Iron(II) and copper(II) paratungstates B: a single-crystal X-ray diffraction study

Gumerova, N.I.; Dobrov, A.; Roller, A.; Rompel, A.

doi:10.1107/S2053229618010021

polyoxometalates

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 74| Part 11| November 2018| Pages 1252-1259

https://doi.org/10.1107/S2053229618010021

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Iron(II) and copper(II) paratungstates B: a single-crystal X-ray diffraction study

Nadiia I. Gumerova,^a Anatolie Dobrov,^a Alexander Roller ^b and Annette Rompel ^a ^*

^aUniversität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Althanstrasse 14, Wien 1090, Austria, and ^bUniversität Wien, Fakultät für Chemie, Zentrum für Röntgenstrukturanalyse, Währinger Strasse 42, Wien 1090, Austria
^*Correspondence e-mail: annette.rompel@univie.ac.at

Edited by J. R. Galán-Mascarós, Institute of Chemical Research of Catalonia (ICIQ), Spain (Received 17 May 2018; accepted 11 July 2018; online 16 October 2018)

Paratungstate B is a common isopolytungstate (IPOT) built of the [W₁₂O₄₀(OH)₂]¹⁰⁻ anion and exhibits a cluster-like construction of 12 W-centred distorted octahedra. Due to a high surface charge density, the paratungstate anion acts as a multidentate ligand forming high-dimensional extended structures, which exhibit unique catalytic and magnetic properties. Two new paradodecatungstate B compounds decorated by iron(II) or copper(II), namely Na₅Fe_2.5[W₁₂O₄₀(OH)₂]·36H₂O (Na₅Fe_2.5paraB) and Na₄Cu₃[W₁₂O₄₀(OH)₂]·28H₂O (Na₄Cu₃paraB), have been synthesized by a convenient aqueous solution method, and structurally characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis. Both compounds crystallize in the triclinic P $[\overline{1}]$ space group. In both compounds, the [W₁₂O₄₀(OH)₂]¹⁰⁻ polyanion acts as a multidentate ligand that links transition-metal and sodium cations, forming a three-dimensional framework.

Keywords: polyoxometalate; POM; isopolytungstate; three-dimensional structure; crystal structure; dodecatungstate; IPOT.

CCDC references: 1843518; 1843519

1. Introduction

The structural diversity of polyoxometalates (Pope, 1983 ) and their proven applications in catalysis (Wang & Yang, 2015 ), nanotechnology (Yamase & Pope, 2002 ), electrochemistry (Sadakane & Steckhan, 1998 ), materials science (Proust et al., 2008 ), molecular magnetism (Clemente-Juan et al., 2012 ), macromolecular crystallography (Bijelic & Rompel, 2015 , 2017 ; Molitor et al., 2017 ) and medicine (Fu et al., 2015 ; Bijelic et al., 2018a ,b ) have encouraged the synthesis of novel polyanions with promising properties. One of the most common isopolytungstates (IPOTs) is paratungstate B, built of the [W₁₂O₄₀(OH)₂]¹⁰⁻ anion that is stable in aqueous acidic solution and exhibits a cluster-like construction of 12 W-centred distorted octahedra (Evans & Rollins, 1976 ; Pope, 1983). Due to a high surface charge density, the paratungstate anion acts as a multidentate ligand, which can coordinate alkaline (Peresypkina et al., 2014 ) and transition-metal cations (Radio et al., 2010 , 2011 ; Gumerova et al., 2015 ), and also act as a precursor (Sokolov et al., 2012 ). By coordinating transition-metal cations, paratungstates can form high-dimensional extended structures, which exhibit unique catalytic (He et al., 2008 ; Chen et al., 2017 ) and magnetic properties (Li et al., 2008 , 2009 ). So far, three paratungstates B with Fe^II and nine with Cu^II as counter-cations have been successfully synthesized and characterized by X-ray diffraction (Table 1). We present herein two novel paratungstates B, one with Fe^II and one with Cu^II, namely the double sodium–iron(II) paratungstate Na₅Fe_2.5[W₁₂O₄₀(OH)₂]·36H₂O (denoted Na₅Fe_2.5paraB) and the double sodium–copper(II) paratungstate Na₄Cu₃[W₁₂O₄₀(OH)₂]·28H₂O (denoted Na₄Cu₃paraB), which were synthesized by a convenient aqueous solution method.

Table 1
Fe^II- and Cu^II-containing paratungstates B [based on the Inorganic Crystal Structure Database (FIZ, Karlsruhe; https://www.fiz-informationsdienste.de/DB/icsd/www-recherche.html) and the Cambridge Structural Database (CSD; Groom et al., 2016 )]

Compounds	Unit-cell parameters a, b and c (Å), and α, β and γ (°)	Volume (Å³), Z and space group	Synthesis details (source of W; W:M^II ratio, with M = Fe, Cu; pH)	Reference
Fe^II
K₆[{Fe(H₂O)₄}₂(H₂W₁₂O₄₂)]·15H₂O	14.9967 (5), 10.3872 (3), 18.8237 (6); 90, 93.407 (1), 90	2927.1 (2), 2, P2₁/n	K₂WO₄; 12:1.4; –	Yang et al. (2003)
(H₃O)₂[{Fe(H₂O)₄Fe(H₂O)₃}₂(H₂W₁₂O₄₂)]·20H₂O	12.1794 (4), 22.4938 (4), 11.6941 (3); 90, 105.731 (2), 90	3083.7 (1), 2, P2₁/c	Li₂WO₄; 12:1.4; –	Yang et al. (2003)
Na₅[{Fe(H₂O)₃}₂{Fe(H₂O)₄}_0.5(H₂W₁₂O₄₂)]·30H₂O	12.121 (2), 12.426 (3), 13.247 (3); 68.33 (3), 71.33 (3), 71.44 (3)	1710.7 (6), 1, P $[\overline{1}]$	Na₂WO₄; 12:1.4; –	Yang et al. (2003)

Cu^II
Na₈[Cu(H₂O)₂(H₂W₁₂O₄₂)]·30H₂O	13.081 (4), 13.160 (6), 20.127 (6); 78.294 (12), 78.524 (11), 72.593 (11)	3201.7 (17), 2, P $[\overline{1}]$	Na₂WO₄; 12:2.4; 4.8	Li et al. (2008)
KNa₃[Cu(H₂O)₂{Cu(H₂O)₃}₂(H₂W₁₂O₄₂)]·16H₂O	10.799 (2), 11.914 (2), 13.377 (3); 70.18 (3), 68.07 (3), 64.80 (3)	1410.9 (5), 1, P $[\overline{1}]$	Na₂[W₁₂O₄₀(OH)₂]; 12:2; 3.5	Li et al. (2009)
[{Na₂(μ-H₂O)₂(H₂O)₆}{Cu(H₂O)₂}{Cu(H₂O)₄}₂{Cu₂(μ-OH)₂(H₂O)₆}(H₂W₁₂O₄₂)]·10H₂O	10.697 (5), 12.921 (5), 13.653 (5); 73.608 (5), 75.671 (5), 67.748 (5)	1654.4 (12), 1, P $[\overline{1}]$	(NH₄)₆[W₁₂O₄₀]; 12:0.4; 6.2	Kong et al. (2010 )
[{Na(H₂O)₄}₂{Cu_0.5(H₂O)}₄{Cu_0.5(H₂O)_1.5}₂(H₄W₁₂O₄₂)]·3H₂O	10.7060 (11), 12.7124 (14), 13.1664 (14); 113.7600 (10), 90.8230 (10), 111.8290 (10)	1493.8 (3), 1, P $[\overline{1}]$	Na₂WO₄; 12:3; 6.5	Gao et al. (2011 )
[Na₂(H₂O)₁₀][Cu₄(H₂O)₁₂(H₂W₁₂O₄₂)]·15H₂O	10.1535 (2), 13.2118 (3), 13.7049 (5); 112.692 (3), 94.771 (3), 102.969 (2)	1623.15 (8), 1, P $[\overline{1}]$	Na₂WO₄; 12:36; 4	Qu et al. (2012)
Cu₃(H₂O)₈[H₆W₁₂O₄₂]	10.6753 (5), 12.7814 (5), 13.0976 (5); 113.737 (4), 90.433 (3), 112.560 (4)	1482.73 (12), 2, P $[\overline{1}]$	(NH₄)₆[W₁₂O₄₀]; 12:36; –	Chen et al. (2017)
(NH₄)₈[Cu(H₂O)₂H₂W₁₂O₄₂]·10H₂O	14.278 (5), 15.435 (5), 24.881 (5); 90, 90, 90	5483 (3), 2, Pbcn	(NH₄)₆[W₁₂O₄₀]; 12:2.5; 4.8	Zhang (2012 )
Na₂Cu₃(CuOH)₂[W₁₂O₄₀(OH)₂]·32H₂O	10.6836 (4), 12.9066 (6), 13.6475 (5); 73.561 (4), 75.685 (3), 67.666 (4)	1648.68 (12), 1, P $[\overline{1}]$	Na₂WO₄; 12:7.5; –	Radio et al. (2014 )
Na₂Cu₅(H₂O)₂₄(OH)₂[H₂W₁₂O₄₂]·10H₂O	10.7140 (8), 12.9476 (9), 13.6696 (10); 73.56, 75.73, 67.69	1661.8 (2), 1, P $[\overline{1}]$	Na₂WO₄; 12:20; 3.8	Qu et al. (2015)

2. Experimental

2.1. Synthesis and crystallization

The reagents were used as purchased from Sigma–Aldrich without further purification.

2.1.1. Synthesis of Na₅Fe_2.5paraB

Iron powder (0.112 g, 2 mmol) was added to a solution (15 ml) of Na₂WO₄·2H₂O (3.96 g, 12 mmol), which was acidified to pH = 2.5 with HCl (1 M). The mixture was stirred in an ultrasonic bath, giving a deep-blue solution, which was left to stand closed at room temperature. The pale-red–brown crystals which grew on the beaker walls were collected after three weeks (yield ∼2 g, ∼53%, based on W). Elemental analysis found (calculated) for Fe_2.5H₇₄Na₅O₇₈W₁₂ (%): Na 3.13 (3.03), Fe 3.71 (3.69), W 56.8 (58.32).

2.1.2. Synthesis of Na₄Cu₃paraB

Sodium orthotungstate Na₂WO₄·2H₂O (5.5 g, 16.7 mmol) was dissolved in water (25 ml) and the pH was adjusted to 8 by adding dilute HNO₃ (1 M). An aqueous solution (10 ml) of Cu(NO₃)₂·3H₂O (0.5 g, 2.1 mmol) was then added dropwise, while the pH was maintained between 3.0 and 4.5 with HNO₃ (1 M). The final mixture was filtered (pH = 4.2) and allowed to stand closed at room temperature. Light-blue crystals formed within two months (yield ∼3.5 g, 69% based on W). Elemental analysis found (calculated) for Cu₃H₅₈Na₄O₇₀W₁₂ (%): Na 2.62 (2.51), Cu 5.13 (5.20), W 59.1 (60.16).

2.2. IR spectroscopy

The title compounds were identified by IR measurements on a Bruker Vertex70 IR Spectrometer equipped with a single-reflection diamond-ATR unit (ATR is attenuated total reflectance) in the range 4000–400 cm⁻¹.

2.3. TGA measurements

Thermogravimetric analysis (TGA) was performed on a Mettler SDTA851e Thermogravimetric Analyzer under a nitrogen flow with a heating rate of 5 K min⁻¹ in the region from 298 to 973 K.

2.4. Elemental analysis

Elemental analysis was conducted using inductive-coupled plasma–mass spectrometry (PerkinElmer Elan 6000 ICP MS) and atomic absorption spectroscopy (PerkinElmer 1100 Flame AAS) in aqueous solutions containing 2% HNO₃. Standards were prepared from single-element standard solutions of concentration 1000 mg l⁻¹ (from Merck, Ultra Scientific and Analytika Prague).

2.5. Powder X-ray diffraction

Powder X-ray diffraction (PXRD) was performed on a Bruker D8 Advance diffractometer, with Cu Kα radiation (λ = 1.54056 Å), a Lynxeye silicon strip detector, a SolX energy dispersive detector and a variable slit aperture of 12 mm. The 2θ range was 8–50°.

2.6. Refinement

In Table 2, the crystallographic characteristics of the two new paratungstates B and the experimental conditions of the data collection and refinement are reported. The positions of the independent H atoms were obtained by difference Fourier techniques and were refined with free isotropic displacement parameters.

Table 2
Experimental details

	Na₄Cu₃paraBM	Na₅Fe_2.5paraB
Crystal data
Chemical formula	Na₄Cu₃[W₁₂O₄₀(OH)₂]·28H₂O	Na₅Fe_2.5[W₁₂O₄₀(OH)₂]·36H₂O
M_r	3621.13	3771.27
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100
a, b, c (Å)	10.6516 (5), 12.7532 (6), 13.0730 (5)	12.3758 (6), 14.7752 (7), 18.8919 (8)
α, β, γ (°)	113.771 (1), 90.443 (1), 112.502 (1)	92.9341 (14), 100.6938 (14), 94.1698 (15)
V (Å³)	1473.65 (11)	3378.1 (3)
Z	1	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	24.53	21.02
Crystal size (mm)	0.13 × 0.07 × 0.02	0.37 × 0.07 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.004, 0.023	0.012, 0.044
No. of measured, independent and observed [I > 2σ(I)] reflections	11292, 5321, 4720	38068, 12318, 10876
R_int	0.048	0.032
(sin θ/λ)_max (Å⁻¹)	0.602	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.05	0.022, 0.058, 1.09
No. of reflections	5321	12318
No. of parameters	463	980
No. of restraints	100	405
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.15, −1.63	1.57, −1.25
Computer programs: APEX3 (Bruker, 2015 ), SAINT (Bruker, 2015), SHELXS97 (Sheldrick, 2008 ), shelXle (Hübschle et al., 2011 ), SHELXL2014 (Sheldrick, 2015 ), SHELXL2016 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg, 2006 ).

Fixed isotropic displacement parameters for all H atoms with a value equal to 1.5U_eq of the corresponding O—H group atom were assigned. Restrained distances for D—H bonds were applied to avoid short D—H⋯H—D interactions. To force correct bonds, specified bonds were added to or removed from the connectivity list.

The disordered water molecules in the coordination spheres of atom Na1 in Na₄Cu₃paraB and of atoms Na4 and Na5 in Na₅Fe_2.5paraB were refined with two positions with fixed occupancy factors of 0.5.

In Na₄Cu₃paraB, part of the disordered water molecules were not modelled and the disordered density was considered using the OLEX2 (Dolomanov et al., 2009 ) implementation of BYPASS (a.k.a. SQUEEZE; Spek, 2015 ). The modelled electron density is consistent with approximately four water molecules per unit cell.

The structures have been deposited with the Inorganic Crystal Structure Database (ICSD) (https://www2.fiz-karlsruhe.de/icsd_home.html) under collection numbers 434558 and 434559.

3. Results and discussion

The syntheses of Na₅Fe_2.5paraB and Na₄Cu₃paraB were carried out with W^VI-to-M^II ratios of W:Fe = 12:2 and W:Cu = 12:1.5, and a pH of 2.5 for Na₅Fe_2.5paraB and 4.2 for Na₄Cu₃paraB, which are different from previously reported conditions (Table 1) and made it possible to obtain compounds with new Fe–Na and Cu–Na compositions. The presence of Na^I as counter-cation in paratungstates B, together with Cu^II or Fe^II, have been observed previously both in excess and in deficiency of the transition-metal ion in the reaction mixture, which had a pH in the range 3.5–6.5 (Table 1). This allows one to conclude that crystallization of paratungstates B as double-alkali–transition-metal salts is more preferable than crystallization of pure transition-metal paratungstates B, regardless of the starting molar ratios of the components and the pH of the reaction system.

