Pb₅In₃Bi₅S₁₇ [Pb_4.94(3)In_3.05(3)Bi_4.99(3)S₁₇] and its structural relationship with Pb₄In₃Bi₇S₁₈

The title phase (penta­lead tri­indium penta­bismuth hepta­deca­sulfide) has been synthesized and structurally characterized. Its structure contains mixed Bi/In, In/Bi and Pb/In positions; all atoms lie on crystallographic mirror planes. The structural relationship between Pb₅In₃Bi₅S₁₇ and a phase known by the formula Pb₄In₃Bi₇S₁₈ is discussed. A comparatively large and complex structural `seed' is defined which is common to both phases. The structural changes within this seed when moving from one phase to the other are described by graphical means.

S1. Comment

In the first half of the 1980s, six different quaternary lead indium bismuth sulfides were synthesized (Reis, 1984), of which four have hitherto been fully characterized with respect to their structures (Krämer, 1983, 1986; Krämer & Reis, 1986; Reis et al., 2012); the other two have been structurally characterized only by the determination of lattice constants and space groups (Reis, 1984). In the course of an attempt to re-synthesize one of these two phases, a new quaternary phase was obtained, and this is described here. The new compound can chemically be described as Pb_4.94 (3)In_3.05 (3)Bi_4.99 (3)S₁₇. For sake of readability it is addressed as Pb₅In₃Bi₅S₁₇ in the following.

Like most of the related structurally known sulfides in this quaternary system and the corresponding sulfidic ternary subsystems, Pb₅In₃Bi₅S₁₇ adopts a structure with one of the unit vectors (b) being close to 4.0 Å. All atoms are distributed between the two layers y = 1/4 and y = 3/4. Fig. 1 shows a projection of the structure onto (010). The bond-length ranges for the different metal atoms (Table 2) are comparable with those known from the binary and ternary subsystem compounds and the other structurally known quaternary sulfides.

Atoms Pb2, Pb3 and Pb4 show an eightfold coordination, like the Pb atoms in Pb₅In_8.4Bi_1.6S₂₀ (Reis et al., 2012). If a distance of 3.748 (3) Å is interpreted as a Pb—S bond, then Pb1 would also be coordinated in this way; otherwise its coordination polyhedron is a distorted octahedron, which is rather unusual for Pb in compounds of this kind (Reis et al., 2012). The assignment of Pb to this metal position should anyway be correct, as indicated by bond-valence sum calculations (Table 2). Pb is also coordinated octahedrally in, for example, PbS (e.g. Ramsdell, 1925). Atoms Pb5F (see below), Bi and In are also coordinated octahedrally, with different degrees of distortion.

As can be seen from the `x' column of Table 2, all In positions have a certain amount of Bi mixed in, while three of the five Bi positions are mixed with a fraction of In, this fraction being very small in one case (Bi3F). `Mixed atoms' of the former kind have also been observed in the structures of Pb₅In_8.4Bi_1.6S₂₀ (Reis et al., 2012), Pb₄In₂Bi₄S₁₃ (Krämer, 1986) and Pb₄In₃Bi₇S₁₈ (Krämer & Reis, 1986). As both elements, Bi and In, carry a valence of +3, the occurrence of such mixed atoms seems chemically reasonable, even though there is an `isotopic' size (radius) difference (Keller & Krämer, 2006) of 0.21 Å between the two elements. As at most 21% of an atom of the respective other kind is mixed in (Table 2), the bond lengths should be affected by at most 0.04 Å. The mean Bi—S and, to a lesser degree, mean In—S bond lengths (Table 2) roughly show the expected behaviour.

Surprisingly, one Pb atom (Pb5F, valence +2) is also apparently mixed with In. The assignment of Pb (instead of Bi) to the corresponding position is strongly suggested by bond-valence sum calculations (Table 2). Pb/In mixing at an octahedrally coordinated position has also been observed in the compound Pb₃In_6.67S₁₃ (Ginderow, 1978), but with In being the dominant partner. Another hint that our assignment is correct will be given in more detail below.

