Phase relationships in homoleptic com­plexes of XeF₂

The structural behaviour of homoleptic xenon difluoride (XeF₂) com­plexes [M(XeF₂)₆][SbF₆]₂ (M = Cu, Zn) under varying tem­per­a­ture and pressure has been investigated, aiming to resolve the disordered Jahn–Teller distortions in the copper com­plex (CuSb). At 200 K, both CuSb and its zinc analogue (ZnSb) crystallize in a layered CdCl₂-type structure with the space group R3. Upon cooling below 170 (CuSb) and 160 K (ZnSb), both systems transition to iso­structural phases in P1, with CuSb assuming an ordered Jahn–Teller distortion. The transformation is driven by the shortening and optimization of the Xe⋯F inter­molecular contacts, forming stronger and more directional inter­actions, rather than by Jahn–Teller effects alone. This is supported by the observation of similar transitions in the Jahn–Teller-inactive Zn system. High-pressure ex­peri­ments up to ∼2.8 GPa at room tem­per­a­ture show the structural stability of the high-symmetry phases, implicating kinetic barriers to further transformation. Additionally, the synthesis and structural characterization of a novel arsenic analogue, [Zn(XeF₂)₆][AsF₆]₂ (ZnAs), reveal similar layered motifs but distinct phase behaviour. Symmetry-mode analyses relate all observed phases through distortions of a common CdCl₂ aristotype.

1. Introduction

The synthesis and characterization of the three binary fluorides of xenon, i.e. XeF₂ (Chernick et al., 1962; Hoppe et al., 1962; Weeks et al., 1962), XeF₄ (Claassen et al., 1962; Chernick et al., 1962; Slivnik et al., 1962a) and XeF₆ (Malm et al., 1963; Weaver et al., 1963; Slivnik et al., 1962b), were described within only a year of Bartlett's first synthesis of a noble-gas com­pound (Bartlett, 1962). Two com­pounds containing both XeF₆ and KrF₂, [F₅Xe(FKrF)AsF₆] and [F₅Xe(FKrF)₂AsF₆], have been reported recently (Lozinšek et al., 2021). XeF₂ can act as a fluoride-ion donor to metal centres in coordination com­plexes (Brock et al., 2013). The coordination chemistry of KrF₂ has also been investigated, though it is more limited than that of XeF₂.

Homoleptic com­plexes with noble-gas fluoride ligands are com­paratively rare, and are observed only for Ca²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ with XeF₂, and for Hg²⁺ with KrF₂ (De Backere & Schrobilgen, 2018). A metal centre in a homoleptic coordination environment of XeF₂ was first reported in [Ca₂(XeF₂)₉(AsF₆)₄] (Tramšek et al., 2004), followed by the syntheses and crystal structures of [M(XeF₂)₆][SbF₆]₂ (M = Cu, Zn; Scheme 1, A = Sb) (Tavčar et al., 2006), with [M(XeF₂)₆][RuF₆]₂ (M = Ni, Cu) being reported recently (Mržljak et al., 2025). [Cu(XeF₂)₆][RuF₆]₂ crystallizes in the space group P, with each Cu centre sitting on an inversion centre and exhibiting a Jahn–Teller distortion, with Cu—F bond lengths between 1.907 (4) and 2.167 (5) Å. By contrast, the Cu and Zn com­plexes with [SbF₆]⁻, as well as [Ni(XeF₂)₆][RuF₆]₂, crystallize in the space group R, with the metal occupying a site such that all ligands have equal M—F bond lengths. This suggests either a dynamic Jahn–Teller distortion or static disorder in copper com­plexes (Deeth & Hitchman, 1986; Bersuker, 2021).

Disorder is an entropy-driven process which arises in crystal structures when there is sufficient thermal energy to access multiple thermodynamically com­petitive configurations. One approach for resolving dynamically disordered structures into ordered forms is to reduce the tem­per­a­ture. Examples of Jahn–Teller ordering in Cu²⁺ chemistry include [Cu{(C₅H₄N)₃CH}₂][NO₃]₂, which shows only one Cu—N EXAFS peak at 295 K, but two at 150 K (Astley et al., 1995). Likewise, the Cu—N bond lengths in [Cu(L)₂][BF₄]₂ [L = 2,6-bis­(pyrazol-1-yl)pyridine] [Cambridge Structural Database (CSD; Groom et al., 2016) refcode PEFQIA] gradually converge on raising the tem­per­a­ture from 31 to 350 K, the structure transforming from Z′ = 3 to Z′ = 1 at 41 K (Beddard et al., 2003).