The main structural elements of Na₅Fe_2.5paraB and Na₄Cu₃paraB are shown in Fig. 1. Both compounds consist of paradodecatungstate B [W₁₂O₄₀(OH)₂]¹⁰⁻ polyanions (Evans & Rollins, 1976; Pope, 1983), sodium and transition-metal cations, and additional water molecules (Fig. 1). The paratungstate B units observed in Na₅Fe_2.5paraB and Na₄Cu₃paraB are structurally identical to previously reported units (Table 1).

Figure 1
Structural elements in Na₅Fe_2.5paraB and Na₄Cu₃paraB. (a) The [W₁₂O₄₀(OH)₂]¹⁰⁻ anion in Na₅Fe_2.5paraB connected to four Na⁺ and six Fe²⁺ ions via terminal O atoms. (b) A fragment of the infinite 1D chain in Na₅Fe_2.5paraB consisting of Na and Fe polyhedra. (c) The [W₁₂O₄₀(OH)₂]¹⁰⁻ anion in Na₄Cu₃paraB connected to six Na⁺ and six Cu²⁺ ions via terminal O atoms. (d) A fragment of the infinite 1D chain in Na₄Cu₃paraB consisting of Na and Cu polyhedra. Colour code: {WO₆} are light-blue or violet octahedra, {W₃O₁₄} are blue octahedra and {W₃O₁₃} are violet octahedra, and Na atoms are green, Fe orange, Cu blue and O red.

In Na₄Cu₃paraB, there is one-half unit of the POM, which lies on an inversion centre, in the asymmetric unit. For Na₅Fe_2.5paraB, there are two independent half-POM units in the asymmetric unit.

The centrosymmetric [W₁₂O₄₀(OH)₂]¹⁰⁻ anion consists of four corner-sharing groups: two {W₃O₁₃} (violet octahedra in Figs. 1a and 1c) and two {W₃O₁₄} (blue octahedra in Figs. 1a and 1c) units. Each {W₃O₁₃} fragment is formed by three edge-sharing {WO₆} octahedra with a common O atom, while in the {W₃O₁₄} triads, the three edge-sharing {WO₆} octahedra are linearly connected with no common O atom to the three W atoms. In the {W₃O₁₃} groups, each octahedron has one terminal O atom, while in the {W₃O₁₄} units, each octahedron has two unshared O atoms (Figs. 1a and 1c). The O atoms connected to the W centres can be classified into three groups. The first group is comprised of terminal O atoms (O_t), each bonded to one W atom. The second group consists of bridging O atoms (O_db), each connected to two W atoms. There are two types of O_db, one bridges two W atoms within the same {W₃O₁₃} or {W₃O₁₄} fragment (O_db1), while the other bridges two W atoms between the different {W₃O₁₃} and {W₃O₁₄} units (O_db2). The third group contains triply bridging O atoms, linked by three W atoms. The triply bridging O atoms exclusively from {W₃O₁₃} are labelled O_tb1, whereas the O atoms bridging three W atoms between {W₃O₁₃} and {W₃O₁₄} units are labelled as O_tb2.

The exact positions of the two protons in [W₁₂O₄₀(OH)₂]¹⁰⁻ were located previously on triply bridging O atoms of {W₃O₁₃} by neutron diffraction (Evans & Prince, 1983 ). Selected bond lengths and angles are presented in Table 3. All the W atoms in [W₁₂O₄₀(OH)₂]¹⁰⁻ exhibit the +VI oxidation state, when applying the bond valence sum (BVS) calculations of Brown & Altermatt (1985 ). For Na₅Fe_2.5paraB and Na₄Cu₃paraB, we got average values of 6.01 and 6.09, respectively. BVS calculations for Fe and Cu sites show that both ions exhibit the +II oxidation state, with a value of 2.12 for Fe and 2.08 for Cu.

Table 3
Selected bond length and angles (Å, °) in Na₅Fe_2.5paraB and Na₄Cu₃paraB

	Na₅Fe_2.5paraB	Na₄Cu₃paraB
W=O_t	1.719 (4)–1.797 (4)	1.710 (8)–1.780 (7)
W—O_db1	1.888 (4)–2.050 (2)	1.872 (7)–2.103 (7)
W—O_db2	1.826 (3)–2.166 (3)	1.805 (7)–2.098 (7)
W—O_tb1	2.201 (3)–2.297 (3)	2.207 (7)–2.273 (7)
W—O_tb2	1.895 (4)–2.259 (4)	1.882 (8)–2.287 (7)
W⋯W (between corner-sharing WO₆)	3.649 (4)–3.878 (5)	3.377 (4)–3.688 (2)
W⋯W (between edge-sharing WO₆)	3.273 (4)–3.352 (4)	3.306 (2)–3.377 (3)
M^II—O (M = Fe or Cu)	2.087 (4)–2.169 (4)	1.918 (7)–2.366 (8)
Na^I—O	2.302 (11)–2.606 (11)	2.345 (9)–2.519 (13)
O—W—O	70.73 (14)–104.38 (17)	154.94 (15)–177.56 (16)
	70.2 (3)–105.6 (3)	152.8 (3)–178.1 (3)

In the crystal structure of Na₅Fe_2.5paraB, the paratungstate anions act as decadentate ligands, which are linked via terminal O atoms to six Fe²⁺ and four Na⁺ cations. There are two crystallographically unique iron centres with different coordination modes (Figs. 1a and 1b). The coordination sphere of one type of Fe²⁺ atom (Fe2) is formed by two O_t from the belt unit {W₃O₁₄} of one [W₁₂O₄₀(OH)₂]¹⁰⁻, one O_t from the capping {W₃O₁₃} group of a neighbouring polyanion and completed by three H₂O molecules. The octahedrally coordinated second Fe²⁺ atom (Fe1) is linked by two O_t from the {W₃O₁₃} units of two neighbouring polyanions, two Na⁺ bridging O atoms and two lattice H₂O molecules. The Fe1 octahedron and three Na(H₂O)₆ units from the infinite one-dimensional (1D) chain share a corner, thereby forming a two-dimensional sheet (2D) in the ab plane (Fig. 1b). Neighbouring sheets are connected to each other by Fe2 cations, giving rise to a complicated three-dimensional structure (Figs. 2 and 3). It should be noted that the double sodium–iron(II) paratungstate B Na₅Fe_2.5[W₁₂O₄₀(OH)₂]·36H₂O reported in this work has the same cationic composition as reported in Na₅[{Fe(H₂O)₃}₂{Fe(H₂O)₄}_0.5(H₂W₁₂O₄₂)]·30H₂O (Yang et al., 2003 ) (Table 1). However, the minor difference with respect to the water content in these two structures leads to a significant change in the unit-cell parameters (Tables 1 and 2) and the motif of crystal packing (Figs. 2 and 3).

Figure 2
The crystal packing of Na₅Fe_2.5paraB, viewed along the b axis. Colour code: {WO₆} are light-blue octahedra and Na atoms are green, Fe yellow and O red.

Figure 3
The crystal packing of Na₅Fe_2.5paraB, viewed along the a axis. Colour code: {WO₆} are light-blue octahedra and Na atoms are green, Fe yellow and O red.

In the crystal structure of Na₄Cu₃paraB, each paratungstate B anion is coordinated to six Cu²⁺ and six Na⁺ via O_t and therefore acts as a dodecadentate ligand (Figs. 1c and 1d). There are three crystallographically unique copper centres with different coordination modes. Two (Cu1 and Cu2) out of three Cu²⁺ cations take part in the formation of infinite chains with alternating Na and Cu polyhedra connected by a common edge (Figs. 1d and 4) and have different coordination environments. The Cu2 atoms are linked by four O_t atoms of the belt-fragment {W₃O₁₄} from two neighbouring [W₁₂O₄₀(OH)₂]¹⁰⁻ anions and two Na⁺ bridging H₂O molecules. The coordination sphere of Cu3 consists of two O_t of the capping {W₃O₁₃} group of a neighbouring polyanion and is completed by four bridging H₂O molecules. The third Cu1 atom coordinates to four O_t atoms of the belt units {W₃O₁₄} from two neighbouring [W₁₂O₄₀(OH)₂]¹⁰⁻ anions and two H₂O molecules. The Cu²⁺ ions exhibit a distorted square–bipyramidal coordination geometry with elongated axial distances [2.365 (7)–2.520 (8) Å]. The three-dimensional (3D) structure of Na₄Cu₃-paraB consists of 2D sheets formed by two chains, namely {[(Na(H₂O)₂)₂W₁₂O₄₀(OH)₂]⁸⁻}_n and {[Na(H₂O)₂–Cu(H₂O)₂–Na(H₂O)₂–Cu(H₂O)₄]⁶⁺}_n parallel to the ab plane (Fig. 4). The 2D sheets are connected along the c axis by [Cu(H₂O)₄]²⁺ cations (Fig. 5). The two [Na(H₂O)₅]⁺ cations, which are connected to O_t of one polyanion and do not participate in the formation of sodium–copper chains, are located in 1D tunnels in the structure of Na₄Cu₃-paraB.

Figure 4
The crystal packing of Na₄Cu₃paraB, viewed along the c axis. Colour code: {WO₆} are light-blue octahedra and Na atoms are green, Cu blue and O red.

Figure 5
The crystal packing of Na₄Cu₃paraB, viewed along the a axis. Colour code: {WO₆} are light-blue octahedra and Na atoms are green, Cu blue and O red.

The results of the powder XRD patterns of Na₅Fe_2.5paraB and Na₄Cu₃paraB have been investigated in the solid state at room temperature (Fig. 6). The simulated powder diffraction pattern was based on the single-crystal structural data. The simulated peak positions are in good agreement with those observed. A comparison of the experimental and simulated powder diffraction patterns confirms that the POTs structures had been solved accurately and that both products consist of a single phase.

Figure 6
Experimental (blue) and simulated (black) X-ray diffraction patterns of (a) Na₄Cu₃paraB and (b) Na₅Fe_2.5paraB.

In the IR spectra of Na₅Fe_2.5paraB and Na₄Cu₃paraB, the characteristic peaks at 975, 950, 932, 867, 676 and 488 cm⁻¹, and at 972, 937, 926, 872, 675 and 493 cm⁻¹, respectively, are attributed to the W=O_t and W—O—W vibrations in the paratungstate anion, which are in agreement with previously reported data (Table 1; Qu et al., 2012 ). The slight peak displacements are due to the effects of different coordination modes of paratungstate B. The peaks at ∼1600 and 3400 cm⁻¹ are attributed to the vibration of water molecules.

The disordered water molecules in Na₄Cu₃paraB were treated with SQUEEZE (Spek, 2015) and the exact number of water molecules was determined by TGA. The TG curve shows a three-step weight-loss process (Fig. 7). The first weight loss of 7.48% in the temperature range 25–125 °C corresponds to all lattice H₂O and water molecules from coordinating Na⁺ and Cu²⁺. The second (2.72%) and third (3.61%) steps in the range 125–500 °C correspond to 13 H₂O molecules coordinating Na⁺ and Cu²⁺. The total weight loss is 13.83%, which results in the formula Na₄Cu₃[W₁₂O₄₀(OH)₂]·28H₂O.

Figure 7
Thermogravimetric curve of Na₄Cu₃paraB.

The success in synthesizing Na₅Fe_2.5paraB and Na₄Cu₃paraB shows that paratungstate B is a versatile building block, which can be modified by metal sites into high-dimensional architectures and the different connection principle of the transition metals has a big impact on the dimensionalities of the frameworks.

Supporting information

CCDC references: 1843518; 1843519

Crystal structure: contains datablocks ando209_p-1, mo_ando241_p-1, global. DOI: https://doi.org/10.1107/S2053229618010021/jr3015sup1.cif

Structure factors: contains datablock ando209_p-1. DOI: https://doi.org/10.1107/S2053229618010021/jr3015ando209_p-1sup2.hkl

Structure factors: contains datablock mo_ando241_p-1. DOI: https://doi.org/10.1107/S2053229618010021/jr3015mo_ando241_p-1sup3.hkl

Computing details top

For both structures, data collection: APEX3; cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and shelXle (Hübschle et al., 2011) for ando209_p-1; SHELXS97 (Sheldrick, 2008) for mo_ando241_p-1. Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for ando209_p-1; SHELXL2016 (Sheldrick, 2015) for mo_ando241_p-1. Molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg, 2006) for ando209_p-1; OLEX2 (Dolomanov et al., 2009) for mo_ando241_p-1. For both structures, software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(ando209_p-1) top

Crystal data top

Na₄Cu₃[W₁₂O₄₀(OH)₂]·28H₂O	Z = 1
M_r = 3621.13	F(000) = 1607
Triclinic, P1	D_x = 4.080 Mg m⁻³
a = 10.6516 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.7532 (6) Å	Cell parameters from 6027 reflections
c = 13.0730 (5) Å	θ = 3.0–30.0°
α = 113.771 (1)°	µ = 24.53 mm⁻¹
β = 90.443 (1)°	T = 100 K
γ = 112.502 (1)°	Plate, blue
V = 1473.65 (11) Å³	0.13 × 0.07 × 0.02 mm

Data collection top

Bruker APEX-II CCD diffractometer	4720 reflections with I > 2σ(I)
Radiation source: sealed xray tube, Incoatec IuS	R_int = 0.048
φ and ω scans	θ_max = 25.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
T_min = 0.004, T_max = 0.023	k = −15→14
11292 measured reflections	l = −11→15
5321 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0463P)² + 6.2838P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 2.15 e Å⁻³
5321 reflections	Δρ_min = −1.63 e Å⁻³
463 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
100 restraints	Extinction coefficient: 0.00022 (6)

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 1.5 times of: All O(H,H) groups 2. Restrained distances Na2-H31A 2.8 with sigma of 0.05 H34B-H25A 2.2 with sigma of 0.02 H34A-H25A 2.2 with sigma of 0.03 H34B_$2-H31B 2.2 with sigma of 0.02 H34A_$4-H31B_$3 2.2 with sigma of 0.02 Cu3-H25A 2.7 with sigma of 0.05 Cu3-H25B 2.3 with sigma of 0.02 H35A-O24 1.8 with sigma of 0.06 H35B-O19 2 with sigma of 0.06 Na1-H27B 2.8 with sigma of 0.05 Na1-H27C = Na1-H27A = Na1-H27D 2.8 with sigma of 0.05 H33B-Na1 2.8 with sigma of 0.02 H33B-O27 2.4 with sigma of 0.05 Na1-H28A 2.7 with sigma of 0.04 H33B-H28A 2.4 with sigma of 0.04 H32A_$3-O26 1.8 with sigma of 0.04 Na2-H31B = Na2-H32B 2.8 with sigma of 0.075 O32-H27B_$5 2.3 with sigma of 0.04 H29A_$1-H22A 2.2 with sigma of 0.02 O31-H31A = O31-H31B = O26-H26B = O26-H26A = O29-H29B = O29-H29A = O30-H30A = O30-H30B = O32-H32A = O32-H32B = O27-H27A = O27-H27B = O22-H22A = O22-H22B = O25-H25A = O25-H25B = O28-H28A = O28-H28B = O33-H33A = O33-H33B 0.87 with sigma of 0.015 Na1_$5-H29A_$5 2.7 with sigma of 0.04 H31A-H31B ~ H32B-H32A ~ H29A-H29B ~ H30A-H30B ~ H26B-H26A ~ H27A-H27B ~ H22A- H22B ~ H25A-H25B ~ H28A-H28B ~ H33A-H33B with sigma of 0.01 3. Uiso/Uaniso restraints and constraints Uanis(O3) ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02 Uanis(O35) ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02 Uanis(O27) = Uanis(O27B) = Uanis(O33) 4. Others Fixed Sof: O27(0.5) H27A(0.5) H27B(0.5) O27B(0.5) H27C(0.5) H27D(0.5) O33(0.2) H33A(0.2) H33B(0.2) O34(0.8) H34A(0.8) H34B(0.8) 5.a Free rotating group: O27B(H27C,H27D), O35(H35A,H35B), O34(H34A,H34B) 5.b Rotating group: O26(H26A,H26B), O30(H30A,H30B)

_smtbx_masks_special_details ? loop_ _smtbx_masks_void_nr _smtbx_masks_void_average_x _smtbx_masks_void_average_y _smtbx_masks_void_average_z _smtbx_masks_void_volume _smtbx_masks_void_count_electrons _smtbx_masks_void_content 1 0.500 0.000 0.000 42.5 50.5 ?

