Crystal structure of hexa­chloro­thallate within a caesium chloride–phospho­tungstate lattice Cs9(TlCl6)(PW12O40)2·9CsCl

Deblonde, G.; Colliard, I.

doi:10.1107/S2056989024005565

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Volume 80| Part 7| July 2024| Pages 721-724

https://doi.org/10.1107/S2056989024005565

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Crystal structure of hexachlorothallate within a caesium chloride–phosphotungstate lattice Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl

Gauthier Deblonde ^a and Ian Colliard ^a ^*

^aPhysical and Life Sciences Directorate, Glenn T. Seaborg Institute, Lawrence Livermore National Laboratory, Livermore, California 94550, USA
^*Correspondence e-mail: colliard1@llnl.gov

Edited by Y. Ozawa, University of Hyogo, Japan (Received 16 April 2024; accepted 10 June 2024; online 14 June 2024)

Crystal formation of caesium thallium chloride phosphotungstates, Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl showcases the ability to capture and crystallize octahedral complexes via the use of polyoxometalates (POMs). The large number of caesium chlorides allows for the POM [α-PW₁₂O₄₀]³⁻ to arrange itself in a cubic close-packing lattice extended framework, in which the voids created enable the capture of the [TlCl₆]³⁻ complex.

Keywords: crystal structure; polyoxometalates; thallium; extended framework.

CCDC reference: 2361833

1. Chemical context

The Keggin ion, [α-XW₁₂O₄₀]ⁿ⁻ (X = B, Si, P, Ga, Ge, etc.), along with many other polyoxometalates (POMs), are renowned for their ability to lose [WO_x] moieties, yielding lacunary POMs (Pope, 1983 ). These lacunary derivatives of the Keggin, [XW₁₁O₃₉]ⁿ⁻, [XW₁₀O₃₆]ⁿ⁻, and [XW₉O₃₄]ⁿ⁻, have been extensively studied as chelators for metal ions, in which they directly bind to cations, for example trivalent lanthanides and actinides (Wang et al., 2024 ). Recently, crystallization of microgram quantities of the radioactive element curium (Cm³⁺) with [XW₁₁O₃₉]ⁿ⁻, showcased the utility of the POM chelators (Colliard et al., 2022 ). However, not all metal ions have been able to coordinate to lacunary Keggin derivatives. In particular, some metals form highly stable complexes with smaller ions, like chlorides, impeding their potential interactions with POM chelators. As such, a new method to capture metal ions has been developed where the metal of choice can be captured in the lattice arrangement of the parent Keggin ion, [α-XW₁₂O₄₀]ⁿ⁻, instead of direct interaction with lacunary Keggin ion ([XW₁₁O₃₉]ⁿ⁻). This allows for the POM-induced crystallization of the halide metal complex.

2. Structural commentary

This new crystal that incorporates thallium(III) into a caesium chloride and phosphotungstates lattice is fully formulated as Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl and crystallizes in the cubic space group Fm $[\overline{3}]$ m with a volume of 12,166.8 (4) Å³, Fig. 1. The crystal features the parent Keggin structure, [α-PW₁₂O₄₀]³⁻, which arises from the successive hydrolysis and condensation reactions of [WO₄]²⁻ in the presence of [PO₄]³⁻ ions as the pH is lowered (ca lower than 7). Briefly, twelve octahedral [WO₆] units can be grouped into four trimer sets [W₃O₁₃]⁸⁻. Each trimer is linked by the central phosphate anion and then to each other, keeping the overall tetrahedral symmetry of the central [PO₄]³⁻. The W—O bond lengths are all consistent with reported values for other POMs (Pope, 1983): W—OPO₃ of 2.347 (8) Å, W—O in the range 1.918 (2)–1.942 (4) Å and W=O of 1.713 (10) Å. The asymmetric unit that describes the Keggin ion is thus represented by the tungsten (W1), oxygen (O1, O2, O3, and O4), and phosphorous (P1) atoms. The tetrahedral symmetry of the Keggin ion thus arises from the tetrahedral symmetry of the central phosphate ion (atoms P1/O1–O4). Atom P1 is on the Wyckoff site 8c, corresponding to $[\overline{4}]$ m3 symmetry, which then extends to O4 with a Wyckoff site of 32f with a symmetry of ·3m. The remaining atoms W1, O1, O2, and O3 thus arrange themselves with the same tetrahedral symmetry, however, now with a Wyckoff site symmetry of ··m. The structure further features the sixfold coordinate Tl³⁺ ion, making a [TlCl₆]³⁻ complex. The arrangement of the complex within the structure is discussed in the next section. Nevertheless, the asymmetric unit that describes the thallium complex is comprised of Tl1 and Cl1 and Wyckoff site symmetries of 4a and 24e, respectively. The symmetry around Tl1 i.e. Wyckoff site 4a is m $[\overline{3}]$ m, with Cl1 having 4mm symmetry. This results in an octahedral complex with six chlorides bound to Tl³⁺. However, the [TlCl₆]³⁻ ion features slightly longer bond lengths between Tl and Cl of 2.613 (12) Å compared to 2.423 Å in KTlCl₄ (ICSD 1527421; Glaser, 1980 ). What is unusual about the structure is the large excess of CsCl crystallizing – nine CsCl per [TlCl₆]³⁻ complex. The asymmetric unit only consists of two unique Cs atoms, Cs1 and Cs2 with Wyckoff sites of 48h and 24e, respectively. These caesium atoms can then thus be thought to coordinate to the other chlorides as well, Cl2, and Cl3. Nevertheless, the excess CsCl becomes significantly important when considering the relative arrangement of the two [PW₁₂O₄₀]³⁻ and the [TlCl₆]³⁻ complex, Fig. 2. All caesium counter-ions are nine-coordinated with Cs—O distances ranging 3.179 (10)–3.221 (7) Å and Cs—Cl ranging from 3.2081 (18)–4.139 (12) Å.

