Crystal structure of bis­[octa­kis­(di­methyl sulfoxide-κO)­ytterbium(III)] penta­bromido­plumbate(II) tribromide di­methyl sulfoxide monosolvate: a ytterbium-doped lead halide perovskite precursor

Kinoshita, T.; Fukumoto, K.; Segawa, H.

doi:10.1107/S2056989023002852

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ISSN: 2056-9890

Volume 79| Part 4| April 2023| Pages 402-405

https://doi.org/10.1107/S2056989023002852

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Crystal structure of bis[octakis(dimethyl sulfoxide-κO)ytterbium(III)] pentabromidoplumbate(II) tribromide dimethyl sulfoxide monosolvate: a ytterbium-doped lead halide perovskite precursor

Takumi Kinoshita,^a ^* Kanna Fukumoto ^b and Hiroshi Segawa ^a,^b

^aGraduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo, 153-8902, Japan, and ^bResearch Center for Advanced Science and Technology (RCAST), The University of, Tokyo 4-6-1, Komaba, Meguro-ku, Tokyo, 153-8904, Japan
^*Correspondence e-mail: utkino@mail.ecc.u-tokyo.ac.jp

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 15 March 2023; accepted 24 March 2023; online 31 March 2023)

A mixture of PbBr₂ and YbBr₃·nH₂O in a dimethyl sulfoxide (DMSO) solution yielded single crystals of a lead halide perovskite precursor with ytterbium, bis[octakis(dimethyl sulfoxide)ytterbium(III)]pentabromidoplumbate(II) tribromide with dimethyl sulfoxide as co-crystallite, [Yb(C₂H₆OS)₈][PbBr₅]_0.5Br_1.5·0.5C₂H₆OS. The complex ions PbBr₅³⁻ and Yb(DMSO)₈³⁺ are present in the crystal together with three Br⁻ ions and DMSO molecules. X-ray crystallography revealed that the Br⁻ ions in YbBr₃ are replaced by the solvent and bound to a Pb^II atom or remain free. The presence of PbBr₅³⁻ units, which are molecular ions with a square-pyramidal structure, is also observed. These single crystals react with a caesium chloride solution, exhibiting near-infrared (NIR) luminescence by visible photoexcitation, suggesting the formation of Yb³⁺-doped lead halide perovskites (CsPbBr_3-xCl_x·Yb³⁺).

Keywords: lead halide perovskite; ytterbium; photoluminescence; crystal structure.

CCDC reference: 2251523

1. Chemical context

Lead halide perovskite crystals have attracted considerable attention in the fields of solar cells and optoelectronics (Lee et al., 2012 ; Burschka et al., 2013 ; Fu et al., 2019 ). Lead halide perovskite crystals have been investigated extensively owing to their facile solution-phase fabrication, high energy-conversion efficiency, and characteristic photoresponse. Lead halide perovskites can easily be prepared by spin coating microcrystalline thin films in solution.

Highly polar solvents, such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), are used in fabricating perovskite thin films by solution processing. Typically, these solvents are removed by thermal annealing using a hot plate or air drying after spin coating, and crystal growth proceeds as the solvent becomes supersaturated. The crystal morphology and crystalline phase depend on the annealing temperature and treatment time (Tenailleau et al., 2019 ; Bi et al., 2014 ; Xiao et al., 2014 ; Jung et al., 2019 ). The morphology of perovskite films, such as the film thickness and grain boundaries, significantly affects the performance of solar cells. Complex formation between Pb atoms and solvent molecules in the perovskite precursor solution significantly influences the film morphology (Ozaki et al., 2017 ; Wakamiya et al., 2014 ; Ozaki et al., 2019 ). The addition of CH₃NH₃I dissolved in 2-propanol to 1D crystals displaced the DMF solvent, forming a 3D perovskite structure. The addition of CH₃NH₃I dissolved in 2-propanol to these 1D crystals suspended in DMF solvent forms a 3D perovskite structure (Wakamiya et al., 2014). The CH₃NH₃I-PbI₂-DMF intermediate formed by CH₃NH₃I addition was also observed during thermal annealing. DMF coordination with the intermediate is thought to be responsible for Ostwald ripening (Guo et al., 2016 ). Additionally, when DMSO was used as the solvent, a PbI₂-(DMSO)₂ complex was formed, in which DMSO was more strongly coordinated to PbI₂ than DMF (Miyamae et al., 1980 ).