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
W1	0.40078 (5)	0.59904 (4)	0.70077 (4)	0.02587 (13)
W2	0.29232 (5)	0.29326 (4)	0.70980 (4)	0.02647 (13)
W3	0.11342 (5)	0.30259 (4)	0.50852 (4)	0.02644 (13)
W4	0.36784 (5)	0.55467 (4)	0.25109 (4)	0.02598 (13)
W5	0.25460 (5)	0.24015 (4)	0.24532 (4)	0.02651 (13)
W6	0.44888 (5)	0.25037 (4)	0.45361 (4)	0.02571 (13)
Cu1	0.5000	0.5000	0.0000	0.0295 (4)
Cu2	0.5000	0.0000	0.5000	0.0318 (4)
Cu3	0.0000	0.0000	0.5000	0.0292 (4)
Na1	0.1011 (5)	0.6455 (5)	0.8881 (4)	0.0388 (11)
Na2	0.2217 (6)	−0.0459 (5)	0.6480 (4)	0.0453 (12)
O1	0.4360 (8)	0.7354 (7)	0.6568 (6)	0.0307 (17)
O2	0.2961 (8)	0.6304 (7)	0.7964 (6)	0.0321 (18)
O3	0.2806 (8)	0.4797 (7)	0.5682 (6)	0.0274 (16)
O4	0.4464 (8)	0.4809 (7)	0.7296 (6)	0.0287 (17)
O5	0.2953 (7)	0.3510 (7)	0.8548 (6)	0.0278 (16)
O6	0.1920 (8)	0.1290 (7)	0.6530 (7)	0.0311 (17)
O7	0.4689 (7)	0.2862 (7)	0.7099 (6)	0.0265 (16)
O8	0.1595 (8)	0.3407 (7)	0.6693 (6)	0.0280 (17)
O9	0.3000 (7)	0.2617 (7)	0.5253 (6)	0.0256 (16)
O10	0.0060 (8)	0.1394 (7)	0.4742 (6)	0.0283 (17)
O11	0.1443 (7)	0.2788 (7)	0.3603 (6)	0.0273 (16)
O12	−0.0075 (8)	0.3650 (7)	0.5232 (6)	0.0303 (17)
O13	0.3723 (8)	0.5048 (7)	0.1034 (6)	0.0303 (17)
O14	0.2479 (8)	0.6201 (7)	0.2670 (6)	0.0292 (17)
O15	0.2601 (8)	0.3979 (7)	0.2454 (6)	0.0285 (17)
O16	0.4167 (8)	0.2715 (7)	0.1837 (6)	0.0277 (17)
O17	0.1273 (8)	0.1263 (7)	0.1285 (6)	0.0321 (18)
O18	0.4261 (8)	0.3860 (7)	0.3991 (6)	0.0270 (16)
O19	0.2939 (8)	0.1433 (7)	0.3058 (6)	0.0278 (16)
O20	0.4522 (8)	0.1175 (7)	0.4616 (6)	0.0308 (17)
O21	0.5820 (8)	0.3799 (7)	0.5722 (6)	0.0278 (17)
O22	0.5004 (8)	0.6562 (7)	−0.0030 (7)	0.0322 (18)
H22A	0.484 (6)	0.641 (10)	−0.074 (3)	0.048*
H22B	0.572 (9)	0.722 (8)	0.045 (6)	0.048*
O23	0.2659 (9)	−0.1426 (8)	0.4500 (7)	0.039 (2)
O24	0.5333 (8)	−0.0689 (7)	0.3444 (7)	0.0329 (18)
O25	0.1090 (9)	−0.0398 (7)	0.3744 (7)	0.039 (2)
H25A	0.110 (4)	−0.105 (2)	0.3192 (19)	0.059*
H25B	0.166 (10)	0.037 (2)	0.392 (8)	0.059*
O26	0.0069 (9)	0.5944 (8)	0.7000 (7)	0.0376 (19)
H26A	−0.0758	0.6059	0.6943	0.056*
H26B	−0.0175	0.5090	0.6477	0.056*
O28	−0.0711 (10)	0.6370 (10)	1.0034 (8)	0.053 (3)
H28A	−0.148 (3)	0.585 (9)	0.954 (3)	0.080*
H28B	−0.056 (11)	0.635 (12)	1.068 (7)	0.080*
O29	0.2535 (9)	0.6809 (10)	1.0510 (8)	0.047 (2)
H29A	0.310 (7)	0.654 (10)	1.013 (4)	0.070*
H29B	0.282 (10)	0.757 (6)	1.107 (9)	0.070*
O30	0.0122 (9)	0.4225 (8)	0.8273 (7)	0.039 (2)
H30A	0.0498	0.3733	0.7612	0.058*
H30B	−0.0916	0.3696	0.7900	0.058*
O31	0.2749 (14)	0.1008 (11)	0.8572 (10)	0.072 (3)
H31A	0.306 (13)	0.060 (8)	0.883 (4)	0.107*
H31B	0.196 (6)	0.105 (11)	0.867 (7)	0.107*
O32	0.2210 (10)	−0.1857 (9)	0.7127 (9)	0.051 (2)
H32A	0.150 (6)	−0.252 (9)	0.712 (13)	0.077*
H32B	0.305 (4)	−0.174 (11)	0.736 (14)	0.077*
O27	0.158 (3)	0.860 (3)	0.922 (2)	0.057 (5)	0.5
H27A	0.246 (5)	0.904 (6)	0.946 (10)	0.086*	0.5
H27B	0.113 (6)	0.858 (6)	0.865 (4)	0.086*	0.5
O27B	0.119 (3)	0.853 (3)	0.960 (2)	0.057 (5)	0.5
H27C	0.0694	0.8626	0.9158	0.086*	0.5
H27D	0.2008	0.9067	0.9675	0.086*	0.5
O35	0.3779 (17)	−0.0594 (14)	0.1911 (10)	0.097 (5)
H35A	0.4125	−0.0615	0.2488	0.145*
H35B	0.3375	−0.0105	0.2126	0.145*
O33	0.004 (6)	0.884 (4)	1.035 (4)	0.057 (5)	0.2
H33A	0.07 (5)	0.951 (12)	1.09 (4)	0.086*	0.2
H33B	−0.012 (17)	0.808 (8)	1.027 (16)	0.086*	0.2
O34	−0.0162 (12)	−0.1184 (11)	0.1541 (9)	0.050 (3)	0.8
H34A	0.0167	−0.0472	0.2126	0.075*	0.8
H34B	−0.0554	−0.1769	0.1746	0.075*	0.8

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.0266 (2)	0.0247 (2)	0.0263 (2)	0.01145 (19)	0.00481 (18)	0.01057 (19)
W2	0.0264 (2)	0.0259 (2)	0.0273 (2)	0.01121 (19)	0.00467 (18)	0.01163 (19)
W3	0.0264 (2)	0.0253 (2)	0.0273 (2)	0.01089 (19)	0.00448 (18)	0.01138 (19)
W4	0.0262 (2)	0.0257 (2)	0.0260 (2)	0.01136 (19)	0.00429 (18)	0.01098 (19)
W5	0.0270 (2)	0.0250 (2)	0.0265 (2)	0.01085 (19)	0.00361 (18)	0.01049 (19)
W6	0.0266 (2)	0.0245 (2)	0.0259 (2)	0.01144 (19)	0.00433 (18)	0.01039 (19)
Cu1	0.0326 (10)	0.0310 (10)	0.0286 (10)	0.0162 (9)	0.0076 (8)	0.0138 (8)
Cu2	0.0351 (11)	0.0298 (10)	0.0326 (10)	0.0152 (9)	0.0068 (8)	0.0142 (9)
Cu3	0.0302 (10)	0.0274 (10)	0.0319 (10)	0.0130 (8)	0.0059 (8)	0.0140 (8)
Na1	0.037 (3)	0.042 (3)	0.039 (3)	0.019 (2)	0.008 (2)	0.017 (2)
Na2	0.045 (3)	0.037 (3)	0.052 (3)	0.015 (2)	0.004 (2)	0.021 (2)
O1	0.027 (4)	0.029 (4)	0.031 (4)	0.009 (3)	0.002 (3)	0.011 (3)
O2	0.032 (4)	0.038 (4)	0.032 (4)	0.017 (4)	0.004 (3)	0.019 (4)
O3	0.028 (4)	0.028 (4)	0.028 (4)	0.009 (3)	0.009 (3)	0.016 (3)
O4	0.031 (4)	0.025 (4)	0.035 (4)	0.015 (3)	0.009 (3)	0.014 (3)
O5	0.023 (4)	0.030 (4)	0.030 (4)	0.010 (3)	0.004 (3)	0.014 (3)
O6	0.031 (4)	0.029 (4)	0.036 (4)	0.015 (3)	0.005 (3)	0.015 (4)
O7	0.024 (4)	0.028 (4)	0.029 (4)	0.012 (3)	0.002 (3)	0.012 (3)
O8	0.026 (4)	0.033 (4)	0.026 (4)	0.011 (3)	0.005 (3)	0.015 (3)
O9	0.026 (4)	0.028 (4)	0.021 (4)	0.009 (3)	0.004 (3)	0.012 (3)
O10	0.028 (4)	0.023 (4)	0.030 (4)	0.007 (3)	0.002 (3)	0.011 (3)
O11	0.023 (4)	0.031 (4)	0.031 (4)	0.013 (3)	0.004 (3)	0.016 (3)
O12	0.032 (4)	0.037 (4)	0.029 (4)	0.017 (4)	0.011 (3)	0.018 (4)
O13	0.028 (4)	0.035 (4)	0.029 (4)	0.013 (3)	0.007 (3)	0.014 (3)
O14	0.031 (4)	0.026 (4)	0.030 (4)	0.011 (3)	0.007 (3)	0.013 (3)
O15	0.029 (4)	0.025 (4)	0.030 (4)	0.009 (3)	0.006 (3)	0.013 (3)
O16	0.034 (4)	0.030 (4)	0.020 (4)	0.015 (3)	0.006 (3)	0.010 (3)
O17	0.039 (5)	0.032 (4)	0.028 (4)	0.017 (4)	0.006 (3)	0.014 (3)
O18	0.028 (4)	0.021 (4)	0.029 (4)	0.008 (3)	0.002 (3)	0.010 (3)
O19	0.025 (4)	0.028 (4)	0.032 (4)	0.012 (3)	0.007 (3)	0.013 (3)
O20	0.033 (4)	0.033 (4)	0.030 (4)	0.016 (4)	0.010 (3)	0.015 (4)
O21	0.024 (4)	0.030 (4)	0.025 (4)	0.008 (3)	0.006 (3)	0.011 (3)
O22	0.033 (5)	0.032 (4)	0.029 (4)	0.017 (4)	0.002 (3)	0.008 (4)
O23	0.037 (5)	0.034 (4)	0.040 (5)	0.016 (4)	0.002 (4)	0.009 (4)
O24	0.032 (4)	0.029 (4)	0.034 (4)	0.013 (4)	0.003 (3)	0.010 (3)
O25	0.043 (5)	0.024 (4)	0.042 (5)	0.010 (4)	0.012 (4)	0.011 (4)
O26	0.036 (5)	0.042 (5)	0.038 (5)	0.020 (4)	0.007 (4)	0.017 (4)
O28	0.043 (6)	0.082 (7)	0.036 (5)	0.032 (5)	0.011 (4)	0.023 (5)
O29	0.044 (5)	0.062 (6)	0.045 (5)	0.031 (5)	0.016 (4)	0.026 (5)
O30	0.036 (5)	0.051 (5)	0.029 (4)	0.021 (4)	0.009 (4)	0.014 (4)
O31	0.102 (10)	0.065 (7)	0.054 (6)	0.043 (7)	0.005 (6)	0.025 (6)
O32	0.039 (5)	0.052 (6)	0.070 (7)	0.021 (5)	0.012 (5)	0.033 (5)
O27	0.070 (15)	0.047 (7)	0.062 (16)	0.028 (10)	0.021 (9)	0.027 (10)
O27B	0.070 (15)	0.047 (7)	0.062 (16)	0.028 (10)	0.021 (9)	0.027 (10)
O35	0.126 (11)	0.088 (9)	0.065 (7)	0.078 (8)	−0.027 (7)	−0.007 (6)
O33	0.070 (15)	0.047 (7)	0.062 (16)	0.028 (10)	0.021 (9)	0.027 (10)
O34	0.047 (7)	0.041 (6)	0.030 (6)	−0.005 (5)	0.010 (5)	0.008 (5)

Geometric parameters (Å, º) top

W1—O1	1.951 (7)	Cu1—O22	2.007 (8)
W1—O2	1.710 (8)	Cu1—O22^iv	2.007 (8)
W1—O3	1.818 (7)	Cu2—Na2	3.542 (6)
W1—O4	1.914 (7)	Cu2—Na2^v	3.542 (6)
W1—O16ⁱ	2.067 (8)	Cu2—O20	1.985 (8)
W1—O18ⁱ	2.260 (8)	Cu2—O20^v	1.985 (8)
W2—O4	2.230 (7)	Cu2—O23	2.345 (8)
W2—O5	1.730 (7)	Cu2—O23^v	2.345 (8)
W2—O6	1.762 (8)	Cu2—O24	1.961 (8)
W2—O7	1.917 (7)	Cu2—O24^v	1.961 (8)
W2—O8	1.884 (8)	Cu3—Na2	3.400 (5)
W2—O9	2.287 (7)	Cu3—Na2ⁱⁱ	3.400 (5)
W3—Na2ⁱⁱ	3.632 (5)	Cu3—O6	2.366 (8)
W3—O3	2.088 (7)	Cu3—O6ⁱⁱ	2.366 (8)
W3—O8	1.968 (7)	Cu3—O10	1.918 (7)
W3—O9	2.268 (8)	Cu3—O10ⁱⁱ	1.918 (7)
W3—O10	1.805 (7)	Cu3—O25ⁱⁱ	2.027 (8)
W3—O11	1.888 (7)	Cu3—O25	2.027 (8)
W3—O12	1.730 (8)	Na1—O2	2.439 (9)
W4—O4ⁱ	2.226 (8)	Na1—O26	2.376 (9)
W4—O7ⁱ	1.963 (7)	Na1—O28	2.380 (10)
W4—O13	1.780 (7)	Na1—O29	2.446 (11)
W4—O14	1.747 (8)	Na1—O30	2.392 (10)
W4—O15	1.855 (7)	Na1—O27	2.41 (3)
W4—O21ⁱ	2.098 (7)	Na1—O27B	2.35 (3)
W5—O11	1.938 (7)	Na2—W3ⁱⁱ	3.632 (5)
W5—O15	1.990 (7)	Na2—O6	2.345 (9)
W5—O16	1.882 (8)	Na2—O10ⁱⁱ	2.459 (9)
W5—O17	1.718 (8)	Na2—O23	2.516 (10)
W5—O18	2.273 (7)	Na2—O24^v	2.432 (10)
W5—O19	1.872 (7)	Na2—O31	2.519 (13)
W6—O1ⁱ	1.920 (8)	Na2—O32	2.260 (10)
W6—O9	1.872 (7)	O1—W6ⁱ	1.920 (8)
W6—O18	2.207 (7)	O4—W4ⁱ	2.226 (8)
W6—O19	2.103 (7)	O5—Cu1^vi	2.413 (7)
W6—O20	1.753 (8)	O7—W4ⁱ	1.963 (7)
W6—O21	1.803 (7)	O10—Na2ⁱⁱ	2.459 (9)
Cu1—O5ⁱⁱⁱ	2.413 (7)	O16—W1ⁱ	2.067 (7)
Cu1—O5ⁱ	2.413 (7)	O18—W1ⁱ	2.260 (8)
Cu1—O13	1.926 (8)	O21—W4ⁱ	2.098 (7)
Cu1—O13^iv	1.926 (8)	O24—Na2^v	2.432 (10)

