vi	97.138 (11)	Na1^ix—Na4—Na3^xi	141.291 (10)
Na4ⁱⁱⁱ—Na1—Na1^vi	71.532 (10)	Na1^xii—Na4—Na3^xi	78.487 (8)
Na4^v—Na1—Na1^vi	133.254 (12)	Na3^x—Na4—Na3^xi	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—Na4^viii	126.09 (2)
O6ⁱⁱ—Na2—O10	155.73 (2)	O3—S1—Na4^viii	55.78 (2)
O9ⁱⁱ—Na2—O10	84.74 (2)	O2—S1—Na4^viii	53.25 (2)
O9ⁱ—Na2—O10	85.998 (19)	S2—S1—Na4^viii	124.926 (9)
O1—Na2—Na2^iv	159.85 (2)	O1—S1—Na3^xiii	133.51 (2)
O6ⁱⁱ—Na2—Na2^iv	115.254 (19)	O3—S1—Na3^xiii	46.299 (19)
O9ⁱⁱ—Na2—Na2^iv	42.140 (14)	O2—S1—Na3^xiii	115.357 (19)
O9ⁱ—Na2—Na2^iv	41.695 (14)	S2—S1—Na3^xiii	62.288 (7)
O10—Na2—Na2^iv	83.775 (16)	Na4^viii—S1—Na3^xiii	78.992 (8)
O1—Na2—Na3	58.132 (15)	S1—S2—Na3^xiii	80.713 (8)
O6ⁱⁱ—Na2—Na3	139.920 (17)	S1—S2—Na4^xiii	123.039 (9)
O9ⁱⁱ—Na2—Na3	81.357 (15)	Na3^xiii—S2—Na4^xiii	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)
Na2^iv—Na2—Na3	102.995 (12)	S1—O2—Na4^viii	98.24 (2)
O1—Na2—Na1	90.813 (17)	Na3—O2—Na4^viii	109.004 (19)
O6ⁱⁱ—Na2—Na1	33.978 (14)	S1—O3—Na3^xiii	108.43 (2)
O9ⁱⁱ—Na2—Na1	138.631 (17)	S1—O3—Na4^viii	95.58 (2)
O9ⁱ—Na2—Na1	75.239 (16)	Na3^xiii—O3—Na4^viii	106.34 (2)
O10—Na2—Na1	127.834 (17)	O4—S3—O5	111.71 (3)
Na2^iv—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)
Na2^iv—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—O3^vii	91.184 (18)	Na1ⁱⁱ—S3—Na3	170.840 (9)
O2—Na3—O3^vii	112.831 (19)	O4—S3—Na1^ix	135.24 (3)
O4—Na3—O3^vii	137.58 (2)	O5—S3—Na1^ix	47.07 (2)
O10—Na3—S2^vii	152.055 (17)	O6—S3—Na1^ix	113.42 (2)
O2—Na3—S2^vii	91.337 (14)	S4—S3—Na1^ix	62.814 (7)
O4—Na3—S2^vii	92.654 (19)	Na1ⁱⁱ—S3—Na1^ix	77.492 (9)
O3^vii—Na3—S2^vii	61.898 (12)	Na3—S3—Na1^ix	103.191 (8)
O10—Na3—S4	83.176 (15)	S3—S4—Na1^ix	79.685 (8)
O2—Na3—S4	157.854 (16)	S3—S4—Na3	77.566 (8)
O4—Na3—S4	62.368 (14)	Na1^ix—S4—Na3	117.727 (9)
O3^vii—Na3—S4	89.069 (14)	S3—S4—Na4ⁱ	138.838 (9)