The two-dimensional projection of the overall structure of Pb₅In₃Bi₅S₁₇ can be seen as a pattern composed of M₂S₂ quadrangles and M₃S₃ hexagons (M = metal; see also Reis et al., 2012) which are, when seen in three dimensions, the cross sections of one-dimensionally infinite columnar aggregates (like rods and ribbons) oriented parallel to b. In Fig. 2, quadrangles containing two Bi (or Bi_x/In_1-x) atoms are shaded dotted grey (blue in the electronic version of the journal), those with two Pb (or Pb_x/In_1-x) atoms are shaded dark grey and those containing two In_x/Bi_1-x atoms light grey (pink in the electronic version). The latter form two different motifs: isolated quadrangles flanked by two S₂Bi(In) units, and chains set up by three corner-sharing quadrangles, each chain flanked by two S₂Bi units. Isolated quadrangles of this kind have also been found in Bi_14.7In_10.3S₃₈ (Yin et al., 2010), while the chain motif is known from Bi₃In₅S₁₂ (Krämer, 1980), Pb_1.6In₈Bi₄S₁₉ (Krämer, 1983) and Pb₅In_8.4Bi_1.6S₂₀ (Reis et al., 2012). Bi(In) forms only one kind of motif composed of three edge-sharing quadrangles, for which we cannot find any prototype in this quaternary system or its subsystems. Pb and Pb(In) generate novel five-membered chains, of which the central three-membered parts occur in Pb₃In_6.67S₁₃ (Ginderow, 1978), and a different kind of five-membered complex, its shape reminiscent of a bow. Similarly shaped Pb complexes have been found (as central parts of slightly larger complexes) in Pb₆In₁₀S₂₁ (Krämer & Berroth, 1980), Pb_1.6In₈Bi₄S₁₉ (Krämer, 1983) and Pb₅In_8.4Bi_1.6S₂₀ (Reis et al., 2012). However, the distribution of the atoms between the two atomic layers perpendicular to b is different in these structures, such that the symmetry of a unique three-dimensional section (two atomic layers) is close to mm2, while it is 1 in Pb₅In₃Bi₅S₁₇. A very similar Bi `bow' complex of symmetry 1 is found in the structure of Bi_14.7In_11.3S₃₈ (Yin et al., 2010).

The Pb₅In₃Bi₅S₁₇ structure is related to the structure of Pb₄In₃Bi₇S₁₈ (Krämer & Reis, 1986); Fig. 3 shows a representation of this latter structure. The published formula [derived mainly by structure-analytical/geometric considerations (Krämer, 2011)] corresponds to a net positive charge of 1.5. In the quaternary phase system Pb–In–Bi–S and its ternary subsystems, a comparatively small number of other structures have been published with such `stoichiometrically unusual' chemical formulae. Besides two Pb–Bi–S structures (Takeuchi et al., 1974, 1979), these are Pb<sub>4</sub>In<sub>9</sub>S<sub>17</sub> (Ginderow, 1978; Arriortua et al., 1983), Bi<sub>3</sub>In<sub>4</sub>S<sub>10</sub>/Bi<sub>14.7</sub>In<sub>11.3</sub>S<sub>38</sub> (Yin et al., 2010) and Pb<sub>1.6</sub>In<sub>8</sub>Bi<sub>4</sub>S<sub>19</sub> (Krämer, 1983, but see also Reis et al., 2012). The corresponding formulae imply unusual oxidation states for the elements involved, for instance in Bi<sub>3</sub>In<sub>4</sub>S<sub>10</sub>/Bi<sub>14.7</sub>In<sub>11.3</sub>S<sub>38</sub> (Yin et al., 2010), where the Bi—Bi bonds indicate the occurrence of lower-valent Bi atoms. Such compounds, known also from other sulfidic phase systems, have been classified `complex sulfides' (Nowacki, 1969). However, by far the majority of structures in all these phase systems have been published under `stoichiometrically normal' formulae. Furthermore, the five quaternary Pb–In–Bi–S phases we have investigated so far (Reis et al., 2012, Topa & Keller, 2011), including the title compound, are also `stoichiometrically normal', as confirmed by analytical electron-microprobe results. If we therefore postulate that Pb₄In₃Bi₇S₁₈ (Krämer & Reis, 1986) should also be described by such a formula, this could be achieved by substituting two Bi atoms by (structure-analytically not distinguishable) Pb atoms to yield the formula Pb₆In₃Bi₅S₁₈. If, additionally, the three In atoms with site-occupancy factors greater than unity (Krämer & Reis, 1986) were interpreted as In_x/Bi_1-x pairs, the approximate result would be the `electrically neutral' formula Pb₆In_2.5Bi_5.5S₁₈.

