research papers
Sodium sulfite heptahydrate and its relation to sodium carbonate heptahydrate
aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
*Correspondence e-mail: matthias.weil@tuwien.ac.at
The monoclinic 2SO3(H2O)7 is characterized by an alternating stacking of (100) cationic sodium–water layers and anionic sulfite layers along [100]. The cationic layers are made up from two types of [Na(H2O)6] octahedra that form linear 1∞[Na(H2O)4/2(H2O)2/1] chains linked by dimeric [Na(H2O)2/2(H2O)4/1]2 units on both sides of the chains. The isolated trigonal–pyramidal sulfite anions are connected to the cationic layers through an intricate network of O—H⋯O hydrogen bonds, together with a remarkable O—H⋯S hydrogen bond, with an O⋯S donor–acceptor distance of 3.2582 (6) Å, which is about 0.05 Å shorter than the average for O—H⋯S hydrogen bonds in thiosalt hydrates and organic sulfur compounds of the type Y—S—Z (Y/Z = C, N, O or S). Structural relationships between monoclinic Na2SO3(H2O)7 and orthorhombic Na2CO3(H2O)7 are discussed in detail.
of NaKeywords: sulfite; O—H⋯S hydrogen bonding; crystal structure; crystal chemistry; heptahydrate; structural similarity.
CCDC reference: 1993827
1. Introduction
Sodium sulfite is used extensively in industrial processes, for example, as an antioxidant and preservative in food industries (E number for food additives E221), as a corrosion inhibitor in aqueous media, as a bleaching agent, as a solubilizing agent for cellulose, straw and wood in the pulp and paper industry, or as an additive in dying processes. In the USA alone, the production of sodium sulfite reached 150 000 tons in 2002 (Weil et al., 2007). Solid sodium sulfite is stable in its anhydrous form and as the heptahydrate. Despite its use at industrial scales, structural details are known only for anhydrous Na2SO3 that crystallizes with two formula units in the trigonal system in the P (Larsson & Kierkegaard, 1969). Bond lengths and near-neighbour distances of sodium sulfite in aqueous solution have been calculated by ab initio quantum mechanical charge field molecular dynamics (QMCF MD) studies and determined experimentally by large-angle X-ray scattering (LAXS) by Eklund et al. (2012). For crystalline Na2SO3(H2O)7, lattice parameters and the (P21/n) have previously been determined from Weissenberg photographs without providing further structural details, except for a close metrical resemblance with orthorhombic Na2CO3(H2O)7 (Dunsmore & Speakman, 1963). To obtain a more detailed picture of the relationship between the heptahydrates of Na2SO3 and Na2CO3, we grew single crystals of Na2SO3(H2O)7 and determined its Indeed, the two heptahydrates show not only a close metrical relationship (Table 1), but also structural similarities, though they belong to different crystal systems and contain differently shaped divalent anions, viz. trigonal–pyramidal SO32− and trigonal–planar CO32−.
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2. Experimental
2.1. Crystallization
Colourless prismatic crystals of Na2SO3(H2O)7 were grown by recrystallization of a commercial anhydrous sample (Merck, p.A. grade) from an aqueous solution at room temperature by slow evaporation over the course of several days. In order to remove adherent mother liquor, the crystals were placed on filter paper and subsequently immersed in Paratone oil. The crystal under investigation was cleaved from a larger specimen.