Lead halide perovskite thin films have been investigated extensively for solar cells and various other fields, including optoelectronics. Recently, the efficient luminescence of rare-earth elements using a lead halide perovskite as an optical absorption antenna was reported by doping ytterbium into a 3D CsPbBr_xCl_3-x perovskite (Kroupa et al., 2018 ; Erickson et al., 2019 ). However, the crystal structure of lead halide perovskites doped with rare-earth elements and their mechanism of formation remains unclear. In this study, precursor single-crystals of a lead halide perovskite doped with rare-earth elements, bis[octakis(dimethyl sulfoxide)ytterbium(III)] pentabromidoplumbate(II) tribromide dimethyl sulfoxide solvate, were successfully prepared, and the structure of the precursor crystal was determined.

2. Structural commentary

The obtained structure exhibits an alternating sequence of PbBr₅³⁻ and 2[Yb(DMSO)₈]³⁺ units (Figs. 1 and 2). The [Yb(DMSO)₈]³⁺ unit is considered to possess three Br⁻ (Br3, Br4) ions as counter-anions. Interestingly, the PbBr₅³⁻ unit exhibits a square-pyramidal structure. Lead halide compounds often show lead-centered octahedral structures, and there have been no previous reports of the PbBr₅³⁻ molecular ion with a square-pyramidal geometry. The free atom Br3 is located on the straight line of the Br2—Pb1 bond, and the Pb1⋯Br3 distance is 6.781 (9) Å (Fig. 1). The free Br3 atom is located at a distance more than twice that of Br2 in the Pb1—Br2 bond [2.814 (4) Å], suggesting that there is no Pb1—Br3 interaction.

Figure 1
Arrangement of [Yb(DMSO)₈]³⁺, [PbBr₃]²⁻ and free Br⁻ anions in the precursor crystal, with displacement ellipsoids at the 50% probability level. The disordered DMSO molecule is omitted for clarity. Symmetry codes: (i) y, $[{1\over 2}]$ − x, z; (ii) $[{1\over 2}]$ − y, x, z; (iii) $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, z; (iv) $[{3\over 2}]$ − x, $[{1\over 2}]$ − y, z.

Figure 2
Perspective view of the precursor crystal structure along [100].

The DMSO molecule as co-crystallite is disordered, and the exact configuration was difficult to determine. Thermogravimetric analysis (TG–DTA) of the crystals revealed a weight loss of 3.4% at approximately 410 K, with an endothermic peak, corresponding to a dissociation of 0.5 equivalents of DMSO relative to Yb (theoretical value 3.1 wt%) (Fig. 3). The crystal structure resembles that of a 1D perovskite with a series of (PbX₅³⁻) units (Wang et al., 1995 ). However, the weak interactions between the Br⁻ ions and DMSO molecules in the gaps between the (PbX₅³⁻) units prevents the 1D perovskite from bridging. All halogen ions were lost when YbBr₃ was added, and DMSO is coordinated to the Yb^III atom instead. Several Br⁻ ions react with PbBr₂ to form PbBr₅³⁻, and therefore YbBr₃ has served as a source of halogen ions in the lead halide perovskite framework.

Figure 3
TG–DTA curves acquired under a nitrogen atmosphere.

3. Photophysical analysis

The precursor crystal did not exhibit any luminescence upon irradiation with visible light. In contrast, the dropwise addition of a methanol solution containing caesium chloride to the precursor crystals, followed by annealing at 473 K for 5 min, resulted in the formation of light-yellow microcrystals. The microcrystals exhibited Yb³⁺-derived near-infrared (NIR) emission at 980 nm upon photoexcitation at 400 nm (Fig. 4). This indicates that the precursor crystals reacted with caesium chloride, and Yb³⁺-doped 3D lead halide perovskite crystals (CsPbBr_3-xCl_x·Yb³⁺) (Erickson et al., 2019) were formed. The NIR luminescence of doped Yb³⁺ was observed, in addition to the visible-light absorption of the lead halide perovskite crystals.

Figure 4
Near-infrared emission from Yb³⁺ after treatment of the precursor crystals with a CsCl methanol solution.