S2^vii—Na3—S4	102.479 (9)	Na1^ix—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—Na1^iv	127.876 (9)
O4—Na3—S3	25.345 (12)	Na1^ix—S4—Na1^iv	88.951 (9)
O3^vii—Na3—S3	117.147 (15)	Na3—S4—Na1^iv	147.809 (9)
S2^vii—Na3—S3	93.535 (8)	Na4ⁱ—S4—Na1^iv	86.748 (8)
S4—Na3—S3	37.573 (5)	S3—O4—Na3	110.46 (3)
O10—Na3—S1^vii	116.459 (16)	S3—O5—Na4	126.64 (3)
O2—Na3—S1^vii	109.280 (14)	S3—O5—Na1^ix	107.13 (2)
O4—Na3—S1^vii	119.167 (19)	Na4—O5—Na1^ix	97.307 (19)
O3^vii—Na3—S1^vii	25.276 (10)	S3—O5—Na1ⁱⁱ	93.72 (2)
S2^vii—Na3—S1^vii	36.999 (5)	Na4—O5—Na1ⁱⁱ	126.97 (2)
S4—Na3—S1^vii	91.884 (8)	Na1^ix—O5—Na1ⁱⁱ	101.88 (2)
S3—Na3—S1^vii	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)
O3^vii—Na3—Na2	126.537 (14)	Na4ⁱⁱⁱ—O7—H1	114.1 (9)
S2^vii—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)
S1^vii—Na3—Na2	151.796 (10)	H1—O7—H2	105.6 (12)
O10—Na3—Na4^viii	76.972 (15)	Na1^xi—O8—Na4ⁱⁱⁱ	109.78 (2)
O2—Na3—Na4^viii	36.505 (13)	Na1^xi—O8—H3	114.0 (9)
O4—Na3—Na4^viii	136.702 (15)	Na4ⁱⁱⁱ—O8—H3	109.3 (9)
O3^vii—Na3—Na4^viii	80.289 (14)	Na1^xi—O8—H4	100.8 (13)
S2^vii—Na3—Na4^viii	90.294 (9)	Na4ⁱⁱⁱ—O8—H4	114.9 (13)
S4—Na3—Na4^viii	157.179 (10)	H3—O8—H4	107.9 (15)
S3—Na3—Na4^viii	161.760 (10)	Na2ⁱⁱ—O9—Na2^xi	96.16 (2)
S1^vii—Na3—Na4^viii	87.044 (8)	Na2ⁱⁱ—O9—H5	128.6 (13)
Na2—Na3—Na4^viii	86.141 (8)	Na2^xi—O9—H5	112.6 (12)
O10—Na3—Na4ⁱ	83.574 (15)	Na2ⁱⁱ—O9—H6	108.2 (10)
O2—Na3—Na4ⁱ	149.322 (16)	Na2^xi—O9—H6	111.5 (9)
O4—Na3—Na4ⁱ	109.170 (15)	H5—O9—H6	99.8 (14)
O3^vii—Na3—Na4ⁱ	37.235 (13)	Na3—O10—Na2	110.79 (2)
S2^vii—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)
S1^vii—Na3—Na4ⁱ	48.157 (6)	Na2—O10—H8	92.0 (10)
Na2—Na3—Na4ⁱ	111.153 (9)	H7—O10—H8	108.4 (13)
Na4^viii—Na3—Na4ⁱ	113.778 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O2^viii	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) top