2.2. Crystallography and refinement
Crystal data, data collection and structure . The of Na2SO3(H2O)7 was originally solved and refined in the P121/n1 (No. 14), with lattice parameters a = 11.8576 (8), b = 7.2197 (5), c = 12.6965 (9) Å and β = 106.7938 (17)° at 100 K (full crystal data in the setting P121/n1 are available in format as supporting information). The values for the lattice parameters at 100 K are in good agreement with the previous study, with values of a = 11.922, b = 7.260, c = 12.765 Å and β = 107.22° obtained at room temperature from Weissenberg film data (note that a and c are interchanged in the original description; Dunsmore & Speakman, 1963). For a better comparison with the reported of β-Na2CO3(H2O)7 (Betzel et al., 1982), the nonconventional setting C1121/a was chosen for the final structural description of Na2SO3(H2O)7, using the matrix (101, 10, 010) for transformation of the to the C-centred cell with c as the unique axis; moreover, the atomic coordinates and the origin of the were chosen to ensure a similar packing of structural building blocks in the two unit cells of Na2SO3(H2O)7 and β-Na2CO3(H2O)7. All H atoms present in the of Na2SO3(H2O)7 were located in a difference Fourier map and were refined freely.
details are summarized in Table 23. Results and discussion
3.1. Crystal structure
In the 2SO3(H2O)7, all atoms (2 Na, 1 S, 10 O and 14 H) are located on general sites. The two sodium cations are surrounded by six water molecules, defining a distorted octahedral in each case. The Na—O distances range from 2.3690 (6) to 2.4952 (6) Å (Table 3), with mean values of 2.42 (4) Å for Na1 and 2.43 (6) Å for Na2, in fairly good agreement with the mean value for Na[6]—O of 2.44 (11) Å calculated for 5520 individual bonds (Gagné & Hawthorne, 2016). The bond valence sums (Brown, 2002) for the sodium cations, as calculated with parameters provided by Brese & O'Keeffe (1991), are 1.15 valence units (v.u.) for Na1 and 1.13 v.u. for Na2, and thus in the expected range for monovalent Na+. The O—Na—O angles deviate clearly from ideal values, with values for trans O atoms in the range 172.149 (16)–176.42 (2)° for Na1 and 165.81 (2)–174.23 (2)° for Na2, and for cis O atoms in the range 81.464 (19)–101.74 (2)° for Na1 and 81.51 (2)–103.23 (2)° for Na2. The two types of [Na(H2O)6] octahedra show a different linkage pattern. Octahedra centred by Na1 share common edges (O8/O10 and O8ii/O10i; see Table 3 for symmetry codes) to form infinite linear 1∞[Na1(H2O)4/2(H2O)2/1] chains running parallel to [001], whereas octahedra centred by Na2 make up dimeric [Na2(H2O)2/2(H2O)4/1]2 units by sharing an edge (O5 and O5iii). In both cases, the corresponding Na—O bonds to the shared O atoms at the edges are the shortest in the respective octahedron. The dimeric units connect adjacent chains by sharing the terminal water molecules (O9 and O7) on both sides of the chains (corner-sharing links). This way, the sodium–water octahedra are assembled by edge- and corner-sharing into an infinite layer extending parallel to (100) (Fig. 1a).
of Na
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The sulfite anion has the characteristic trigonal–pyramidal configuration, with the SIV atom occupying the pyramidal position. Atom S1 is 0.5912 (4) Å above the basal plane formed by atoms O1, O2 and O3. The S—O bond lengths are in a narrow range 1.5224 (5)–1.5338 (5) Å [mean 1.527 (6) Å], just like the O—S—O angles [105.85 (3)–106.07 (3)°; mean 105.93 (16)°]. Again, these values are in good agreement with the grand mean SIV—O bond length of 1.529 (15) Å calculated for 90 bonds and with the O—SIV—O angles in the range ∼99–107° with a mean value of ∼104° (Gagné & Hawthorne, 2018). The bond valence sum for atom S1 is 4.12 v.u., using the parameters of Brese & O'Keeffe (1991) for calculation. The sulfite anions are isolated from the sodium–water layer, lying alternatingly on both sides outside of an individual layer. In this way, cationic sodium–water layers at x ≃ 0, are sandwiched by sulfite layers at x ≃ , and stacked along [100], with the sulfite anions situated approximately at the height in y where the [Na2O2/2O4/1]2 dimers are linked to the 1∞[Na1(H2O)4/2(H2O)2/1] chains (Fig. 2a).