4. Database survey

The Inorganic Crystal Structure Database (ICSD) (ICSD, 2023 ) did not include any closely related structures. For [Yb(DMSO)₈]³⁺ units, tetrakis[1,4-bis(phenylsulfinyl)butane]ytterbium(III) triperchlorate (Li et al., 2004 ) and catena-[octakis(dimethyl sulfoxide)ytterbium heptakis(dimethyl sulfoxide)ytterbium hexakis(μ₃-sulfido)dodecakis(μ₂-sulfido)hexasulfidohexasilverhexatungsten] (Zhang et al., 2011 ) are present in the database.

5. Synthesis and crystallization

PbBr₂ and YbBr₃·nH₂O were dissolved in DMSO (anhydrous, Fujifilm Wako Pure Chemicals) to prepare a 0.5 M solution. The solution was heated to 373 K using a hot plate; acetone was added gradually to obtain colourless needle-like crystals (Fig. 5).

Figure 5
Photographs of crystals in solution and of the single crystal used for the measurement.

6. Refinement

The crystal data, data collection, and structural refinement details are summarized in Table 1. Because the precursor crystals contain numerous heavy atoms, it was difficult to analyze the residual electrons of these atoms; therefore, an empirical absorption correction using spherical harmonics was applied. The residual electron densities Δρ_max and Δρ_min of 8.97 and −1.78 e Å⁻³ are located 0.912 and 0.918 Å, respectively, from the Pd atom. H atoms were positioned geometrically (C—H = 0.98 Å) and refined as riding with U_iso(H) = 1.5U_eq(C). Various atoms were refined with fixed occupancies: S5 (0.25) C9 (0.5) H9A (0.5) H9B (0.5) H9C (0.5).

Table 1
Experimental details

Crystal data
Chemical formula	[Yb(C₂H₆OS)₈][PbBr₅]_0.5Br_1.5·0.5C₂H₆OS
M_r	1260.36
Crystal system, space group	Tetragonal, P4/ncc
Temperature (K)	93
a, c (Å)	14.3940 (2), 40.6538 (8)
V (Å³)	8422.9 (3)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	16.57
Crystal size (mm)	0.50 × 0.36 × 0.04

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD. (2019). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Oxfordshire, England.]$ )
T_min, T_max	0.195, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23286, 4274, 3579
R_int	0.108
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.225, 1.08
No. of reflections	4274
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	8.97, −1.78
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD. (2019). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Oxfordshire, England.]$ ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2251523

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023002852/tx2065sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023002852/tx2065Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2019); cell refinement: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2019); data reduction: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2019); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Bis[octakis(dimethyl sulfoxide-κO)ytterbium(III)] pentabromidoplumbate(II) tribromide dimethyl sulfoxide monosolvate top

