Crystal structure of hexa­sodium tetra­serinolium paratungstate B deca­hydrate, [Na6{(CH2OH)2CHNH3}4][W12O40(OH)2]·10H2O

Sifaki, K.; Gumerova, N.I.; Giester, G.; Rompel, A.

doi:10.1107/S2056989022000457

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ISSN: 2056-9890

Volume 78| Part 2| February 2022| Pages 207-210

https://doi.org/10.1107/S2056989022000457

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Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

Kleanthi Sifaki,^a ‡ Nadiia I. Gumerova,^a ^*‡ Gerald Giester ^b and Annette Rompel ^a

^aUniversität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Althanstr. 14, Wien 1090, Austria, and ^bUniversität Wien, Fakultät für Geowissenschaften, Geographie und Astronomie, Institut für Mineralogie und Kristallographie, Althanstr. 14, Wien 1090, Austria
^*Correspondence e-mail: nadiia.gumerova@univie.ac.at

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 November 2021; accepted 12 January 2022; online 18 January 2022)

The title polyoxometalate-based organic–inorganic hybrid compound, [Na₆(C₃H₁₀NO₂)₄][W₁₂O₄₀(OH)₂]·10H₂O, consists of a di-μ₃-hydroxido-tetra-μ₃-oxido-octadeca-μ-oxido-octadecaoxidododecatungstate (paradodecatungstate B) anion, [W₁₂O₄₀(OH)₂]^10–, and six sodium cations coordinated by the oxygen ions of the polyanions, serinol ligands protonated at the N atom, and water molecules. The centrosymmetric paratungstate B anion shows characteristic features in terms of bond lengths and angles. The three-dimensional framework structure is established by bonding of the sodium cations with oxygen ions of the paratungstate B anions and a network consisting of N—H⋯O and O—H⋯O hydrogen bonds of medium strength between the protonated serinol cations, water molecules and the paratungstate B anions. The title compound was also characterized by means of elemental analysis, IR spectroscopy and thermogravimetric analysis.

Keywords: crystal structure; metal oxide; polyoxometalate; isopolytungstate; organic–inorganic hybrid; alkoxo ligand.

CCDC reference: 2121767

1. Chemical context

Polyoxometalates (POMs) are discrete anionic molecular clusters of metal oxide entities, which usually consist of transition metals of groups V and VI in their highest oxidation states. POMs exist at a unique interface between monomeric oxometalates and polymeric metal oxides and have a wide range of applications (Pope, 1983 ; Gumerova & Rompel, 2020 ). To date, a variety of strategies have been developed and used to build POM-based hybrid materials by varying the reaction conditions such as the type of addenda ions, organic ligands, pH, solvents, the molar ratio of the starting materials or the reaction environments. The [W₁₂O₄₀(OH)₂]^10– paratungstate B anion is stable in aqueous acidic solution and has a cluster-like structure of twelve W-centered distorted octahedra {WO₆} (Evans & Rollins, 1976 ; Pope, 1983). Due to its high surface charge density q/m = 0.83 (q = net charge, m = number of metal ions), the paratungstate B anion can act as a multidentate ligand for alkaline (Peresypkina et al., 2014 ) or transition-metal cations (Radio et al., 2010 , 2011 ; Gumerova et al., 2015 , 2018 ) and as a precursor for the synthesis of catalytically active sandwich-type polyoxotungstates (POTs) (Sokolov et al., 2012 ).

A search in the Cambridge Structural Database (version 5.42, update of November 2021; Groom et al., 2016 ) revealed that seventeen organic–inorganic hybrid paratungstates B have been structurally characterized so far. We are expanding the class of hybrid paratungstates by using serinol (C₃H₉NO₂; 2-amino-1,3-propandiol), which has not previously been used in its protonated form as a counter-cation for paratungstates and can coordinate to metal cations in different ways via its –NH₂ or HOCH₂– groups and thus influences both the structure and the properties of the compound significantly (Sifaki et al., 2021 ). Serinol is a very stable, readily water-soluble, non-toxic, odorless, biodegradable compound that is used as a versatile starting material in organic synthesis and as an additive for material applications, such as composite materials (Barbera et al., 2020 ; Andreessen & Steinbüchel, 2011 ). In POM synthesis, due to its amino group, serinol can be regarded as an alkoxylation ligand and/or as a buffer compound (pK_a = 12.2; Chemicalbook, 2021 ). With its protonated amine group it can also act as a counter-cation.

2. Structural commentary

The asymmetric unit of the title compound is made up of half of the paratungstate B polyoxoanion, [W₁₂O₄₀(OH)₂]^10–, three sodium cations coordinated by water molecules, terminal oxygen atoms of the paratungstate anion and the oxygen atoms of HOCH₂– groups from two serinol cations protonated at the N atoms [(CH₂OH)₂CHNH₃⁺] (Fig. 1). An inversion center creates a full unit with formula [Na₆((CH₂OH)₂CHNH₃)₄][W₁₂O₄₀(OH)₂]·10H₂O (Fig. 2). The centrosymmetric paratungstate B anion [W₁₂O₄₀(OH)₂]^10– is structurally very similar to previously described ones (Radio et al., 2010, 2011; Gumerova et al., 2015, 2018) and consists of four groups, viz. two {W₃O₁₃} and two {W₃O₁₄} units, with common vertices (Fig. 1). In the {W₃O₁₃} groups each {WO₆} octahedron has a terminal oxygen atom, while in the {W₃O₁₄} units each {WO₆} octahedron has two unshared oxygen ions (Fig. 1). The oxygen atoms associated with the central W ions can be divided into three groups: 1) terminal oxygen ions (O_t), each bonded to a W ion (magenta labeling in Fig. 1); 2) bridging oxygen ions (O_db), each connected to two W ions (blue labeling in Fig. 1); 3) triply bridging oxygen ions (O_tb) linked to three W ions (green labeling in Fig. 1).

Figure 1
The principal building units in the crystal structure of [Na₆((CH₂OH)₂CHNH₃)₄][W₁₂O₄₀(OH)₂]·10H₂O. The asymmetric unit was doubled considering the inversion center, and coordination spheres for all cations were completed. Labeling of all atoms of asymmetric unit is shown; non-labeled atoms are generated by symmetry operation −x + 1, −y + 1, −z + 1. The oxygen atoms in the paratungstate B anion are labeled according to their coordination mode: magenta for the terminal, blue for the double bridging, green for the triply bridging oxygen ions. Displacement ellipsoids are drawn at the 50% probability level. Color code: W, dark gray; Na, green; C, gray; N, blue; O, red.