O1—W1—O16ⁱ	82.4 (3)	O24—Cu2—Na2^v	41.1 (2)
O1—W1—O18ⁱ	70.2 (3)	O24^v—Cu2—Na2^v	138.9 (2)
O2—W1—O1	99.5 (3)	O24^v—Cu2—Na2	41.1 (2)
O2—W1—O3	104.1 (4)	O24—Cu2—O20	87.1 (3)
O2—W1—O4	102.2 (3)	O24—Cu2—O20^v	92.9 (3)
O2—W1—O16ⁱ	94.8 (3)	O24^v—Cu2—O20^v	87.1 (3)
O2—W1—O18ⁱ	164.6 (3)	O24^v—Cu2—O20	92.9 (3)
O3—W1—O1	93.2 (3)	O24—Cu2—O23	93.9 (3)
O3—W1—O4	94.1 (3)	O24^v—Cu2—O23^v	93.9 (3)
O3—W1—O16ⁱ	161.1 (3)	O24—Cu2—O23^v	86.1 (3)
O3—W1—O18ⁱ	88.3 (3)	O24^v—Cu2—O23	86.1 (3)
O4—W1—O1	154.6 (3)	O24^v—Cu2—O24	180.0
O4—W1—O16ⁱ	82.8 (3)	Na2—Cu3—Na2ⁱⁱ	180.0
O4—W1—O18ⁱ	85.7 (3)	O6ⁱⁱ—Cu3—Na2ⁱⁱ	43.6 (2)
O16ⁱ—W1—O18ⁱ	72.9 (3)	O6—Cu3—Na2	43.6 (2)
O4—W2—O9	77.3 (3)	O6—Cu3—Na2ⁱⁱ	136.4 (2)
O5—W2—O4	91.7 (3)	O6ⁱⁱ—Cu3—Na2	136.4 (2)
O5—W2—O6	105.6 (3)	O6—Cu3—O6ⁱⁱ	180.0 (3)
O5—W2—O7	98.5 (3)	O10—Cu3—Na2	134.8 (2)
O5—W2—O8	98.8 (3)	O10—Cu3—Na2ⁱⁱ	45.2 (2)
O5—W2—O9	167.4 (3)	O10ⁱⁱ—Cu3—Na2ⁱⁱ	134.8 (2)
O6—W2—O4	161.2 (3)	O10ⁱⁱ—Cu3—Na2	45.2 (2)
O6—W2—O7	96.2 (3)	O10ⁱⁱ—Cu3—O6	86.7 (3)
O6—W2—O8	99.2 (3)	O10ⁱⁱ—Cu3—O6ⁱⁱ	93.3 (3)
O6—W2—O9	86.2 (3)	O10—Cu3—O6	93.3 (3)
O7—W2—O4	73.6 (3)	O10—Cu3—O6ⁱⁱ	86.7 (3)
O7—W2—O9	84.4 (3)	O10—Cu3—O10ⁱⁱ	180.0
O8—W2—O4	85.1 (3)	O10—Cu3—O25	89.1 (3)
O8—W2—O7	152.8 (3)	O10—Cu3—O25ⁱⁱ	90.9 (3)
O8—W2—O9	74.4 (3)	O10ⁱⁱ—Cu3—O25	90.9 (3)
O3—W3—Na2ⁱⁱ	159.2 (2)	O10ⁱⁱ—Cu3—O25ⁱⁱ	89.1 (3)
O3—W3—O9	76.3 (3)	O25—Cu3—Na2	85.0 (3)
O8—W3—Na2ⁱⁱ	115.9 (2)	O25ⁱⁱ—Cu3—Na2ⁱⁱ	85.0 (3)
O8—W3—O3	79.4 (3)	O25—Cu3—Na2ⁱⁱ	95.0 (3)
O8—W3—O9	73.4 (3)	O25ⁱⁱ—Cu3—Na2	95.0 (3)
O9—W3—Na2ⁱⁱ	120.3 (2)	O25ⁱⁱ—Cu3—O6ⁱⁱ	96.9 (3)
O10—W3—Na2ⁱⁱ	37.5 (3)	O25ⁱⁱ—Cu3—O6	83.1 (3)
O10—W3—O3	163.0 (3)	O25—Cu3—O6	96.9 (3)
O10—W3—O8	90.7 (3)	O25—Cu3—O6ⁱⁱ	83.1 (3)
O10—W3—O9	87.7 (3)	O25—Cu3—O25ⁱⁱ	180.0 (4)
O10—W3—O11	97.4 (3)	O2—Na1—O29	81.7 (3)
O11—W3—Na2ⁱⁱ	82.2 (2)	O26—Na1—O2	80.5 (3)
O11—W3—O3	87.2 (3)	O26—Na1—O28	111.0 (4)
O11—W3—O8	157.1 (3)	O26—Na1—O29	161.9 (4)
O11—W3—O9	85.5 (3)	O26—Na1—O30	86.2 (3)
O12—W3—Na2ⁱⁱ	71.8 (3)	O26—Na1—O27	84.4 (8)
O12—W3—O3	93.1 (3)	O28—Na1—O2	165.5 (4)
O12—W3—O8	97.5 (3)	O28—Na1—O29	86.1 (3)
O12—W3—O9	167.0 (3)	O28—Na1—O30	84.9 (4)
O12—W3—O10	101.9 (4)	O28—Na1—O27	94.3 (6)
O12—W3—O11	101.7 (3)	O30—Na1—O2	87.1 (3)
O7ⁱ—W4—O4ⁱ	72.8 (3)	O30—Na1—O29	89.7 (4)
O7ⁱ—W4—O21ⁱ	79.7 (3)	O30—Na1—O27	169.6 (9)
O13—W4—O4ⁱ	88.2 (3)	O27—Na1—O2	95.8 (7)
O13—W4—O7ⁱ	91.2 (3)	O27—Na1—O29	100.6 (9)
O13—W4—O15	98.3 (3)	O27B—Na1—O2	110.2 (7)
O13—W4—O21ⁱ	164.6 (3)	O27B—Na1—O26	92.8 (8)
O14—W4—O4ⁱ	164.9 (3)	O27B—Na1—O28	78.9 (6)
O14—W4—O7ⁱ	95.4 (3)	O27B—Na1—O29	96.3 (9)
O14—W4—O13	101.8 (3)	O27B—Na1—O30	162.2 (8)
O14—W4—O15	101.3 (3)	Cu2—Na2—W3ⁱⁱ	118.32 (15)
O14—W4—O21ⁱ	91.5 (3)	Cu3—Na2—W3ⁱⁱ	60.12 (9)
O15—W4—O4ⁱ	88.2 (3)	Cu3—Na2—Cu2	100.18 (13)
O15—W4—O7ⁱ	158.6 (3)	O6—Na2—W3ⁱⁱ	101.7 (3)
O15—W4—O21ⁱ	86.6 (3)	O6—Na2—Cu2	93.5 (2)
O21ⁱ—W4—O4ⁱ	77.3 (3)	O6—Na2—Cu3	44.0 (2)
O11—W5—O15	81.1 (3)	O6—Na2—O10ⁱⁱ	76.0 (3)
O11—W5—O18	80.1 (3)	O6—Na2—O23	102.4 (3)
O15—W5—O18	80.2 (3)	O6—Na2—O24^v	87.4 (3)
O16—W5—O11	154.7 (3)	O6—Na2—O31	76.2 (4)
O16—W5—O15	86.7 (3)	O10ⁱⁱ—Na2—W3ⁱⁱ	26.54 (17)
O16—W5—O18	76.0 (3)	O10ⁱⁱ—Na2—Cu2	113.4 (2)
O17—W5—O11	100.9 (3)	O10ⁱⁱ—Na2—Cu3	33.59 (18)
O17—W5—O15	101.6 (3)	O10ⁱⁱ—Na2—O23	76.4 (3)
O17—W5—O16	103.2 (3)	O10ⁱⁱ—Na2—O31	123.3 (4)
O17—W5—O18	178.1 (3)	O23—Na2—W3ⁱⁱ	77.0 (2)
O17—W5—O19	102.1 (3)	O23—Na2—Cu2	41.4 (2)
O19—W5—O11	89.2 (3)	O23—Na2—Cu3	79.5 (2)
O19—W5—O15	155.7 (3)	O23—Na2—O31	158.1 (4)
O19—W5—O16	93.1 (3)	O24^v—Na2—W3ⁱⁱ	150.1 (3)
O19—W5—O18	76.2 (3)	O24^v—Na2—Cu2	32.0 (2)
O1ⁱ—W6—O18	72.0 (3)	O24^v—Na2—Cu3	115.8 (2)
O1ⁱ—W6—O19	81.2 (3)	O24^v—Na2—O10ⁱⁱ	141.2 (3)
O9—W6—O1ⁱ	154.3 (3)	O24^v—Na2—O23	73.3 (3)
O9—W6—O18	84.3 (3)	O24^v—Na2—O31	84.8 (4)
O9—W6—O19	82.9 (3)	O31—Na2—W3ⁱⁱ	125.0 (4)
O19—W6—O18	73.4 (3)	O31—Na2—Cu2	116.7 (4)
O20—W6—O1ⁱ	100.5 (3)	O31—Na2—Cu3	111.2 (3)
O20—W6—O9	100.5 (3)	O32—Na2—W3ⁱⁱ	80.5 (3)
O20—W6—O18	166.0 (3)	O32—Na2—Cu2	106.6 (3)
O20—W6—O19	94.0 (3)	O32—Na2—Cu3	139.6 (3)
O20—W6—O21	102.8 (4)	O32—Na2—O6	156.0 (4)
O21—W6—O1ⁱ	93.7 (3)	O32—Na2—O10ⁱⁱ	106.6 (4)
O21—W6—O9	95.7 (3)	O32—Na2—O23	101.3 (4)
O21—W6—O18	89.6 (3)	O32—Na2—O24^v	102.6 (4)
O21—W6—O19	163.0 (3)	O32—Na2—O31	83.0 (4)
O5ⁱ—Cu1—O5ⁱⁱⁱ	180.0 (4)	W6ⁱ—O1—W1	119.2 (4)
O13^iv—Cu1—O5ⁱⁱⁱ	95.3 (3)	W1—O2—Na1	165.1 (4)
O13—Cu1—O5ⁱⁱⁱ	84.7 (3)	W1—O3—W3	138.3 (4)
O13—Cu1—O5ⁱ	95.3 (3)	W1—O4—W2	124.5 (4)
O13^iv—Cu1—O5ⁱ	84.7 (3)	W1—O4—W4ⁱ	138.3 (4)
O13—Cu1—O13^iv	180.0	W4ⁱ—O4—W2	95.7 (3)
O13^iv—Cu1—O22^iv	89.8 (3)	W2—O5—Cu1^vi	124.8 (4)
O13—Cu1—O22^iv	90.2 (3)	W2—O6—Cu3	128.5 (4)
O13^iv—Cu1—O22	90.2 (3)	W2—O6—Na2	136.6 (4)
O13—Cu1—O22	89.8 (3)	Na2—O6—Cu3	92.4 (3)
O22—Cu1—O5ⁱⁱⁱ	96.7 (3)	W2—O7—W4ⁱ	116.8 (4)
O22^iv—Cu1—O5ⁱ	96.7 (3)	W2—O8—W3	118.1 (4)
O22—Cu1—O5ⁱ	83.3 (3)	W3—O9—W2	93.0 (3)
O22^iv—Cu1—O5ⁱⁱⁱ	83.3 (3)	W6—O9—W2	124.6 (4)
O22—Cu1—O22^iv	180.0	W6—O9—W3	140.5 (4)
Na2^v—Cu2—Na2	180.0	W3—O10—Cu3	142.8 (4)
O20—Cu2—Na2^v	89.6 (2)	W3—O10—Na2ⁱⁱ	116.0 (4)
O20—Cu2—Na2	90.4 (2)	Cu3—O10—Na2ⁱⁱ	101.2 (3)
O20^v—Cu2—Na2^v	90.4 (2)	W3—O11—W5	147.9 (4)
O20^v—Cu2—Na2	89.6 (2)	W4—O13—Cu1	141.2 (5)
O20—Cu2—O20^v	180.00 (15)	W4—O15—W5	147.1 (4)
O20—Cu2—O23	90.5 (3)	W5—O16—W1ⁱ	115.9 (3)
O20—Cu2—O23^v	89.5 (3)	W1ⁱ—O18—W5	95.2 (3)
O20^v—Cu2—O23	89.5 (3)	W6—O18—W1ⁱ	96.7 (3)
O20^v—Cu2—O23^v	90.5 (3)	W6—O18—W5	96.3 (3)
O23^v—Cu2—Na2^v	45.2 (2)	W5—O19—W6	114.1 (4)
O23^v—Cu2—Na2	134.8 (2)	W6—O20—Cu2	165.2 (5)
O23—Cu2—Na2	45.2 (2)	W6—O21—W4ⁱ	138.5 (4)
O23—Cu2—Na2^v	134.8 (2)	Cu2—O23—Na2	93.5 (3)
O23^v—Cu2—O23	180.0	Cu2—O24—Na2^v	107.0 (4)
O24—Cu2—Na2	138.9 (2)

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

(mo_ando241_p-1) top

Crystal data top

Na₅Fe_2.5[W₁₂O₄₀(OH)₂]·36H₂O	Z = 2
M_r = 3771.27	F(000) = 3388
Triclinic, P1	D_x = 3.708 Mg m⁻³
a = 12.3758 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.7752 (7) Å	Cell parameters from 9822 reflections
c = 18.8919 (8) Å	θ = 2.2–25.5°
α = 92.9341 (14)°	µ = 21.02 mm⁻¹
β = 100.6938 (14)°	T = 100 K
γ = 94.1698 (15)°	Needle, clear light orange
V = 3378.1 (3) Å³	0.37 × 0.07 × 0.04 mm

Data collection top

Bruker D8 Venture diffractometer	10876 reflections with I > 2σ(I)
Radiation source: sealed xray tube, Incoatec IuS	R_int = 0.032
φ and ω scans	θ_max = 25.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −14→14
T_min = 0.012, T_max = 0.044	k = −17→17
38068 measured reflections	l = −22→22
12318 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0176P)² + 7.2977P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.005
S = 1.09	Δρ_max = 1.57 e Å⁻³
12318 reflections	Δρ_min = −1.25 e Å⁻³
980 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2016), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
405 restraints	Extinction coefficient: 0.000312 (12)