In Fig. 3, we have introduced Pb in place of Bi for the two `Bi' atoms with coordination numbers greater than 6 (see also Reis et al., 2012). The corresponding atoms are indicated by asterisks (*), and the quadrangles (rectangles) formed by them are shaded medium grey (blue–grey in the electronic version). Note that, if we accept these replacements, the one-dimensionally infinite Pb motif (two-dimensionally infinite if seen in three dimensions) in Fig. 3 would contain a third form (also of symmetry 1) of a Pb bow complex (see above) in two different alternating orientations.

Whether or not the Bi/Pb replacements of Fig. 3 are correct, the following discussion is valid. In both Figs. 2 and 3, a large central section has been emphasized by very light grey (light green in the electronic version) and a dotted outline. While the patterns of the shaded quadrangles are rather different in the two figures, the two structures are in fact practically identical with respect to the observed types of atoms and their connectivity within these two central sections (possible `contamination' of Bi by In being neglected). In a layer of thickness b, each section contains 60 atoms, which is 100% (94% in Fig. 3) of the respective numbers of atoms per unit cell. If only lattice-translationally non-equivalent atoms are counted, the above figures become 40 atoms/67% (44 atoms/69% in Fig. 3). Thus, there is a comparatively large and complex common `seed' which is developed by the formation of appropriate interfaces and the application of two different translation lattices into the two different structures, such that the two unit cells of similar size (1477 versus 1582 ų) are not much larger than the seed itself. In Fig. 4, the two structures are superimposed such that the unit-cell centres coincide. The geometric changes within the central sections in the transition Pb₅In₃Bi₅S₁₇ → Pb₄In₃Bi₇S₁₈ become visible and give an idea of how flexible such a part of a sulfidic framework can be when exposed to a change in the external crystal field. The difference between the two structures originates, of course, in the difference in chemical composition. The close relationship between the structures is anticipated by the similarity of the stoichiometric coefficients in the two chemical formulae Pb₅In₃Bi₅S₁₇ and Pb₄In₃Bi₇S₁₈ (Pb₆In_2.5Bi_5.5S₁₈).

Finally, cComparing the two structures in more detail can give an additional hint that our assignment of a Pb(In) atom in Fig. 2 is correct. In Fig. 3 we have one Bi motif, emphasized by dotted grey (dotted blue in the electronic version), with a central linear ladder-like structure composed of seven edge-sharing (slightly distorted) rectangles. If the Pb(In) atoms were replaced by Bi(In) in Fig. 2, we would get a very similar Bi motif in this structure, also with a central ladder-like structure composed of seven edge-sharing quadrangles. However, the ladder would not be linear, because the central one of these quadrangles [at (1/2, y, 0)] differs substantially from a rectangle. In fact the (two-dimensional) S—Pb(In)—S angle in Fig. 2 (112°) is about 20° larger than the corresponding S—Bi—S angles in Fig. 3 (90±5°). Taking into account that the complete environments (all vicinal atoms) of the two corresponding quadrangles in Figs. 2 and 3 are identical, such a severe structural change would not be understandable if the Pb(In) position in Fig. 2 was actually also occupied by Bi or Bi(In) as in Fig. 3.

Related literature

For related literature, see: Advanced (2002); Arriortua et al. (1983); Ginderow (1978); Keller & Krämer (2006); Krämer (1980, 1983, 1986, 2011); Krämer & Berroth (1980); Krämer & Reis (1986); Nowacki (1969); Ramsdell (1925); Reis (1984); Reis et al. (2012); Spek (2009); Takeuchi et al. (1974, 1979); Topa & Keller (2011); Yin et al. (2010).

S2. Experimental

For the preparation of the reactants, PbS, In₂S₃, and Bi₂S₃, see Reis et al. (2012). The title phase was obtained via two variants (A and B, see Table 1) of the following procedure.

A mixture of PbS, In₂S₃, Bi₂S₃ and I₂ (the latter serving as a transport agent) was filled into a quartz ampoule of length L and internal diameter D (Table 1). The ampoule was sealed under vacuum and placed in a slanting fashion in a two-zone half-shell furnace with vertical arrangement of the two halves. The lower half, containing the reaction mixture, was heated to 823 K, the upper half to 753 K.