Crystal data top

O₃S₂·5(H₂O)·2(Na)	F(000) = 512
M_r = 248.18	D_x = 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

Data collection top

Stoe StadiVari diffractometer	6486 independent reflections
Radiation source: Genix 3D HF Mo	5525 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.026
Detector resolution: 5.81 pixels mm^-1	θ_max = 42.3°, θ_min = 3.0°
ω scans	h = −11→11
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −40→40
T_min = 0.868, T_max = 1.000	l = −14→9
64240 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)] = 0.020	Hydrogen site location: difference Fourier map
wR(F²) = 0.047	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0269P)² + 0.0151P] where P = (F_o² + 2F_c²)/3
6486 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Na1—O1ⁱ	2.3682 (4)	S1—S2	2.0266 (1)
Na1—O4	2.3850 (4)	S1—Na2^vi	3.3793 (2)
Na1—O5ⁱⁱ	2.4052 (4)	S2—Na2ⁱ	3.2961 (3)
Na1—O6	2.4152 (4)	O1—Na1^vi	2.3683 (4)
Na1—O2ⁱⁱⁱ	2.4170 (4)	O1—Na2^vi	2.4004 (4)
Na1—O7	2.4227 (4)	O2—Na1^vii	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—Na1^v	2.4052 (4)
Na2—O6	2.3223 (4)	O5—H3	0.820 (13)
Na2—O5	2.3506 (4)	O5—H4	0.809 (13)
Na2—O8^iv	2.3686 (4)	O6—H5	0.847 (14)
Na2—O1ⁱ	2.4004 (4)	O6—H6	0.850 (13)
Na2—O7^v	2.4090 (4)	O7—Na2ⁱⁱ	2.4090 (4)
Na2—S2^vi	3.2960 (3)	O7—H7	0.824 (13)
Na2—S1ⁱ	3.3793 (2)	O7—H8	0.812 (13)
Na2—Na1^v	3.3879 (3)	O8—Na2^viii	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)	S2^vi—Na2—S1ⁱ	152.425 (7)
O1ⁱ—Na1—O5ⁱⁱ	167.632 (16)	O6—Na2—Na1^v	131.763 (13)
O4—Na1—O5ⁱⁱ	85.687 (14)	O5—Na2—Na1^v	45.224 (10)
O1ⁱ—Na1—O6	83.813 (14)	O8^iv—Na2—Na1^v	129.225 (13)
O4—Na1—O6	92.752 (15)	O1ⁱ—Na2—Na1^v	87.492 (11)
O5ⁱⁱ—Na1—O6	83.881 (14)	O7^v—Na2—Na1^v	45.643 (10)
O1ⁱ—Na1—O2ⁱⁱⁱ	104.997 (15)	S2^vi—Na2—Na1^v	85.113 (6)
O4—Na1—O2ⁱⁱⁱ	105.640 (15)	S1ⁱ—Na2—Na1^v	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)	O8^iv—Na2—Na1	104.388 (12)
O4—Na1—O7	170.292 (17)	O1ⁱ—Na2—Na1	42.257 (10)
O5ⁱⁱ—Na1—O7	86.177 (14)	O7^v—Na2—Na1	143.813 (13)
O6—Na1—O7	81.115 (14)	S2^vi—Na2—Na1	137.109 (8)
O2ⁱⁱⁱ—Na1—O7	79.197 (14)	S1ⁱ—Na2—Na1	63.600 (6)
O1ⁱ—Na1—Na2ⁱⁱ	138.122 (13)	Na1^v—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—Na2^vi	38.016 (16)
O5ⁱⁱ—Na1—Na2	124.885 (12)	O2—S1—Na2^vi	75.695 (16)
O6—Na1—Na2	41.191 (10)	O3—S1—Na2^vi	138.961 (15)
O2ⁱⁱⁱ—Na1—Na2	141.432 (13)	S2—S1—Na2^vi	109.327 (6)
O7—Na1—Na2	81.849 (11)	S1—S2—Na2ⁱ	114.539 (6)
Na2ⁱⁱ—Na1—Na2	118.197 (9)	S1—O1—Na1^vi	141.43 (2)
O1ⁱ—Na1—H8	81.3 (3)	S1—O1—Na2^vi	119.88 (2)
O4—Na1—H8	172.1 (3)	Na1^vi—O1—Na2^vi	94.775 (14)
O5ⁱⁱ—Na1—H8	100.6 (3)	S1—O2—Na1^vii	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—Na1^v	90.850 (14)
Na2—Na1—H8	82.0 (3)	Na2—O5—H3	124.9 (9)
O6—Na2—O5	87.830 (15)	Na1^v—O5—H3	110.0 (9)
O6—Na2—O8^iv	97.981 (16)	Na2—O5—H4	108.0 (9)
O5—Na2—O8^iv	156.443 (17)	Na1^v—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)
O8^iv—Na2—O1ⁱ	109.318 (16)	Na2—O6—H5	117.9 (9)
O6—Na2—O7^v	172.157 (17)	Na1—O6—H5	109.3 (9)
O5—Na2—O7^v	87.719 (15)	Na2—O6—H6	128.0 (9)
O8^iv—Na2—O7^v	83.664 (14)	Na1—O6—H6	102.3 (8)
O1ⁱ—Na2—O7^v	101.611 (15)	H5—O6—H6	101.4 (12)
O6—Na2—S2^vi	94.048 (12)	Na2ⁱⁱ—O7—Na1	89.042 (14)
O5—Na2—S2^vi	75.443 (11)	Na2ⁱⁱ—O7—H7	107.4 (9)
O8^iv—Na2—S2^vi	81.366 (12)	Na1—O7—H7	134.1 (9)
O1ⁱ—Na2—S2^vi	169.304 (13)	Na2ⁱⁱ—O7—H8	126.3 (8)
O7^v—Na2—S2^vi	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)	Na2^viii—O8—H9	109.5 (10)
O8^iv—Na2—S1ⁱ	114.344 (13)	Na2^viii—O8—H10	127.3 (10)
O1ⁱ—Na2—S1ⁱ	22.102 (9)	H9—O8—H10	106.5 (13)
O7^v—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.