Special details top

Refinement. _olex2_refinement_description

1. Fixed Uiso At 1.5 times of: All O(H,H) groups 2. Restrained distances H64A-H61B_$1 2.2 with sigma of 0.02 H59B-H63B 2.2 with sigma of 0.02 H63B_$2-H71A 2.2 with sigma of 0.02 H71A-H63B_$2 2.2 with sigma of 0.05 H49B-Na1 2.7 with sigma of 0.01 H51B-O35_$4 2.3 with sigma of 0.04 H51A-H51B 1.41 with sigma of 0.01 O51-H51A = O51-H51B 0.87 with sigma of 0.01 H52A-Na3 2.7 with sigma of 0.01 O52-H52B = O52-H52A 0.87 with sigma of 0.01 H52A-H52B 1.41 with sigma of 0.01 H53A-O36 2 with sigma of 0.04 H53A-H53B 1.41 with sigma of 0.01 O53-H53A = O53-H53B 0.87 with sigma of 0.01 H77B-H28A 2.2 with sigma of 0.02 H77A-H28A 2.2 with sigma of 0.02 O77-H77A = O77-H77B = O28-H28B = O28-H28A 0.87 with sigma of 0.01 H77A-H77B = H28B-H28A 1.41 with sigma of 0.01 H49B-Na2 2.7 with sigma of 0.01 Na2-H49A 2.7 with sigma of 0.02 O50-H50A ~ O50-H50B ~ O51-H51A ~ O51-H51B ~ O48-H48A ~ O48-H48B ~ O47-H47B O47-H47A ~ O65-H65B ~ O65-H65A ~ O64-H64A ~ O64-H64B ~ O74-H74A ~ O74-H74B O63-H63A ~ O63-H63B ~ O60-H60B ~ O60-H60A ~ O167-H16B ~ O167-H16A ~ O67-H67B O67-H67A ~ O27-H27B ~ O27-H27A ~ O28-H28A ~ O28-H28B ~ O77-H77A ~ O77-H77B with sigma of 0.02 3. Others Fixed Sof: O66(0.5) O67(0.5) H67A(0.5) H67B(0.5) O166(0.5) O167(0.5) H16A(0.5) H16B(0.5) 4.a Free rotating group: O49(H49A,H49B), O62(H62A,H62B), O57(H57A,H57B), O68(H68A,H68B), O69(H69A, H69B), O70(H70A,H70B), O71(H71A,H71B), O72(H72A,H72B), O73(H73A,H73B) 4.b Rotating group: O22(H22A,H22B), O23(H23A,H23B), O24(H24A,H24B), O27(H27A,H27B), O29(H29A, H29B), O47(H47A,H47B), O48(H48A,H48B), O50(H50A,H50B), O54(H54A,H54B), O55(H55A,H55B), O56(H56A,H56B), O58(H58A,H58B), O59(H59A,H59B), O60(H60A,H60B), O61(H61A,H61B), O63(H63A,H63B), O64(H64A,H64B), O65(H65A,H65B), O74(H74A, H74B), O67(H67A,H67B), O167(H16A,H16B)

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
W1	0.43982 (2)	0.96245 (2)	1.17681 (2)	0.01193 (6)
W2	0.25947 (2)	0.81700 (2)	1.03223 (2)	0.01230 (6)
W3	0.39839 (2)	0.69804 (2)	0.93379 (2)	0.01231 (6)
W4	0.61176 (2)	0.80885 (2)	0.88516 (2)	0.01207 (6)
W5	0.34632 (2)	0.93167 (2)	0.87838 (2)	0.01145 (5)
W6	0.41877 (2)	1.15417 (2)	0.92471 (2)	0.01161 (6)
W7	0.09965 (2)	0.79501 (2)	0.57766 (2)	0.01183 (6)
W8	0.24036 (2)	0.68517 (2)	0.47575 (2)	0.01201 (6)
W9	0.15423 (2)	0.56265 (2)	0.62612 (2)	0.01127 (5)
W10	0.08150 (2)	0.34469 (2)	0.56793 (2)	0.01140 (6)
W11	−0.06153 (2)	0.45282 (2)	0.67587 (2)	0.01177 (6)
W12	−0.11444 (2)	0.68342 (2)	0.62245 (2)	0.01181 (6)
Fe1	0.000000	1.000000	0.500000	0.0146 (2)
Fe2	0.07450 (6)	0.82233 (5)	0.76386 (4)	0.01358 (16)
Fe3	0.42245 (6)	0.66855 (5)	0.74623 (4)	0.01375 (16)
Na1	0.500000	0.000000	0.500000	0.0205 (7)
Na2	0.28394 (19)	0.13921 (14)	0.60840 (11)	0.0213 (5)
Na3	0.50905 (19)	0.63218 (14)	0.41748 (11)	0.0193 (5)
Na4	−0.00109 (19)	1.11946 (14)	0.90833 (12)	0.0205 (5)
Na5	0.19312 (19)	1.34276 (14)	0.89244 (12)	0.0216 (5)
Na6	0.000000	1.500000	1.000000	0.0270 (7)
O75	0.1001 (3)	0.8950 (2)	0.53226 (19)	0.0156 (8)
O77	0.0108 (3)	1.0403 (3)	0.6088 (2)	0.0216 (9)
H77A	−0.022 (3)	1.079 (2)	0.634 (2)	0.032*
H77B	0.0826 (10)	1.056 (3)	0.6221 (19)	0.032*
O1	0.3979 (3)	0.9495 (2)	1.25833 (19)	0.0168 (8)
O78	−0.2529 (3)	0.7055 (2)	0.60234 (19)	0.0157 (8)
O2	0.5723 (3)	1.0360 (2)	1.20459 (19)	0.0141 (8)
O76	0.1546 (3)	1.0778 (2)	0.49860 (19)	0.0167 (8)
O3	0.5139 (3)	0.8592 (2)	1.16577 (18)	0.0141 (8)
O4	0.3706 (3)	1.0748 (2)	1.14768 (19)	0.0149 (8)
O5	0.5025 (3)	0.9800 (2)	1.07220 (18)	0.0127 (7)
O6	0.3153 (3)	0.9044 (2)	1.10875 (19)	0.0137 (8)
O7	0.2386 (3)	0.7250 (2)	1.08414 (19)	0.0177 (8)
O8	0.4370 (3)	0.7922 (2)	1.03049 (18)	0.0138 (8)
O9	0.3135 (3)	0.9243 (2)	0.96673 (19)	0.0144 (8)
O10	0.1258 (3)	0.8510 (2)	1.00611 (19)	0.0162 (8)
O11	0.2618 (3)	0.7439 (2)	0.94416 (18)	0.0140 (8)
O12	0.3941 (3)	0.6005 (2)	0.98167 (19)	0.0165 (8)
O13	0.5521 (3)	0.7084 (2)	0.93601 (19)	0.0145 (8)
O14	0.3535 (3)	0.6564 (2)	0.84180 (18)	0.0142 (8)
O15	0.7498 (3)	0.7843 (2)	0.90512 (19)	0.0163 (8)
O16	0.5632 (3)	0.7473 (2)	0.80024 (19)	0.0154 (8)
O17	0.4373 (3)	0.8345 (2)	0.88711 (19)	0.0148 (8)
O18	0.3123 (3)	1.0590 (2)	0.87348 (18)	0.0135 (7)
O19	0.2265 (3)	0.8848 (2)	0.82087 (19)	0.0157 (8)
O20	0.3779 (3)	1.1284 (2)	1.00996 (18)	0.0135 (8)
O21	0.3490 (3)	1.2486 (2)	0.90007 (19)	0.0162 (8)
O22	0.4906 (3)	0.5437 (2)	0.7766 (2)	0.0176 (8)
H22A	0.471921	0.525896	0.818159	0.026*
H22B	0.565119	0.549590	0.783409	0.026*
O23	0.4817 (3)	0.6504 (2)	0.6488 (2)	0.0189 (8)
H23A	0.534097	0.610923	0.653309	0.028*
H23B	0.511449	0.703254	0.636478	0.028*
O24	0.3712 (3)	0.7970 (2)	0.71232 (19)	0.0170 (8)
H24A	0.400970	0.812752	0.674860	0.026*
H24B	0.392232	0.840087	0.747703	0.026*
O25	0.2710 (3)	0.6072 (2)	0.68784 (19)	0.0145 (8)
O26	0.1417 (3)	0.8342 (2)	0.67012 (19)	0.0163 (8)
O27	0.0118 (3)	0.8350 (2)	0.85913 (19)	0.0175 (8)
H27A	−0.019350	0.780861	0.870617	0.026*
H27B	−0.041858	0.874914	0.855558	0.026*
O28	0.0044 (3)	0.9491 (2)	0.73617 (19)	0.0171 (8)
H28A	0.025 (4)	0.961 (3)	0.6950 (14)	0.026*
H28B	0.025 (5)	0.999 (2)	0.7650 (19)	0.026*
O29	0.1294 (3)	0.6937 (2)	0.7944 (2)	0.0171 (8)
H29A	0.120845	0.654521	0.755798	0.026*
H29B	0.090838	0.670087	0.825449	0.026*
O30	−0.0686 (3)	0.7429 (2)	0.70806 (19)	0.0173 (8)
O31	−0.0565 (3)	0.7844 (2)	0.57317 (19)	0.0130 (7)
O32	0.0612 (3)	0.6594 (2)	0.62006 (19)	0.0152 (8)
O33	0.0626 (3)	0.7070 (2)	0.47893 (19)	0.0138 (8)
O34	0.1905 (3)	0.5774 (2)	0.53939 (19)	0.0158 (8)
O35	0.2371 (3)	0.7542 (2)	0.56669 (18)	0.0149 (8)
O36	0.2569 (3)	0.7839 (2)	0.42933 (19)	0.0150 (8)
O37	0.3757 (3)	0.6545 (2)	0.49892 (19)	0.0163 (8)
O38	−0.1295 (3)	0.5646 (2)	0.65250 (19)	0.0146 (8)
O39	−0.1851 (3)	0.3951 (2)	0.60394 (19)	0.0137 (7)
O40	−0.1030 (3)	0.4288 (2)	0.7553 (2)	0.0177 (8)
O41	0.0140 (3)	0.3492 (2)	0.65924 (18)	0.0134 (7)
O42	0.0032 (3)	0.4785 (2)	0.57249 (18)	0.0134 (8)
O43	0.0721 (3)	0.5233 (2)	0.70755 (19)	0.0143 (8)
O44	−0.1231 (3)	0.6218 (2)	0.51595 (18)	0.0128 (7)
O45	0.1879 (3)	0.4362 (2)	0.62501 (18)	0.0134 (7)
O46	0.1513 (3)	0.2498 (2)	0.58872 (19)	0.0157 (8)
O47	0.3478 (3)	0.2254 (2)	0.7211 (2)	0.0203 (9)
H47A	0.376148	0.281108	0.714149	0.030*
H47B	0.400373	0.197678	0.748989	0.030*
O48	0.2635 (4)	0.0174 (3)	0.6787 (2)	0.0340 (11)
H48A	0.329102	0.003969	0.702825	0.051*
H48B	0.232193	−0.032050	0.651118	0.051*
O49	0.4680 (4)	0.0895 (3)	0.6048 (2)	0.0229 (9)
H49A	0.505130	0.135577	0.631042	0.034*
H49B	0.466632	0.046477	0.634452	0.034*
O50	0.7003 (3)	0.0214 (2)	0.5578 (2)	0.0216 (9)
H50A	0.709887	0.009412	0.604986	0.032*
H50B	0.727030	0.080448	0.559699	0.032*
O51	0.5203 (4)	0.1320 (3)	0.4330 (2)	0.0265 (9)
H51A	0.478 (4)	0.139 (4)	0.3902 (16)	0.040*
H51B	0.5888 (17)	0.150 (4)	0.427 (3)	0.040*
O52	0.6197 (4)	0.7649 (2)	0.4778 (2)	0.0215 (9)
H52A	0.663 (3)	0.7394 (10)	0.5110 (18)	0.032*
H52B	0.577 (4)	0.797 (4)	0.499 (2)	0.032*
O53	0.4156 (3)	0.7413 (3)	0.3450 (2)	0.0232 (9)
H53A	0.355 (2)	0.745 (4)	0.362 (2)	0.035*
H53B	0.397 (4)	0.728 (4)	0.2988 (8)	0.035*
O54	0.6019 (3)	0.6050 (2)	0.32011 (19)	0.0185 (8)
H54A	0.569316	0.556728	0.292040	0.028*
H54B	0.671969	0.594865	0.336455	0.028*
O55	0.6443 (3)	0.5476 (2)	0.4892 (2)	0.0193 (8)
H55A	0.713115	0.572858	0.490711	0.029*
H55B	0.640827	0.489651	0.470739	0.029*
O56	0.4026 (3)	0.4899 (2)	0.3769 (2)	0.0205 (8)
H56A	0.351594	0.497092	0.338263	0.031*
H56B	0.369101	0.469394	0.411358	0.031*
O58	0.1426 (3)	1.0451 (2)	0.9812 (2)	0.0220 (9)
H58A	0.208095	1.069437	0.976634	0.033*
H58B	0.137172	0.986597	0.967312	0.033*
O59	0.1030 (3)	1.0982 (2)	0.8154 (2)	0.0196 (8)
H59A	0.172924	1.082290	0.833307	0.029*
H59B	0.111317	1.150360	0.791637	0.029*
O60	−0.1092 (3)	0.9738 (2)	0.8820 (2)	0.0231 (9)
H60A	−0.166090	0.977993	0.846658	0.035*
H60B	−0.134022	0.956833	0.920654	0.035*
O61	0.3140 (3)	1.4191 (2)	0.9940 (2)	0.0229 (9)
H61A	0.369086	1.458527	0.980717	0.034*
H61B	0.352070	1.378925	1.025227	0.034*
O62	0.1017 (4)	1.2528 (3)	0.9709 (2)	0.0218 (9)
H62A	0.145760	1.229523	1.005333	0.033*
H62B	0.060640	1.285112	0.993112	0.033*
O63	0.1595 (3)	1.2692 (2)	0.7723 (2)	0.0204 (8)
H63A	0.214911	1.286341	0.744070	0.031*
H63B	0.090044	1.282058	0.742511	0.031*
O64	−0.1812 (4)	1.4738 (3)	0.9349 (2)	0.0286 (10)
H64A	−0.234836	1.515714	0.949155	0.043*
H64B	−0.218263	1.412264	0.938246	0.043*
O65	−0.0222 (4)	1.3617 (3)	1.0594 (2)	0.0269 (9)
H65A	−0.092383	1.350512	1.064955	0.040*
H65B	0.021278	1.365054	1.103450	0.040*
O74	0.2373 (4)	1.4742 (3)	0.8282 (2)	0.0339 (11)
H74A	0.277054	1.459042	0.795994	0.051*
H74B	0.275256	1.516954	0.859008	0.051*
O66	0.0455 (9)	1.4372 (6)	0.8932 (6)	0.025 (2)	0.5
O67	−0.0980 (10)	1.2057 (8)	0.8245 (6)	0.040 (3)	0.5
H67A	−0.172297	1.223060	0.834440	0.061*	0.5