Figure 2
The crystal packing of [Na₆((CH₂OH)₂CHNH₃)₄][W₁₂O₄₀(OH)₂]·10H₂O viewed along the a axis. Color code: {WO₆}: gray octahedra; Na: green; C: gray; N: blue; O: red.

3. Supramolecular features

The paratungstate B anion is bound to twelve Na⁺ cations via both terminal (O_t) and bridging oxygen atoms (O_db). Each of the surrounding four Na1 cations and six Na3 cations are coordinated by the O atoms of two polyanions, while two Na2 cations are bound to one terminal oxygen atom of the polyanion and to the O atoms of two serinolium cations, which are further connected to the Na3 cations via the HOCH₂– groups. Thus, a three-dimensional framework is established in the crystal structure by connecting paratungstate B anions through Ot—Na1—Ot, Ot—Na3—Ot and Ot—Na2–serinolium—Na3—Ot bridges (Fig. 2). An intimate network of N—H⋯O and O—H⋯O hydrogen bonds of medium strength between the protonated serinol ligands, polyoxoanions and water molecules consolidates the crystal packing (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O22—H22A⋯O1ⁱ	0.67 (7)	2.11 (7)	2.757 (5)	163 (8)
O23—H23A⋯O16ⁱ	0.78 (7)	2.04 (7)	2.802 (5)	165 (7)
O23—H23B⋯O16ⁱⁱ	0.91 (7)	1.91 (7)	2.811 (5)	175 (6)
O25—H25⋯O3ⁱⁱⁱ	0.73 (6)	2.05 (7)	2.761 (5)	164 (7)
O26—H26⋯O15ⁱ	0.88 (7)	1.88 (7)	2.730 (5)	160 (6)
O27—H27⋯O2ⁱⁱⁱ	0.67 (7)	2.04 (7)	2.696 (5)	165 (8)
O28—H28A⋯O21^iv	0.75 (8)	2.01 (8)	2.735 (6)	160 (8)
O29—H29⋯O10^v	0.81 (6)	1.91 (7)	2.692 (5)	163 (6)
N1—H1B⋯O15ⁱⁱⁱ	0.91	1.82	2.723 (5)	170
N2—H2B⋯O24	0.91	1.96	2.867 (6)	172
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

4. Database survey

A search in the Cambridge Structural Database (CSD; version 5.42, update of November 2021; Groom et al., 2016) indicated 17 structures with the formula search [`W₁₂O₄₂' or `W₁₂O₄₀(OH)₂'], including eleven structures with only organic cations and six structures with organic and transition-metal cations. The 17 compounds deposited in the CSD all crystallize in centrosymmetric space groups, and the bond lengths in the paratungstate B anion are very similar to those observed in the title structure. A similar structure containing sodium and a protonated imidazole as counter-cations, viz. Na₂(HIm)₈[W₁₂O₄₀(OH)₂]·10H₂O (HIm: imidazolium), is comprised of infinite inorganic chains built up from [W₁₂O₄₀(OH)₂]^10– anions and sodium cations. Adjacent chains are further connected by hydrogen-bonding interactions between imidazolium cations, water molecules, and polyoxoanions (Chaalia et al., 2012 ).

5. Synthesis and crystallization

To obtain the title compound, Na₂WO₄·2H₂O (0.495 g, 1.5 mmol) was dissolved in 5 ml of distilled water and acidified with 1 M HCl to pH 3. Serinol (0.075 g, 0.8 mmol) was then added to the acidified orthotungstate solution, which increased the pH to 6.7. The reaction mixture was then heated to 363 K and stirred for 1 h, cooled to room temperature and left covered with parafilm. Colorless block-shaped crystals were filtered off after one week from the mother liquor, washed with water and ethanol and then air-dried (yield 0.12 g; 27%, based on W). Elemental analysis (%) for C₁₂H₆₂N₄Na₆O₆₀W₁₂ (calculated): C 3.23 (4.04), H 1.71 (1.75), N 1.41 (1.57), O 26.68 (26.92). FT–IR (cm⁻¹): 3340 (s), 2952 (sh), 2889 (sh), 1614 (s), 1450 (m), 1066 (w), 1037 (m), 996 (w), 930 (s), 896 (s), 794 (s), 681 (s), 620 (m), 478 (s), 456 (s), 428 (s), 310 (s). Mass loss observed in thermogravimetric analysis in the temperature range 298–1073 K (calculated for four protonated serinol ligands, ten crystal water molecules and one water molecule from the anion): 16.67% (16.78%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The positions of the H atoms of the water molecules (O22, O23, O24, O28) were obtained by difference-Fourier techniques and were refined with free isotropic displacement parameters and O—H distances restrained to 0.95 (2) Å. The disordered water molecule (O30) was refined with two positions (O30A and O30B), with free occupancy factors to a total of 100%. H atoms bound to N or C atoms were placed in idealized positions (N—H = 0.91 Å and C—H = 0.99 or 1.00 Å for CH₂ and CH groups, respectively) and refined in riding modes, with U_iso(H) values set to 1.5U_eq(N) or to 1.2U_eq(C). Three H-atom positions could not be included in the final model: two H-atom positions from the disordered water molecule (O30A and O30B), and one H atom that should be located inside the paratungstate B anion on the triply bridging O8 atom, which was previously proven by neutron diffraction (Evans & Prince, 1983 ).

Table 2
Experimental details

Crystal data
Chemical formula	[Na₆((C₁₂H₄₀N₄O₈)][W₁₂O₄₀(OH)₂]·10H₂O
M_r	3566.79
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	12.0541 (8), 12.0821 (8), 12.7050 (8)
α, β, γ (°)	73.180 (2), 65.308 (2), 64.345 (2)
V (Å³)	1502.07 (17)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	23.04
Crystal size (mm)	0.05 × 0.05 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.245, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	39702, 5490, 5404
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.043, 1.25
No. of reflections	5490
No. of parameters	472
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.99, −1.62
Computer programs: APEX3 and SAINT (Bruker, 2016 ), olex2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2121767

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000457/wm5630sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000457/wm5630Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Hexasodium tetraserinolium di-µ₃-hydroxido-tetra-µ₃-oxido-octadeca-µ-oxido-octadecaoxidododecatungstate decahydrate top