Variant A. After two weeks, a bunch of thin long black needles (about 35 mg) of the title compound had grown at the cooler end of the ampoule. One of the crystal needles obtained was used for the X-ray structure analysis. Two other crystal needles were chemically analysed using a JEOL Superprobe JXA-8600 electron microprobe, controlled by the Probe for Windows system of programs (Advanced MicroBeam, 2002), and operated at 25 kV and 20 nA with a beam diameter of 5 µm. Wavelength-dispersion data were collected using the following standards and emission lines: PbS (Pb Lα), InAs (In Lα), Bi₂S₃ (Bi Lα) and Sb₂S₃ (S Kα). The raw data were corrected using the on-line ZAF-4 procedure (Advanced MicroBeam, 2002). Averaged results for ten electron-probe analyses (five per crystal) are Pb 34.6 (1), In 12.1 (1), Bi 35.2 (2) and S 18.6 (1), total 100.4 (3) wt%. After reduction of all figures to sum to a total of 100%, this corresponds to the chemical formula Pb_4.90 (3)In_3.10 (3)Bi_4.95 (3)S₁₇ with a net charge of 0.0 (3) (for an explanation of the formula syntax, see Reis et al., 2012). In good agreement with these results, an atomic absorption spectroscopy (AAS) analysis of a 15 mg sample of the crystals yielded the following results: Pb 33.9, In 11.2 and Bi 34.3 wt%.

It should be noted that we were not able to synthesize the title phase a second time via variant A. However, we obtained it reproducibly by variant B (Table 1), for which the relative quantities of the binary sulfides had been calculated from the known composition of the compound.

Variant B. After one week, some crystal needles (about 15 mg) had grown in the cooler part of the ampoule. They showed an unknown powder diffractogram and were not investigated any further. In the hot part, a carpet of long thin black needles had grown on top of a bulk which had formed from the reaction mixture. Both the needles and the bulk showed the powder diffractogram of the title phase. Refined lattice parameters differed by less than 0.02 Å and 0.04° from those obtained from the sample synthesized by variant A.

S3. Refinement

Single-crystal data were collected from one of the crystals obtained via synthesis variant A (above). The reported lattice parameters were refined from powder diffraction data. After solving the structure by direct methods, refinement showed that seven of the 13 metal positions had site-occupancy factors (s.o.f.) differing significantly from 1. Of these, four comparatively electron-rich positions were initially modelled with Bi_x/In_1-x atom pairs, with the two atoms of each pair constrained to have the same coordinates and displacement coefficients. In Fig. 2, one of these positions is labelled as Bi(In). To the remaining three positions, In_x/Bi_1-x atom pairs were correspondingly assigned. In Fig. 2, one of these positions is labelled as In(Bi). The other five metal positions were tentatively modelled as three Pb atoms [coordination number (CN) = 8] and two Bi atoms (CN = 6). However, the results of the bond-valence sum calculations (Table 2) strongly suggested replacing one of the Bi atoms with a Pb atom (Pb1) and one of the Bi_x/In_1-x pairs with a Pb_x/In_1-x pair [Pb5F in Fig. 1 and Table 2; Pb(In) in Fig. 2].

In the final refinements, the reflections 001 and 101 were exluded, as they had been identified as outliers by checkCIF (Spek, 2009). Of the 24 unique minima < -2.5 e Å^-3 in the final ΔF map, two have S atoms as closest neighbours: minima of -2.95 and -2.55/ e Å^-3 at distances of 1.64 and 0.89 Å from S5 or S1, respectively. As a reason for this, we assume deficiencies in the numerical absorption correction, as these minima disappeared when an empirical absorption correction was applied.