Since (∂S/∂P)_T = −αV (where α is the thermal expansion coefficient, V the volume and T the tem­per­a­ture) is negative for most materials, another mechanism for reducing the effect of entropy S is to increase the pressure P. Pressure has been used to resolve dynamic Jahn–Teller effects, but this has been less extensively studied than the use of tem­per­a­ture. In (Ph₄P)₂IC₆₀ (Francis et al., 2012), the dynamic distortion exhibited by the C₆₀⁻ anion is resolved to a static distortion at 2 GPa, as identified by the splitting of degenerate vibrational modes. Although application of pressure to resolve Jahn–Teller disorder in copper com­plexes appears not to have been investigated, successive pressure-induced switching of the Jahn–Teller distortions along the N—Cu—N, O—Cu—O and F—Cu—F axes has been observed in the coordination polymer [CuF₂(H₂O)₂(pyrazine)₂]₂ (Halder et al., 2011).

This article aims to explore the effect of tem­per­a­ture and pressure on the Jahn–Teller disorder in [Cu(XeF₂)₆][SbF₆]₂ (CuSb, Fig. 1). The Xe atoms in CuSb and all other xenon com­pounds show a strong tendency to form short directional contacts to atoms bearing lone pairs, especially fluorine. The directionality of these contacts has been investigated using theoretical methods (Kirshenboim & Kozuch, 2016; Gomila & Frontera, 2020) and, as we show below, a number of them in the ambient-tem­per­a­ture disordered structure of CuSb can be regarded as non-optimal. Thus, although it is highly moisture sensitive and somewhat difficult to prepare and handle, this material is an ideal candidate for exploring the capacity of external conditions to reduce the effects of entropy and resolve disorder in crystal structures by driving the selection of optimal inter­molecular inter­actions.

Figure 1 Packing in the crystal structure of CuSb-I. (a) View along [010] showing the stacking of the layers along the c axis. (b) The layers viewed along [001], with the short intra­layer Xe—F⋯Xe cation–cation contacts repre­sent­ed by dashed bonds. The colour scheme here and in the other figures is red for Cu and purple for Sb. XeF2 ligands are shown in `stick' format in part (a).

The article also describes parallel experiments on the analogous and structurally related zinc-containing systems [Zn(XeF₂)₆][SbF₆]₂ (ZnSb) and [Zn(XeF₂)₆][AsF₆]₂ (ZnAs). The Zn atom in these com­pounds is not Jahn–Teller active and the results provide a control for defining the role of the Jahn–Teller effect itself in driving the phase transitions described.

2. Experimental

2.1. Synthetic procedures

2.1.1. Sources of materials

XeF₂ was synthesized via the photosynthetic method from F₂ (Solvay Fluor, 98–99%) and Xe (Messer, 99.99%) (Šmalc & Lutar, 1992). ZnF₂ (99.995%) and CuF₂ (99.5%) were ob­tained from Thermo Fisher Scientific. Hydrogen fluoride (Linde, 99.995%) was treated with K₂NiF₆ (Advance Re­search Chemicals, 99.9%) prior to use. Halocarbon oil 11-14 (Halocarbon Products Corp.), Fomblin Z60 and Fomblin Z25 (Synquest Laboratories) were used as pressure-transmitting media (Motaln et al., 2025). Perfluoro­deca­lin was used as supplied from Sigma–Aldrich (batch number STBH2228). M(SbF₆)₂ (M = Cu, Zn) were prepared from the corresponding metal difluorides, SbF₃ (Sigma–Aldrich, 99.8%) and excess F₂ in anhydrous HF (Gantar et al., 1987).

Caution! Anhydrous HF (aHF), F₂, XeF₂, AsF₅, SbF₅ and their com­pounds must be handled with extreme care in a well-ventilated fume hood, with appropriate protective equipment worn at all times.

2.1.2. Synthesis of [M(XeF₂)₆][SbF₆]₂ (M = Cu or Zn; CuSb and ZnSb)

The salts [M(XeF₂)₆][SbF₆]₂ (M = Cu or Zn) were synthesized from XeF₂ and the corresponding M(SbF₆)₂ salt in aHF [Equation (1)] (Tavčar et al., 2006). An h-shaped FEP reaction-crystallization vessel equipped with a PCTFE valve was assembled (see supporting information, Fig. S1) and exposed to ca 0.5 atm (1 atm = 101325 Pa) of elemental fluorine for 12 h, followed by evacuation under dynamic vacuum for 3 h prior to use. In the case of the zinc derivative, Zn(SbF₆)₂ (58.2 mg, 0.108 mmol) was combined with XeF₂ (173.4 mg, 1.02 mmol) in the reaction branch of the vessel under nitro­gen. aHF (ca 1.5 ml) was condensed into the vessel at 77 K, before gentle warming and stirring to dissolve the solids. The colourless solution was stirred for 12 h, before transfer to the crystallization arm of the vessel. A tem­per­a­ture gradient of 5–10 K was applied between the arms of the vessel to promote slow evaporation of aHF over a period of six weeks, resulting in a batch of colourless crystals. These were cooled to 230 K and dried under dynamic vacuum. The Cu derivative was prepared in a similar manner using Cu(SbF₆)₂ (76.4 mg, 0.143 mmol) and XeF₂ (231.1 mg, 1.36 mmol).