Crystal data top

[Na₆(C₃H₁₀NO₂)₄][W₁₂O₄₀(OH)₂]·10H₂O	Z = 1
M_r = 3566.79	F(000) = 1596
Triclinic, P1	D_x = 3.943 Mg m⁻³
a = 12.0541 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.0821 (8) Å	Cell parameters from 9742 reflections
c = 12.7050 (8) Å	θ = 2.2–33.1°
α = 73.180 (2)°	µ = 23.04 mm⁻¹
β = 65.308 (2)°	T = 200 K
γ = 64.345 (2)°	Block, clear colourless
V = 1502.07 (17) Å³	0.05 × 0.05 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	5404 reflections with I > 2σ(I)
Radiation source: sealed x-ray tube	R_int = 0.038
φ and ω scans	θ_max = 25.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −14→14
T_min = 0.245, T_max = 0.747	k = −14→14
39702 measured reflections	l = −15→15
5490 independent reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.043	w = 1/[σ²(F_o²) + (0.0095P)² + 5.2022P] where P = (F_o² + 2F_c²)/3
S = 1.25	(Δ/σ)_max = 0.002
5490 reflections	Δρ_max = 0.99 e Å⁻³
472 parameters	Δρ_min = −1.61 e Å⁻³
6 restraints

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.

Refinement. olex2_refinement_description 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups, All O(H) groups At 1.5 times of: All N(H,H,H) groups, All O(H,H) groups 2. Uiso/Uaniso restraints and constraints O30A ~ O30B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A 3. Others Sof(O30A)=1-FVAR(1) Sof(O30B)=FVAR(1) 4.a Ternary CH refined with riding coordinates: C2(H2), C5(H5) 4.b Secondary CH2 refined with riding coordinates: C1(H1D,H1E), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B) 4.c Idealised Me refined as rotating group: N1(H1A,H1B,H1C), N2(H2A,H2B,H2C)