Figure 1
[Polyhedral representation of the Keggin ion, [α-PW₁₂O₄₀]³⁻ (left), and [TlCl₆]³⁻ (right). W in maroon, O in red, P in blue, Cl in green and Tl in brown, with excess CsCl omitted for clarity]

Figure 2
Ball-and-stick representation of [α-PW₁₂O₄₀]³⁻ and [TlCl₆]³⁻, showcasing the connectivity with the excess CsCl. W in maroon, O in red, P in blue, Cl in green and Tl in brown.

3. Supramolecular features

The supramolecular assembly of the crystal is particularly interesting and departs from the typical structures observed with the Keggin ion. The [PW₁₂O₄₀]³⁻ anion herein behaves like a super-atom. Super-atoms are nano-sized structures that mimic atomic behavior, in particular in the lattice formations (Colliard et al., 2020 ). In this structure, the [PW₁₂O₄₀]³⁻ anion can be thought to arrange itself in a cubic close packing within the unit cell. The Wyckoff letter of P1 (8c) and the single phosphorous per Keggin reveals there are eight Keggin ions per unit cell, which is consistent with the face-centered cubic space group Fm $[\overline{3}]$ m. Caesium counter-ions link all the [PW₁₂O₄₀]³⁻ anions together, forming an extended framework. As a result of this close cubic packing, the octahedral [TlCl₆]³⁻ ions can fill in the octahedral voids left by the cubic close packing of the Keggin ions. Since the synthesis conditions were limited to a 1:2 ratio of Tl³⁺ to [PW₁₂O₄₀]³⁻, the [TlCl₆]³⁻ only fills half of the octahedral voids, Fig. 3.

Figure 3
Ball-and-stick representation of the unit cell viewed along (111) showing the cubic close packing of [α-PW₁₂O₄₀]³⁻ by additionally overlapping the blue spheres to see the ABC layers. The [TlCl₆]³⁻ ion thus fills half the octahedral voids. W in maroon, O in red, P in blue, Cl in green and Tl in brown.

4. Database survey

A search of the Cambridge Crystallographic Database (CSD, accessed in April 2024; Groom et al., 2016 ) was performed for closely related thallium caesium phosphotungstates. First, in a unit-cell search [a = b = c = 22.9999 (4) Å, and α = β = γ = 90°, with tolerance of 2% each], with face centering, 29 results were found, none of which contained any tungstates or thallium. With a primitive centering, 95 results were found, again none of which contained any tungstates or thallium. Therefore, a second search was conducted based on the general formula TlPW₁₂O₄₀ with the option to allow other elements in the molecule and no results were obtained. As such, the search was expanded to another formula search for any structures with W, O, and Tl, none of which consisted of phosphotungstates and/or thallium compounds. Only one compound containing K, W, O, and Tl was found, but this additionally contains uranium and is not comprised of the Keggin structure (Balboni & Burns, 2014 ).