Crystalline reaction products were identified as a mixture of [M(XeF₂)₆][SbF₆]₂ and [Xe₂F₃][SbF₆] [Equations (1) and (2); M = Cu or Zn] using single-crystal X-ray diffraction. [M(XeF₂)₆][SbF₆]₂ were apparently the minor products based on random sampling of the visually indistinguishable crystals.

2.1.3. Synthesis of [Zn(XeF₂)₆][AsF₆]₂ (ZnAs)

XeF₂ (273.1 mg, 1.61 mmol) was combined with ZnF₂ (21.7 mg, 0.21 mmol) in a similar reaction vessel to that described in Section 2.1.2. aHF (ca 1.7 ml) was condensed into the reaction vessel at 77 K, before gentle warming and stirring to dissolve the solids. AsF₅ (74.8 mg, 0.44 mmol) was condensed into the reaction vessel gradually in six approximately equal aliquots, warming and stirring the solution to ensure full dissolution of AsF₅ between additions. Warming to room tem­per­a­ture yielded a pale-yellow solution which was stirred for 12 h. Crystallization, as described in Section 2.1.2, yielded pale-yellow crystals. [Zn(XeF₂)₆][AsF₆]₂ [ZnAs, Equa­tion (3)] and [Xe₂F₃][AsF₆] [Equation (4)] were identified as the crystalline products by single-crystal X-ray dif­fraction, with the dominant phase found being the homoleptic com­plex.

Attempted synthesis of [Cu(XeF₂)₆][AsF₆]₂ from CuF₂ using a similar procedure was unsuccessful, with the only detected reaction products being [Xe₂F₃][AsF₆], CuF₂ and XeF₂.

2.2. X-ray diffraction data collection and processing

2.2.1. Low-tem­per­a­ture single-crystal X-ray diffraction

Single crystals of ZnAs, ZnSb and CuSb were selected under perfluoro­deca­lin and mounted on a Bruker AXS D8 Venture diffractometer equipped with an Oxford Cryosystems low-tem­per­a­ture device operating at 200 K. Diffraction data were collected between 200 and 80 K in increments of 10 K using Ag or Mo Kα radiation (λ = 0.56083 and 0.71073 Å, respectively) generated using Incoatec microsources. A further data set was collected at 30 K for CuSb using an Oxford Cryosystems N-Helix low-tem­per­a­ture device. Cooling induced transitions to new phases in both CuSb and ZnSb. Different phases are distinguished using Roman numerals, i.e. CuSb-I, CuSb-II, etc. The variation of unit-cell volume with tem­per­a­ture is shown in Fig. S2 and Tables S1–S3 of the supporting information.

The data were processed in APEX5 (Bruker, 2024) and integrated using SAINT. Corrections for absorption and other systematic errors were applied using the multi-scan procedures in SADABS or TWINABS (Krause et al., 2015). The structures were solved using dual-space methods (SHELXT; Sheldrick, 2015a) and refinement of all structures was against |F|² using SHELXL (Sheldrick, 2015b) from within the OLEX-2 inter­face (Dolomanov et al., 2009) or CRYSTALS (Betteridge et al., 2003).

With the exception of CuSb-I, all datasets were affected by twinning or the presence of multiple domains. The sample of ZnSb-I was split into two domains related by a 115.7° rotation about [01]. Data were integrated over both domains and those reflections containing a contribution from the major domain used in the structure refinement. The domain scale factor refined to 0.278 (2). CuSb-II was twinned via a 120° rotation about [10] but also split. The reference domain was dominant (estimated scale factor ∼0.9) and the most suc­cessful data reduction strategy was to ignore the twinning during integration and then apply the twin law to those data where the maximum deviation from integral values in the transformed Miller indices was 0.25 or less. The scale factor refined to 0.0651 (15). Diffraction data for ZnSb-II contained contributions from at least eight different domains. The first domain was dominant and, after some experimentation, only the second twin domain (generated by a twofold rotation about [100]) was included in the integration, but refinements against the `detwinned' dataset output by TWINABS proved to give the best agreement statistics. Data for ZnAs-I were <!?tlsb=-0.1pt>integrated over three domains generated by 180 and 93.5° rotations about [101]. All three domains were used in the structure analysis, with final domain scale factors of 0.4578 (14) and 0.0757 (14), respectively. Further details of the twin handling are available in the CIFs in the supporting information.

