1. Chemical context
Thiosulfates containing the S2O32– 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 [00]; (b) section of two layers of S2O32− 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, 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 S2O32– 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, S2O32– 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).
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) x+1, y, z. | |
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) x+1, y, z; (ii) ; (iii) ; (iv) ; (v) . | |
| 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 S2O32– 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 S2O32– 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 S2O32– 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 S2O32– 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.
| 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 | Mr | 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) | Tmin, Tmax | 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 | Rint | 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 | 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). | |
Supporting information
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 |
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 |
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 | 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 | |
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(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 |
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 | 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)* | |
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—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. |
Hydrogen-bond geometry (Å, º) top 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. |
Crystal data top 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 |
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 | 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 | |
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(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 |
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 | 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)* | |
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—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. |
Hydrogen-bond geometry (Å, º) top 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. |
Crystal data top 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 |
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 | 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 | |
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(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 |
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 | 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)* | |
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—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. |
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···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. |
Crystal data top 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 |
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 | 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 | |
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(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 |
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 | 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)* | |
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—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. |
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···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. |
References
Barberá, J. J., Metzger, A. & Wolf, M. (2012). Ullmanns Encyclopedia of Industrial Chemistry, vol. 34, pp. 695–704. Weinheim: Wiley-CH. Google Scholar
Benda, H. von & von Benda, K. (1979). Z. Naturforsch. Teil B, 34, 957–968. CrossRef Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bunte, H. (1874). Ber. Dtsch. Chem. Ges. 7, 646–648. CrossRef Google Scholar
Chan, E. J., Skelton, B. W. & White, A. H. (2008). Z. Anorg. Allg. Chem. 634, 2825–2844. CrossRef CAS Google Scholar
Christensen, A. N., Hazell, R. G., Hewat, A. W. & O'Reilly, K. P. J. (1991). Acta Chem. Scand. 45, 469–473. CrossRef ICSD CAS Web of Science Google Scholar
Csordás, L. (1969). Acta Chim. Acad. Sci. Hung. 62, 371–393. Google Scholar
Dalton, E. Z., Blomberg, W. R. & Villa, E. M. (2021). Cryst. Growth Des. 21, 3071–3081. CrossRef CAS Google Scholar
Edwards, D. A. & Woolf, A. A. (1985). Polyhedron, 4, 513–516. CrossRef CAS Google Scholar
Elerman, Y., Bats, J. W. & Fuess, H. (1983). Acta Cryst. C39, 515–518. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Gagné, O. C. & Hawthorne, F. C. (2016). Acta Cryst. B72, 602–625. Web of Science CrossRef IUCr Journals Google Scholar
Guarini, G. G. T. & Piccini, S. (1988). J. Chem. Soc. Faraday Trans. 1, 84, 331–342. Google Scholar
Held, P. & Bohatý, L. (2004). Acta Cryst. C60, i97–i100. Web of Science CrossRef ICSD CAS IUCr Journals Google Scholar
Hesse, W., Leutner, B., Böhn, K.-H. & Walker, N. P. C. (1993). Acta Cryst. C49, 363–365. CrossRef CAS IUCr Journals Google Scholar
Hopfinger, M., Zischka, F., Seifert, M. & Kornath, A. J. (2018). Z. Anorg. Allg. Chem. 644, 574–579. Web of Science CrossRef CAS Google Scholar
Klein, W. (2020). Acta Cryst. E76, 197–200. CrossRef IUCr Journals Google Scholar
Kumar Paul, A., Madras, G. & Natarajan, S. (2009). Phys. Chem. Chem. Phys. 11, 11285–11296. CrossRef CAS PubMed Google Scholar
Lehner, A. J., Schindler, L. V. & Röhr, C. (2013). Z. Naturforsch. Teil B, 68, 323–337. CrossRef CAS Google Scholar
Lisensky, G. C. & Levy, H. A. (1978). Acta Cryst. B34, 1975–1977. CrossRef ICSD CAS IUCr Journals Web of Science Google Scholar
Manojlović-Muir, L. A. (1975). Acta Cryst. B31, 135–139. CrossRef ICSD IUCr Journals Web of Science Google Scholar
Nirsha, B. H., Serebrennikova, G. M., Oboznenko, Yu. V., Zhadanov, B. V., Safonova, V. I. & Olikova, V. A. (1982). Zh. Neorg. Khim. 27, 3035–3038. CAS Google Scholar
Padmanabhan, V. M., Yadava, V. S., Navarro, Q. O., Garcia, A., Karsono, L., Suh, I. H. & Chien, L. S. (1971). Acta Cryst. B27, 253–257. CrossRef IUCr Journals Google Scholar
Picon, M. (1924). C. R. Hebd. Seances Acad. Sci. 178, 700–703. CAS Google Scholar
Prasad, S. M. & Rani, A. (2001). Acta Cryst. E57, i67–i69. CrossRef IUCr Journals Google Scholar
Pyykkö, P. & Atsumi, M. (2009). Chem. Eur. J. 15, 12770–12779. Web of Science CrossRef PubMed Google Scholar
Rettig, S. J. & Trotter, J. (1987). Acta Cryst. C43, 2260–2262. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sándor, E. & Csordás, L. (1961). Acta Cryst. 14, 237–243. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2015). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Taylor, P. G. & Beevers, C. A. (1952). Acta Cryst. 5, 341–344. CrossRef ICSD CAS IUCr Journals Web of Science Google Scholar
Teng, S. T., Fuess, H. & Bats, J. W. (1984). Acta Cryst. C40, 1785–1787. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Tiemann, E., Hoeft, J., Lovas, F. J. & Johnson, D. R. (1974). J. Chem. Phys. 60, 5000–5004. CrossRef CAS Google Scholar
Uraz, A. A. & Armaǧan, N. (1977). Acta Cryst. B33, 1396–1399. CrossRef CAS IUCr Journals Google Scholar
Winkler, V., Schlosser, M. & Pfitzner, A. (2016). Z. Naturforsch. Teil B, 71, 579–584. CrossRef CAS Google Scholar
Young, S. W. & Burke, W. E. (1906). J. Am. Chem. Soc. 28, 315–347. CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
ISSN: 2056-9890
Open
access