From all refined stoichiometric x values (see above), the chemical formula Pb_4.94In_3.05Bi_5.02S₁₇ results. It corresponds to a net positive charge of 0.07 and has therefore been slightly modified to Pb_4.94 (3)In_3.05 (3)Bi_4.99 (3)S₁₇ (with a net charge of zero), such that all stoichiometric coefficients of the metal elements differ by 0.04 to 0.05 from those in the electron-microprobe formula (from which the standard deviations were transferred).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SCHAKAL 99 (Keller, 2004); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of Pb5In3Bi5S17, viewed along the b axis. Atoms and bonds in the layer further from the viewer are drawn paler. Some very long Pb—S bonds [3.748 (3) Å] are represented by dashed lines. Primed and double-primed atoms are generated by the symmetry codes (-x + 1, y + 1/2, -z + 1) and (-x + 1, y - 1/2, -z + 1), respectively.
	Fig. 2. The structure of Pb5In3Bi5S17. For the meaning of the dotted outline and the shading scheme, see the Comment.
	Fig. 3. The structure of Pb4In3Bi7S18 (Krämer & Reis, 1986). For the meaning of the asterisks (*), the dotted outline and the shading scheme, and for a possible alternative to the chemical formula, see the Comment.
	Fig. 4. A superposition of the two structures of Pb5In3Bi5S17 and Pb4In3Bi7S18. Atoms and bonds are drawn as shaded areas for the former and as outlines for the latter. Outlines of the central sections (see the Comment) are drawn dotted black (dotted grey).