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
W1	0.42560 (2)	0.74680 (2)	0.16437 (2)	0.00609 (5)
W2	0.38107 (2)	0.76530 (2)	0.46722 (2)	0.00492 (5)
W3	0.43557 (2)	0.58129 (2)	0.71174 (2)	0.00468 (5)
W4	0.70356 (2)	0.65943 (2)	0.21152 (2)	0.00538 (5)
W5	0.66091 (2)	0.68816 (2)	0.50890 (2)	0.00550 (5)
W6	0.79490 (2)	0.36191 (2)	0.62441 (2)	0.00589 (5)
Na1	0.2506 (2)	0.6297 (2)	0.05508 (18)	0.0188 (4)
Na2	0.2644 (2)	0.32264 (19)	0.11025 (19)	0.0195 (5)
Na3	−0.1267 (2)	−0.09506 (18)	0.40382 (18)	0.0166 (4)
O1	0.3975 (3)	0.7093 (3)	0.0574 (3)	0.0103 (7)
O2	0.2557 (3)	0.7800 (3)	0.2802 (3)	0.0091 (7)
O3	0.4137 (3)	0.9003 (3)	0.1124 (3)	0.0119 (7)
O4	0.6114 (3)	0.6631 (3)	0.1144 (3)	0.0077 (7)
O5	0.4911 (3)	0.7439 (3)	0.3094 (3)	0.0068 (6)
O6	0.2927 (3)	0.6703 (3)	0.4788 (3)	0.0098 (7)
O7	0.2695 (3)	0.9141 (3)	0.4594 (3)	0.0114 (7)
O8	0.5351 (3)	0.5906 (3)	0.5163 (3)	0.0061 (6)
O9	0.5209 (3)	0.8146 (3)	0.4727 (3)	0.0070 (6)
O10	0.3393 (3)	0.7379 (3)	0.6367 (3)	0.0058 (6)
O11	0.3480 (3)	0.5000 (3)	0.6978 (3)	0.0096 (7)
O12	0.3556 (3)	0.6163 (3)	0.8530 (3)	0.0108 (7)
O13	0.5815 (3)	0.4361 (3)	0.7240 (3)	0.0077 (7)
O14	0.5651 (3)	0.6687 (3)	0.6669 (3)	0.0081 (7)
O15	0.7266 (3)	0.7992 (3)	0.1354 (3)	0.0116 (7)
O16	0.8550 (3)	0.5513 (3)	0.1411 (3)	0.0092 (7)
O17	0.7336 (3)	0.6599 (3)	0.3434 (3)	0.0088 (7)
O18	0.7542 (3)	0.7663 (3)	0.5051 (3)	0.0113 (7)
O19	0.7760 (3)	0.5146 (3)	0.5302 (3)	0.0090 (7)
O20	0.9485 (3)	0.2716 (3)	0.5427 (3)	0.0104 (7)
O21	0.8303 (3)	0.3935 (3)	0.7318 (3)	0.0113 (7)
O22	0.3854 (4)	0.4292 (4)	0.1050 (4)	0.0193 (9)
H22A	0.447 (7)	0.401 (7)	0.068 (6)	0.029*
H22B	0.397 (7)	0.418 (6)	0.174 (6)	0.029*
O23	0.1180 (4)	0.5313 (4)	0.0558 (3)	0.0156 (8)
H23A	0.138 (7)	0.511 (6)	−0.005 (6)	0.023*
H23B	0.032 (7)	0.540 (6)	0.087 (6)	0.023*
O24	0.1349 (4)	0.3728 (4)	0.3060 (4)	0.0203 (9)
H24A	0.155 (7)	0.334 (6)	0.368 (6)	0.030*
H24B	0.143 (8)	0.423 (7)	0.300 (7)	0.030*
O25	0.3957 (4)	0.1204 (3)	0.1540 (4)	0.0187 (8)
H25	0.390 (7)	0.070 (6)	0.137 (6)	0.022*
O26	0.1374 (4)	0.2320 (4)	0.0943 (4)	0.0260 (9)
H26	0.161 (7)	0.230 (6)	0.018 (6)	0.031*
O27	0.0421 (4)	−0.0116 (4)	0.3221 (4)	0.0269 (10)
H27	0.101 (7)	−0.057 (7)	0.313 (7)	0.032*
O28	−0.0593 (4)	−0.2184 (4)	0.2434 (4)	0.0249 (9)
H28A	−0.002 (8)	−0.277 (7)	0.247 (7)	0.037*
H28B	−0.118 (8)	−0.237 (7)	0.254 (7)	0.037*
O29	0.7568 (4)	0.0498 (4)	0.2733 (4)	0.0182 (8)
H29	0.735 (6)	0.119 (6)	0.287 (6)	0.022*
N1	0.6651 (4)	0.0491 (4)	0.0932 (4)	0.0135 (9)
H1A	0.620503	0.082305	0.041998	0.020*
H1B	0.694572	−0.035013	0.100535	0.020*
H1C	0.734329	0.074419	0.066187	0.020*
N2	−0.0763 (4)	0.3259 (4)	0.3009 (4)	0.0123 (9)
H2A	−0.109556	0.387738	0.249053	0.018*
H2B	−0.004148	0.332753	0.301037	0.018*
H2C	−0.137617	0.331930	0.373678	0.018*
C1	0.4520 (5)	0.0653 (5)	0.2438 (5)	0.0165 (11)
H1D	0.472355	−0.025201	0.257484	0.020*
H1E	0.388654	0.099437	0.317357	0.020*
C2	0.5768 (5)	0.0910 (4)	0.2092 (4)	0.0107 (10)
H2	0.554428	0.182003	0.203335	0.013*
C3	0.6425 (5)	0.0233 (5)	0.2991 (5)	0.0162 (11)
H3A	0.580025	0.047163	0.376761	0.019*
H3B	0.667484	−0.066948	0.302642	0.019*
C4	0.0445 (5)	0.1009 (4)	0.3328 (5)	0.0147 (11)
H4A	0.135127	0.100118	0.299111	0.018*
H4B	0.008737	0.113215	0.415968	0.018*
C5	−0.0397 (5)	0.2030 (4)	0.2660 (4)	0.0127 (10)
H5	−0.122474	0.187396	0.290152	0.015*
C6	0.0209 (5)	0.2060 (5)	0.1362 (5)	0.0187 (11)
H6A	0.041210	0.124953	0.115096	0.022*
H6B	−0.041824	0.270265	0.098737	0.022*
O30B	0.9054 (14)	0.105 (2)	−0.080 (3)	0.048 (6)	0.48 (5)
O30A	0.8950 (11)	0.1308 (12)	−0.026 (2)	0.035 (5)	0.52 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.00509 (9)	0.00748 (9)	0.00526 (10)	−0.00281 (7)	−0.00147 (7)	0.00021 (7)
