The channel structure of trithallium penta­anti­m­on­ate(V), Tl₃Sb₅O₁₄

Single crystals of Tl₃Sb₅O₁₄ were grown by solid-state reaction in a corundum crucible under air (1273 K, 12 h). The structure was determined by single-crystal X-ray diffraction. It is isotypic to the K₃Sb₅O₁₄, Rb₃Sb₅O₁₄ and Cs₃Sb₅O₁₄ analogues with ortho­rhom­bic Pbam symmetry and cell parameters a = 24.2899 (9) Å, b = 7.1931 (3) Å, c = 7.4182 (3) Å. The Sb atoms form irregular [SbO₆] octa­hedra, which are linked via edges and corners into a triperiodic network. The Tl⁺ ions are located in distinct channels of the network extending along [010] and [001].

1. Chemical context

During an extensive study of M[SbF₆] compounds (M = Li, NH₄, Na, Tl), precursors in the form of MSbO₃ were synthesized. Whereas the chosen conditions (1273 K, 12 h) yielded the expected product for LiSbO₃ and NaSbO₃, the Tl-poor title compound Tl₃Sb₅O₁₄ was inadvertently obtained in the case of Tl. TlSbO₃ was later successfully synthesized at 1073 K. In fact, prior syntheses of TlSbO₃ were performed at even lower temperatures (Bouchama & Tournoux, 1975).

The analogues K₃Sb₅O₁₄ (Hong, 1974), Rb₃Sb₅O₁₄ and Cs₃Sb₅O₁₄ (Hirschle et al., 2001) have been synthesized at 1373 K using more involved routes. The first structural characterization of K₃Sb₅O₁₄ was published by Aurivillius (1966). However, the author gives an incorrect Sohncke space-group symmetry of type Pba2, which was later corrected to Pbam by (Hong, 1974).

Hong (1974) noted unusual enlargement of the atomic displacement parameters (ADP) of K in K₃Sb₅O₁₄, which are located in distinct channels, suggesting ion conductivity. In fact, the author could partially substitute K for Rb, Ag and Tl in the respective nitrate salt melts. Accordingly, it is expected that the hitherto structurally uncharacterized Ag₃Sb₅O₁₄ likewise exists. In contrast, substitution with the smaller Na⁺ ion in an NaNO₃ melt led to a collapse of the structure and formation of the Na-poor Na₂Sb₄O₁₁. The instability of M₃Sb₅O₁₄ with small ions might explain the successful syntheses of MSbO₃ (M = Li, Na) at 1273 K.

2. Structural commentary

Tl₃Sb₅O₁₄ crystallizes in the space group Pbam and is isotypic to M₃Sb₅O₁₄ (M = K, Rb, Cs). Two different settings of the Pbam space group were used to describe the structures: a > b by Hong (1974) and a < b by Hirschle et al. (2001). These are equivalent descriptions, because the (a′, b′, c′) = (b, −a, c) operation is an element of the affine normalizer of the Pbam space group. Herein we use the original setting and atom labeling of Hong (1974).

In structures of the M₃Sb₅O₁₄ type, the monovalent metal atoms M are located in channels of a triperiodic network formed by [SbO₆] octa­hedra. There are two distinct channels parallel to [010], both with _yb2₁m symmetry (Fig. 1). In one channel, the M1 atoms are located in zigzag chains and bridged by the M3 atoms, which are located at the boundary of the channels (Fig. 2). In the second channel, the M2 atoms are likewise arranged in the form of zigzag lines (Fig. 2). All of the M atoms are located on or very close to the reflection plane of the channels. Additionally, channels with a smaller diameter extend in the [001] direction (Fig. 3). For K₃Sb₅O₁₄, Hong (1974) reports excessive enlargement of the ADPs of the K1 and K2 atoms in the [010] and [001] directions of the channels, with the `thermal motions' in these directions being `eight times bigger' than in the [100] direction. The Tl1 and Tl2 atoms in the title compound show a much milder enlargement of the ADPs. The ratio of the mean-square displacement of the longest and shortest principal axes of the ADP tensor is 3.2 for Tl1 and 2.9 for Tl2. Note that the value for Tl2 is not directly comparable, since it was refined as disordered about the reflection plane. However, even when placing the atom on the reflection plane, the ratio increases to only 3.2. From these values, it appears that Tl₃Sb₅O₁₄ is not a prime candidate for ion conductivity, at least at the measurement temperature of 100 K. For Rb₃Sb₅O₁₄ and Cs₃Sb₅O₁₄, similarly mild enlargement of the ADPs has been reported (Hirschle et al., 2001). In contrast to the Tl₃Sb₅O₁₄ title compound, these were derived from data collected at room temperature.