pentalead triindium pentabismuth heptadecasulfide

Crystal data

Pb4.93In3.05Bi5.02S17	Z = 2
Mr = 2966.21	F(000) = 2485
Monoclinic, P21/m	Dx = 6.665 Mg m^−3
Hall symbol: -P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 23.030 (3) Å	θ = 2.7–30.0°
b = 3.985 (1) Å	µ = 61.33 mm^−1
c = 17.275 (5) Å	T = 293 K
β = 111.33 (1)°	Needle, black
V = 1476.8 (6) Å^3	0.16 × 0.03 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4880 independent reflections
Radiation source: fine-focus sealed tube	3979 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.111
ϕ and ω scans	θmax = 30.0°, θmin = 1.8°
Absorption correction: integration (SHELXTL; Sheldrick, 2008)	h = −32→32
Tmin = 0.127, Tmax = 0.399	k = −5→5
22185 measured reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0392P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 2.89 e Å^−3
4880 reflections	Δρmin = −3.52 e Å^−3
190 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00046 (4)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pb1	0.01997 (2)	0.7500	−0.10032 (3)	0.03032 (13)
Pb2	0.15779 (2)	0.7500	0.13368 (3)	0.02579 (12)
Pb3	0.56783 (2)	0.7500	0.32169 (3)	0.03025 (13)
Pb4	0.76656 (2)	0.7500	0.39855 (3)	0.03312 (13)
Pb5F	0.539891 (19)	0.7500	−0.06630 (3)	0.01984 (15)	0.935 (5)
In15	0.539891 (19)	0.7500	−0.06630 (3)	0.01984 (15)	0.065 (5)
Bi1	0.117697 (19)	0.2500	0.33441 (2)	0.01972 (11)
Bi2	0.347587 (18)	0.7500	−0.17130 (2)	0.01703 (10)
Bi3F	0.259481 (19)	0.2500	−0.01540 (2)	0.01885 (15)	0.987 (5)
In23	0.259481 (19)	0.2500	−0.01540 (2)	0.01885 (15)	0.013 (5)
Bi4F	0.155645 (19)	0.7500	−0.22435 (2)	0.01693 (15)	0.843 (5)
In24	0.155645 (19)	0.7500	−0.22435 (2)	0.01693 (15)	0.157 (5)
Bi5F	0.36842 (2)	0.7500	0.18968 (3)	0.01860 (16)	0.788 (5)
In25	0.36842 (2)	0.7500	0.18968 (3)	0.01860 (16)	0.212 (5)
In1F	0.42533 (3)	0.2500	0.45033 (4)	0.0178 (3)	0.944 (5)
Bi11	0.42533 (3)	0.2500	0.45033 (4)	0.0178 (3)	0.056 (5)
In2F	0.95377 (3)	0.7500	0.40838 (4)	0.0208 (3)	0.851 (5)
Bi12	0.95377 (3)	0.7500	0.40838 (4)	0.0208 (3)	0.149 (5)
In3F	0.27375 (3)	0.7500	0.39596 (4)	0.0174 (2)	0.804 (4)
Bi13	0.27375 (3)	0.7500	0.39596 (4)	0.0174 (2)	0.196 (4)
S1	−0.07193 (12)	0.7500	−0.03344 (16)	0.0194 (6)
S2	0.17626 (14)	0.7500	−0.04158 (19)	0.0251 (6)
S3	0.36533 (13)	0.7500	0.02027 (16)	0.0211 (6)
S4	0.56244 (13)	0.7500	0.14076 (17)	0.0220 (6)
S5	0.74707 (13)	0.7500	0.20787 (18)	0.0253 (7)
S6	0.92725 (14)	0.7500	0.24631 (18)	0.0238 (6)
S7	0.27728 (13)	0.2500	0.14278 (16)	0.0225 (6)
S8	0.46013 (13)	0.2500	0.22108 (16)	0.0226 (6)
S9	0.66474 (12)	0.2500	0.32775 (15)	0.0166 (5)
S10	0.86325 (13)	0.2500	0.38221 (15)	0.0189 (6)
S11	0.06758 (12)	0.7500	0.20872 (16)	0.0192 (6)