The seven independent water molecules possess approximately tetrahedral coordination arrangements (including hydrogen bonds), except for O9, and five of them each bridge two sodium cations (O5, O7, O8, O9 and O10), whereas two are each bonded to only one sodium cation (O4 and O6). An intricate network of O—H⋯O hydrogen bonds between the water molecules and the sulfite O atoms link the anionic layers to adjacent cationic layers, thus establishing a three-dimensional hydrogen-bonded network structure (Fig. 2a). Based on the donor–acceptor distances between 2.7204 (7) and 2.9110 (8) Å (Table 4), the hydrogen-bonding strength is moderate according to the classification of Jeffrey (1997). Most of these hydrogen bonds are donated to sulfite atoms O1, O2 and O3 (Fig. 3a). Thereby, atom O1 is the acceptor of three, O2 of four and O3 of three hydrogen bonds. It is worth noting that the S—O bond lengths reflect this situation nicely, with S1—O2 = 1.5338 (5) Å being about 0.01 Å longer than the remaining two. The O9 water molecule, bonded to Na1, Na2 and via H9A to O2, lacks a clearcut hydrogen bond for its second H atom (H9B), which points to H6B of the O6—H6B⋯O3 hydrogen bond [H9B(x, y − , z + )⋯H6B = 2.49 Å], while distances from O9(x, y − , z + ) to O6 and O3 exceed 3.3 Å.
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In addition to the interactions between water molecules and sulfite O atoms, there are two hydrogen bonds between water molecules only (O7⋯O6vi and O10⋯O4ii; symmetry codes refer to Table 4), and, as a pecularity, an O—H⋯S hydrogen bond between O8 and S1vii. In general, S⋯H interactions involving divalent S atoms are considered as weak hydrogen bonds (Allen et al., 1997). The H⋯S hydrogen-bonding strength becomes even weaker for H⋯SO3 contacts because the S atom is positively polarized in an SO32− anion with partial double-bond character for the S—O bonds (Nyberg & Larsson, 1973). The hydrogen-bond acceptor ability of divalent sulfur was evaluated some time ago from 1811 substructures of mostly organic compounds, i.e. Y—S—Z systems (Y/Z = C, N, O or S) as acceptor groups retrieved from the Cambridge Structural Database, giving a mean intermolecular >S⋯H distance of 2.67 (5) Å for O—H donors and a mean S⋯O distance of 3.39 (4) Å (Allen et al., 1997; Groom et al., 2016). In comparison, the first ever reported determination of an inorganic compound with an O—H⋯S hydrogen bond and a clear location of the H atoms, viz. BaS2O3(H2O) from neutron single-crystal diffraction data (Manojlović-Muir, 1969), revealed a considerably shorter S⋯H distance of 2.367 (4) Å and a likewise shorter S⋯O distance of 3.298 (4) Å. The O—H⋯S angle in BaS2O3·H2O was determined as 163 (3)°. Corresponding values of the O—H⋯S hydrogen bond in the of Na2SO3(H2O)7 are somewhat larger at 2.455 (14) Å for H8B⋯S1vii (X-ray data), slightly shorter at 3.2582 (6) Å for O8⋯S1vii and similar at 164.5 (13)° for the O8—H8B⋯S1vii angle. A comparable O⋯S distance of 3.326 Å was found as the mean value for 86 hydrogen-bonding interactions between water molecules and S atoms in a variety of thiosalt hydrates, such as Schlippes salt, Na3SbS4(H2O)9 (Mikenda et al., 1989). A literature search indicated that the O—H⋯S hydrogen bond in the title compound appears to be unprecedented thus far among hydrated sulfites. This suggests that in sulfite hydrates, O—H⋯O hydrogen bonding is clearly preferred over O—H⋯S hydrogen bonding and that a certain structural motif is needed to induce O—H⋯S hydrogen bonding like in the title compound. Invoking the results of an electron deformation density study of MgSO3(H2O)6 (Bats et al., 1986), the coordination capability of the sulfite S atom via its electron lone-pair lobe at the apex of the SO3 pyramid is not unexpected, but this capability seems to be weak in the context of hydrogen bonding because otherwise more examples with features comparable to the title compound would have been encountered already. As soon as covalent bonding comes into play, the coordination capability of the sulfite S atom is well documented by transition-metal complexes like K2[Pd(SO3)2]·H2O (Messer et al., 1979) or K2[Hg(SO3)2]·2.25H2O (Weil et al., 2010), with metal–sulfur bonds, or by hydrogen sulfites like CsHSO3 (Johansson et al., 1980) or K5(HSO3)(S2O5) (Magnusson et al., 1983) that contain HSO3− anions with hydrogen covalently bonded to sulfur.