5. Synthesis and crystallization

All materials herein were purchased and used as is, with no need for further purification: NaCl (≥99.9%), NaCH₃COO (≥99.9%), caesium chloride (>99.99%), Na₂WO₄·2H₂O (≥99%), phosphoric acid, and thallium trichloride (>99.9%) were purchased from chemical providers (VWR and Millipore Sigma) and used as received. All solutions were prepared using deionized water purified by reverse osmosis cartridge system (>= 18.2 MΩ.cm). All experiments were performed in a temperature-controlled room (22°C). Na₉PW₉O₃₄·7H₂O was prepared by dissolving 12 g of Na₂WO₄·2H₂O in 15 mL of H₂O. 0.4 mL of 85% H₃PO₄ was added dropwise. Afterwards the pH was adjusted to 7–7.5 with glacial acetic acid (2.25 mL). During the addition, a white solid formed immediately. The solid-solution slurry was left to stir for an hour, after which the solid was filtered under vacuum. [PW₉O₃₄]⁹⁻ converts to [PW₁₁O₃₉]⁷⁻ instantaneously at pH 5.5 (Contant et al., 1990 ). A thallium(III) nitrate solution was prepared by dissolving the corresponding Tl(NO₃)₃ in 0.1 M HCl. After this, the Tl³⁺ solution was added to a 1 mL 200 µM Na₉PW₉O₃₄·7H₂O solution in 0.1 M acetate buffer at pH 5.5 at a 1:2 stoichiometry. For crystallization, 6 M CsCl was titrated in 5–50 µL to 1:2 stochiometric solutions (10 to 100 µL, at pH 5.5, 100 mM acetate buffer) with a final pH of 5.5 during crystallization. After 1–5 days at ambient conditions, several cube-shaped single crystals of PW₁₂-TlCsCl were visible to the naked eye. XRD-quality crystals were then mounted and characterized, while the rest were characterized through Raman microscopy. Raman spectra were collected using a Senterra II confocal Raman microscope (Bruker), equipped with high resolution gratings (1200 lines mm⁻¹) and a 532 nm laser source (operated at 15 mW), and a TE-cooled CCD detector. Reported spectra are the average of at least 2–5 different spots per sample, each spot analysis consisting of 2 binned 16 scans. The integration time was set to 2000 ms per scan. No damage to the sample was observed due to the laser irradiation. Infrared spectra were collected using a Cary 630 FTIR instrument (Agilent Technologies) equipped with an attenuated total reflectance (diamond ATR) cell. Selected Raman data (cm⁻¹): ν(W=O^t) 961, and ν(O—W—O) 246, 156, and 91; selected IR data (cm⁻¹): 1157, 1118, 922, and 782 (Fig. 4).

Figure 4
Solid-state Raman and IR (inset) spectra for Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl with H₃PW₁₂O₄₀ as a comparison.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All atoms were refined anisotropically. The only issue resulting from the high Z for tungsten and Cs was that high residual Q-peaks of 10% of Z A⁻³ remained (Massa & Gould, 2004 ); the highest residual Q-peak at 3.9 located at (½, ½, ½) could not reasonably be assigned to any of the elements already present (or those present during synthesis).

Table 1
Experimental details

Crystal data
Chemical formula	Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl
M_r	17765.68
Crystal system, space group	Cubic, Fm $[\overline{3}]$ m
Temperature (K)	298
a (Å)	22.9963 (3)
V (Å³)	12161.1 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	29.66
Crystal size (mm)	0.10 × 0.09 × 0.07

Data collection
Diffractometer	Rigaku Oxford Diffraction, Synergy Custom DW system, Pilatus 300K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.702, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6187, 977, 923
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.747

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.20
No. of reflections	977
No. of parameters	47
Δρ_max, Δρ_min (e Å⁻³)	3.92, −4.62
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2361833

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005565/ox2004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005565/ox2004Isup2.hkl

checkCIF report

Computing details top

Caesium thallium chloride phosphotungstate top

Crystal data top

Cs₉(TlCl₆)(PW₁₂O₄₀)₂·9CsCl	Mo Kα radiation, λ = 0.71073 Å
M_r = 17765.68	Cell parameters from 3426 reflections
Cubic, Fm3m	θ = 3.8–31.4°
a = 22.9963 (3) Å	µ = 29.66 mm⁻¹
V = 12161.1 (4) Å³	T = 298 K
Z = 2	Cube, clear colourless
F(000) = 15088	0.10 × 0.09 × 0.07 mm
D_x = 4.852 Mg m⁻³