S12	0.21345 (13)	0.2500	0.28585 (16)	0.0219 (6)
S13	0.37132 (13)	0.7500	0.34800 (16)	0.0210 (6)
S14	0.53115 (12)	0.2500	0.43652 (15)	0.0168 (5)
S15	0.67203 (12)	0.7500	0.50365 (15)	0.0164 (5)
S16	0.81871 (12)	0.2500	0.55213 (15)	0.0177 (5)
S17	0.96822 (13)	0.7500	0.56430 (17)	0.0207 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0315 (3)	0.0251 (3)	0.0311 (2)	0.000	0.00742 (19)	0.000
Pb2	0.0273 (2)	0.0226 (3)	0.0264 (2)	0.000	0.00854 (17)	0.000
Pb3	0.0347 (3)	0.0246 (3)	0.0368 (2)	0.000	0.0194 (2)	0.000
Pb4	0.0317 (3)	0.0249 (3)	0.0384 (3)	0.000	0.0075 (2)	0.000
Pb5F	0.0185 (2)	0.0199 (3)	0.0223 (2)	0.000	0.00892 (16)	0.000
In15	0.0185 (2)	0.0199 (3)	0.0223 (2)	0.000	0.00892 (16)	0.000
Bi1	0.01830 (19)	0.0213 (2)	0.02050 (18)	0.000	0.00812 (15)	0.000
Bi2	0.01613 (19)	0.0185 (2)	0.01659 (17)	0.000	0.00614 (14)	0.000
Bi3F	0.0194 (2)	0.0194 (3)	0.01581 (19)	0.000	0.00409 (15)	0.000
In23	0.0194 (2)	0.0194 (3)	0.01581 (19)	0.000	0.00409 (15)	0.000
Bi4F	0.0164 (2)	0.0180 (3)	0.0156 (2)	0.000	0.00482 (15)	0.000
In24	0.0164 (2)	0.0180 (3)	0.0156 (2)	0.000	0.00482 (15)	0.000
Bi5F	0.0195 (2)	0.0214 (3)	0.0146 (2)	0.000	0.00597 (16)	0.000
In25	0.0195 (2)	0.0214 (3)	0.0146 (2)	0.000	0.00597 (16)	0.000
In1F	0.0137 (4)	0.0194 (5)	0.0203 (4)	0.000	0.0061 (3)	0.000
Bi11	0.0137 (4)	0.0194 (5)	0.0203 (4)	0.000	0.0061 (3)	0.000
In2F	0.0203 (4)	0.0204 (4)	0.0200 (4)	0.000	0.0056 (3)	0.000
Bi12	0.0203 (4)	0.0204 (4)	0.0200 (4)	0.000	0.0056 (3)	0.000
In3F	0.0143 (3)	0.0190 (4)	0.0186 (3)	0.000	0.0056 (2)	0.000
Bi13	0.0143 (3)	0.0190 (4)	0.0186 (3)	0.000	0.0056 (2)	0.000
S1	0.0170 (12)	0.0201 (15)	0.0195 (11)	0.000	0.0049 (10)	0.000
S2	0.0182 (13)	0.0229 (16)	0.0307 (14)	0.000	0.0046 (11)	0.000
S3	0.0202 (13)	0.0222 (16)	0.0207 (12)	0.000	0.0072 (10)	0.000
S4	0.0189 (12)	0.0217 (16)	0.0255 (13)	0.000	0.0079 (10)	0.000
S5	0.0171 (13)	0.0253 (17)	0.0313 (14)	0.000	0.0060 (11)	0.000
S6	0.0220 (13)	0.0240 (17)	0.0276 (13)	0.000	0.0119 (11)	0.000
S7	0.0221 (13)	0.0279 (17)	0.0192 (12)	0.000	0.0094 (10)	0.000
S8	0.0221 (13)	0.0260 (17)	0.0175 (11)	0.000	0.0046 (10)	0.000
S9	0.0177 (12)	0.0176 (14)	0.0148 (10)	0.000	0.0061 (9)	0.000
S10	0.0181 (12)	0.0246 (16)	0.0155 (11)	0.000	0.0079 (9)	0.000
S11	0.0166 (12)	0.0190 (15)	0.0212 (12)	0.000	0.0057 (9)	0.000
S12	0.0183 (12)	0.0327 (18)	0.0176 (11)	0.000	0.0098 (10)	0.000
S13	0.0239 (13)	0.0242 (16)	0.0137 (10)	0.000	0.0055 (9)	0.000
S14	0.0166 (11)	0.0200 (15)	0.0148 (10)	0.000	0.0070 (9)	0.000
S15	0.0154 (11)	0.0192 (14)	0.0131 (10)	0.000	0.0036 (9)	0.000
S16	0.0189 (12)	0.0196 (15)	0.0146 (10)	0.000	0.0060 (9)	0.000
S17	0.0189 (12)	0.0215 (16)	0.0254 (13)	0.000	0.0125 (10)	0.000