The numerical values of the atomic distances for crystalline Na2SO3(H2O)7 (Tables 3 and 4) are in good agreement with those of aqueous Na2SO3 solutions determined from LAXS studies, with S—O = 1.53 Å for the sulfite group and Na—O = 2.41 Å for the sodium—water distances (Eklund et al., 2012). In the latter study, the S⋯Owater distance in solution was determined as 3.68 Å, which is considerably longer than in the solid state, giving further evidence for a weak but existing O—H⋯S hydrogen bond in the crystalline material.
3.2. Comparison with Na2CO3(H2O)7
The close structural relationship between monoclinic Na2SO3(H2O)7 and orthorhombic Na2CO3(H2O)7 (Table 1) becomes evident from the similar arrangement of the principal building units in the crystal structures. The same type of cationic sodium–water layers made up from edge- and corner-sharing [Na(H2O)6] octahedra [mean Na—O distance = 2.43 (4) Å and O—Na—O angles = 81–102 and 164–180°; Fig. 1b] is present in the carbonate, likewise situated at x ≃ 0, in the (Fig. 2b). The carbonate groups do not show pyramidalization (Zemann, 1981) and occupy the same space as the sulfite groups between adjacent layers close to the [Na(H2O)2/2(H2O)4/1]2 dimers.
The main difference between the two structures is related to the orientation of the [Na(H2O)2/2(H2O)4/1]2 dimers in the layers. Whereas in the sulfite structure, the dimers at y ≃ 0 and in one layer and also the accompanying anions close to them have the same orientation relative to (100), in the carbonate structure, the orientation of every second dimer (at y ≃ ) and the accompanying anions in a layer is reversed due to the presence of the c-glide plane (Fig. 2).
The hydrogen-bonding schemes in the two heptahydrates are similar (Fig. 3). In the carbonate structure, the anions are likewise hydrogen bonded to water molecules through medium–strong hydrogen bonds [O⋯O = 2.690 (5)–3.060 (4) Å, with an additional weak interaction of 3.223 (5) Å]. In analogy, two water–water O—H⋯O interactions with donor–acceptor distances of 2.827 (5) and 2.766 (5) Å are also observed. However, in contrast to the central sulfite S atom with its free electron lone pair, the central C atom of the carbonate anion cannot act as a hydrogen-bond acceptor, and thus this interaction is missing in the carbonate structure.
3.3. Comparison with related compounds
Crystal structures with sulfite groups anchored exclusively by hydrogen bonds are at present restricted to the title compound Na2SO3(H2O)7, to NH4SO3(H2O) (Battelle & Trueblood, 1965; Durand et al., 1977) and to MgSO3(H2O)6 (Andersen & Lindqvist, 1984; Bats et al., 1986). In MgSO3(H2O)6, which is built up from [Mg(H2O)6] octahedra and isolated SO3 pyramids within a lattice of the type R3, and with Mg and S atoms both located on threefold rotation axes, there are two independent water molecules that donate, apart from one water–water hydrogen bond, three water–Osulfite hydrogen bonds to each sulfite O atom, comparable to O1 and O3 in Na2SO3(H2O)7, but with shorter O⋯O distances [2.687 (3), 2.701 (3) and 2.726 (3) Å] than in the latter. An electron deformation density study of MgSO3(H2O)6 (Bats et al., 1986) proved the presence of an extended lone-pair lobe at the apex of the SO3 pyramid, but neither MgSO3(H2O)6 nor NH4SO3(H2O) contain O—H⋯S or N—H⋯S hydrogen bonds.