Data collection top

Rigaku Oxford Diffraction, Synergy Custom DW system, Pilatus 300K diffractometer	923 reflections with I > 2σ(I)
Detector resolution: 5.8140 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 32.1°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −19→33
T_min = 0.702, T_max = 1.000	k = −18→31
6187 measured reflections	l = −30→33
977 independent reflections

Refinement top

Refinement on F²	47 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0429P)² + 1815.4844P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.116	(Δ/σ)_max = 0.001
S = 1.20	Δρ_max = 3.92 e Å⁻³
977 reflections	Δρ_min = −4.62 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
W1	0.35861 (2)	0.64139 (2)	0.74467 (2)	0.01874 (18)
Tl1	0.500000	0.500000	1.000000	0.0431 (8)
Cs1	0.34865 (6)	0.500000	0.84865 (6)	0.0432 (4)
Cs2	0.500000	0.500000	0.70636 (17)	0.0628 (8)
P1	0.250000	0.750000	0.750000	0.0151 (19)
Cl2	0.250000	0.500000	0.750000	0.049 (2)
Cl1	0.500000	0.500000	0.8864 (5)	0.057 (3)
O2	0.3797 (4)	0.7015 (3)	0.7985 (3)	0.0178 (16)
O3	0.3161 (3)	0.6010 (4)	0.6839 (3)	0.0213 (18)
O1	0.4101 (3)	0.5899 (3)	0.7606 (4)	0.028 (2)
O4	0.2910 (3)	0.7090 (3)	0.7090 (3)	0.013 (3)
Cl3	0.3672 (9)	0.500000	0.6328 (9)	0.061 (9)	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.0172 (2)	0.0172 (2)	0.0219 (3)	0.00357 (17)	−0.00094 (12)	0.00094 (12)
Tl1	0.0431 (8)	0.0431 (8)	0.0431 (8)	0.000	0.000	0.000
Cs1	0.0501 (6)	0.0295 (7)	0.0501 (6)	0.000	−0.0033 (7)	0.000
Cs2	0.0426 (8)	0.0426 (8)	0.103 (3)	0.000	0.000	0.000
P1	0.0151 (19)	0.0151 (19)	0.0151 (19)	0.000	0.000	0.000
Cl2	0.065 (4)	0.016 (3)	0.065 (4)	0.000	0.013 (5)	0.000
Cl1	0.060 (4)	0.060 (4)	0.051 (6)	0.000	0.000	0.000
O2	0.016 (4)	0.019 (2)	0.019 (2)	−0.003 (2)	0.003 (2)	0.002 (3)
O3	0.024 (3)	0.016 (4)	0.024 (3)	0.001 (2)	0.004 (4)	−0.001 (2)
O1	0.027 (3)	0.027 (3)	0.029 (5)	0.010 (4)	0.001 (3)	−0.001 (3)
O4	0.013 (3)	0.013 (3)	0.013 (3)	0.000 (3)	0.000 (3)	0.000 (3)
Cl3	0.078 (14)	0.025 (11)	0.078 (14)	0.000	0.034 (17)	0.000

Geometric parameters (Å, º) top

W1—Cs1	4.0425 (8)	Cs1—O2ⁱⁱ	3.211 (9)
W1—Cs1ⁱ	4.0425 (8)	Cs1—O1	3.221 (7)
W1—O2ⁱⁱ	1.918 (2)	Cs1—O1ⁱⁱ	3.221 (7)
W1—O2	1.918 (2)	Cs1—O1^x	3.221 (7)
W1—O3	1.942 (4)	Cs1—O1^ix	3.221 (7)
W1—O3ⁱⁱⁱ	1.942 (4)	Cs2—Cl1	4.139 (12)
W1—O1	1.713 (10)	Cs2—O1^x	3.179 (10)
W1—O4	2.347 (8)	Cs2—O1	3.179 (10)
Tl1—Cl1^iv	2.613 (12)	Cs2—O1^xi	3.179 (10)
Tl1—Cl1^v	2.613 (12)	Cs2—O1^xii	3.179 (10)
Tl1—Cl1^vi	2.613 (12)	Cs2—Cl3^xiii	3.492 (9)
Tl1—Cl1	2.613 (12)	Cs2—Cl3	3.492 (9)
Tl1—Cl1^vii	2.613 (12)	Cs2—Cl3^xii	3.492 (9)
Tl1—Cl1^viii	2.613 (12)	Cs2—Cl3ⁱⁱⁱ	3.492 (9)
Cs1—Cl2	3.2081 (18)	P1—O4	1.633 (14)
Cs1—Cl1^v	3.587 (3)	P1—O4^xiv	1.633 (14)
Cs1—Cl1	3.587 (3)	P1—O4^xv	1.633 (14)
Cs1—O2^ix	3.211 (9)	P1—O4^xvi	1.633 (14)