Hydrogen-bond geometry (Å, º) top

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···O3^vi	0.809 (13)	2.074 (13)	2.8736 (5)	169.2 (12)
O6—H5···O4^vi	0.847 (14)	1.993 (14)	2.8365 (6)	173.8 (13)
O6—H6···S2^ix	0.850 (13)	2.495 (13)	3.3404 (4)	173.6 (12)
O7—H7···S2^iv	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) top

Crystal data top

O₃S₂·5(H₂O)·2(Na)	F(000) = 512
M_r = 248.18	D_x = 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

Data collection top

Stoe StadiVari diffractometer	5006 independent reflections
Radiation source: Genix 3D HF Mo	4212 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.023
Detector resolution: 5.81 pixels mm^-1	θ_max = 38.1°, θ_min = 3.4°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015)	k = −37→37
T_min = 0.869, T_max = 1.000	l = −12→12
56700 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)] = 0.019	Hydrogen site location: difference Fourier map
wR(F²) = 0.052	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0284P)² + 0.0519P] where P = (F_o² + 2F_c²)/3
5006 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Na1—O1ⁱ	2.3750 (5)	S1—S2	2.0216 (2)
Na1—O4	2.3872 (6)	S1—Na2^vi	3.3761 (3)
Na1—O5ⁱⁱ	2.4138 (6)	S2—Na2ⁱ	3.3060 (3)
Na1—O6	2.4193 (6)	O1—Na1^vi	2.3750 (5)
Na1—O2ⁱⁱⁱ	2.4210 (5)	O1—Na2^vi	2.4020 (6)
Na1—O7	2.4294 (6)	O2—Na1^vii	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—Na1^v	2.4138 (6)
Na2—O5	2.3536 (6)	O5—H3	0.836 (13)
Na2—O8^iv	2.3717 (6)	O5—H4	0.786 (13)
Na2—O1ⁱ	2.4021 (6)	O6—H5	0.859 (14)
Na2—O7^v	2.4157 (6)	O6—H6	0.860 (14)
Na2—S2^vi	3.3060 (3)	O7—Na2ⁱⁱ	2.4157 (6)
Na2—S1ⁱ	3.3761 (3)	O7—H7	0.818 (14)
Na2—Na1^v	3.3978 (4)	O7—H8	0.857 (14)
S1—O1	1.4637 (5)	O8—Na2^viii	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—Na1^v	87.607 (15)
O1ⁱ—Na1—O5ⁱⁱ	167.57 (2)	O7^v—Na2—Na1^v	45.635 (14)
O4—Na1—O5ⁱⁱ	85.708 (19)	S2^vi—Na2—Na1^v	85.025 (8)
O1ⁱ—Na1—O6	83.704 (19)	S1ⁱ—Na2—Na1^v	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)	O8^iv—Na2—Na1	104.229 (16)
O4—Na1—O2ⁱⁱⁱ	106.02 (2)	O1ⁱ—Na2—Na1	42.288 (13)
O5ⁱⁱ—Na1—O2ⁱⁱⁱ	86.693 (19)	O7^v—Na2—Na1	144.062 (17)
O6—Na1—O2ⁱⁱⁱ	158.46 (2)	S2^vi—Na2—Na1	137.059 (10)
O1ⁱ—Na1—O7	93.07 (2)	S1ⁱ—Na2—Na1	63.609 (7)