Crystal data top

[Yb(C₂H₆OS)₈][PbBr₅]_0.5Br_1.5·0.5C₂H₆OS	D_x = 1.988 Mg m⁻³
M_r = 1260.36	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, P4/ncc	Cell parameters from 8591 reflections
a = 14.3940 (2) Å	θ = 4.4–74.7°
c = 40.6538 (8) Å	µ = 16.57 mm⁻¹
V = 8422.9 (3) Å³	T = 93 K
Z = 8	Plate, colourless
F(000) = 4864	0.50 × 0.36 × 0.04 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3579 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.108
ω scans	θ_max = 74.9°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −16→17
T_min = 0.195, T_max = 1.000	k = −12→17
23286 measured reflections	l = −35→50
4274 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.080	H-atom parameters constrained
wR(F²) = 0.225	w = 1/[σ²(F_o²) + (0.152P)² + 25.6573P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
4274 reflections	Δρ_max = 8.97 e Å⁻³
203 parameters	Δρ_min = −1.78 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)
Pb1	0.250000	0.250000	0.50704 (2)	0.0340 (3)
Yb1	0.750000	0.250000	0.37362 (2)	0.0190 (3)
Br1	0.43356 (6)	0.34068 (6)	0.49553 (2)	0.0349 (3)
Br3	0.250000	0.250000	0.34023 (5)	0.0559 (6)
Br4	0.49813 (6)	0.50187 (6)	0.250000	0.0608 (7)
S4	0.54958 (13)	0.14251 (13)	0.40874 (5)	0.0303 (4)
S3	0.53965 (14)	0.27929 (16)	0.33522 (5)	0.0345 (5)
S2	0.76666 (17)	0.46366 (15)	0.33661 (5)	0.0377 (5)
S1	0.64007 (15)	0.41439 (19)	0.42370 (6)	0.0500 (7)
O3	0.6392 (4)	0.3125 (4)	0.33952 (15)	0.0344 (12)
O1	0.7248 (4)	0.3778 (4)	0.40597 (15)	0.0356 (12)
O4	0.6108 (4)	0.2258 (4)	0.40211 (14)	0.0284 (11)
O2	0.8176 (4)	0.3738 (4)	0.34489 (14)	0.0314 (12)
C7	0.4353 (5)	0.1886 (7)	0.4131 (2)	0.0363 (18)
H7A	0.435947	0.238849	0.429408	0.055*
H7B	0.393082	0.139411	0.420479	0.055*
H7C	0.414022	0.212997	0.391917	0.055*
C4	0.7484 (6)	0.4587 (9)	0.2931 (3)	0.048 (3)
H4A	0.807678	0.446497	0.281992	0.071*
H4B	0.723157	0.518084	0.285400	0.071*
H4C	0.704475	0.408721	0.287950	0.071*
O5	0.750000	0.750000	0.3018 (5)	0.100 (9)
C8	0.5663 (7)	0.1162 (8)	0.4512 (3)	0.050 (2)
H8A	0.628770	0.090851	0.454460	0.075*
H8B	0.520014	0.070349	0.458222	0.075*
H8C	0.559160	0.173003	0.464263	0.075*
C5	0.4723 (7)	0.3819 (8)	0.3353 (3)	0.052 (3)
H5A	0.476672	0.411699	0.356951	0.078*
H5B	0.407268	0.366359	0.330720	0.078*
H5C	0.495481	0.424428	0.318416	0.078*
C6	0.5276 (11)	0.2517 (8)	0.2925 (3)	0.060 (3)
H6A	0.532561	0.308699	0.279429	0.090*
H6B	0.466864	0.222907	0.288694	0.090*
H6C	0.576829	0.208406	0.285983	0.090*
C3	0.8528 (10)	0.5533 (7)	0.3366 (3)	0.065 (4)
H3A	0.888786	0.550183	0.357047	0.097*
H3B	0.822330	0.614034	0.335028	0.097*
H3C	0.894404	0.544800	0.317779	0.097*
C1	0.6579 (9)	0.3911 (13)	0.4651 (3)	0.080 (5)
H1A	0.659188	0.323712	0.468536	0.119*
H1B	0.607311	0.418331	0.478018	0.119*
H1C	0.717213	0.418025	0.472066	0.119*
C2	0.6643 (11)	0.5360 (10)	0.4257 (4)	0.095 (6)
H2A	0.731670	0.545755	0.425340	0.143*
H2B	0.638504	0.561609	0.446075	0.143*
H2C	0.636020	0.567247	0.406771	0.143*