Cs1ⁱ—W1—Cs1	75.01 (5)	O1^x—Cs1—O1ⁱⁱ	164.5 (3)
O2ⁱⁱ—W1—Cs1	51.2 (3)	O1^ix—Cs1—O1ⁱⁱ	79.9 (3)
O2ⁱⁱ—W1—Cs1ⁱ	102.2 (3)	Cs1^xii—Cs2—Cs1	93.54 (8)
O2—W1—Cs1	102.2 (3)	Cs1ⁱ—Cs2—Cs1^xii	62.02 (5)
O2—W1—Cs1ⁱ	51.2 (3)	Cs1ⁱ—Cs2—Cs1	62.02 (5)
O2—W1—O2ⁱⁱ	87.0 (5)	Cl1—Cs2—Cs1^xii	46.77 (4)
O2—W1—O3	159.5 (3)	Cl1—Cs2—Cs1ⁱ	46.77 (4)
O2—W1—O3ⁱⁱⁱ	88.9 (4)	Cl1—Cs2—Cs1	46.77 (4)
O2ⁱⁱ—W1—O3	88.9 (4)	O1—Cs2—Cs1^xii	101.85 (18)
O2ⁱⁱ—W1—O3ⁱⁱⁱ	159.5 (3)	O1—Cs2—Cs1ⁱ	42.05 (13)
O2—W1—O4	85.2 (3)	O1^xi—Cs2—Cs1	101.84 (18)
O2ⁱⁱ—W1—O4	85.2 (3)	O1^xii—Cs2—Cs1	101.84 (18)
O3ⁱⁱⁱ—W1—Cs1ⁱ	90.7 (3)	O1—Cs2—Cs1	42.05 (13)
O3ⁱⁱⁱ—W1—Cs1	149.1 (2)	O1^xi—Cs2—Cs1ⁱ	42.05 (13)
O3—W1—Cs1	90.7 (3)	O1^x—Cs2—Cs1	42.05 (12)
O3—W1—Cs1ⁱ	149.1 (2)	O1^x—Cs2—Cs1ⁱ	101.85 (18)
O3ⁱⁱⁱ—W1—O3	87.9 (5)	O1^xii—Cs2—Cs1ⁱ	101.85 (18)
O3—W1—O4	74.4 (3)	O1^xi—Cs2—Cs1^xii	42.05 (12)
O3ⁱⁱⁱ—W1—O4	74.4 (3)	O1^xii—Cs2—Cs1^xii	42.05 (13)
O1—W1—Cs1	50.0 (2)	O1^x—Cs2—Cs1^xii	101.85 (18)
O1—W1—Cs1ⁱ	50.0 (2)	O1^x—Cs2—Cl1	66.9 (2)
O1—W1—O2	100.7 (4)	O1^xii—Cs2—Cl1	66.9 (2)
O1—W1—O2ⁱⁱ	100.7 (4)	O1—Cs2—Cl1	66.9 (2)
O1—W1—O3	99.9 (3)	O1^xi—Cs2—Cl1	66.9 (2)
O1—W1—O3ⁱⁱⁱ	99.9 (3)	O1—Cs2—O1^xi	81.15 (15)
O1—W1—O4	171.9 (4)	O1^xi—Cs2—O1^xii	81.15 (15)
O4—W1—Cs1	134.59 (15)	O1—Cs2—O1^xii	133.8 (4)
O4—W1—Cs1ⁱ	134.59 (15)	O1—Cs2—O1^x	81.15 (15)
Cl1^vi—Tl1—Cl1^vii	180.0	O1^xi—Cs2—O1^x	133.8 (4)
Cl1^v—Tl1—Cl1^iv	180.0	O1^x—Cs2—O1^xii	81.15 (15)
Cl1^v—Tl1—Cl1	90.000 (1)	O1^xi—Cs2—Cl3^xii	67.7 (4)
Cl1^vi—Tl1—Cl1^viii	90.000 (1)	O1^xi—Cs2—Cl3^xiii	139.38 (7)
Cl1^vii—Tl1—Cl1	90.000 (1)	O1^xii—Cs2—Cl3	139.38 (7)
Cl1^vi—Tl1—Cl1^v	90.000 (1)	O1^x—Cs2—Cl3^xii	139.38 (6)
Cl1^viii—Tl1—Cl1^iv	90.000 (2)	O1^xii—Cs2—Cl3^xiii	67.7 (4)
Cl1^vii—Tl1—Cl1^v	90.000 (3)	O1—Cs2—Cl3ⁱⁱⁱ	67.7 (4)
Cl1^vi—Tl1—Cl1	90.000 (1)	O1—Cs2—Cl3^xiii	139.38 (7)