Figure 1 Tl3Sb5O14 viewed down [010], Tl (green), Sb (gray) and O (red) atoms are represented by ellipsoids drawn at the 50% probability level.

Figure 2 Tl atoms in Tl3Sb5O14 viewed down [001] with inter­atomic distances. For Tl2⋯Tl2 contacts, two inter­atomic distances are given since the Tl2 atom was refined as disordered about the reflection plane parallel to (001).

Figure 3 Tl3Sb5O14 viewed down [001]. Atom color codes as in Fig. 1.

All Sb atoms are coordinated by six O atoms forming highly irregular [SbO₆] octa­hedra (Table 1) with O—Sb—O cis angles ranging from 73.37 (17) to 103.83 (13)° and trans angles up to 150.66 (16)°. As noted by Hirschle et al. (2001), the framework can be described as being composed of four distinct parts: two infinite octa­hedra chains and two edge-connected pairs of octa­hedra. In general, these elements are connected via corners but there is an additional connection between a pair and a chain via an edge.

Table 1
Selected geometric parameters (Å, °)

Tl1—Tl3^i	3.3972 (4)	Sb2—O10	1.919 (3)
Tl1—Tl1^ii	3.4507 (7)	Sb2—O2^iv	1.983 (4)
Tl1—Tl3^iii	3.6130 (4)	Sb2—O2^vii	2.140 (4)
Tl3—Tl1^iv	3.3972 (4)	Sb2—O4^vii	2.215 (4)
Tl3—Tl1^v	3.6129 (4)	Sb3—O5^iii	1.952 (4)
Tl1—O3	2.565 (4)	Sb3—O5	1.979 (4)
Tl2—O6	2.775 (4)	Sb3—O9^ix	1.998 (3)
Tl3—O5	2.495 (4)	Sb3—O9	1.998 (3)
Sb1—O8^vi	1.925 (3)	Sb3—O7^ix	2.002 (3)
Sb1—O8	1.925 (3)	Sb3—O7	2.002 (3)
Sb1—O6^vii	1.971 (4)	Sb4—O3	1.9233 (15)
Sb1—O1^viii	1.996 (2)	Sb4—O7	1.936 (3)
Sb1—O1	1.996 (2)	Sb4—O9^x	1.954 (3)
Sb1—O2	2.081 (4)	Sb4—O8	1.975 (3)
Sb2—O6	1.911 (4)	Sb4—O4	2.0284 (11)
Sb2—O10^vi	1.919 (3)	Sb4—O10^x	2.041 (3)
O8^vi—Sb1—O8	96.70 (16)	O5^iii—Sb3—O5	171.04 (9)
O8^vi—Sb1—O6^vii	90.34 (11)	O5^iii—Sb3—O9^ix	99.04 (11)
O8—Sb1—O6^vii	90.34 (11)	O5—Sb3—O9^ix	87.50 (11)
O8^vi—Sb1—O1^viii	90.74 (11)	O5^iii—Sb3—O9	99.03 (11)
O8—Sb1—O1^viii	171.91 (11)	O5—Sb3—O9	87.50 (11)
O6^vii—Sb1—O1^viii	92.82 (8)	O9^ix—Sb3—O9	85.66 (16)
O8^vi—Sb1—O1	171.91 (11)	O5^iii—Sb3—O7^ix	87.14 (11)
O8—Sb1—O1	90.74 (11)	O5—Sb3—O7^ix	87.54 (11)
O6^vii—Sb1—O1	92.82 (8)	O9^ix—Sb3—O7^ix	83.44 (11)
O1^viii—Sb1—O1	81.67 (15)	O9—Sb3—O7^ix	168.21 (11)
O8^vi—Sb1—O2	90.17 (11)	O5^iii—Sb3—O7	87.14 (11)
O8—Sb1—O2	90.17 (11)	O5—Sb3—O7	87.54 (11)
O6^vii—Sb1—O2	179.23 (15)	O9^ix—Sb3—O7	168.21 (11)
O1^viii—Sb1—O2	86.60 (8)	O9—Sb3—O7	83.44 (11)
O1—Sb1—O2	86.60 (8)	O7^ix—Sb3—O7	107.02 (16)
O6—Sb2—O10^vi	96.40 (9)	O3—Sb4—O7	93.31 (15)
O6—Sb2—O10	96.40 (9)	O3—Sb4—O9^x	99.82 (14)
O10^vi—Sb2—O10	150.66 (16)	O7—Sb4—O9^x	92.53 (12)
O6—Sb2—O2^iv	100.16 (16)	O3—Sb4—O8	83.01 (13)
O10^vi—Sb2—O2^iv	101.78 (8)	O7—Sb4—O8	88.19 (12)
O10—Sb2—O2^iv	101.78 (8)	O9^x—Sb4—O8	177.03 (11)
O6—Sb2—O2^vii	173.53 (15)	O3—Sb4—O4	160.89 (15)
O10^vi—Sb2—O2^vii	85.12 (9)	O7—Sb4—O4	103.83 (13)
O10—Sb2—O2^vii	85.12 (9)	O9^x—Sb4—O4	87.96 (13)
O2^iv—Sb2—O2^vii	73.37 (17)	O8—Sb4—O4	89.07 (13)
O6—Sb2—O4^vii	90.22 (16)	O3—Sb4—O10^x	84.03 (14)
O10^vi—Sb2—O4^vii	76.83 (8)	O7—Sb4—O10^x	177.09 (11)
O10—Sb2—O4^vii	76.83 (8)	O9^x—Sb4—O10^x	89.09 (11)
O2^iv—Sb2—O4^vii	169.63 (15)	O8—Sb4—O10^x	90.31 (11)
O2^vii—Sb2—O4^vii	96.25 (14)	O4—Sb4—O10^x	78.63 (13)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .

A qu­anti­tative comparison of Tl₃Sb₅O₁₄ and the alkali-metal analogues M₃Sb₅O₁₄ (M = K, Rb, Cs) was performed using the COMPSTRU (de la Flor et al., 2016) module of the Bilbao Crystallographic Server (Aroyo et al., 2006). The Tl2 atom was moved onto the reflection plane to make the sets of Wyckoff positions compatible. The degree of lattice distortion with respect to the Tl compound is S = 0.0042 (M = K), S = 0.0048 (M = Rb) and S = 0.0262 (M = Cs). This shows that the K, Rb and Tl compounds feature very similar cell parameters, with the volume increasing slightly according to K > Rb > Tl (Table 2). In contrast, the lattice of Cs₃Sb₅O₁₄ features a pronounced distortion with a ca 11% larger unit-cell volume. The enlargement affects foremost the a and b lattice parameters, whereas c is smaller than for the Tl compound. We therefore presume that the unit-cell volume for the M = K, Rb, Tl compounds is mostly determined by the triperiodic anti­monate network, which cannot contract any further. The minimum size of the channels may explain the collapse of the structure when attempting to replace K by Na, as reported by Hong (1974).

Table 2
Comparison of unit-cell parameters (Å, ų) of the M3Sb₅O₁₄ structures

The setting of the M = Rb and M = Cs compounds was adjusted to the setting used in this work.

Compound	K3Sb5O14	Rb3Sb5O14	Cs3Sb5O14	Tl3Sb5O14
a	24.247 (4)	24.478 (2)	26.251 (5)	24.2899 (9)
b	7.157 (2)	7.1881 (9)	7.4337 (13)	7.1931 (3)
c	7.334 (2)	7.331 (2)	7.396 (3)	7.4182 (3)
V	1272.7 (3)	1289.8 (4)	1443.3 (7)	1296.11 (9)

The degree of similarity likewise shows a close relationship of the M = K (Δ = 0.022) and M = Rb (Δ = 0.035) compounds with Tl₃Sb₅O₁₄, whereas the atomic positions in Cs₃Sb₅O₁₄ differ distinctly (Δ = 0.178). In particular, the positions of the O atoms that coordinate to the Tl2 atoms feature a strong deviation (d_max = 0.6356 Å for the O4 atom) showing a distinct distortion of the [SbO₆] octa­hedra around the respective channels. Thus, it appears that the Tl2 channels are responsible for the distinct enlargement of the unit cell of Cs₃Sb₅O₁₄.