H67B	−0.118922	1.176966	0.772875	0.061*	0.5
O166	0.0109 (11)	1.3927 (8)	0.8881 (6)	0.036 (3)	0.5
O167	−0.1337 (10)	1.1537 (9)	0.8069 (7)	0.047 (3)	0.5
H16A	−0.120091	1.218036	0.783218	0.070*	0.5
H16B	−0.219353	1.157915	0.813213	0.070*	0.5
O57	0.3650 (4)	0.6621 (3)	0.2063 (2)	0.0269 (9)
H57A	0.426675	0.650088	0.193605	0.040*
H57B	0.322656	0.684798	0.170648	0.040*
O68	0.8504 (4)	0.6607 (2)	0.8242 (2)	0.0222 (9)
H68A	0.874753	0.686576	0.789231	0.033*
H68B	0.811052	0.697443	0.843819	0.033*
O69	0.6958 (3)	0.5233 (3)	0.7662 (2)	0.0230 (9)
H69A	0.706601	0.467755	0.777240	0.034*
H69B	0.749060	0.560225	0.790897	0.034*
O70	0.4874 (4)	0.4128 (3)	0.8762 (2)	0.0258 (9)
H70A	0.526630	0.411288	0.919288	0.039*
H70B	0.422232	0.385367	0.874613	0.039*
O71	0.9183 (3)	0.1787 (2)	0.6740 (2)	0.0227 (9)
H71A	0.945097	0.231566	0.664001	0.034*
H71B	0.851249	0.167453	0.649725	0.034*
O72	0.7852 (4)	0.9728 (3)	0.7021 (2)	0.0282 (10)
H72A	0.741468	0.923175	0.697101	0.042*
H72B	0.751210	1.018193	0.715589	0.042*
O73	0.6434 (4)	0.8229 (2)	0.6820 (2)	0.0211 (9)
H73A	0.614540	0.802804	0.717447	0.032*
H73B	0.681198	0.781510	0.666241	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01172 (12)	0.01254 (10)	0.01175 (11)	0.00075 (8)	0.00268 (8)	0.00154 (8)
W2	0.01205 (12)	0.01225 (10)	0.01259 (11)	0.00030 (8)	0.00248 (8)	0.00132 (8)
W3	0.01267 (12)	0.01148 (10)	0.01268 (11)	0.00047 (8)	0.00234 (8)	0.00094 (8)
W4	0.01198 (12)	0.01195 (10)	0.01232 (11)	0.00099 (8)	0.00236 (8)	0.00104 (8)
W5	0.01123 (12)	0.01134 (10)	0.01177 (10)	0.00078 (8)	0.00211 (8)	0.00128 (8)
W6	0.01164 (12)	0.01129 (10)	0.01178 (10)	0.00095 (8)	0.00183 (8)	0.00125 (8)
W7	0.01197 (12)	0.01111 (10)	0.01233 (10)	0.00082 (8)	0.00213 (8)	0.00099 (8)
W8	0.01164 (12)	0.01182 (10)	0.01258 (11)	0.00048 (8)	0.00245 (8)	0.00124 (8)
W9	0.01105 (12)	0.01091 (10)	0.01184 (10)	0.00080 (8)	0.00205 (8)	0.00127 (8)
W10	0.01133 (12)	0.01107 (10)	0.01177 (10)	0.00089 (8)	0.00202 (8)	0.00114 (8)
W11	0.01170 (12)	0.01198 (10)	0.01187 (11)	0.00078 (8)	0.00277 (8)	0.00146 (8)
W12	0.01179 (12)	0.01161 (10)	0.01209 (11)	0.00098 (8)	0.00230 (8)	0.00121 (8)
Fe1	0.0158 (6)	0.0140 (5)	0.0141 (5)	0.0019 (4)	0.0030 (4)	0.0021 (4)
Fe2	0.0130 (4)	0.0142 (3)	0.0132 (4)	0.0001 (3)	0.0022 (3)	0.0005 (3)
Fe3	0.0133 (4)	0.0137 (3)	0.0140 (4)	−0.0001 (3)	0.0023 (3)	0.0005 (3)
Na1	0.0215 (18)	0.0183 (15)	0.0213 (16)	0.0016 (13)	0.0035 (13)	0.0010 (12)
Na2	0.0235 (13)	0.0208 (10)	0.0191 (11)	0.0053 (10)	0.0010 (9)	0.0018 (9)
Na3	0.0198 (13)	0.0191 (10)	0.0198 (11)	0.0021 (9)	0.0057 (9)	0.0023 (9)
Na4	0.0204 (13)	0.0220 (11)	0.0208 (11)	0.0027 (9)	0.0074 (9)	0.0044 (9)
Na5	0.0222 (13)	0.0223 (11)	0.0206 (11)	0.0046 (10)	0.0032 (9)	0.0024 (9)
Na6	0.0214 (19)	0.0287 (17)	0.0322 (19)	0.0043 (15)	0.0050 (15)	0.0118 (14)
O75	0.014 (2)	0.0130 (17)	0.0200 (19)	0.0037 (15)	0.0038 (15)	0.0025 (14)
O77	0.019 (2)	0.025 (2)	0.020 (2)	0.0053 (17)	0.0017 (17)	−0.0017 (16)
O1	0.017 (2)	0.0177 (18)	0.0156 (19)	−0.0001 (16)	0.0028 (15)	−0.0009 (15)
O78	0.014 (2)	0.0158 (17)	0.0178 (19)	0.0008 (15)	0.0033 (15)	0.0003 (14)
O2	0.013 (2)	0.0142 (17)	0.0142 (18)	−0.0001 (15)	0.0011 (15)	0.0016 (14)
O76	0.017 (2)	0.0150 (17)	0.0184 (19)	0.0002 (15)	0.0045 (16)	0.0013 (15)
O3	0.016 (2)	0.0140 (17)	0.0128 (18)	0.0000 (15)	0.0045 (15)	0.0042 (14)
O4	0.015 (2)	0.0136 (17)	0.0171 (19)	0.0022 (15)	0.0052 (15)	0.0009 (14)
O5	0.013 (2)	0.0111 (16)	0.0135 (18)	−0.0014 (15)	0.0024 (15)	−0.0003 (14)
O6	0.012 (2)	0.0143 (17)	0.0159 (18)	0.0033 (15)	0.0039 (15)	0.0011 (14)
O7	0.021 (2)	0.0144 (17)	0.0174 (19)	−0.0015 (16)	0.0046 (16)	0.0022 (15)
O8	0.014 (2)	0.0127 (17)	0.0147 (18)	0.0021 (15)	0.0019 (15)	0.0028 (14)
O9	0.016 (2)	0.0135 (17)	0.0138 (18)	0.0016 (15)	0.0025 (15)	0.0016 (14)
O10	0.015 (2)	0.0137 (17)	0.0184 (19)	−0.0022 (15)	0.0012 (15)	−0.0007 (14)
O11	0.011 (2)	0.0149 (17)	0.0148 (18)	−0.0024 (15)	0.0003 (15)	−0.0010 (14)
O12	0.018 (2)	0.0147 (17)	0.0169 (19)	0.0038 (16)	0.0033 (16)	0.0023 (14)
O13	0.012 (2)	0.0163 (17)	0.0146 (18)	0.0023 (15)	0.0002 (15)	0.0003 (14)
O14	0.015 (2)	0.0183 (18)	0.0095 (17)	0.0022 (15)	0.0027 (14)	0.0003 (14)
O15	0.014 (2)	0.0161 (18)	0.0182 (19)	0.0009 (15)	0.0013 (15)	0.0007 (15)
O16	0.016 (2)	0.0160 (17)	0.0133 (18)	−0.0009 (15)	0.0020 (15)	−0.0003 (14)
O17	0.014 (2)	0.0129 (17)	0.0180 (19)	0.0029 (15)	0.0039 (15)	0.0044 (14)
O18	0.013 (2)	0.0138 (17)	0.0147 (18)	0.0038 (15)	0.0028 (15)	0.0027 (14)
O19	0.018 (2)	0.0138 (17)	0.0160 (19)	0.0027 (15)	0.0029 (15)	0.0021 (14)
O20	0.014 (2)	0.0128 (17)	0.0136 (18)	−0.0009 (15)	0.0037 (15)	−0.0009 (14)
O21	0.016 (2)	0.0149 (17)	0.0171 (19)	0.0007 (15)	0.0018 (15)	0.0016 (15)
O22	0.013 (2)	0.0175 (18)	0.021 (2)	0.0005 (16)	0.0000 (16)	0.0004 (15)
O23	0.017 (2)	0.0179 (18)	0.023 (2)	0.0025 (16)	0.0065 (16)	0.0014 (15)
O24	0.022 (2)	0.0154 (18)	0.0125 (18)	0.0026 (16)	0.0007 (16)	0.0007 (14)
O25	0.016 (2)	0.0141 (17)	0.0139 (18)	0.0022 (15)	0.0029 (15)	0.0005 (14)
O26	0.014 (2)	0.0159 (17)	0.0192 (19)	0.0007 (15)	0.0035 (15)	0.0003 (15)
O27	0.017 (2)	0.0180 (18)	0.0181 (19)	0.0028 (16)	0.0035 (16)	0.0023 (15)
O28	0.020 (2)	0.0147 (17)	0.0152 (19)	−0.0001 (16)	0.0015 (16)	−0.0009 (15)
O29	0.020 (2)	0.0152 (18)	0.0157 (19)	0.0030 (16)	0.0017 (16)	−0.0011 (14)
O30	0.018 (2)	0.0194 (18)	0.0145 (19)	0.0013 (16)	0.0019 (15)	0.0023 (15)
O31	0.0106 (19)	0.0127 (16)	0.0159 (18)	0.0025 (15)	0.0019 (14)	0.0028 (14)
O32	0.017 (2)	0.0133 (17)	0.0163 (19)	0.0012 (15)	0.0047 (15)	0.0034 (14)
O33	0.014 (2)	0.0131 (17)	0.0152 (18)	0.0025 (15)	0.0036 (15)	0.0031 (14)
O34	0.018 (2)	0.0128 (17)	0.0180 (19)	0.0031 (15)	0.0075 (16)	0.0005 (14)
O35	0.012 (2)	0.0174 (18)	0.0143 (18)	−0.0024 (15)	0.0029 (15)	−0.0012 (14)
O36	0.018 (2)	0.0109 (17)	0.0161 (18)	−0.0002 (15)	0.0039 (15)	0.0011 (14)
O37	0.014 (2)	0.0140 (17)	0.0188 (19)	−0.0014 (15)	−0.0003 (15)	−0.0019 (14)
O38	0.011 (2)	0.0153 (17)	0.0182 (19)	0.0011 (15)	0.0034 (15)	0.0029 (14)
O39	0.013 (2)	0.0149 (17)	0.0137 (18)	0.0044 (15)	0.0017 (15)	0.0020 (14)
O40	0.016 (2)	0.0197 (18)	0.0183 (19)	0.0029 (16)	0.0049 (16)	0.0037 (15)
O41	0.014 (2)	0.0143 (17)	0.0115 (17)	0.0004 (15)	0.0025 (15)	0.0025 (14)
O42	0.016 (2)	0.0116 (16)	0.0119 (17)	−0.0014 (15)	0.0004 (15)	0.0010 (14)
O43	0.013 (2)	0.0158 (17)	0.0140 (18)	0.0013 (15)	0.0023 (15)	−0.0011 (14)
O44	0.0098 (19)	0.0121 (16)	0.0155 (18)	−0.0009 (14)	0.0016 (14)	−0.0020 (14)
O45	0.012 (2)	0.0141 (17)	0.0145 (18)	0.0036 (15)	0.0038 (15)	0.0017 (14)
O46	0.015 (2)	0.0143 (17)	0.0172 (19)	0.0001 (15)	0.0023 (15)	0.0014 (14)
O47	0.023 (2)	0.0176 (18)	0.020 (2)	0.0025 (17)	0.0021 (17)	0.0033 (15)
O48	0.032 (3)	0.027 (2)	0.035 (3)	−0.010 (2)	−0.013 (2)	0.0112 (19)
O49	0.029 (3)	0.0205 (19)	0.019 (2)	0.0028 (18)	0.0034 (17)	0.0034 (16)
O50	0.023 (2)	0.0148 (18)	0.026 (2)	0.0003 (17)	0.0049 (18)	−0.0003 (16)
O51	0.026 (2)	0.027 (2)	0.027 (2)	−0.0014 (19)	0.0041 (18)	0.0060 (18)
O52	0.023 (2)	0.0185 (19)	0.021 (2)	0.0062 (17)	−0.0009 (17)	0.0043 (16)
O53	0.021 (2)	0.030 (2)	0.021 (2)	0.0054 (18)	0.0070 (17)	0.0020 (18)
O54	0.019 (2)	0.0185 (18)	0.0167 (19)	0.0018 (16)	0.0011 (16)	0.0002 (15)
O55	0.019 (2)	0.0170 (18)	0.022 (2)	0.0009 (16)	0.0042 (17)	0.0041 (16)
O56	0.020 (2)	0.0204 (19)	0.021 (2)	−0.0001 (17)	0.0053 (17)	0.0002 (16)
O58	0.022 (2)	0.0171 (19)	0.030 (2)	0.0059 (17)	0.0077 (18)	0.0077 (16)
O59	0.020 (2)	0.0163 (18)	0.022 (2)	0.0026 (16)	0.0018 (17)	0.0020 (15)
O60	0.021 (2)	0.023 (2)	0.024 (2)	0.0038 (17)	0.0026 (17)	0.0005 (17)
O61	0.027 (2)	0.0155 (18)	0.026 (2)	0.0017 (17)	0.0041 (18)	0.0049 (16)
O62	0.021 (2)	0.021 (2)	0.023 (2)	0.0034 (17)	0.0019 (17)	0.0039 (16)
O63	0.019 (2)	0.0216 (19)	0.020 (2)	0.0010 (17)	0.0016 (16)	0.0040 (16)
O64	0.027 (3)	0.018 (2)	0.042 (3)	0.0026 (18)	0.009 (2)	0.0024 (18)
O65	0.026 (2)	0.030 (2)	0.025 (2)	0.0000 (19)	0.0054 (18)	0.0091 (18)
O74	0.044 (3)	0.026 (2)	0.026 (2)	−0.008 (2)	−0.003 (2)	0.0047 (18)
O66	0.024 (6)	0.024 (5)	0.025 (5)	0.003 (4)	0.001 (4)	0.002 (5)
O67	0.030 (7)	0.075 (9)	0.028 (6)	0.033 (6)	0.017 (5)	0.027 (6)
O166	0.050 (8)	0.043 (7)	0.021 (5)	0.025 (6)	0.011 (5)	0.011 (5)
O167	0.029 (7)	0.079 (9)	0.042 (7)	0.013 (6)	0.021 (6)	0.033 (7)
O57	0.034 (3)	0.027 (2)	0.019 (2)	0.008 (2)	0.0013 (18)	0.0053 (17)
O68	0.025 (2)	0.0220 (19)	0.022 (2)	−0.0006 (18)	0.0110 (17)	0.0005 (16)
O69	0.017 (2)	0.0207 (19)	0.029 (2)	−0.0010 (17)	0.0008 (17)	0.0005 (17)
O70	0.025 (3)	0.031 (2)	0.020 (2)	−0.0015 (19)	−0.0007 (17)	0.0079 (18)
O71	0.023 (2)	0.0154 (18)	0.028 (2)	−0.0029 (17)	0.0007 (18)	0.0046 (16)
O72	0.024 (3)	0.021 (2)	0.041 (3)	0.0019 (18)	0.011 (2)	−0.0005 (19)
O73	0.026 (2)	0.0209 (19)	0.019 (2)	0.0026 (18)	0.0106 (17)	0.0032 (16)