Cl1^viii—Tl1—Cl1^v	90.000 (3)	O1^xi—Cs2—Cl3ⁱⁱⁱ	67.7 (4)
Cl1^viii—Tl1—Cl1	180.0	O1^x—Cs2—Cl3^xiii	67.7 (4)
Cl1^vi—Tl1—Cl1^iv	90.000 (3)	O1—Cs2—Cl3^xii	139.38 (7)
Cl1^iv—Tl1—Cl1	90.000 (1)	O1^xii—Cs2—Cl3^xii	67.7 (4)
Cl1^vii—Tl1—Cl1^iv	90.000 (1)	O1^x—Cs2—Cl3	67.7 (4)
Cl1^vii—Tl1—Cl1^viii	90.000 (1)	O1^x—Cs2—Cl3ⁱⁱⁱ	139.38 (7)
W1^ix—Cs1—W1^x	54.562 (17)	O1—Cs2—Cl3	67.7 (4)
W1—Cs1—W1^ix	135.56 (5)	O1^xi—Cs2—Cl3	139.38 (7)
W1—Cs1—W1^x	107.09 (3)	O1^xii—Cs2—Cl3ⁱⁱⁱ	139.38 (7)
Cl2—Cs1—W1^ix	67.78 (2)	Cl3—Cs2—Cs1^xii	165.7 (5)
Cl2—Cs1—W1^x	67.78 (2)	Cl3^xii—Cs2—Cs1	165.7 (5)
Cl2—Cs1—W1	67.78 (2)	Cl3—Cs2—Cs1	72.2 (5)
Cl2—Cs1—Cl1	148.99 (18)	Cl3^xiii—Cs2—Cs1^xii	109.4 (3)
Cl2—Cs1—Cl1^v	148.99 (18)	Cl3^xii—Cs2—Cs1ⁱ	109.4 (3)
Cl2—Cs1—O2^ix	59.49 (15)	Cl3ⁱⁱⁱ—Cs2—Cs1^xii	109.4 (3)
Cl2—Cs1—O2ⁱⁱ	59.49 (15)	Cl3ⁱⁱⁱ—Cs2—Cs1	109.4 (3)
Cl2—Cs1—O1	82.27 (15)	Cl3^xii—Cs2—Cs1^xii	72.2 (5)
Cl2—Cs1—O1^x	82.27 (15)	Cl3ⁱⁱⁱ—Cs2—Cs1ⁱ	72.2 (5)
Cl2—Cs1—O1ⁱⁱ	82.27 (15)	Cl3—Cs2—Cs1ⁱ	109.4 (3)
Cl2—Cs1—O1^ix	82.27 (15)	Cl3^xiii—Cs2—Cs1ⁱ	165.7 (5)
Cl1^v—Cs1—W1	124.07 (5)	Cl3^xiii—Cs2—Cs1	109.4 (3)
Cl1—Cs1—W1^x	95.05 (11)	Cl3—Cs2—Cl1	119.0 (5)
Cl1^v—Cs1—W1^ix	95.05 (11)	Cl3ⁱⁱⁱ—Cs2—Cl1	119.0 (5)
Cl1—Cs1—W1^ix	124.07 (5)	Cl3^xiii—Cs2—Cl1	119.0 (5)
Cl1—Cs1—W1	95.05 (11)	Cl3^xii—Cs2—Cl1	119.0 (5)
Cl1^v—Cs1—W1^x	124.07 (5)	Cl3ⁱⁱⁱ—Cs2—Cl3^xii	76.4 (4)
Cl1—Cs1—Cl1^v	62.0 (4)	Cl3—Cs2—Cl3ⁱⁱⁱ	76.4 (4)
O2^ix—Cs1—W1^x	27.76 (3)	Cl3—Cs2—Cl3^xiii	76.4 (4)
O2ⁱⁱ—Cs1—W1^ix	120.06 (13)	Cl3^xiii—Cs2—Cl3^xii	76.4 (4)
O2^ix—Cs1—W1	120.06 (13)	Cl3—Cs2—Cl3^xii	122.1 (10)
O2ⁱⁱ—Cs1—W1^x	120.06 (13)	Cl3^xiii—Cs2—Cl3ⁱⁱⁱ	122.1 (10)
O2ⁱⁱ—Cs1—W1	27.76 (3)	O4^xvi—P1—O4^xiv	109.471 (3)
O2^ix—Cs1—W1^ix	27.76 (3)	O4—P1—O4^xiv	109.471 (1)
O2^ix—Cs1—Cl1	115.80 (13)	O4^xiv—P1—O4^xv	109.471 (2)