W2	0.00343 (9)	0.00618 (9)	0.00481 (10)	−0.00225 (7)	−0.00065 (7)	−0.00056 (7)
W3	0.00345 (9)	0.00601 (9)	0.00437 (10)	−0.00258 (7)	−0.00026 (7)	−0.00063 (7)
W4	0.00401 (9)	0.00709 (9)	0.00488 (10)	−0.00339 (7)	0.00000 (7)	−0.00063 (7)
W5	0.00430 (9)	0.00760 (9)	0.00575 (10)	−0.00427 (7)	−0.00078 (7)	−0.00051 (7)
W6	0.00366 (9)	0.00720 (9)	0.00671 (10)	−0.00237 (7)	−0.00130 (7)	−0.00083 (7)
Na1	0.0206 (11)	0.0287 (12)	0.0124 (10)	−0.0171 (10)	−0.0008 (9)	−0.0044 (9)
Na2	0.0148 (10)	0.0173 (10)	0.0248 (12)	−0.0047 (9)	−0.0068 (9)	−0.0020 (9)
Na3	0.0135 (10)	0.0150 (10)	0.0215 (11)	−0.0074 (8)	−0.0073 (9)	0.0029 (8)
O1	0.0080 (16)	0.0132 (17)	0.0082 (17)	−0.0048 (14)	0.0000 (13)	−0.0018 (13)
O2	0.0094 (16)	0.0104 (16)	0.0090 (17)	−0.0048 (14)	−0.0031 (14)	−0.0011 (13)
O3	0.0143 (18)	0.0096 (16)	0.0126 (18)	−0.0055 (14)	−0.0058 (15)	0.0012 (13)
O4	0.0070 (16)	0.0101 (16)	0.0045 (16)	−0.0027 (13)	−0.0010 (13)	−0.0010 (13)
O5	0.0052 (15)	0.0071 (15)	0.0071 (16)	−0.0013 (13)	−0.0026 (13)	−0.0001 (12)
O6	0.0111 (17)	0.0153 (17)	0.0043 (16)	−0.0079 (14)	−0.0004 (13)	−0.0017 (13)
O7	0.0098 (17)	0.0085 (16)	0.0120 (18)	−0.0016 (14)	−0.0022 (14)	−0.0008 (13)
O8	0.0032 (15)	0.0079 (15)	0.0069 (16)	−0.0031 (13)	−0.0001 (13)	−0.0012 (12)
O9	0.0036 (15)	0.0071 (15)	0.0088 (16)	−0.0021 (13)	−0.0003 (13)	−0.0013 (12)
O10	0.0017 (15)	0.0078 (15)	0.0059 (16)	−0.0012 (12)	0.0006 (12)	−0.0019 (12)
O11	0.0103 (17)	0.0112 (16)	0.0078 (17)	−0.0075 (14)	−0.0010 (14)	0.0006 (13)
O12	0.0072 (16)	0.0120 (16)	0.0103 (18)	−0.0029 (14)	−0.0008 (14)	−0.0017 (13)
O13	0.0056 (16)	0.0111 (16)	0.0066 (16)	−0.0041 (13)	−0.0014 (13)	−0.0009 (13)
O14	0.0071 (16)	0.0094 (16)	0.0085 (17)	−0.0042 (13)	−0.0022 (13)	−0.0011 (13)
O15	0.0125 (17)	0.0122 (17)	0.0109 (17)	−0.0074 (14)	−0.0018 (14)	−0.0011 (13)
O16	0.0040 (15)	0.0124 (16)	0.0095 (17)	−0.0036 (13)	0.0010 (13)	−0.0029 (13)
O17	0.0076 (16)	0.0137 (16)	0.0076 (17)	−0.0069 (14)	−0.0009 (13)	−0.0027 (13)
O18	0.0126 (17)	0.0139 (17)	0.0102 (17)	−0.0105 (15)	−0.0005 (14)	−0.0012 (14)
O19	0.0063 (16)	0.0088 (16)	0.0090 (17)	−0.0021 (13)	−0.0022 (13)	0.0011 (13)
O20	0.0071 (16)	0.0113 (16)	0.0126 (18)	−0.0037 (14)	−0.0027 (14)	−0.0018 (13)
O21	0.0102 (17)	0.0154 (17)	0.0099 (17)	−0.0070 (14)	−0.0016 (14)	−0.0026 (14)
O22	0.0098 (19)	0.033 (2)	0.015 (2)	−0.0058 (18)	0.0002 (16)	−0.0137 (18)
O23	0.0132 (19)	0.026 (2)	0.0117 (19)	−0.0114 (17)	−0.0014 (16)	−0.0046 (16)
O24	0.027 (2)	0.024 (2)	0.019 (2)	−0.0165 (19)	−0.0117 (18)	0.0022 (18)
O25	0.019 (2)	0.0128 (18)	0.028 (2)	−0.0040 (16)	−0.0139 (17)	−0.0027 (16)
O26	0.031 (2)	0.039 (2)	0.013 (2)	−0.024 (2)	0.0030 (18)	−0.0063 (18)
O27	0.013 (2)	0.012 (2)	0.052 (3)	−0.0004 (16)	−0.010 (2)	−0.0046 (19)
O28	0.013 (2)	0.028 (2)	0.033 (2)	−0.0048 (18)	−0.0076 (19)	−0.0059 (19)
O29	0.0168 (19)	0.0132 (18)	0.032 (2)	−0.0031 (16)	−0.0137 (17)	−0.0076 (16)
N1	0.018 (2)	0.010 (2)	0.010 (2)	−0.0072 (18)	−0.0023 (18)	0.0010 (16)
N2	0.008 (2)	0.015 (2)	0.011 (2)	−0.0023 (17)	−0.0015 (17)	−0.0014 (17)
C1	0.014 (3)	0.022 (3)	0.015 (3)	−0.008 (2)	−0.005 (2)	−0.002 (2)
C2	0.010 (2)	0.007 (2)	0.013 (3)	−0.0018 (19)	−0.003 (2)	−0.0036 (19)
C3	0.019 (3)	0.013 (2)	0.017 (3)	−0.005 (2)	−0.008 (2)	−0.001 (2)
C4	0.014 (3)	0.013 (2)	0.016 (3)	−0.003 (2)	−0.005 (2)	−0.003 (2)
C5	0.005 (2)	0.016 (2)	0.018 (3)	−0.006 (2)	−0.002 (2)	−0.003 (2)
C6	0.016 (3)	0.021 (3)	0.022 (3)	−0.004 (2)	−0.012 (2)	−0.003 (2)
O30B	0.048 (7)	0.092 (10)	0.028 (11)	−0.052 (7)	−0.011 (7)	0.000 (9)
O30A	0.046 (6)	0.048 (7)	0.027 (10)	−0.030 (5)	−0.017 (5)	0.001 (5)