Bond lengths (Å)

Pb1—S1	2.755 (3)	In3F—S15^vi	2.6386 (16)
Pb1—S1^i	2.9546 (19)	In3F—S13	2.663 (3)
Pb1—S1^ii	2.9546 (19)	In3F—S12	2.7559 (19)
Pb1—S11^ii	2.9656 (19)	In3F—S12^iii	2.7559 (19)
Pb1—S11^i	2.9656 (19)	S1—Pb2^ii	2.8962 (18)
Pb1—S2	3.366 (3)	S1—Pb2^i	2.8962 (18)
Pb2—S11	2.821 (3)	S1—Pb1^i	2.9545 (19)
Pb2—S1^ii	2.8962 (18)	S1—Pb1^ii	2.9545 (19)
Pb2—S1^i	2.8962 (18)	S2—In23^iii	2.687 (2)
Pb2—S12^iii	3.174 (2)	S2—Bi3F^iii	2.687 (2)
Pb2—S12	3.174 (2)	S3—In15^v	2.847 (2)
Pb2—S2	3.207 (3)	S3—Pb5F^v	2.847 (2)
Pb2—S7^iii	3.354 (2)	S3—In15^iv	2.847 (2)
Pb2—S7	3.355 (2)	S3—Pb5F^iv	2.847 (2)
Pb3—S9^iii	2.965 (2)	S3—In23^iii	3.033 (2)
Pb3—S9	2.965 (2)	S3—Bi3F^iii	3.033 (2)
Pb3—S4	3.083 (3)	S4—Bi2^v	2.783 (2)
Pb3—S14^iii	3.137 (2)	S4—Bi2^iv	2.783 (2)
Pb3—S14	3.137 (2)	S4—In15^iv	2.996 (2)
Pb3—S8	3.163 (2)	S4—Pb5F^iv	2.996 (2)
Pb3—S8^iii	3.163 (2)	S4—In15^v	2.996 (2)
Pb3—S15	3.186 (2)	S4—Pb5F^v	2.996 (2)
Pb4—S9	2.980 (2)	S5—Bi2^iv	2.849 (2)
Pb4—S9^iii	2.980 (2)	S5—Bi2^v	2.849 (2)
Pb4—S10^iii	3.077 (2)	S5—In24^v	2.934 (2)
Pb4—S10	3.077 (2)	S5—Bi4F^v	2.934 (2)
Pb4—S5	3.159 (3)	S5—In24^iv	2.934 (2)
Pb4—S16	3.183 (2)	S5—Bi4F^iv	2.934 (2)
Pb4—S16^iii	3.183 (2)	S5—Bi3F^iv	3.273 (3)
Pb4—S15	3.303 (3)	S5—In23^iv	3.273 (3)
Pb5F—S8^iv	2.674 (3)	S6—In24^iv	2.689 (2)
Pb5F—S3^v	2.847 (2)	S6—Bi4F^iv	2.689 (2)
Pb5F—S3^iv	2.847 (2)	S6—In24^v	2.689 (2)
Pb5F—S4^iv	2.995 (2)	S6—Bi4F^v	2.689 (2)
Pb5F—S4^v	2.995 (2)	S7—In25^viii	2.792 (2)
Pb5F—S4	3.422 (3)	S7—Bi5F^viii	2.792 (2)
Bi1—S12	2.629 (3)	S7—Pb2^viii	3.354 (2)
Bi1—S16^vi	2.8050 (18)	S8—In15^iv	2.674 (3)
Bi1—S16^vii	2.8050 (18)	S8—Pb5F^iv	2.674 (3)
Bi1—S11^viii	2.8625 (19)	S8—In25^viii	2.809 (2)
Bi1—S11	2.8625 (19)	S8—Bi5F^viii	2.809 (2)
Bi1—S17^vi	3.081 (3)	S8—Pb3^viii	3.163 (2)
Bi2—S9^iv	2.613 (3)	S9—Bi2^iv	2.613 (3)
Bi2—S4^v	2.783 (2)	S9—Pb3^viii	2.965 (2)
Bi2—S4^iv	2.783 (2)	S9—Pb4^viii	2.980 (2)
Bi2—S5^iv	2.849 (2)	S10—In24^iv	2.600 (3)
Bi2—S5^v	2.849 (2)	S10—Bi4F^iv	2.600 (3)
Bi2—S3	3.183 (3)	S10—Bi12^viii	2.799 (2)
Bi3F—S7	2.612 (3)	S10—In2F^viii	2.799 (2)
Bi3F—S2	2.687 (2)	S10—Pb4^viii	3.077 (2)
Bi3F—S2^viii	2.687 (2)	S11—Bi1^iii	2.8625 (19)
Bi3F—S3	3.033 (2)	S11—Pb1^ii	2.9657 (19)
Bi3F—S3^viii	3.033 (2)	S11—Pb1^i	2.9657 (19)
Bi3F—S5^iv	3.273 (3)	S12—Bi13^viii	2.7559 (19)
Bi4F—S10^iv	2.601 (3)	S12—In3F^viii	2.7559 (19)
Bi4F—S6^iv	2.689 (2)	S12—Pb2^viii	3.174 (2)
Bi4F—S6^v	2.689 (2)	S13—Bi11^iii	2.6538 (18)
Bi4F—S5^v	2.934 (2)	S13—In1F^iii	2.6538 (18)
Bi4F—S5^iv	2.934 (2)	S14—Bi11^vi	2.7147 (17)
Bi4F—S2	3.017 (3)	S14—In1F^vi	2.7147 (17)
Bi5F—S13	2.711 (3)	S14—Bi11^vii	2.7147 (17)
Bi5F—S7	2.792 (2)	S14—In1F^vii	2.7147 (17)
Bi5F—S7^iii	2.792 (2)	S14—Pb3^viii	3.137 (2)
Bi5F—S8^iii	2.809 (2)	S15—Bi11^vi	2.637 (3)
Bi5F—S8	2.809 (2)	S15—In1F^vi	2.637 (3)
Bi5F—S3	2.901 (3)	S15—Bi13^xi	2.6386 (16)
In1F—S14	2.534 (3)	S15—In3F^xi	2.6386 (16)
In1F—S15^vi	2.637 (3)	S15—Bi13^vi	2.6386 (16)
In1F—S13^viii	2.6537 (18)	S15—In3F^vi	2.6386 (16)
In1F—S13	2.6537 (18)	S16—Bi13^vi	2.594 (3)
In1F—S14^vi	2.7147 (17)	S16—In3F^vi	2.594 (3)
In1F—S14^vii	2.7147 (17)	S16—Bi1^vi	2.8050 (18)
In2F—S17	2.591 (3)	S16—Bi1^vii	2.8050 (18)
In2F—S17^ix	2.6085 (19)	S16—Pb4^viii	3.183 (2)
In2F—S17^x	2.6085 (19)	S17—Bi12^ix	2.6085 (19)
In2F—S6	2.640 (3)	S17—In2F^ix	2.6085 (19)
In2F—S10	2.799 (2)	S17—Bi12^x	2.6085 (19)
In2F—S10^iii	2.799 (2)	S17—In2F^x	2.6085 (19)
In3F—S16^vi	2.594 (3)	S17—Bi1^vi	3.081 (3)
In3F—S15^xi	2.6386 (16)

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