O2^ix—Cs1—Cl1^v	115.80 (13)	O4—P1—O4^xv	109.5
O2ⁱⁱ—Cs1—Cl1^v	115.80 (13)	O4^xvi—P1—O4^xv	109.5
O2ⁱⁱ—Cs1—Cl1	115.80 (13)	O4—P1—O4^xvi	109.471 (6)
O2^ix—Cs1—O2ⁱⁱ	119.0 (3)	Cs1^xvii—Cl2—Cs1	180.0
O2^ix—Cs1—O1^ix	51.58 (18)	Tl1—Cl1—Cs1ⁱ	103.99 (18)
O2^ix—Cs1—O1	119.00 (17)	Tl1—Cl1—Cs1	103.99 (18)
O2ⁱⁱ—Cs1—O1^x	119.00 (17)	Tl1—Cl1—Cs1^xii	103.99 (18)
O2^ix—Cs1—O1ⁱⁱ	119.00 (17)	Tl1—Cl1—Cs1^vii	103.99 (18)
O2ⁱⁱ—Cs1—O1ⁱⁱ	51.58 (18)	Tl1—Cl1—Cs2	180.0
O2ⁱⁱ—Cs1—O1	51.58 (18)	Cs1^vii—Cl1—Cs1ⁱ	152.0 (4)
O2^ix—Cs1—O1^x	51.58 (18)	Cs1ⁱ—Cl1—Cs1^xii	86.65 (8)
O2ⁱⁱ—Cs1—O1^ix	119.00 (17)	Cs1—Cl1—Cs1ⁱ	86.65 (8)
O1—Cs1—W1^x	96.87 (16)	Cs1—Cl1—Cs1^vii	86.65 (8)
O1^ix—Cs1—W1	144.24 (15)	Cs1—Cl1—Cs1^xii	152.0 (4)
O1^x—Cs1—W1^x	24.05 (18)	Cs1^vii—Cl1—Cs1^xii	86.65 (8)
O1^ix—Cs1—W1^ix	24.05 (18)	Cs1—Cl1—Cs2	76.01 (18)
O1^ix—Cs1—W1^x	77.22 (18)	Cs1^xii—Cl1—Cs2	76.01 (18)
O1ⁱⁱ—Cs1—W1^x	144.24 (15)	Cs1^vii—Cl1—Cs2	76.01 (18)
O1ⁱⁱ—Cs1—W1^ix	96.87 (16)	Cs1ⁱ—Cl1—Cs2	76.01 (18)
O1—Cs1—W1	24.05 (18)	W1—O2—W1^xviii	150.0 (5)
O1^x—Cs1—W1	96.87 (16)	W1—O2—Cs1ⁱ	101.0 (3)
O1—Cs1—W1^ix	144.24 (15)	W1^xviii—O2—Cs1ⁱ	101.0 (3)
O1^x—Cs1—W1^ix	77.22 (18)	W1^xix—O3—W1	119.7 (4)
O1ⁱⁱ—Cs1—W1	77.22 (18)	W1—O1—Cs1ⁱ	105.9 (3)
O1^x—Cs1—Cl1^v	120.27 (19)	W1—O1—Cs1	105.9 (3)
O1—Cs1—Cl1	74.1 (2)	W1—O1—Cs2	144.6 (5)
O1^x—Cs1—Cl1	74.1 (2)	Cs1ⁱ—O1—Cs1	99.7 (3)
O1ⁱⁱ—Cs1—Cl1^v	74.1 (2)	Cs2—O1—Cs1	96.6 (2)
O1^ix—Cs1—Cl1	120.27 (19)	Cs2—O1—Cs1ⁱ	96.6 (2)
O1^ix—Cs1—Cl1^v	74.1 (2)	W1—O4—W1ⁱⁱⁱ	91.4 (4)
O1ⁱⁱ—Cs1—Cl1	120.27 (19)	W1^xix—O4—W1ⁱⁱⁱ	91.4 (4)
O1—Cs1—Cl1^v	120.27 (19)	W1—O4—W1^xix	91.4 (4)
O1ⁱⁱ—Cs1—O1	98.0 (4)	P1—O4—W1ⁱⁱⁱ	124.3 (3)
O1^ix—Cs1—O1^x	98.0 (3)	P1—O4—W1^xix	124.3 (3)
O1^x—Cs1—O1	79.9 (3)	P1—O4—W1	124.3 (3)
O1^ix—Cs1—O1	164.5 (3)	Cs2^xx—Cl3—Cs2	147.9 (10)