Geometric parameters (Å, º) top

W1—O1	1.729 (4)	Fe1—O77ⁱⁱⁱ	2.087 (4)
W1—O2	1.873 (4)	Fe1—O77	2.087 (4)
W1—O3	1.859 (3)	Fe1—O76ⁱⁱⁱ	2.165 (4)
W1—O4	1.979 (3)	Fe1—O76	2.165 (4)
W1—O5	2.273 (3)	Fe2—O19	2.108 (4)
W1—O6	1.930 (4)	Fe2—O26	2.101 (4)
W2—O6	1.882 (3)	Fe2—O27	2.093 (4)
W2—O7	1.748 (3)	Fe2—O28	2.169 (4)
W2—O8	2.259 (4)	Fe2—O29	2.136 (4)
W2—O9	2.201 (3)	Fe2—O30	2.122 (4)
W2—O10	1.754 (4)	Fe3—O14	2.145 (3)
W2—O11	1.943 (3)	Fe3—O16	2.087 (4)
W3—O8	2.195 (3)	Fe3—O22	2.145 (4)
W3—O11	1.905 (4)	Fe3—O23	2.116 (4)
W3—O12	1.743 (3)	Fe3—O24	2.136 (3)
W3—O13	1.890 (4)	Fe3—O25	2.106 (4)
W3—O14	1.786 (3)	Na1—O49	2.434 (4)
W3—O17	2.297 (3)	Na1—O49^iv	2.434 (4)
W4—O4ⁱ	1.869 (3)	Na1—O50	2.507 (4)
W4—O13	1.980 (3)	Na1—O50^iv	2.507 (4)
W4—O15	1.748 (4)	Na1—O51^iv	2.402 (4)
W4—O16	1.782 (3)	Na1—O51	2.402 (4)
W4—O17	2.226 (4)	Na2—Na3^v	4.194 (3)
W4—O20ⁱ	2.122 (3)	Na2—O76^vi	2.460 (4)
W5—O2ⁱ	2.071 (4)	Na2—O46	2.394 (4)
W5—O5ⁱ	2.224 (4)	Na2—O47	2.395 (4)
W5—O9	1.796 (3)	Na2—O48	2.317 (4)
W5—O17	1.883 (3)	Na2—O49	2.456 (5)
W5—O18	1.960 (3)	Na2—O52^v	2.606 (4)
W5—O19	1.743 (4)	Na3—Na2^v	4.194 (3)
W6—O3ⁱ	2.043 (3)	Na3—O37	2.484 (4)
W6—O5ⁱ	2.271 (3)	Na3—O52	2.412 (4)
W6—O8ⁱ	1.923 (4)	Na3—O53	2.392 (5)
W6—O18	1.942 (4)	Na3—O54	2.375 (4)
W6—O20	1.826 (3)	Na3—O55	2.416 (4)
W6—O21	1.732 (4)	Na3—O56	2.408 (4)
W7—O75	1.746 (3)	Na4—Na5	3.996 (3)
W7—O26	1.781 (4)	Na4—O10^vii	2.477 (4)
W7—O31	1.913 (4)	Na4—O58	2.407 (5)
W7—O32	2.247 (3)	Na4—O59	2.383 (4)
W7—O33	2.174 (3)	Na4—O60	2.427 (4)
W7—O35	1.888 (4)	Na4—O62	2.395 (4)
W8—O33	2.258 (4)	Na4—O67	2.302 (11)
W8—O34	2.166 (3)	Na4—O167	2.382 (13)
W8—O35	1.961 (3)	Na5—Na6	4.167 (2)
W8—O36	1.759 (3)	Na5—O21	2.447 (4)
W8—O37	1.750 (4)	Na5—O61	2.380 (4)
W8—O39ⁱⁱ	1.860 (3)	Na5—O62	2.418 (4)
W9—O25	1.743 (4)	Na5—O63	2.416 (4)
W9—O32	1.895 (4)	Na5—O74	2.424 (4)
W9—O34	1.797 (4)	Na5—O66	2.379 (11)
W9—O42	2.213 (4)	Na5—O166	2.412 (12)
W9—O43	2.079 (4)	Na6—Na5^viii	4.167 (2)
W9—O45	1.943 (3)	Na6—O64^viii	2.344 (4)
W10—O33ⁱⁱ	1.922 (4)	Na6—O64	2.344 (4)
W10—O41	2.052 (3)	Na6—O65	2.404 (4)
W10—O42	2.268 (3)	Na6—O65^viii	2.404 (4)
W10—O44ⁱⁱ	1.835 (3)	Na6—O66	2.358 (11)
W10—O45	1.947 (4)	Na6—O66^viii	2.358 (11)
W10—O46	1.724 (4)	Na6—O166^viii	2.606 (11)
W11—O38	1.942 (3)	Na6—O166	2.606 (11)
W11—O39	1.958 (4)	O2—W5ⁱ	2.071 (3)
W11—O40	1.719 (4)	O76—Na2^ix	2.460 (4)
W11—O41	1.892 (3)	O3—W6ⁱ	2.043 (3)
W11—O42	2.283 (3)	O4—W4ⁱ	1.869 (3)
W11—O43	1.870 (4)	O5—W5ⁱ	2.224 (3)
W12—O78	1.743 (4)	O5—W6ⁱ	2.271 (3)
W12—O30	1.775 (4)	O8—W6ⁱ	1.923 (4)
W12—O31	1.960 (3)	O10—Na4^vii	2.477 (4)
W12—O32	2.237 (4)	O20—W4ⁱ	2.122 (3)
W12—O38	1.879 (3)	O33—W10ⁱⁱ	1.922 (4)
W12—O44	2.146 (3)	O39—W8ⁱⁱ	1.860 (3)
Fe1—O75ⁱⁱⁱ	2.100 (3)	O44—W10ⁱⁱ	1.835 (3)
Fe1—O75	2.100 (3)	O52—Na2^v	2.606 (4)

O67a—Na4—Na5	72.3 (3)	O38—W12—O44	86.63 (14)
O167b—Na4—Na5	91.8 (3)	O44—W12—O32	76.83 (13)
O67a—Na4—O10^vii	91.4 (3)	O75ⁱⁱⁱ—Fe1—O75	180.00 (17)
O1—W1—O2	102.23 (16)	O75—Fe1—O76	84.52 (14)
O1—W1—O3	102.82 (16)	O75ⁱⁱⁱ—Fe1—O76ⁱⁱⁱ	84.51 (14)
O1—W1—O4	100.36 (16)	O75—Fe1—O76ⁱⁱⁱ	95.48 (14)
O1—W1—O5	177.56 (16)	O75ⁱⁱⁱ—Fe1—O76	95.49 (14)
O1—W1—O6	102.08 (16)	O77—Fe1—O75	88.54 (15)
O167b—Na4—O10^vii	92.8 (3)	O77ⁱⁱⁱ—Fe1—O75ⁱⁱⁱ	88.54 (15)
O167b—Na4—O58	160.3 (3)	O77ⁱⁱⁱ—Fe1—O75	91.46 (15)
O67a—Na4—O58	164.0 (3)	O77—Fe1—O75ⁱⁱⁱ	91.46 (15)
O167b—Na4—O59	80.4 (3)	O77ⁱⁱⁱ—Fe1—O77	180.0 (2)
O67a—Na4—O59	82.0 (3)	O77—Fe1—O76ⁱⁱⁱ	89.27 (15)
O67a—Na4—O60	100.9 (3)	O77ⁱⁱⁱ—Fe1—O76ⁱⁱⁱ	90.73 (15)
O167b—Na4—O60	79.8 (3)	O77ⁱⁱⁱ—Fe1—O76	89.27 (15)
O67a—Na4—O62	91.2 (3)	O77—Fe1—O76	90.73 (15)
O167b—Na4—O62	112.6 (3)	O76ⁱⁱⁱ—Fe1—O76	180.0
O66a—Na5—Na4	91.9 (2)	O19—Fe2—O28	94.86 (14)
O2—W1—O4	86.64 (15)	O19—Fe2—O29	88.73 (14)
O2—W1—O5	75.66 (14)	O19—Fe2—O30	172.37 (14)
O2—W1—O6	154.94 (15)	O26—Fe2—O19	86.58 (14)
O166b—Na5—Na4	74.3 (3)	O26—Fe2—O28	84.95 (14)
O66a—Na5—Na6	28.3 (3)	O26—Fe2—O29	99.31 (14)
O166b—Na5—Na6	35.4 (3)	O26—Fe2—O30	93.00 (14)
O166b—Na5—O21	163.0 (3)	O27—Fe2—O19	88.57 (15)
O3—W1—O2	92.10 (16)	O27—Fe2—O26	170.10 (14)
O3—W1—O4	156.51 (14)	O27—Fe2—O28	86.87 (14)
O3—W1—O5	76.16 (13)	O27—Fe2—O29	89.20 (14)
O3—W1—O6	88.40 (15)	O27—Fe2—O30	92.94 (15)
O4—W1—O5	80.82 (13)	O29—Fe2—O28	174.61 (15)
O6—W1—O4	83.09 (15)	O30—Fe2—O28	92.69 (14)
O6—W1—O5	80.15 (14)	O30—Fe2—O29	83.82 (14)
O6—W2—O8	86.58 (14)	O16—Fe3—O14	93.57 (14)
O6—W2—O9	82.77 (14)	O16—Fe3—O22	92.74 (14)
O6—W2—O11	155.70 (15)	O16—Fe3—O23	94.67 (15)
O7—W2—O6	97.75 (16)	O16—Fe3—O24	83.16 (14)
O7—W2—O8	93.99 (16)	O16—Fe3—O25	171.65 (14)
O7—W2—O9	170.19 (16)	O22—Fe3—O14	83.38 (14)
O7—W2—O10	102.74 (17)	O23—Fe3—O14	167.85 (14)
O7—W2—O11	95.65 (15)	O23—Fe3—O22	87.31 (14)
O66a—Na5—O21	176.3 (3)	O23—Fe3—O24	88.30 (14)
O66a—Na5—O61	96.4 (3)	O24—Fe3—O14	101.55 (14)
O166b—Na5—O62	71.7 (3)	O24—Fe3—O22	173.74 (15)
O66a—Na5—O62	84.3 (3)	O25—Fe3—O14	87.26 (14)
O66a—Na5—O63	105.1 (3)	O25—Fe3—O22	95.61 (14)
O166b—Na5—O63	97.0 (3)	O25—Fe3—O23	85.89 (14)
O166b—Na5—O74	88.6 (3)	O25—Fe3—O24	88.53 (14)
O66a—Na5—O74	74.2 (3)	O49—Na1—O49^iv	180.0
O66a^viii—Na6—Na5^viii	28.5 (3)	O49—Na1—O50^iv	94.06 (13)
O166b—Na6—Na5^viii	147.6 (3)	O49^iv—Na1—O50^iv	85.94 (13)
O66a—Na6—Na5^viii	151.5 (3)	O49^iv—Na1—O50	94.06 (13)
O166b^viii—Na6—Na5	147.6 (3)	O49—Na1—O50	85.94 (13)
O66a^viii—Na6—Na5	151.5 (3)	O50^iv—Na1—O50	180.0
O166b^viii—Na6—Na5^viii	32.4 (3)	O51—Na1—O49^iv	87.15 (13)
O166b—Na6—Na5	32.4 (3)	O51—Na1—O49	92.85 (13)
O9—W2—O8	76.25 (13)	O51^iv—Na1—O49	87.15 (13)
O10—W2—O6	100.05 (16)	O51^iv—Na1—O49^iv	92.85 (13)
O10—W2—O8	160.90 (15)	O51^iv—Na1—O50^iv	90.54 (14)
O10—W2—O9	86.76 (15)	O51—Na1—O50^iv	89.46 (14)
O10—W2—O11	96.62 (16)	O51^iv—Na1—O50	89.46 (14)
O11—W2—O8	72.31 (14)	O51—Na1—O50	90.54 (14)
O11—W2—O9	80.65 (13)	O51—Na1—O51^iv	180.0
O8—W3—O17	77.47 (13)	O76^vi—Na2—Na3^v	115.31 (11)
O11—W3—O8	74.48 (14)	O76^vi—Na2—O52^v	85.72 (14)
O11—W3—O17	85.82 (14)	O46—Na2—Na3^v	80.08 (10)
O12—W3—O8	94.71 (15)	O46—Na2—O76^vi	76.13 (14)
O12—W3—O11	100.68 (16)	O46—Na2—O47	83.98 (14)
O12—W3—O13	97.09 (16)	O46—Na2—O49	151.08 (16)
O12—W3—O14	103.75 (16)	O46—Na2—O52^v	83.19 (14)
O12—W3—O17	168.24 (16)	O47—Na2—Na3^v	69.12 (11)
O13—W3—O8	85.38 (14)	O47—Na2—O76^vi	158.13 (17)
O13—W3—O11	154.04 (14)	O47—Na2—O49	92.49 (15)
O13—W3—O17	73.75 (14)	O47—Na2—O52^v	101.02 (15)
O14—W3—O8	160.44 (14)	O48—Na2—Na3^v	144.46 (14)
O14—W3—O11	95.49 (16)	O48—Na2—O76^vi	97.84 (16)
O14—W3—O13	98.50 (16)	O48—Na2—O46	122.29 (18)
O14—W3—O17	85.19 (14)	O48—Na2—O47	85.06 (16)
O4ⁱ—W4—O13	158.70 (15)	O48—Na2—O49	85.78 (16)
O4ⁱ—W4—O17	87.50 (14)	O48—Na2—O52^v	154.45 (18)
O4ⁱ—W4—O20ⁱ	87.80 (14)	O49—Na2—Na3^v	71.91 (11)
O13—W4—O17	73.81 (14)	O49—Na2—O76^vi	109.31 (15)
O13—W4—O20ⁱ	78.33 (13)	O49—Na2—O52^v	69.29 (14)
O15—W4—O4ⁱ	99.78 (16)	O52^v—Na2—Na3^v	31.89 (9)
O15—W4—O13	96.69 (16)	O37—Na3—Na2^v	116.60 (11)
O15—W4—O16	102.35 (17)	O52—Na3—Na2^v	34.80 (10)
O15—W4—O17	166.45 (15)	O52—Na3—O37	88.80 (14)
O15—W4—O20ⁱ	91.54 (16)	O52—Na3—O55	85.00 (15)
O16—W4—O4ⁱ	98.64 (16)	O53—Na3—Na2^v	66.75 (11)
O16—W4—O13	90.86 (15)	O53—Na3—O37	86.52 (14)
O16—W4—O17	87.68 (16)	O53—Na3—O52	83.44 (15)
O16—W4—O20ⁱ	163.37 (16)	O53—Na3—O55	165.38 (17)
O20ⁱ—W4—O17	77.24 (14)	O53—Na3—O56	104.30 (16)
O2ⁱ—W5—O5ⁱ	73.17 (13)	O54—Na3—Na2^v	69.01 (10)
O9—W5—O2ⁱ	161.79 (16)	O54—Na3—O37	167.68 (17)
O9—W5—O5ⁱ	88.63 (15)	O54—Na3—O52	100.05 (16)
O9—W5—O17	94.60 (16)	O54—Na3—O53	86.01 (15)
O9—W5—O18	92.85 (15)	O54—Na3—O55	87.22 (15)
O17—W5—O2ⁱ	83.63 (14)	O54—Na3—O56	86.22 (14)
O17—W5—O5ⁱ	86.14 (15)	O55—Na3—Na2^v	98.71 (11)
O66a—Na6—Na5	28.5 (3)	O55—Na3—O37	102.18 (14)
O66a—Na6—O65^viii	81.5 (3)	O56—Na3—Na2^v	153.79 (12)
O66a^viii—Na6—O65^viii	98.5 (3)	O56—Na3—O37	86.15 (14)
O66a^viii—Na6—O65	81.5 (3)	O56—Na3—O52	170.45 (16)
O66a—Na6—O65	98.5 (3)	O56—Na3—O55	88.15 (15)
O66a—Na6—O66^viii	180.0	O10^vii—Na4—Na5	110.91 (11)
O166b—Na6—O166^viii	180.0	O58—Na4—Na5	94.56 (12)
Na5—O166b—Na6	112.2 (5)	O58—Na4—O10^vii	102.18 (15)
Na6—O66a—Na5	123.2 (5)	O58—Na4—O60	89.00 (15)
O17—W5—O18	156.21 (16)	O59—Na4—Na5	68.57 (10)
O18—W5—O2ⁱ	82.29 (14)	O59—Na4—O10^vii	173.18 (17)
O18—W5—O5ⁱ	71.47 (14)	O59—Na4—O58	84.62 (15)
O19—W5—O2ⁱ	94.39 (15)	O59—Na4—O60	95.17 (15)
O19—W5—O5ⁱ	163.66 (14)	O59—Na4—O62	98.88 (15)
O19—W5—O9	103.63 (17)	O60—Na4—Na5	162.87 (13)
O19—W5—O17	103.30 (16)	O60—Na4—O10^vii	84.57 (14)
O19—W5—O18	96.82 (16)	O62—Na4—Na5	34.07 (10)
O3ⁱ—W6—O5ⁱ	72.91 (13)	O62—Na4—O10^vii	82.69 (14)
O8ⁱ—W6—O3ⁱ	84.52 (15)	O62—Na4—O58	82.18 (15)
O8ⁱ—W6—O5ⁱ	85.68 (14)	O62—Na4—O60	162.60 (16)
O8ⁱ—W6—O18	155.62 (15)	Na4—Na5—Na6	90.45 (5)
O18—W6—O3ⁱ	82.76 (14)	O21—Na5—Na4	88.71 (11)
O18—W6—O5ⁱ	70.73 (14)	O21—Na5—Na6	148.08 (11)
O20—W6—O3ⁱ	160.28 (14)	O61—Na5—Na4	122.47 (12)
O20—W6—O5ⁱ	87.38 (14)	O61—Na5—Na6	73.42 (11)
O20—W6—O8ⁱ	94.35 (16)	O61—Na5—O21	80.23 (14)
O20—W6—O18	90.72 (15)	O61—Na5—O62	90.73 (15)
O21—W6—O3ⁱ	96.16 (15)	O61—Na5—O63	151.18 (18)
O21—W6—O5ⁱ	165.95 (15)	O61—Na5—O74	85.58 (15)
O21—W6—O8ⁱ	102.36 (16)	O61—Na5—O166	108.6 (3)
O21—W6—O18	99.63 (16)	O62—Na5—Na4	33.69 (10)
O21—W6—O20	103.29 (16)	O62—Na5—Na6	68.87 (11)
O75—W7—O26	103.42 (16)	O62—Na5—O21	94.18 (15)
O75—W7—O31	94.64 (16)	O62—Na5—O74	157.62 (18)
O75—W7—O32	167.01 (16)	O63—Na5—Na4	76.45 (11)
O75—W7—O33	93.94 (15)	O63—Na5—Na6	131.93 (13)
O75—W7—O35	100.95 (16)	O63—Na5—O21	78.65 (14)
O26—W7—O31	98.53 (16)	O63—Na5—O62	110.12 (15)
O26—W7—O32	85.41 (14)	O63—Na5—O74	82.05 (15)
O26—W7—O33	161.89 (14)	O74—Na5—Na4	150.39 (14)
O26—W7—O35	95.91 (16)	O74—Na5—Na6	88.95 (13)
O31—W7—O32	74.41 (14)	O74—Na5—O21	106.88 (17)
O31—W7—O33	84.98 (14)	Na5^viii—Na6—Na5	180.0
O33—W7—O32	78.40 (13)	O64—Na6—Na5	106.43 (10)
O35—W7—O31	155.66 (14)	O64^viii—Na6—Na5^viii	106.43 (11)
O35—W7—O32	87.39 (14)	O64—Na6—Na5^viii	73.57 (10)
O35—W7—O33	75.47 (14)	O64^viii—Na6—Na5	73.57 (11)
O34—W8—O33	76.31 (13)	O64—Na6—O64^viii	180.0
O35—W8—O33	72.16 (14)	O64—Na6—O65^viii	89.83 (14)
O35—W8—O34	79.27 (14)	O64—Na6—O65	90.17 (15)
O36—W8—O33	92.20 (15)	O64^viii—Na6—O65	89.83 (14)
O36—W8—O34	167.70 (15)	O64^viii—Na6—O65^viii	90.17 (15)
O36—W8—O35	93.19 (15)	O64^viii—Na6—O66	96.6 (3)
O36—W8—O39ⁱⁱ	97.99 (15)	O64—Na6—O66	83.4 (3)
O37—W8—O33	162.25 (15)	O64—Na6—O66^viii	96.6 (3)
O37—W8—O34	88.05 (15)	O64^viii—Na6—O66^viii	83.4 (3)
O37—W8—O35	97.00 (16)	O64—Na6—O166^viii	105.8 (3)
O37—W8—O36	102.61 (17)	O64—Na6—O166	74.2 (3)
O37—W8—O39ⁱⁱ	101.14 (16)	O64^viii—Na6—O166^viii	74.2 (3)
O39ⁱⁱ—W8—O33	86.20 (15)	O64^viii—Na6—O166	105.8 (3)
O39ⁱⁱ—W8—O34	85.75 (14)	O65—Na6—Na5	81.74 (11)
O39ⁱⁱ—W8—O35	156.00 (15)	O65^viii—Na6—Na5^viii	81.74 (11)
O25—W9—O32	103.17 (16)	O65—Na6—Na5^viii	98.26 (11)
O25—W9—O34	104.38 (17)	O65^viii—Na6—Na5	98.26 (11)
O25—W9—O42	163.37 (14)	O65—Na6—O65^viii	180.0
O25—W9—O43	92.49 (15)	O65—Na6—O166^viii	95.1 (3)
O25—W9—O45	97.59 (16)	O65^viii—Na6—O166^viii	84.9 (3)
O32—W9—O42	84.68 (14)	O65^viii—Na6—O166	95.1 (3)
O32—W9—O43	84.03 (14)	O65—Na6—O166	84.9 (3)
O32—W9—O45	155.61 (16)	W7—O75—Fe1	141.2 (2)
O34—W9—O32	94.46 (15)	W1—O2—W5ⁱ	115.40 (17)
O34—W9—O42	89.37 (15)	Fe1—O76—Na2^ix	123.52 (16)
O34—W9—O43	162.93 (16)	W1—O3—W6ⁱ	116.84 (17)
O34—W9—O45	92.62 (15)	W4ⁱ—O4—W1	147.3 (2)
O43—W9—O42	73.56 (13)	W5ⁱ—O5—W1	95.76 (13)
O45—W9—O42	72.07 (14)	W5ⁱ—O5—W6ⁱ	97.18 (14)
O45—W9—O43	82.42 (14)	W6ⁱ—O5—W1	94.06 (12)
O33ⁱⁱ—W10—O41	84.49 (14)	W2—O6—W1	149.1 (2)
O33ⁱⁱ—W10—O42	85.99 (14)	W3—O8—W2	95.05 (14)
O33ⁱⁱ—W10—O45	155.71 (15)	W6ⁱ—O8—W2	137.59 (17)
O41—W10—O42	72.95 (13)	W6ⁱ—O8—W3	125.95 (18)
O44ⁱⁱ—W10—O33ⁱⁱ	94.56 (15)	W5—O9—W2	137.20 (18)
O44ⁱⁱ—W10—O41	160.62 (14)	W2—O10—Na4^vii	123.67 (18)
O44ⁱⁱ—W10—O42	87.67 (14)	W3—O11—W2	117.26 (18)
O44ⁱⁱ—W10—O45	91.49 (15)	W3—O13—W4	117.31 (18)
O45—W10—O41	82.10 (14)	W3—O14—Fe3	133.7 (2)
O45—W10—O42	70.76 (13)	W4—O16—Fe3	138.8 (2)
O46—W10—O33ⁱⁱ	102.68 (16)	W4—O17—W3	93.90 (13)
O46—W10—O41	95.21 (15)	W5—O17—W3	125.71 (18)
O46—W10—O42	164.79 (15)	W5—O17—W4	139.11 (18)
O46—W10—O44ⁱⁱ	103.85 (16)	W6—O18—W5	119.54 (18)
O46—W10—O45	98.64 (16)	W5—O19—Fe2	172.3 (2)
O38—W11—O39	84.45 (15)	W6—O20—W4ⁱ	138.94 (18)
O38—W11—O42	81.24 (14)	W6—O21—Na5	154.0 (2)
O39—W11—O42	79.88 (14)	W9—O25—Fe3	169.9 (2)
O40—W11—O38	102.46 (16)	W7—O26—Fe2	135.4 (2)
O40—W11—O39	101.77 (16)	W12—O30—Fe2	137.9 (2)
O40—W11—O41	100.97 (16)	W7—O31—W12	116.06 (17)
O40—W11—O42	176.04 (16)	W9—O32—W7	124.93 (18)
O40—W11—O43	102.78 (17)	W9—O32—W12	139.49 (18)
O41—W11—O38	156.18 (15)	W12—O32—W7	94.25 (13)
O41—W11—O39	86.64 (15)	W7—O33—W8	95.16 (14)
O41—W11—O42	75.46 (13)	W10ⁱⁱ—O33—W7	125.80 (18)
O43—W11—O38	87.92 (15)	W10ⁱⁱ—O33—W8	137.86 (18)
O43—W11—O39	155.33 (15)	W9—O34—W8	139.68 (18)
O43—W11—O41	91.09 (15)	W7—O35—W8	116.42 (18)
O43—W11—O42	75.78 (14)	W8—O37—Na3	127.58 (19)
O78—W12—O30	102.32 (17)	W12—O38—W11	147.9 (2)
O78—W12—O31	97.07 (15)	W8ⁱⁱ—O39—W11	150.9 (2)
O78—W12—O32	166.24 (15)	W11—O41—W10	116.54 (16)
O78—W12—O38	99.83 (16)	W9—O42—W10	96.86 (14)
O78—W12—O44	91.39 (15)	W9—O42—W11	95.65 (13)
O30—W12—O31	91.54 (15)	W10—O42—W11	95.01 (12)
O30—W12—O32	88.42 (16)	W11—O43—W9	114.98 (17)
O30—W12—O38	99.13 (16)	W10ⁱⁱ—O44—W12	136.52 (18)
O30—W12—O44	163.89 (16)	W9—O45—W10	119.05 (18)
O31—W12—O32	73.79 (13)	W10—O46—Na2	166.1 (2)
O31—W12—O44	78.25 (13)	Na1—O49—Na2	120.25 (17)
O38—W12—O31	157.54 (15)	Na3—O52—Na2^v	113.31 (16)
O38—W12—O32	86.74 (14)	Na4—O62—Na5	112.24 (17)