3. Synthesis and crystallization

A mixture of 0.682 g TlNO₃ and 0.373 g Sb₂O₃ (which makes for an approximate molar ratio of 1:1 for Tl:Sb) was heated in a corundum crucible at 1273 K for 12 h in air. From the reaction, a dark-orange powder was obtained. The single crystals formed as rectangular-prismatic plates. Crystals were isolated under a polarizing microscope and cut to an appropriate size for single crystal diffraction of a highly absorbing crystal.

4. Refinement

Crystal data, data collection and structure refinement are summarized in Table 3. A starting model was generated using the coordinates of K₃Sb₅O₁₄ (Hong, 1974). Owing to distinct peaks in the difference-Fourier map, the Tl2 atom was removed from the reflection plane and refined as disordered. Even though the refined distance of the atom from the reflection plane is minute, the residuals improved significantly {R[I > 2σ(I)] from 0.028 to 0.023}, which might be in part due to the increased number of anisotropic displacement parameters.

Table 3
Experimental details

Crystal data
Chemical formula	Tl3Sb5O14
Mr	1445.86
Crystal system, space group	Orthorhombic, Pbam
Temperature (K)	250
a, b, c (Å)	24.2899 (9), 7.1931 (3), 7.4182 (3)
V (Å^3)	1296.11 (9)
Z	4
Radiation type	Mo Kα
μ (mm^−1)	47.48
Crystal size (mm)	0.11 × 0.06 × 0.02
Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2021)
Tmin, Tmax	0.010, 0.058
No. of measured, independent and observed [I > 2σ(I)] reflections	27499, 3084, 2850
Rint	0.051
(sin θ/λ)max (Å^−1)	0.812
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.023, 0.055, 1.07
No. of reflections	3084
No. of parameters	121
Δρmax, Δρmin (e Å^−3)	2.55, −1.52
Computer programs: APEX3 and SAINT-Plus (Bruker, 2021), SHELXL2014/7 (Sheldrick, 2015), DIAMOND (Putz & Brandenburg, 2021) and publCIF (Westrip, 2010).

Supporting information

Computing details

Data collection: APEX3 (Bruker, 2021); cell refinement: APEX3 (Bruker, 2021); data reduction: SAINT-Plus (Bruker, 2021); program(s) used to solve structure: undef; program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Putz & Brandenburg, 2021); software used to prepare material for publication: publCIF (Westrip, 2010).

Trithallium pentaantimonate(V)

Crystal data

Tl3Sb5O14	Dx = 7.410 Mg m^−3
Mr = 1445.86	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbam	Cell parameters from 9928 reflections
a = 24.2899 (9) Å	θ = 2.8–35.3°
b = 7.1931 (3) Å	µ = 47.48 mm^−1
c = 7.4182 (3) Å	T = 250 K
V = 1296.11 (9) Å^3	Plate, colourless
Z = 4	0.11 × 0.06 × 0.02 mm
F(000) = 2440

Data collection

Bruker Kappa APEXII CCD diffractometer	2850 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω– and φ–scans	θmax = 35.3°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2021)	h = −39→39
Tmin = 0.010, Tmax = 0.058	k = −11→11
27499 measured reflections	l = −12→12
3084 independent reflections