Cs1—W1—O1—Cs1ⁱ	−105.3 (5)	O3—W1—O1—Cs1	−82.6 (4)
Cs1ⁱ—W1—O1—Cs1	105.3 (5)	O3ⁱⁱⁱ—W1—O1—Cs2	−44.8 (3)
Cs1ⁱ—W1—O1—Cs2	−127.4 (2)	O3—W1—O1—Cs2	44.8 (3)
Cs1—W1—O1—Cs2	127.4 (2)	O4^xvi—P1—O4—W1^xix	180.000 (1)
O2—W1—O1—Cs1ⁱ	−8.2 (4)	O4^xv—P1—O4—W1	−60.000 (1)
O2—W1—O1—Cs1	97.1 (3)	O4^xv—P1—O4—W1^xix	60.000 (1)
O2ⁱⁱ—W1—O1—Cs1ⁱ	−97.1 (3)	O4^xiv—P1—O4—W1^xix	−60.000 (1)
O2ⁱⁱ—W1—O1—Cs1	8.2 (4)	O4^xvi—P1—O4—W1ⁱⁱⁱ	−60.000 (1)
O2ⁱⁱ—W1—O1—Cs2	135.5 (2)	O4^xiv—P1—O4—W1	180.000 (1)
O2—W1—O1—Cs2	−135.5 (2)	O4^xiv—P1—O4—W1ⁱⁱⁱ	60.000 (1)
O3ⁱⁱⁱ—W1—O1—Cs1	−172.1 (3)	O4^xv—P1—O4—W1ⁱⁱⁱ	180.000 (1)
O3—W1—O1—Cs1ⁱ	172.1 (3)	O4^xvi—P1—O4—W1	60.000 (2)
O3ⁱⁱⁱ—W1—O1—Cs1ⁱ	82.6 (4)

Symmetry codes: (i) y, −z+3/2, x+1/2; (ii) z−1/2, −x+1, −y+3/2; (iii) −y+1, z, −x+1; (iv) −z+3/2, −x+1, −y+3/2; (v) z−1/2, x, y+1/2; (vi) −y+1, −z+3/2, −x+3/2; (vii) y, z−1/2, x+1/2; (viii) −x+1, −y+1, −z+2; (ix) z−1/2, x, −y+3/2; (x) x, −y+1, z; (xi) −x+1, y, z; (xii) −x+1, −y+1, z; (xiii) −y+1, −z+1, −x+1; (xiv) −x+1/2, −y+3/2, z; (xv) −x+1/2, y, −z+3/2; (xvi) x, −y+3/2, −z+3/2; (xvii) −x+1/2, −y+1, −z+3/2; (xviii) −y+1, −z+3/2, x+1/2; (xix) −z+1, −x+1, y; (xx) −z+1, −x+1, −y+1.

Acknowledgements

We are grateful to the Lawrence Livermore National Laboratory (LLNL) and the Seaborg Institute (GTSI) for their continued support. Release number: LLNL-JRNL-862928.

Funding information

Funding for this research was provided by: U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry Program (contract No. DE-AC52-07NA27344).

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