O4—Na1—O7	169.96 (2)	Na1^v—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—Na2^vi	38.16 (2)
O2ⁱⁱⁱ—Na1—Na2ⁱⁱ	67.367 (14)	O2—S1—Na2^vi	75.51 (2)
O7—Na1—Na2ⁱⁱ	45.307 (14)	O3—S1—Na2^vi	138.89 (2)
O1ⁱ—Na1—Na2	42.885 (14)	S2—S1—Na2^vi	109.377 (8)
O4—Na1—Na2	98.391 (16)	S1—S2—Na2ⁱ	114.600 (8)
O5ⁱⁱ—Na1—Na2	124.870 (16)	S1—O1—Na1^vi	141.35 (3)
O6—Na1—Na2	41.148 (13)	S1—O1—Na2^vi	119.72 (3)
O2ⁱⁱⁱ—Na1—Na2	141.592 (17)	Na1^vi—O1—Na2^vi	94.828 (18)
O7—Na1—Na2	81.785 (15)	S1—O2—Na1^vii	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—O8^iv	97.82 (2)	H1—O4—H2	102.6 (12)
O5—Na2—O8^iv	156.45 (2)	Na2—O5—Na1^v	90.905 (19)
O6—Na2—O1ⁱ	85.146 (19)	Na2—O5—H3	124.4 (9)
O5—Na2—O1ⁱ	94.10 (2)	Na1^v—O5—H3	110.7 (8)
O8^iv—Na2—O1ⁱ	109.10 (2)	Na2—O5—H4	110.0 (9)
O6—Na2—O7^v	171.97 (2)	Na1^v—O5—H4	119.5 (9)
O5—Na2—O7^v	87.654 (19)	H3—O5—H4	102.6 (12)
O8^iv—Na2—O7^v	83.76 (2)	Na2—O6—Na1	95.66 (2)
O1ⁱ—Na2—O7^v	101.82 (2)	Na2—O6—H5	116.3 (9)
O6—Na2—S2^vi	94.040 (15)	Na1—O6—H5	111.7 (9)
O5—Na2—S2^vi	75.245 (14)	Na2—O6—H6	126.7 (9)
O8^iv—Na2—S2^vi	81.549 (16)	Na1—O6—H6	103.2 (9)
O1ⁱ—Na2—S2^vi	169.337 (17)	H5—O6—H6	102.2 (12)
O7^v—Na2—S2^vi	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)
O8^iv—Na2—S1ⁱ	114.306 (17)	Na2ⁱⁱ—O7—H8	126.5 (9)
O1ⁱ—Na2—S1ⁱ	22.118 (12)	Na1—O7—H8	97.7 (9)
O7^v—Na2—S1ⁱ	81.039 (15)	H7—O7—H8	103.1 (12)
S2^vi—Na2—S1ⁱ	152.391 (10)	Na2^viii—O8—H9	110.1 (10)
O6—Na2—Na1^v	131.833 (17)	Na2^viii—O8—H10	130.1 (10)
O5—Na2—Na1^v	45.260 (14)	H9—O8—H10	105.0 (13)
O8^iv—Na2—Na1^v	129.328 (17)

Hydrogen-bond geometry (Å, º) top

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···O3^vi	0.786 (13)	2.109 (13)	2.8811 (7)	167.3 (12)
O6—H5···O4^vi	0.859 (14)	1.984 (14)	2.8423 (8)	176.3 (13)
O6—H6···S2^ix	0.860 (14)	2.495 (14)	3.3488 (5)	171.7 (12)
O7—H7···S2^iv	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.

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Volume 79| Part 1| January 2023| Pages 44-49

https://doi.org/10.1107/S2056989022011975

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of sodium thio­sulfate dihydrate and comparison to the penta­hydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structure of sodium thiosulfate dihydrate and comparison to the pentahydrate

3. Supramolecular features