Geometric parameters (Å, º) top

W1—O1	1.743 (3)	Na2—O25	2.321 (4)
W1—O2	1.906 (3)	Na2—O26	2.328 (5)
W1—O3	1.742 (3)	Na3—O7^iv	2.684 (4)
W1—O4	1.914 (3)	Na3—O18^v	2.411 (4)
W1—O5	2.274 (3)	Na3—O20^vi	2.458 (4)
W1—O13ⁱ	2.270 (3)	Na3—O27	2.375 (5)
W2—O5	1.905 (3)	Na3—O28	2.522 (5)
W2—O6	1.818 (3)	Na3—O29^vii	2.434 (4)
W2—O7	1.723 (3)	O22—H22A	0.68 (7)
W2—O8	2.259 (3)	O22—H22B	0.90 (7)
W2—O9	2.047 (3)	O23—H23A	0.78 (7)
W2—O10	1.956 (3)	O23—H23B	0.91 (7)
W3—O8	2.255 (3)	O24—H24A	0.86 (7)
W3—O10	1.953 (3)	O24—H24B	0.63 (7)
W3—O11	1.807 (3)	O25—H25	0.73 (7)
W3—O12	1.723 (3)	O25—C1	1.422 (7)
W3—O13	1.896 (3)	O26—H26	0.89 (7)
W3—O14	2.052 (3)	O26—C6	1.420 (7)
W4—O4	1.957 (3)	O27—H27	0.67 (7)
W4—O5	2.227 (3)	O27—C4	1.418 (6)
W4—O11ⁱ	2.140 (3)	O28—H28A	0.75 (8)
W4—O15	1.761 (3)	O28—H28B	0.79 (8)
W4—O16	1.757 (3)	O29—H29	0.81 (7)
W4—O17	1.858 (3)	O29—C3	1.432 (6)
W5—O8	2.251 (3)	N1—H1A	0.9100
W5—O9	1.845 (3)	N1—H1B	0.9100
W5—O14	1.856 (3)	N1—H1C	0.9100
W5—O17	1.980 (3)	N1—C2	1.489 (6)
W5—O18	1.734 (3)	N2—H2A	0.9100
W5—O19	1.965 (3)	N2—H2B	0.9100
W6—O2ⁱ	1.966 (3)	N2—H2C	0.9100
W6—O6ⁱ	2.189 (3)	N2—C5	1.498 (6)
W6—O13	2.228 (3)	C1—H1D	0.9900
W6—O19	1.864 (3)	C1—H1E	0.9900
W6—O20	1.731 (3)	C1—C2	1.525 (7)
W6—O21	1.765 (3)	C2—H2	1.0000
Na1—Na2	3.513 (3)	C2—C3	1.502 (7)
Na1—O1	2.365 (4)	C3—H3A	0.9900
Na1—O12ⁱⁱ	2.360 (4)	C3—H3B	0.9900
Na1—O21ⁱ	2.440 (4)	C4—H4A	0.9900
Na1—O22	2.339 (5)	C4—H4B	0.9900
Na1—O23	2.365 (4)	C4—C5	1.517 (7)
Na1—O30Bⁱⁱⁱ	2.96 (3)	C5—H5	1.0000
Na1—O30Aⁱⁱⁱ	2.668 (12)	C5—C6	1.496 (7)
Na2—O4ⁱⁱⁱ	2.606 (4)	C6—H6A	0.9900
Na2—O22	2.299 (4)	C6—H6B	0.9900
Na2—O23	2.471 (4)	O30B—O30A	0.772 (14)
Na2—O24	2.409 (5)