S5	0.7808 (8)	0.7165 (8)	0.2655 (2)	0.0300 (17)	0.25
C9	0.684 (2)	0.686 (2)	0.2475 (5)	0.075 (11)	0.5
H9A	0.697334	0.666771	0.224902	0.113*	0.5
H9B	0.641419	0.739136	0.247289	0.113*	0.5
H9C	0.655988	0.634559	0.259618	0.113*	0.5
Br2	0.250000	0.250000	0.57625 (11)	0.0958 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0241 (3)	0.0241 (3)	0.0539 (5)	0.000	0.000	0.000
Yb1	0.0228 (3)	0.0217 (3)	0.0124 (4)	−0.00053 (15)	0.000	0.000
Br1	0.0260 (4)	0.0325 (5)	0.0460 (5)	−0.0026 (3)	−0.0052 (3)	0.0051 (3)
Br3	0.0723 (10)	0.0723 (10)	0.0233 (10)	0.000	0.000	0.000
Br4	0.0775 (10)	0.0775 (10)	0.0274 (8)	0.0460 (12)	0.0088 (6)	0.0088 (6)
S4	0.0305 (9)	0.0285 (8)	0.0320 (10)	−0.0019 (7)	0.0069 (7)	0.0006 (7)
S3	0.0304 (9)	0.0498 (11)	0.0235 (9)	−0.0071 (8)	−0.0053 (7)	0.0102 (9)
S2	0.0557 (12)	0.0316 (10)	0.0257 (10)	−0.0024 (8)	−0.0002 (9)	0.0059 (8)
S1	0.0289 (10)	0.0675 (15)	0.0536 (14)	0.0111 (9)	−0.0110 (9)	−0.0388 (12)
O3	0.027 (3)	0.043 (3)	0.033 (3)	−0.001 (2)	−0.006 (2)	0.010 (2)
O1	0.042 (3)	0.037 (3)	0.028 (3)	0.004 (3)	0.002 (3)	−0.010 (2)
O4	0.026 (3)	0.033 (3)	0.025 (3)	−0.006 (2)	0.003 (2)	0.008 (2)
O2	0.037 (3)	0.031 (3)	0.026 (3)	−0.001 (2)	−0.001 (2)	0.010 (2)
C7	0.021 (3)	0.050 (5)	0.038 (4)	−0.002 (3)	0.004 (3)	0.009 (4)
C4	0.044 (5)	0.065 (7)	0.035 (5)	0.001 (4)	−0.013 (4)	0.016 (5)
O5	0.137 (14)	0.137 (14)	0.026 (9)	0.000	0.000	0.000
C8	0.039 (5)	0.069 (6)	0.041 (5)	−0.005 (4)	0.005 (4)	0.027 (5)
C5	0.041 (5)	0.068 (7)	0.048 (6)	0.020 (5)	0.010 (4)	0.011 (5)
C6	0.088 (9)	0.063 (7)	0.030 (5)	−0.009 (5)	−0.015 (6)	−0.008 (4)
C3	0.099 (9)	0.042 (5)	0.053 (6)	−0.036 (6)	−0.018 (6)	0.013 (5)
C1	0.067 (7)	0.139 (13)	0.033 (5)	−0.054 (8)	0.013 (5)	−0.018 (7)
C2	0.088 (10)	0.074 (9)	0.124 (13)	0.039 (8)	−0.033 (9)	−0.066 (9)
S5	0.030 (7)	0.026 (7)	0.034 (4)	0.008 (2)	−0.006 (3)	0.005 (3)
C9	0.10 (2)	0.11 (2)	0.018 (9)	−0.06 (2)	0.002 (10)	−0.030 (11)
Br2	0.1033 (18)	0.1033 (18)	0.081 (3)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Pb1—Br1	2.9839 (9)	C7—H7A	0.9800
Pb1—Br1ⁱ	2.9840 (9)	C7—H7B	0.9800
Pb1—Br1ⁱⁱ	2.9840 (9)	C7—H7C	0.9800
Pb1—Br1ⁱⁱⁱ	2.9840 (9)	C4—H4A	0.9800
Pb1—Br2	2.814 (4)	C4—H4B	0.9800
Yb1—S3^iv	3.4324 (19)	C4—H4C	0.9800
Yb1—S3	3.4325 (19)	O5—S5	1.616 (18)
Yb1—S2^iv	3.432 (2)	C8—H8A	0.9800
Yb1—S2	3.432 (2)	C8—H8B	0.9800
Yb1—O3	2.297 (5)	C8—H8C	0.9800
Yb1—O3^iv	2.297 (5)	C5—H5A	0.9800
Yb1—O1	2.290 (6)	C5—H5B	0.9800
Yb1—O1^iv	2.290 (6)	C5—H5C	0.9800
Yb1—O4	2.341 (5)	C6—H6A	0.9800
Yb1—O4^iv	2.341 (5)	C6—H6B	0.9800
Yb1—O2^iv	2.342 (5)	C6—H6C	0.9800
Yb1—O2	2.342 (5)	C3—H3A	0.9800
S4—O4	1.512 (6)	C3—H3B	0.9800
S4—C7	1.783 (8)	C3—H3C	0.9800
S4—C8	1.784 (10)	C1—H1A	0.9800
S3—O3	1.521 (6)	C1—H1B	0.9800
S3—C5	1.767 (10)	C1—H1C	0.9800
S3—C6	1.790 (11)	C2—H2A	0.9800
S2—O2	1.525 (6)	C2—H2B	0.9800
S2—C4	1.792 (11)	C2—H2C	0.9800
S2—C3	1.789 (10)	S5—C9	1.63 (3)
S1—O1	1.511 (6)	C9—H9A	0.9800
S1—C1	1.734 (13)	C9—H9B	0.9800
S1—C2	1.786 (15)	C9—H9C	0.9800