A further comparison with other hydrated sodium compounds comprised of related oxo anions shows no close structural relationship to the title heptahydrate. For example, Na2SO4(H2O)7 (Oswald et al., 2008) (I41/amd, Z = 4) has a completely different arrangement of the principal building units. Its is comprised of [Na(H2O)]6 octahedra concatenated by edge- and corner-sharing into a three-dimensional network with isolated tetrahedral sulfate anions hydrogen bonded to the chains. Also, for sodium compounds with analogous trigonal–pyramidal oxoanions and the same charge, i.e. XO32−, with X = Se and Te, no phases related structurally or compositionally to Na2SO3(H2O)7 are known. For Na2SeO3, the anhydrous form (P21/c, Z = 4) is made up from [NaO6] octahedra and trigonal–pyramidal SeO32− anions (Wickleder, 2002), and is isotypic with Na2TeO3 (Masse et al., 1980). Hydrated forms are known only for the pentahydrates Na2SeO3(H2O)5 (Mereiter, 2013) and Na2TeO3(H2O)5 (Philippot et al., 1979) that are, surprisingly, not isotypic (Pbcm, with Z = 8, and C2/c, with Z = 8, respectively). These structures are based on two- or three-dimensional assemblies of [NaO5] polyhedra (Se) and [NaO6] octahedra (Se and Te), to which SeO3/TeO3 groups are bonded via two (Se) or one (Te) O atom. The [NaO6] octahedra in these two salts share common faces and edges but no vertices. As pointed out by Philippot et al. (1979) for Na2TeO3(H2O)5 and confirmed also for Na2SeO3(H2O)5 (Mereiter, 2013), the electron lone pair of Se and Te in these structures shows no attracting interactions with neighbouring H atoms. This might be one reason why hydrates of Na2SeO3 and Na2TeO3 do not crystallize in the Na2SO3(H2O)7 structure and vice versa.
Supporting information
CCDC reference: 1993827
https://doi.org/10.1107/S2053229620004404/ep3004sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229620004404/ep3004Isup2.hkl
https://doi.org/10.1107/S2053229620004404/ep3004sup3.txt
with full numerical data (setting P121/n1). DOI:Supporting information file. DOI: https://doi.org/10.1107/S2053229620004404/ep3004Isup4.cml
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ATOMS (Dowty, 2006) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).H14Na2O10S | F(000) = 1056 |
Mr = 252.15 | Dx = 1.610 Mg m−3 |
Monoclinic, C1121/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C_2ac | Cell parameters from 8292 reflections |
a = 14.6563 (8) Å | θ = 2.8–36.0° |
b = 19.7180 (9) Å | µ = 0.42 mm−1 |