O1—W1—O2	99.34 (14)	O24—Na2—Na1	82.89 (12)
O1—W1—O4	97.41 (14)	O24—Na2—O4ⁱⁱⁱ	163.49 (15)
O1—W1—O5	165.62 (13)	O24—Na2—H22A	99.6 (17)
O1—W1—O13ⁱ	90.34 (13)	O24—Na2—O23	83.19 (15)
O2—W1—O4	152.13 (14)	O24—Na2—H23A	99.9 (16)
O2—W1—O5	85.31 (13)	O24—Na2—H24B	14.0 (16)
O2—W1—O13ⁱ	72.81 (12)	O25—Na2—Na1	141.81 (13)
O3—W1—O1	101.50 (15)	O25—Na2—O4ⁱⁱⁱ	95.66 (14)
O3—W1—O2	97.16 (15)	O25—Na2—H22A	91.2 (16)
O3—W1—O4	101.13 (15)	O25—Na2—O23	175.41 (17)
O3—W1—O5	91.33 (14)	O25—Na2—H23A	158.6 (16)
O3—W1—O13ⁱ	165.73 (14)	O25—Na2—O24	99.07 (17)
O4—W1—O5	73.49 (12)	O25—Na2—H24B	107.6 (17)
O4—W1—O13ⁱ	85.00 (12)	O25—Na2—O26	84.84 (16)
O13ⁱ—W1—O5	77.96 (11)	O26—Na2—Na1	133.01 (14)
O5—W2—O8	85.93 (12)	O26—Na2—O4ⁱⁱⁱ	91.27 (14)
O5—W2—O9	84.55 (13)	O26—Na2—H22A	162.9 (17)
O5—W2—O10	155.42 (13)	O26—Na2—O23	90.92 (16)
O6—W2—O5	95.34 (14)	O26—Na2—H23A	82.9 (15)
O6—W2—O8	88.22 (13)	O26—Na2—O24	97.41 (16)
O6—W2—O9	160.42 (14)	O26—Na2—H24B	108.9 (17)
O6—W2—O10	91.33 (13)	O18^v—Na3—O7^iv	99.45 (13)
O7—W2—O5	104.66 (15)	O18^v—Na3—O20^vi	82.68 (13)
O7—W2—O6	103.57 (16)	O18^v—Na3—O28	79.23 (14)
O7—W2—O8	163.09 (14)	O18^v—Na3—O29^vii	104.03 (14)
O7—W2—O9	95.34 (14)	O20^vi—Na3—O7^iv	118.30 (13)
O7—W2—O10	96.66 (14)	O20^vi—Na3—O28	82.88 (14)
O9—W2—O8	72.23 (11)	O27—Na3—O7^iv	88.69 (14)
O10—W2—O8	70.63 (12)	O27—Na3—O18^v	162.22 (16)
O10—W2—O9	81.39 (13)	O27—Na3—O20^vi	79.54 (14)
O10—W3—O8	70.79 (12)	O27—Na3—O28	98.85 (17)
O10—W3—O14	82.41 (13)	O27—Na3—O29^vii	92.51 (16)
O11—W3—O8	87.05 (13)	O28—Na3—O7^iv	158.61 (15)
O11—W3—O10	92.51 (14)	O29^vii—Na3—O7^iv	83.56 (13)
O11—W3—O13	94.39 (14)	O29^vii—Na3—O20^vi	156.19 (16)
O11—W3—O14	160.06 (14)	O29^vii—Na3—O28	76.17 (15)
O12—W3—O8	164.22 (13)	W1—O1—Na1	135.79 (18)
O12—W3—O10	97.08 (14)	W1—O2—W6ⁱ	117.99 (16)
O12—W3—O11	103.95 (15)	W1—O4—W4	117.48 (16)
O12—W3—O13	103.07 (15)	W1—O4—Na2ⁱⁱⁱ	116.67 (15)
O12—W3—O14	95.83 (14)	W4—O4—Na2ⁱⁱⁱ	116.38 (15)
O13—W3—O8	87.06 (13)	W2—O5—W1	125.33 (15)
O13—W3—O10	156.41 (13)	W2—O5—W4	137.59 (16)
O13—W3—O14	83.45 (13)	W4—O5—W1	94.63 (12)
O14—W3—O8	73.06 (12)	W2—O6—W6ⁱ	139.38 (17)
O4—W4—O5	73.85 (12)	W2—O7—Na3^iv	137.29 (18)
O4—W4—O11ⁱ	81.97 (13)	W3—O8—W2	97.22 (12)
O11ⁱ—W4—O5	77.76 (12)	W5—O8—W2	94.75 (11)
O15—W4—O4	92.61 (14)	W5—O8—W3	94.52 (12)
O15—W4—O5	96.44 (14)	W5—O9—W2	116.91 (15)
O15—W4—O11ⁱ	172.94 (14)	W3—O10—W2	120.08 (15)
O15—W4—O17	96.69 (15)	W3—O11—W4ⁱ	136.32 (18)
O16—W4—O4	96.54 (14)	W3—O12—Na1^viii	170.67 (19)
O16—W4—O5	160.85 (13)	W3—O13—W1ⁱ	126.28 (15)
O16—W4—O11ⁱ	84.60 (13)	W3—O13—W6	137.29 (16)
O16—W4—O15	100.58 (15)	W6—O13—W1ⁱ	95.12 (12)
O16—W4—O17	99.46 (15)	W5—O14—W3	115.64 (16)
O17—W4—O4	159.66 (14)	W4—O17—W5	148.36 (18)
O17—W4—O5	87.12 (13)	W5—O18—Na3^ix	150.89 (19)
O17—W4—O11ⁱ	87.11 (13)	W6—O19—W5	146.16 (18)
O9—W5—O8	76.09 (12)	W6—O20—Na3^vi	132.86 (18)
O9—W5—O14	93.33 (14)	W6—O21—Na1ⁱ	135.54 (18)
O9—W5—O17	86.47 (14)	Na1—O22—H22A	122 (6)
O9—W5—O19	154.74 (14)	Na1—O22—H22B	114 (4)
O14—W5—O8	76.78 (12)	Na2—O22—Na1	98.47 (16)
O14—W5—O17	156.72 (13)	Na2—O22—H22A	104 (6)
O14—W5—O19	87.83 (14)	Na2—O22—H22B	113 (4)
O17—W5—O8	80.60 (12)	H22A—O22—H22B	104 (7)
O18—W5—O8	178.51 (14)	Na1—O23—Na2	93.15 (15)
O18—W5—O9	102.80 (15)	Na1—O23—H23A	113 (5)
O18—W5—O14	102.35 (15)	Na1—O23—H23B	138 (4)
O18—W5—O17	100.38 (14)	Na2—O23—H23A	88 (5)
O18—W5—O19	101.57 (15)	Na2—O23—H23B	113 (4)
O19—W5—O8	79.64 (12)	H23A—O23—H23B	101 (6)
O19—W5—O17	82.74 (13)	Na2—O24—H24A	126 (5)
O2ⁱ—W6—O6ⁱ	77.66 (13)	Na2—O24—H24B	98 (7)
O2ⁱ—W6—O13	72.73 (12)	H24A—O24—H24B	101 (8)
O6ⁱ—W6—O13	76.98 (12)	Na2—O25—H25	118 (5)
O19—W6—O2ⁱ	156.59 (14)	C1—O25—Na2	130.9 (3)
O19—W6—O6ⁱ	84.75 (13)	C1—O25—H25	107 (5)
O19—W6—O13	88.45 (13)	Na2—O26—H26	106 (4)
O20—W6—O2ⁱ	94.54 (14)	C6—O26—Na2	150.9 (3)
O20—W6—O6ⁱ	90.10 (14)	C6—O26—H26	100 (4)
O20—W6—O13	163.39 (13)	Na3—O27—H27	110 (6)
O20—W6—O19	100.87 (15)	C4—O27—Na3	131.5 (3)
O20—W6—O21	101.60 (16)	C4—O27—H27	112 (6)
O21—W6—O2ⁱ	95.80 (14)	Na3—O28—H28A	110 (6)
O21—W6—O6ⁱ	167.09 (14)	Na3—O28—H28B	107 (6)
O21—W6—O13	90.50 (14)	H28A—O28—H28B	108 (8)
O21—W6—O19	98.20 (15)	Na3^x—O29—H29	108 (5)
O1—Na1—Na2	130.03 (12)	C3—O29—Na3^x	107.8 (3)
O1—Na1—O21ⁱ	87.94 (13)	C3—O29—H29	109 (5)
O1—Na1—O30Bⁱⁱⁱ	75.4 (4)	H1A—N1—H1B	109.5
O1—Na1—O30Aⁱⁱⁱ	82.9 (4)	H1A—N1—H1C	109.5
O12ⁱⁱ—Na1—Na2	90.80 (11)	H1B—N1—H1C	109.5
O12ⁱⁱ—Na1—O1	91.95 (13)	C2—N1—H1A	109.5
O12ⁱⁱ—Na1—O21ⁱ	169.87 (16)	C2—N1—H1B	109.5
O12ⁱⁱ—Na1—O23	87.84 (14)	C2—N1—H1C	109.5
O12ⁱⁱ—Na1—O30Bⁱⁱⁱ	106.9 (5)	H2A—N2—H2B	109.5
O12ⁱⁱ—Na1—O30Aⁱⁱⁱ	94.4 (6)	H2A—N2—H2C	109.5
O21ⁱ—Na1—Na2	81.56 (10)	H2B—N2—H2C	109.5
O21ⁱ—Na1—O30Bⁱⁱⁱ	82.9 (6)	C5—N2—H2A	109.5
O21ⁱ—Na1—O30Aⁱⁱⁱ	95.6 (6)	C5—N2—H2B	109.5
O22—Na1—Na2	40.33 (11)	C5—N2—H2C	109.5
O22—Na1—O1	89.70 (15)	O25—C1—H1D	109.6
O22—Na1—O12ⁱⁱ	92.67 (15)	O25—C1—H1E	109.6
O22—Na1—O21ⁱ	77.19 (14)	O25—C1—C2	110.2 (4)
O22—Na1—O23	84.94 (15)	H1D—C1—H1E	108.1
O22—Na1—O30Bⁱⁱⁱ	155.5 (6)	C2—C1—H1D	109.6
O22—Na1—O30Aⁱⁱⁱ	169.9 (6)	C2—C1—H1E	109.6
O23—Na1—Na2	44.61 (11)	N1—C2—C1	108.4 (4)
O23—Na1—O1	174.62 (17)	N1—C2—H2	109.3
O23—Na1—O21ⁱ	91.32 (14)	N1—C2—C3	110.2 (4)
O23—Na1—O30Bⁱⁱⁱ	109.8 (4)	C1—C2—H2	109.3
O23—Na1—O30Aⁱⁱⁱ	102.5 (4)	C3—C2—C1	110.2 (4)
O30Bⁱⁱⁱ—Na1—Na2	149.3 (2)	C3—C2—H2	109.3
O30Aⁱⁱⁱ—Na1—Na2	146.5 (3)	O29—C3—C2	112.1 (4)
O30Aⁱⁱⁱ—Na1—O30Bⁱⁱⁱ	14.6 (2)	O29—C3—H3A	109.2
Na1—Na2—H22A	51.3 (16)	O29—C3—H3B	109.2
Na1—Na2—H23A	51.3 (15)	C2—C3—H3A	109.2
Na1—Na2—H24B	69.2 (17)	C2—C3—H3B	109.2
O4ⁱⁱⁱ—Na2—Na1	80.92 (9)	H3A—C3—H3B	107.9
O4ⁱⁱⁱ—Na2—H22A	72.6 (17)	O27—C4—H4A	110.5
O4ⁱⁱⁱ—Na2—H23A	67.2 (16)	O27—C4—H4B	110.5
O4ⁱⁱⁱ—Na2—H24B	150.2 (17)	O27—C4—C5	106.2 (4)
O22—Na2—Na1	41.20 (11)	H4A—C4—H4B	108.7
O22—Na2—O4ⁱⁱⁱ	83.35 (14)	C5—C4—H4A	110.5
O22—Na2—H22A	15.0 (16)	C5—C4—H4B	110.5
O22—Na2—O23	83.43 (15)	N2—C5—C4	110.1 (4)
O22—Na2—H23A	90.4 (15)	N2—C5—H5	107.2
O22—Na2—O24	86.63 (15)	C4—C5—H5	107.2
O22—Na2—H24B	74.3 (17)	C6—C5—N2	111.0 (4)
O22—Na2—O25	100.64 (16)	C6—C5—C4	113.9 (4)
O22—Na2—O26	172.64 (19)	C6—C5—H5	107.2
H22A—Na2—H23A	95 (2)	O26—C6—C5	110.7 (4)
H22A—Na2—H24B	88 (2)	O26—C6—H6A	109.5
O23—Na2—Na1	42.24 (10)	O26—C6—H6B	109.5
O23—Na2—O4ⁱⁱⁱ	82.65 (13)	C5—C6—H6A	109.5
O23—Na2—H22A	92.4 (16)	C5—C6—H6B	109.5
O23—Na2—H23A	17.7 (15)	H6A—C6—H6B	108.1
O23—Na2—H24B	75.5 (17)	O30A—O30B—Na1ⁱⁱⁱ	60.3 (18)
H23A—Na2—H24B	93 (2)	O30B—O30A—Na1ⁱⁱⁱ	105 (2)