Br1—Pb1—Br1ⁱⁱⁱ	161.96 (5)	O4—S4—C8	105.2 (4)
Br1ⁱ—Pb1—Br1ⁱⁱ	161.96 (5)	C7—S4—C8	96.1 (4)
Br1—Pb1—Br1ⁱ	88.591 (8)	O3—S3—Yb1	32.3 (2)
Br1ⁱⁱⁱ—Pb1—Br1ⁱⁱ	88.591 (8)	O3—S3—C5	104.7 (5)
Br1—Pb1—Br1ⁱⁱ	88.591 (8)	O3—S3—C6	105.8 (6)
Br1ⁱⁱⁱ—Pb1—Br1ⁱ	88.591 (8)	C5—S3—Yb1	125.8 (4)
Br2—Pb1—Br1ⁱⁱ	99.02 (3)	C5—S3—C6	97.8 (6)
Br2—Pb1—Br1	99.02 (3)	C6—S3—Yb1	120.0 (5)
Br2—Pb1—Br1ⁱⁱⁱ	99.02 (3)	O2—S2—Yb1	34.6 (2)
Br2—Pb1—Br1ⁱ	99.02 (3)	O2—S2—C4	104.8 (5)
S3^iv—Yb1—S3	125.90 (7)	O2—S2—C3	106.2 (5)
S2—Yb1—S3^iv	81.32 (5)	C4—S2—Yb1	112.8 (4)
S2^iv—Yb1—S3^iv	75.66 (5)	C3—S2—Yb1	134.0 (4)
S2—Yb1—S3	75.66 (5)	C3—S2—C4	97.5 (5)
S2^iv—Yb1—S3	81.32 (5)	O1—S1—C1	106.0 (6)
S2—Yb1—S2^iv	128.01 (8)	O1—S1—C2	101.9 (6)
O3^iv—Yb1—S3	112.72 (15)	C1—S1—C2	96.7 (8)
O3—Yb1—S3^iv	112.72 (15)	S3—O3—Yb1	126.9 (3)
O3^iv—Yb1—S3^iv	20.75 (15)	S1—O1—Yb1	133.0 (4)
O3—Yb1—S3	20.74 (15)	S4—O4—Yb1	134.8 (4)
O3^iv—Yb1—S2	92.18 (16)	S2—O2—Yb1	123.8 (3)
O3—Yb1—S2	55.45 (15)	S4—C7—H7A	109.5
O3^iv—Yb1—S2^iv	55.45 (15)	S4—C7—H7B	109.5
O3—Yb1—S2^iv	92.18 (16)	S4—C7—H7C	109.5
O3^iv—Yb1—O3	105.8 (3)	H7A—C7—H7B	109.5
O3—Yb1—O4^iv	146.6 (2)	H7A—C7—H7C	109.5
O3—Yb1—O4	76.3 (2)	H7B—C7—H7C	109.5
O3^iv—Yb1—O4^iv	76.3 (2)	S2—C4—H4A	109.5
O3^iv—Yb1—O4	146.6 (2)	S2—C4—H4B	109.5
O3—Yb1—O2	71.92 (18)	S2—C4—H4C	109.5
O3^iv—Yb1—O2^iv	71.92 (18)	H4A—C4—H4B	109.5
O3^iv—Yb1—O2	73.06 (19)	H4A—C4—H4C	109.5
O3—Yb1—O2^iv	73.05 (19)	H4B—C4—H4C	109.5
O1—Yb1—S3^iv	119.98 (17)	S4—C8—H8A	109.5
O1^iv—Yb1—S3	119.98 (17)	S4—C8—H8B	109.5
O1—Yb1—S3	91.31 (17)	S4—C8—H8C	109.5
O1^iv—Yb1—S3^iv	91.31 (17)	H8A—C8—H8B	109.5
O1—Yb1—S2^iv	163.81 (17)	H8A—C8—H8C	109.5
O1^iv—Yb1—S2^iv	62.82 (16)	H8B—C8—H8C	109.5
O1—Yb1—S2	62.82 (16)	S3—C5—H5A	109.5
O1^iv—Yb1—S2	163.81 (17)	S3—C5—H5B	109.5
O1—Yb1—O3^iv	140.5 (2)	S3—C5—H5C	109.5
O1^iv—Yb1—O3^iv	85.5 (2)	H5A—C5—H5B	109.5
O1—Yb1—O3	85.5 (2)	H5A—C5—H5C	109.5
O1^iv—Yb1—O3	140.5 (2)	H5B—C5—H5C	109.5