c = 7.2197 (5) Å | T = 100 K |
β = 90° | Fragment, colourless |
V = 2081.1 (2) Å3 | 0.15 × 0.13 × 0.12 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | 4222 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
ω– and φ–scan | θmax = 36.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −24→23 |
Tmin = 0.675, Tmax = 0.747 | k = −32→30 |
16909 measured reflections | l = −11→11 |
4845 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | All H-atom parameters refined |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0304P)2 + 0.806P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.003 |
4845 reflections | Δρmax = 0.89 e Å−3 |
174 parameters | Δρmin = −0.33 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Na1 | 0.49508 (2) | 0.24227 (2) | 1.10868 (4) | 0.00970 (6) | |
Na2 | 0.55111 (2) | 0.06011 (2) | 1.35665 (4) | 0.01015 (6) | |
S1 | 0.76676 (2) | −0.13751 (2) | 1.37190 (2) | 0.00782 (4) | |
O1 | 0.71232 (3) | −0.11448 (2) | 1.53732 (7) | 0.01115 (8) | |
O2 | 0.85230 (3) | −0.08810 (3) | 1.36082 (6) | 0.01132 (8) | |
O3 | 0.70978 (4) | −0.12350 (3) | 1.20165 (7) | 0.01248 (9) | |
O4 | 0.69179 (4) | 0.12961 (3) | 1.36691 (7) | 0.01302 (9) | |
O5 | 0.60016 (4) | −0.01074 (3) | 1.59875 (7) | 0.01119 (8) | |
O6 | 0.60771 (4) | −0.01777 (3) | 1.11731 (7) | 0.01330 (9) | |
O7 | 0.50388 (4) | 0.12044 (3) | 1.08692 (7) | 0.01129 (8) | |
O8 | 0.39237 (4) | 0.23269 (3) | 1.36393 (7) | 0.01119 (8) | |
O9 | 0.49463 (4) | 0.36695 (3) | 1.11835 (7) | 0.01244 (9) | |
O10 | 0.39308 (4) | 0.24819 (3) | 0.85559 (7) | 0.01182 (9) | |
H4A | 0.7253 (10) | 0.1272 (7) | 1.454 (2) | 0.040 (4)* | |
H4B | 0.7270 (10) | 0.1258 (7) | 1.280 (2) | 0.043 (4)* | |
H5A | 0.6351 (9) | −0.0397 (7) | 1.5804 (18) | 0.026 (3)* | |
H5B | 0.6230 (10) | 0.0138 (7) | 1.6763 (19) | 0.036 (4)* | |
H6A | 0.6299 (9) | 0.0083 (7) | 1.047 (2) | 0.035 (4)* | |
H6B | 0.6429 (10) | −0.0432 (8) | 1.1470 (18) | 0.033 (4)* | |
H7A | 0.5492 (9) | 0.1157 (6) | 1.0255 (19) | 0.030 (3)* | |
H7B | 0.4660 (10) | 0.0941 (7) | 1.053 (2) | 0.034 (4)* | |
H8A | 0.3667 (10) | 0.1966 (7) | 1.3816 (17) | 0.032 (4)* | |
H8B | 0.3519 (10) | 0.2597 (7) | 1.3636 (16) | 0.026 (3)* | |
H9A | 0.4574 (10) | 0.3785 (7) | 1.192 (2) | 0.030 (3)* | |
H9B | 0.5427 (11) | 0.3788 (7) | 1.1579 (19) | 0.034 (4)* | |
H10A | 0.3612 (10) | 0.2819 (8) | 0.8574 (17) | 0.032 (4)* | |
H10B | 0.3596 (10) | 0.2171 (7) | 0.8447 (17) | 0.026 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.01001 (12) | 0.01018 (12) | 0.00894 (11) | 0.00089 (9) | −0.00002 (8) | 0.00018 (8) |