Na2—O25—C1—C2	−81.3 (5)	O11ⁱ—W4—O17—W5	−70.5 (3)
Na2—O26—C6—C5	−28.2 (9)	O12—W3—O11—W4ⁱ	−55.6 (3)
Na3—O27—C4—C5	−70.6 (6)	O12—W3—O13—W1ⁱ	60.5 (2)
Na3^x—O29—C3—C2	−169.3 (3)	O12—W3—O13—W6	−136.2 (2)
O2—W1—O1—Na1	−25.9 (3)	O13ⁱ—W1—O1—Na1	46.8 (3)
O2ⁱ—W6—O19—W5	47.2 (6)	O13—W3—O11—W4ⁱ	49.1 (3)
O2ⁱ—W6—O20—Na3^vi	−50.9 (2)	O13—W6—O19—W5	11.3 (3)
O2ⁱ—W6—O21—Na1ⁱ	−30.6 (3)	O13—W6—O20—Na3^vi	−90.0 (5)
O3—W1—O1—Na1	−125.2 (3)	O13—W6—O21—Na1ⁱ	42.1 (3)
O4—W1—O1—Na1	131.8 (2)	O14—W3—O11—W4ⁱ	132.0 (3)
O4—W4—O17—W5	−13.1 (6)	O14—W3—O13—W1ⁱ	155.0 (2)
O5—W1—O1—Na1	82.1 (6)	O14—W3—O13—W6	−41.7 (2)
O5—W2—O6—W6ⁱ	−42.3 (3)	O14—W5—O9—W2	−76.39 (18)
O5—W2—O7—Na3^iv	−150.8 (2)	O14—W5—O18—Na3^ix	−153.2 (4)
O5—W4—O17—W5	7.4 (3)	O15—W4—O17—W5	103.5 (3)
O6—W2—O7—Na3^iv	109.9 (2)	O16—W4—O17—W5	−154.6 (3)
O6ⁱ—W6—O19—W5	88.4 (3)	O17—W5—O9—W2	80.29 (17)
O6ⁱ—W6—O20—Na3^vi	−128.5 (2)	O17—W5—O14—W3	−13.9 (4)
O6ⁱ—W6—O21—Na1ⁱ	28.1 (8)	O17—W5—O18—Na3^ix	31.8 (4)
O7—W2—O6—W6ⁱ	64.3 (3)	O18—W5—O9—W2	−179.85 (17)
O8—W2—O6—W6ⁱ	−128.0 (3)	O18—W5—O14—W3	178.84 (17)
O8—W2—O7—Na3^iv	−23.3 (6)	O19—W5—O9—W2	15.6 (4)
O8—W3—O11—W4ⁱ	135.9 (2)	O19—W5—O14—W3	−79.79 (17)
O8—W3—O13—W1ⁱ	−131.77 (19)	O19—W5—O18—Na3^ix	116.5 (4)
O8—W3—O13—W6	31.6 (2)	O19—W6—O20—Na3^vi	146.9 (2)
O8—W5—O9—W2	−0.89 (15)	O19—W6—O21—Na1ⁱ	130.6 (2)
O8—W5—O14—W3	0.08 (15)	O20—W6—O19—W5	177.5 (3)
O9—W2—O6—W6ⁱ	−131.0 (3)	O20—W6—O21—Na1ⁱ	−126.5 (3)
O9—W2—O7—Na3^iv	−65.0 (3)	O21—W6—O19—W5	−79.0 (3)
O9—W5—O14—W3	74.95 (18)	O21—W6—O20—Na3^vi	46.0 (3)
O9—W5—O18—Na3^ix	−56.9 (4)	O25—C1—C2—N1	−54.2 (5)
O10—W2—O6—W6ⁱ	161.4 (3)	O25—C1—C2—C3	−174.9 (4)
O10—W2—O7—Na3^iv	16.9 (3)	O27—C4—C5—N2	163.1 (4)
O10—W3—O11—W4ⁱ	−153.5 (2)	O27—C4—C5—C6	−71.6 (5)
O10—W3—O13—W1ⁱ	−151.6 (2)	N1—C2—C3—O29	63.4 (5)
O10—W3—O13—W6	11.8 (5)	N2—C5—C6—O26	61.3 (5)
O11—W3—O13—W1ⁱ	−45.0 (2)	C1—C2—C3—O29	−177.0 (4)
O11—W3—O13—W6	118.4 (2)	C4—C5—C6—O26	−63.6 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22A···O1ⁱⁱⁱ	0.67 (7)	2.11 (7)	2.757 (5)	163 (8)
O23—H23A···O16ⁱⁱⁱ	0.78 (7)	2.04 (7)	2.802 (5)	165 (7)
O23—H23B···O16^vii	0.91 (7)	1.91 (7)	2.811 (5)	175 (6)
O25—H25···O3^xi	0.73 (6)	2.05 (7)	2.761 (5)	164 (7)
O26—H26···O15ⁱⁱⁱ	0.88 (7)	1.88 (7)	2.730 (5)	160 (6)
O27—H27···O2^xi	0.67 (7)	2.04 (7)	2.696 (5)	165 (8)
O28—H28A···O21^vi	0.75 (8)	2.01 (8)	2.735 (6)	160 (8)
O29—H29···O10ⁱ	0.81 (6)	1.91 (7)	2.692 (5)	163 (6)
N1—H1B···O15^xi	0.91	1.82	2.723 (5)	170
N2—H2B···O24	0.91	1.96	2.867 (6)	172

Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (vi) −x+1, −y, −z+1; (vii) x−1, y, z; (xi) x, y−1, z.

Footnotes

‡https://www.bpc.unvie.ac.at

Acknowledgements

We thank Dr Elias Tanuhadi for help with the TGA measurements.

Funding information

Funding for this research was provided by: Austrian Science Fund (grant No. P33089 to Annette Rompel; grant No. P33927 to Nadiia I. Gumerova); Erasmus+ (studentship No. 1016/2020 to Kleanthi Sifaki).

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