Refinement

Refinement on F^2	Primary atom site location: isomorphous structure methods
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0199P)^2 + 6.584P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.023	(Δ/σ)max = 0.001
wR(F^2) = 0.055	Δρmax = 2.55 e Å^−3
S = 1.07	Δρmin = −1.52 e Å^−3
3084 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
121 parameters	Extinction coefficient: 0.00075 (4)
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Tl1	0.01569 (2)	0.23393 (5)	0.5000	0.03732 (8)
Tl2	0.29264 (2)	0.12150 (6)	−0.0170 (5)	0.0353 (4)	0.5
Tl3	0.38418 (2)	0.10536 (4)	0.5000	0.03177 (7)
Sb1	0.05715 (2)	0.41738 (4)	0.0000	0.00993 (6)
Sb2	0.43805 (2)	0.40456 (4)	0.0000	0.01042 (6)
Sb3	0.25558 (2)	0.32863 (4)	0.5000	0.00998 (6)
Sb4	0.14535 (2)	0.11009 (3)	0.26233 (3)	0.01011 (5)
O1	0.0000	0.5000	0.1759 (5)	0.0131 (6)
O2	0.01735 (15)	0.1611 (5)	0.0000	0.0130 (6)
O3	0.11974 (15)	0.1728 (6)	0.5000	0.0139 (6)
O4	0.14514 (15)	0.0305 (5)	0.0000	0.0124 (6)
O5	0.28203 (16)	0.0685 (5)	0.5000	0.0146 (6)
O6	0.40613 (16)	0.1618 (5)	0.0000	0.0146 (6)
O7	0.21049 (11)	0.2637 (4)	0.2830 (4)	0.0144 (5)
O8	0.10390 (11)	0.3355 (4)	0.1939 (4)	0.0138 (4)
O9	0.31369 (11)	0.3832 (4)	0.3169 (4)	0.0136 (4)
O10	0.42520 (10)	0.4563 (4)	0.2502 (3)	0.0132 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tl1	0.01779 (11)	0.04162 (17)	0.05255 (18)	0.00612 (10)	0.000	0.000
Tl2	0.01922 (12)	0.04252 (19)	0.0442 (12)	−0.00204 (11)	−0.0027 (2)	0.0106 (5)
Tl3	0.01232 (10)	0.02797 (13)	0.05504 (18)	0.00031 (8)	0.000	0.000
Sb1	0.00754 (12)	0.01037 (13)	0.01187 (12)	0.00045 (9)	0.000	0.000
Sb2	0.00826 (12)	0.01106 (13)	0.01193 (12)	0.00000 (9)	0.000	0.000
Sb3	0.00756 (11)	0.01032 (13)	0.01205 (12)	−0.00028 (9)	0.000	0.000
Sb4	0.00803 (9)	0.01136 (10)	0.01094 (9)	0.00039 (6)	−0.00072 (6)	−0.00010 (7)
O1	0.0106 (14)	0.0163 (16)	0.0123 (13)	0.0028 (12)	0.000	0.000
O2	0.0080 (14)	0.0098 (15)	0.0214 (16)	−0.0005 (11)	0.000	0.000
O3	0.0107 (15)	0.0223 (18)	0.0086 (13)	0.0045 (13)	0.000	0.000
O4	0.0119 (14)	0.0150 (16)	0.0101 (13)	−0.0016 (12)	0.000	0.000
O5	0.0114 (15)	0.0106 (15)	0.0217 (16)	−0.0008 (12)	0.000	0.000
O6	0.0113 (15)	0.0087 (15)	0.0238 (17)	−0.0011 (12)	0.000	0.000
O7	0.0123 (11)	0.0159 (12)	0.0150 (10)	−0.0035 (9)	−0.0031 (9)	0.0011 (9)
O8	0.0142 (11)	0.0128 (11)	0.0144 (10)	0.0034 (9)	−0.0038 (9)	−0.0013 (9)
O9	0.0119 (10)	0.0125 (11)	0.0165 (10)	−0.0029 (8)	0.0023 (9)	−0.0003 (9)
O10	0.0093 (10)	0.0161 (11)	0.0141 (10)	0.0003 (8)	0.0005 (8)	0.0001 (9)

Geometric parameters (Å, º)