Na2 | 0.01087 (13) | 0.01032 (12) | 0.00923 (11) | 0.00053 (9) | −0.00029 (8) | 0.00100 (8) |
S1 | 0.00777 (6) | 0.00762 (6) | 0.00812 (6) | 0.00102 (4) | −0.00010 (4) | 0.00042 (4) |
O1 | 0.0113 (2) | 0.0120 (2) | 0.01032 (18) | 0.00238 (16) | 0.00291 (14) | −0.00012 (14) |
O2 | 0.0090 (2) | 0.0124 (2) | 0.01216 (19) | −0.00153 (16) | 0.00037 (14) | 0.00118 (15) |
O3 | 0.0144 (2) | 0.0131 (2) | 0.01010 (19) | 0.00150 (17) | −0.00474 (15) | 0.00016 (15) |
O4 | 0.0119 (2) | 0.0158 (2) | 0.0114 (2) | 0.00138 (17) | 0.00043 (16) | 0.00018 (16) |
O5 | 0.0113 (2) | 0.0101 (2) | 0.01232 (19) | 0.00204 (16) | −0.00185 (15) | −0.00181 (15) |
O6 | 0.0132 (2) | 0.0122 (2) | 0.0147 (2) | 0.00227 (17) | 0.00056 (16) | 0.00217 (16) |
O7 | 0.0112 (2) | 0.0112 (2) | 0.01143 (19) | 0.00058 (16) | 0.00061 (15) | −0.00022 (15) |
O8 | 0.0099 (2) | 0.0104 (2) | 0.01337 (19) | 0.00126 (16) | 0.00133 (15) | 0.00157 (15) |
O9 | 0.0139 (2) | 0.0117 (2) | 0.01171 (19) | 0.00068 (17) | 0.00033 (16) | −0.00053 (15) |
O10 | 0.0101 (2) | 0.0117 (2) | 0.0136 (2) | 0.00013 (17) | −0.00087 (15) | −0.00148 (15) |
Na1—O10 | 2.3690 (6) | Na2—O4 | 2.3939 (6) |
Na1—O8 | 2.3785 (6) | Na2—O7 | 2.4093 (6) |
Na1—O10i | 2.4199 (6) | Na2—O6 | 2.4928 (6) |
Na1—O7 | 2.4199 (6) | Na2—O9i | 2.4952 (6) |
Na1—O8ii | 2.4436 (6) | S1—O3 | 1.5224 (5) |
Na1—O9 | 2.4599 (6) | S1—O1 | 1.5234 (5) |
Na2—O5iii | 2.3787 (6) | S1—O2 | 1.5338 (5) |
Na2—O5 | 2.3805 (6) | ||
O5iii—Na2—O5 | 88.41 (2) | H4A—O4—H4B | 101.7 (15) |
O5iii—Na2—O4 | 165.81 (2) | Na2iii—O5—Na2 | 91.59 (2) |
O5—Na2—O4 | 91.68 (2) | Na2iii—O5—H5A | 110.7 (9) |
O5iii—Na2—O7 | 91.10 (2) | Na2—O5—H5A | 122.0 (9) |
O5—Na2—O7 | 173.08 (2) | Na2iii—O5—H5B | 119.4 (10) |
O4—Na2—O7 | 90.48 (2) | Na2—O5—H5B | 106.9 (10) |
O5iii—Na2—O6 | 100.56 (2) | H5A—O5—H5B | 106.6 (14) |
O5—Na2—O6 | 91.13 (2) | Na2—O6—H6A | 100.9 (10) |
O4—Na2—O6 | 93.62 (2) | Na2—O6—H6B | 118.2 (10) |
O7—Na2—O6 | 82.177 (19) | H6A—O6—H6B | 110.0 (14) |
O5iii—Na2—O9i | 81.51 (2) | Na2—O7—Na2 | 118.38 (2) |
O5—Na2—O9i | 83.523 (19) | Na2—O7—H7A | 96.9 (9) |
O4—Na2—O9i | 84.40 (2) | Na1—O7—H7A | 104.6 (9) |
O7—Na2—O9i | 103.23 (2) | Na2—O7—H7B | 98.3 (10) |
O6—Na2—O9i | 174.23 (2) | Na1—O7—H7B | 127.0 (10) |
O10—Na1—O8 | 101.74 (2) | H7A—O7—H7B | 107.6 (13) |
O10—Na1—O10i | 172.170 (15) | Na1—O8—Na1i | 97.465 (19) |
O8—Na1—O10i | 81.77 (2) | Na1—O8—H8A | 117.0 (9) |