O1^iv—Yb1—O1	109.9 (3)	S3—C6—H6A	109.5
O1^iv—Yb1—O4	74.4 (2)	S3—C6—H6B	109.5
O1^iv—Yb1—O4^iv	72.5 (2)	S3—C6—H6C	109.5
O1—Yb1—O4	72.5 (2)	H6A—C6—H6B	109.5
O1—Yb1—O4^iv	74.4 (2)	H6A—C6—H6C	109.5
O1^iv—Yb1—O2^iv	75.0 (2)	H6B—C6—H6C	109.5
O1^iv—Yb1—O2	146.2 (2)	S2—C3—H3A	109.5
O1—Yb1—O2	75.0 (2)	S2—C3—H3B	109.5
O1—Yb1—O2^iv	146.2 (2)	S2—C3—H3C	109.5
O4^iv—Yb1—S3^iv	59.21 (14)	H3A—C3—H3B	109.5
O4^iv—Yb1—S3	164.14 (15)	H3A—C3—H3C	109.5
O4—Yb1—S3	59.21 (14)	H3B—C3—H3C	109.5
O4—Yb1—S3^iv	164.14 (15)	S1—C1—H1A	109.5
O4^iv—Yb1—S2	91.35 (15)	S1—C1—H1B	109.5
O4^iv—Yb1—S2^iv	114.21 (15)	S1—C1—H1C	109.5
O4—Yb1—S2^iv	91.35 (15)	H1A—C1—H1B	109.5
O4—Yb1—S2	114.22 (15)	H1A—C1—H1C	109.5
O4^iv—Yb1—O4	120.7 (3)	H1B—C1—H1C	109.5
O4^iv—Yb1—O2^iv	135.7 (2)	S1—C2—H2A	109.5
O4—Yb1—O2	135.7 (2)	S1—C2—H2B	109.5
O4^iv—Yb1—O2	77.2 (2)	S1—C2—H2C	109.5
O4—Yb1—O2^iv	77.2 (2)	H2A—C2—H2B	109.5
O2^iv—Yb1—S3^iv	92.66 (14)	H2A—C2—H2C	109.5
O2—Yb1—S3^iv	60.01 (15)	H2B—C2—H2C	109.5
O2—Yb1—S3	92.66 (14)	O5—S5—C9	104.8 (10)
O2^iv—Yb1—S3	60.00 (15)	S5—C9—H9A	109.5
O2—Yb1—S2^iv	119.48 (15)	S5—C9—H9B	109.5
O2^iv—Yb1—S2^iv	21.68 (15)	S5—C9—H9C	109.5
O2^iv—Yb1—S2	119.48 (15)	H9A—C9—H9B	109.5
O2—Yb1—S2	21.68 (15)	H9A—C9—H9C	109.5
O2—Yb1—O2^iv	120.2 (3)	H9B—C9—H9C	109.5
O4—S4—C7	105.1 (4)

C7—S4—O4—Yb1	−151.3 (5)	C6—S3—O3—Yb1	−121.5 (5)
C4—S2—O2—Yb1	−108.9 (5)	C3—S2—O2—Yb1	148.6 (5)
C8—S4—O4—Yb1	107.9 (5)	C1—S1—O1—Yb1	105.7 (6)
C5—S3—O3—Yb1	135.8 (5)	C2—S1—O1—Yb1	−153.7 (7)

Symmetry codes: (i) y, −x+1/2, z; (ii) −y+1/2, x, z; (iii) −x+1/2, −y+1/2, z; (iv) −x+3/2, −y+1/2, z.

Acknowledgements

The authors thank Dr Hiroyasu Sato (Rigaku) for his support with the structure analysis.

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. 18H02069); New Energy and Industrial Technology Development Organization.

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