Tl1—Tl3^i	3.3972 (4)	Sb2—Sb2^x	3.3079 (6)
Tl1—Tl1^ii	3.4507 (7)	Sb3—O5^iii	1.952 (4)
Tl1—Tl3^iii	3.6130 (4)	Sb3—O5	1.979 (4)
Tl2—Tl2^iv	0.252 (7)	Sb3—O9^xi	1.998 (3)
Tl3—Tl1^v	3.3972 (4)	Sb3—O9	1.998 (3)
Tl3—Tl1^vi	3.6129 (4)	Sb3—O7^xi	2.002 (3)
Tl1—O3	2.565 (4)	Sb3—O7	2.002 (3)
Tl2—O6	2.775 (4)	Sb4—O3	1.9233 (15)
Tl3—O5	2.495 (4)	Sb4—O7	1.936 (3)
Tl3—Sb3	3.5123 (4)	Sb4—O9^xii	1.954 (3)
Sb1—O8^iv	1.925 (3)	Sb4—O8	1.975 (3)
Sb1—O8	1.925 (3)	Sb4—O4	2.0284 (11)
Sb1—O6^vii	1.971 (4)	Sb4—O10^xii	2.041 (3)
Sb1—O1^viii	1.996 (2)	Sb4—Sb2^xiii	3.1743 (3)
Sb1—O1	1.996 (2)	O1—Sb1^viii	1.996 (2)
Sb1—O2	2.081 (4)	O2—Sb2^i	1.983 (4)
Sb1—Sb1^viii	3.0199 (6)	O2—Sb2^xiii	2.140 (4)
Sb2—O6	1.911 (4)	O3—Sb4^xi	1.9233 (15)
Sb2—O10^iv	1.919 (3)	O4—Sb4^iv	2.0283 (11)
Sb2—O10	1.919 (3)	O4—Sb2^xiii	2.215 (4)
Sb2—O2^v	1.983 (4)	O5—Sb3^vi	1.952 (4)
Sb2—O2^vii	2.140 (4)	O6—Sb1^xiii	1.971 (4)
Sb2—O4^vii	2.215 (4)	O6—Tl2^iv	2.775 (4)
Sb2—Sb4^vii	3.1742 (3)	O9—Sb4^ix	1.954 (3)
Sb2—Sb4^ix	3.1742 (3)	O10—Sb4^ix	2.042 (3)
O3—Tl1—Tl3^i	169.98 (10)	Sb4^vii—Sb2—Sb2^x	112.786 (12)
O3—Tl1—Tl1^ii	92.89 (10)	Sb4^ix—Sb2—Sb2^x	112.786 (12)
Tl3^i—Tl1—Tl1^ii	97.130 (13)	O5^iii—Sb3—O5	171.04 (9)
O3—Tl1—Tl3^iii	57.56 (10)	O5^iii—Sb3—O9^xi	99.04 (11)
Tl3^i—Tl1—Tl3^iii	112.419 (11)	O5—Sb3—O9^xi	87.50 (11)
Tl1^ii—Tl1—Tl3^iii	150.451 (14)	O5^iii—Sb3—O9	99.03 (11)
Tl2^iv—Tl2—O6	87.40 (7)	O5—Sb3—O9	87.50 (11)
O5—Tl3—Tl1^v	166.21 (9)	O9^xi—Sb3—O9	85.66 (16)
O5—Tl3—Sb3	33.32 (9)	O5^iii—Sb3—O7^xi	87.14 (11)
Tl1^v—Tl3—Sb3	132.896 (12)	O5—Sb3—O7^xi	87.54 (11)
O5—Tl3—Tl1^vi	126.21 (9)	O9^xi—Sb3—O7^xi	83.44 (11)
Tl1^v—Tl3—Tl1^vi	67.581 (11)	O9—Sb3—O7^xi	168.21 (11)
Sb3—Tl3—Tl1^vi	159.523 (11)	O5^iii—Sb3—O7	87.14 (11)
O8^iv—Sb1—O8	96.70 (16)	O5—Sb3—O7	87.54 (11)
O8^iv—Sb1—O6^vii	90.34 (11)	O9^xi—Sb3—O7	168.21 (11)
O8—Sb1—O6^vii	90.34 (11)	O9—Sb3—O7	83.44 (11)
O8^iv—Sb1—O1^viii	90.74 (11)	O7^xi—Sb3—O7	107.02 (16)
O8—Sb1—O1^viii	171.91 (11)	O5^iii—Sb3—Tl3	145.11 (12)
O6^vii—Sb1—O1^viii	92.82 (8)	O5—Sb3—Tl3	43.84 (11)
O8^iv—Sb1—O1	171.91 (11)	O9^xi—Sb3—Tl3	57.42 (8)
O8—Sb1—O1	90.74 (11)	O9—Sb3—Tl3	57.42 (8)
O6^vii—Sb1—O1	92.82 (8)	O7^xi—Sb3—Tl3	112.32 (8)
O1^viii—Sb1—O1	81.67 (15)	O7—Sb3—Tl3	112.32 (8)
O8^iv—Sb1—O2	90.17 (11)	O3—Sb4—O7	93.31 (15)
O8—Sb1—O2	90.17 (11)	O3—Sb4—O9^xii	99.82 (14)