O10—Na1—O7 | 94.44 (2) | Na1i—O8—H8A | 109.6 (9) |
O8—Na1—O7 | 92.86 (2) | Na1—O8—H8B | 115.3 (8) |
O10i—Na1—O7 | 92.36 (2) | Na1i—O8—H8B | 112.2 (9) |
O10—Na1—O8ii | 81.464 (19) | H8A—O8—H8B | 105.3 (14) |
O8—Na1—O8ii | 172.149 (16) | Na1—O9—Na2ii | 125.08 (2) |
O10i—Na1—O8ii | 94.20 (2) | Na1—O9—H9A | 110.5 (10) |
O7—Na1—O8ii | 94.04 (2) | Na2ii—O9—H9A | 97.1 (10) |
O10—Na1—O9 | 85.75 (2) | Na1—O9—H9B | 104.1 (11) |
O8—Na1—O9 | 90.60 (2) | Na2ii—O9—H9B | 112.2 (11) |
O10i—Na1—O9 | 87.22 (2) | H9A—O9—H9B | 106.7 (14) |
O7—Na1—O9 | 176.42 (2) | Na1—O10—Na1ii | 98.38 (2) |
O8ii—Na1—O9 | 82.451 (19) | Na1—O10—H10A | 114.6 (9) |
O3—S1—O1 | 105.85 (3) | Na1ii—O10—H10A | 111.2 (9) |
O3—S1—O2 | 106.07 (3) | Na1—O10—H10B | 114.4 (10) |
O1—S1—O2 | 105.87 (3) | Na1ii—O10—H10B | 112.4 (9) |
Na2—O4—H4A | 119.9 (11) | H10A—O10—H10B | 106.0 (14) |
Na2—O4—H4B | 116.4 (11) |
Symmetry codes: (i) −x+1, −y+1/2, z+1/2; (ii) −x+1, −y+1/2, z−1/2; (iii) −x+1, −y, −z+3. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O3iv | 0.800 (15) | 2.031 (16) | 2.8216 (8) | 169.7 (15) |
O4—H4B···O1v | 0.821 (16) | 1.983 (16) | 2.7904 (7) | 167.8 (15) |
O5—H5A···O1 | 0.804 (13) | 1.947 (13) | 2.7503 (7) | 175.9 (13) |
O5—H5B···O2iv | 0.798 (15) | 1.994 (15) | 2.7694 (7) | 163.9 (15) |
O6—H6A···O2v | 0.777 (14) | 2.072 (14) | 2.8206 (7) | 161.8 (14) |
O6—H6B···O3 | 0.774 (15) | 1.962 (15) | 2.7204 (7) | 166.5 (15) |
O7—H7A···O2v | 0.810 (13) | 1.976 (14) | 2.7761 (7) | 169.3 (13) |
O7—H7B···O6vi | 0.773 (14) | 2.171 (14) | 2.9110 (8) | 160.7 (15) |
O8—H8A···O1iii | 0.792 (15) | 2.009 (15) | 2.7900 (7) | 168.9 (13) |
O8—H8B···S1vii | 0.825 (14) | 2.455 (14) | 3.2582 (6) | 164.5 (13) |
O9—H9A···O2vii | 0.807 (14) | 2.106 (14) | 2.9096 (7) | 174.0 (14) |
O10—H10A···O4ii | 0.839 (15) | 1.962 (15) | 2.7908 (8) | 169.5 (14) |
O10—H10B···O3vi | 0.762 (14) | 2.069 (14) | 2.8210 (7) | 169.1 (14) |
Symmetry codes: (ii) −x+1, −y+1/2, z−1/2; (iii) −x+1, −y, −z+3; (iv) −x+3/2, −y, z+1/2; (v) −x+3/2, −y, z−1/2; (vi) −x+1, −y, −z+2; (vii) x−1/2, y+1/2, z. |
Na2SO3(H2O)7 | Na2CO3(H2O)7 | |
a | 14.6563 (8) | 14.492 (7) |
b | 19.7180 (9) | 19.490 (5) |
c | 7.2197 (5) | 7.017 (3) |
α | 90 | 90 |
β | 90 | 90 |
γ | 94.0997 (17) | 90 |
V (Å3) | 2081.1 (2) | 1981.95 |
T (K) | 100 | RT |
Space group | C1121/a | Pbca |
Acknowledgements
The X-ray centre of TU Wien is acknowledged for providing access to the single-crystal X-ray diffractometer.
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