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+1, −z+1; (iii) −x, −y+2, −z+1; (iv) −x+1, −y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, y−1, z; (vii) −x, −y+2, −z+2; (viii) −x, −y+3, −z+2; (ix) x, y+1, z.

Fe^II and Cu^II containing paratungstates B [based on the Inorganic Crystal Structure Database (FIZ, Karlsruhe; https://www.fiz-informationsdienste.de/DB/icsd/www-recherche.html) and the Cambridge Structural Database (CSD; Groom et al., 2016)] top

Compounds	Unit-cell parameters a, b and c (Å) and α, β and γ (°)	Volume (Å³), Z and space group	Synthesis details (source of W; W:M^II ratio; M= Fe, Cu; pH)	Reference
Fe^II
K₆[{Fe(H₂O)₄}₂(H₂W₁₂O₄₂)]·15H₂O	14.9967 (5), 10.3872 (3), 18.8237 (6); 90, 93.407 (1), 90	2927.1 (2), 2, P2₁/n	K₂WO₄; 12:1.4; ?	Yang et al. (2003)
(H₃O)₂[{Fe(H₂O)₄Fe(H₂O)₃}₂(H₂W₁₂O₄₂)]·20H₂O	12.1794 (4), 22.4938 (4), 11.6941 (3); 90, 105.731 (2), 90	3083.7 (1), 2, P2₁/c	Li₂WO₄; 12:1.4; ?	Yang et al. (2003)
Na₅[{Fe(H₂O)₃}₂{Fe(H₂O)₄}_0.5(H₂W₁₂O₄₂)]·30H₂O	12.121 (2), 12.426 (3), 13.247 (3); 68.33 (3), 71.33 (3), 71.44 (3)	1710.7 (6), 1, P1	Na₂WO₄; 12:1.4; –	Yang et al. (2003)
Cu^II
Na₈[Cu(H₂O)₂(H₂W₁₂O₄₂)].30H₂O	13.081 (4), 13.160 (6), 20.127 (6); 78.294 (12), 78.524 (11), 72.593 (11)	3201.7 (17), 2, P1	Na₂WO₄; 12:2.4; 4.8	Li et al. (2008)
KNa₃[Cu(H₂O)₂{Cu(H₂O)₃}₂(H₂W₁₂O₄₂)]·16H₂O	10.799 (2), 11.914 (2), 13.377 (3); 70.18 (3), 68.07 (3), 64.80 (3)	1410.9 (5), 1, P1	Na₂[W₁₂O₄₀(OH)₂]; 12:2; 3.5	Li et al. (2009)
\ [{Na₂(µ-H₂O)₂(H₂O)₆}{Cu(H₂O)₂}{Cu(H₂O)₄}₂\ {Cu₂(µ-OH)₂(H₂O)₆}(H₂W₁₂O₄₂)]·10H₂O	10.697 (5), 12.921 (5), 13.653 (5); 73.608 (5), 75.671 (5), 67.748 (5)	1654.4 (12), 1, P1	(NH₄)₆[W₁₂O₄₀]; 12:0.4; 6.2	Kong et al. (2010)
\ [{Na(H₂O)₄}₂{Cu_0.5(H₂O)}₄{Cu_0.5(H₂O)_1.5}₂\ (H₄W₁₂O₄₂)]?3H₂O	10.7060 (11), 12.7124 (14), 13.1664 (14); 113.7600 (10), 90.8230 (10), 111.8290 (10)	1493.8 (3), 1, P1	Na₂WO₄; 12:3; 6.5	Gao et al. (2011)
[Na₂(H₂O)₁₀][Cu₄(H₂O)₁₂(H₂W₁₂O₄₂)]·15H₂O	10.1535 (2), 13.2118 (3), 13.7049 (5); 112.692 (3), 94.771 (3), 102.969 (2)	1623.15 (8), 1, P1	Na₂WO₄; 12:36; 4	Qu et al. (2012)
Cu₃(H₂O)₈[H₆W₁₂O₄₂]	10.6753 (5), 12.7814 (5), 13.0976 (5); 113.737 (4), 90.433 (3), 112.560 (4)	1482.73 (12), 2, P1	(NH₄)₆[W₁₂O₄₀]; 12:36; –	Chen et al. (2017)
(NH₄)₈[Cu(H₂O)₂H₂W₁₂O₄₂]·10H₂O	14.278 (5), 15.435 (5), 24.881 (5); 90, 90, 90	5483 (3), 2, Pbcn	(NH₄)₆[W₁₂O₄₀]; 12:2.5; 4.8	Zhang (2012)
Na₂Cu₃(CuOH)₂[W₁₂O₄₀(OH)₂].32H₂O	10.6836 (4), 12.9066 (6), 13.6475 (5); 73.561 (4), 67.666 (4)	1648.68 (12), 1, P1	Na₂WO₄; 12:7.5; –	Radio et al. (2014)
Na₂Cu₅(H₂O)₂₄(OH)₂[H₂W₁₂O₄₂]·10H₂O	10.7140 (8), 12.9476 (9), 13.6696 (10); 73.56, 75.73, 67.69	1661.8 (2), 1, P1	Na₂WO₄; 12:20; 3.8	Qu et al., 2015

Selected bond length and angles (Å, °) in Na₅Fe_2.5paraB and Na₃Cu₄paraBM top

	Na₅Fe_2.5paraB	Na₃Cu₄paraB
W═O_t	1.719 (4)-1.797 (4)	1.710 (8)–1.780 (7)
W—O_db1	1.888 (4)–2.050 (2)	1.872 (7)–2.103 (7)
W—O_db2	1.826 (3)–2.166 (3)	1.805 (7)–2.098 (7)
W—O_tb1	2.201 (3)–2.297 (3)	2.207 (7)–2.273 (7)
W—O_tb2	1.895 (4)–2.259 (4)	1.882 (8)–2.287 (7)
W···W (between corner-sharing WO₆)	3.649 (4)–3.878 (5)	3.377 (4)–3.688 (2)
W···W (between edge-sharing WO₆)	3.273 (4)–3.352 (4)	3.306 (2)–3.377 (3)
M^II—O (M = Fe or Cu)	2.087 (4)–2.169 (4)	1.918 (7)–2.366 (8)
Na^I—O	2.302 (11)–2.606 (11)	2.345 (9)–2.519 (13)
O—W—O	70.73 (14)–104.38 (17)	154.94 (15)–177.56 (16)
	70.2 (3)–105.6 (3)	152.8 (3)–178.1 (3)

Acknowledgements

The authors are grateful to Assistant Professor Dr P. Unfried for support with the TGA and to Associate Professor K. Richter and M. Andraghetti for help with PXRD measurements at the Department of Inorganic Chemistry, University of Vienna. We thank RNDr Marek Bujdoš, PhD, for support with the ICP–MS and AAS analysis at the Institute of Laboratory Research on Geomaterials, Comenius Univiversity in Bratislava. We wish to thank E. Al-Sayed, MSc, and Dr J. Breibeck for valuable discussions regarding this work.

Funding information

Funding for this research was provided by: Austrian Science Fund (award No. M2203 to N. Gumerova; award No. P27534 to A. Rompel).

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