O6^vii—Sb1—O2	179.23 (15)	O7—Sb4—O9^xii	92.53 (12)
O1^viii—Sb1—O2	86.60 (8)	O3—Sb4—O8	83.01 (13)
O1—Sb1—O2	86.60 (8)	O7—Sb4—O8	88.19 (12)
O8^iv—Sb1—Sb1^viii	131.51 (8)	O9^xii—Sb4—O8	177.03 (11)
O8—Sb1—Sb1^viii	131.51 (8)	O3—Sb4—O4	160.89 (15)
O6^vii—Sb1—Sb1^viii	93.72 (11)	O7—Sb4—O4	103.83 (13)
O1^viii—Sb1—Sb1^viii	40.84 (8)	O9^xii—Sb4—O4	87.96 (13)
O1—Sb1—Sb1^viii	40.84 (8)	O8—Sb4—O4	89.07 (13)
O2—Sb1—Sb1^viii	85.51 (10)	O3—Sb4—O10^xii	84.03 (14)
O6—Sb2—O10^iv	96.40 (9)	O7—Sb4—O10^xii	177.09 (11)
O6—Sb2—O10	96.40 (9)	O9^xii—Sb4—O10^xii	89.09 (11)
O10^iv—Sb2—O10	150.66 (16)	O8—Sb4—O10^xii	90.31 (11)
O6—Sb2—O2^v	100.16 (16)	O4—Sb4—O10^xii	78.63 (13)
O10^iv—Sb2—O2^v	101.78 (8)	O3—Sb4—Sb2^xiii	117.70 (12)
O10—Sb2—O2^v	101.78 (8)	O7—Sb4—Sb2^xiii	146.72 (8)
O6—Sb2—O2^vii	173.53 (15)	O9^xii—Sb4—Sb2^xiii	93.61 (8)
O10^iv—Sb2—O2^vii	85.12 (9)	O8—Sb4—Sb2^xiii	84.23 (8)
O10—Sb2—O2^vii	85.12 (9)	O4—Sb4—Sb2^xiii	43.86 (10)
O2^v—Sb2—O2^vii	73.37 (17)	O10^xii—Sb4—Sb2^xiii	35.42 (7)
O6—Sb2—O4^vii	90.22 (16)	Sb1^viii—O1—Sb1	98.33 (15)
O10^iv—Sb2—O4^vii	76.83 (8)	Sb2^i—O2—Sb1	131.46 (19)
O10—Sb2—O4^vii	76.83 (8)	Sb2^i—O2—Sb2^xiii	106.63 (17)
O2^v—Sb2—O4^vii	169.63 (15)	Sb1—O2—Sb2^xiii	121.92 (17)
O2^vii—Sb2—O4^vii	96.25 (14)	Sb4—O3—Sb4^xi	132.9 (2)
O6—Sb2—Sb4^vii	99.60 (9)	Sb4—O3—Tl1	111.03 (11)
O10^iv—Sb2—Sb4^vii	38.07 (8)	Sb4^xi—O3—Tl1	111.03 (11)
O10—Sb2—Sb4^vii	113.51 (8)	Sb4^iv—O4—Sb4	147.2 (2)
O2^v—Sb2—Sb4^vii	136.95 (5)	Sb4^iv—O4—Sb2^xiii	96.76 (11)
O2^vii—Sb2—Sb4^vii	85.49 (8)	Sb4—O4—Sb2^xiii	96.76 (11)
O4^vii—Sb2—Sb4^vii	39.39 (3)	Sb3^vi—O5—Sb3	133.2 (2)
O6—Sb2—Sb4^ix	99.60 (9)	Sb3^vi—O5—Tl3	124.01 (18)
O10^iv—Sb2—Sb4^ix	113.51 (8)	Sb3—O5—Tl3	102.84 (16)
O10—Sb2—Sb4^ix	38.07 (8)	Sb2—O6—Sb1^xiii	129.2 (2)
O2^v—Sb2—Sb4^ix	136.95 (5)	Sb2—O6—Tl2	119.90 (17)
O2^vii—Sb2—Sb4^ix	85.49 (8)	Sb1^xiii—O6—Tl2	110.88 (16)
O4^vii—Sb2—Sb4^ix	39.39 (3)	Sb2—O6—Tl2^iv	119.90 (17)
Sb4^vii—Sb2—Sb4^ix	75.620 (11)	Sb1^xiii—O6—Tl2^iv	110.88 (16)
O6—Sb2—Sb2^x	138.46 (12)	Tl2—O6—Tl2^iv	5.21 (15)
O10^iv—Sb2—Sb2^x	93.86 (8)	Sb4—O7—Sb3	130.09 (14)
O10—Sb2—Sb2^x	93.86 (8)	Sb1—O8—Sb4	138.08 (15)
O2^v—Sb2—Sb2^x	38.31 (11)	Sb4^ix—O9—Sb3	131.67 (14)
O2^vii—Sb2—Sb2^x	35.07 (10)	Sb2—O10—Sb4^ix	106.51 (12)
O4^vii—Sb2—Sb2^x	131.32 (10)

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