A non-standard setting of the unit cell of ZnAs-I was used to facilitate com­parison with ZnSb-II.

2.2.2. High-pressure single-crystal X-ray diffraction

Crystals suitable for high-pressure single-crystal diffraction were selected under nitro­gen in a glovebox equipped with a Nikon SMZ1500 video microscope, which has an operating distance suitable for manipulation of diamond anvil cells (DACs). The DACs were of a miniature Merrill–Bassett (Merrill & Bassett, 1974) or a mini-BX80 design (Kantor et al., 2012), both with half-opening angles of 38° and fitted with Boehler–Almax type II diamond anvils of culet diameter 600 or 700 µm ob­tained from Almax easyLab (Boehler & De Hantsetters, 2004). The sample chamber was constructed using rhenium gaskets of thickness 200 µm indented in different experiments to between 75 and 110 µm with holes of diameter 300 and 500 µm drilled by spark erosion. The materials studied are highly oxidizing, and we observed differing sensitivities to the pressure-transmitting media reported by Motaln et al. (2025). The final structures reported were ob­tained using Halocarbon Oil 11-14 for ZnAs, Fomblin Z25 for CuSb and Z60 for ZnSb. Pressure was determined using the ruby fluorescence method (Shen et al., 2020).

High-pressure X-ray diffraction data were recorded for CuSb and ZnSb at the Extreme Conditions Beamline (P02.2) at DESY (Liermann et al., 2015) using synchrotron radiation of wavelength 0.2906 Å, and for ZnAs at Diamond Light Source I-15 Extreme Conditions Beamline using radiation of wavelength 0.1582 Å. Pressure was increased in steps of ∼0.5 GPa up to approximately 2.78 GPa; beyond this pressure, the quality of the diffraction patterns had deteriorated and they could not be indexed reliably. Data were processed using CrysAlis PRO (Rigaku, 2023). Corrections for absorption and gasket shading were applied using the multi-scan method (Blessing, 1995; Rigaku, 2023). Structures were solved and refined as described above, the starting model at each pressure point was taken from the previous point in the series. All atomic positions were refined with anisotropic displacement parameters (ADPs) subject to enhanced rigid-bond restraints (Thorn et al., 2012). The structure of ZnAs-II required an additional restraint in which As2—F and As4—F distances were restrained to 1.72 (2) Å, and F⋯F distances restrained to 2.43 (2) Å to maintain an octa­hedral geometry. Equivalent distance and ADP similarity restraints were also used to maintain reasonable bond lengths and ADPs.

Listings of selected crystal and refinement data are available in Tables 1–3, with data for all structures available in CIF format in the supporting information. Structures were visualized using Mercury (Macrae et al., 2020) or DIAMOND (Version 4; Putz & Brandenberg, 2024). Structure analysis was performed using PLATON (Spek, 2020). Continuous shape measures were calculated using SHAPE (Alvarez et al., 2002; Cirera et al., 2005).

Table 1
Crystal and refinement data for CuSb and ZnSb in phases I and II

Chemical formula	[Cu(XeF2)6][SbF6]2 (CuSb-I)	[Cu(XeF2)6][SbF6]2 (CuSb-II)	[Zn(XeF2)6][SbF6]2 (ZnSb-I)	[Zn(XeF2)6][SbF6]2 (ZnSb-II)
Phase	I	II	I	II
Temperature (K)	200	170	200	160
Mr	1550.84	1550.84	1552.67	1552.63
Crystal system, space group	Trigonal, R	Triclinic, P	Trigonal, R	Triclinic, P
a, b, c (Å)	10.0302 (3), 10.0302 (3), 22.4539 (9)	9.4864 (13), 13.7227 (17), 19.880 (3)	10.0781 (4), 10.0781 (4), 22.4417 (13)	9.4869 (10), 13.7005 (16), 20.057 (2)
α, β, γ (°)	90, 90, 120	89.503 (4), 88.661 (4), 87.490 (4)	90, 90, 120	89.469 (3), 88.697 (3), 86.951 (3)
V (Å^3)	1956.33 (13)	2584.7 (6)	1974.0 (2)	2602.4 (5)
Z	3	4	3	4
Radiation type	Ag Kα, λ = 0.56086 Å	Ag Kα, λ = 0.56086 Å	Ag Kα, λ = 0.56086 Å	Ag Kα, λ = 0.56086 Å
μ (mm^−1)	5.57	5.62	5.65	5.63
Crystal size (mm)	0.40 × 0.30 × 0.10	0.40 × 0.30 × 0.10	0.30 × 0.25 × 0.20	0.30 × 0.25 × 0.20
Data collection
No. of measured, independent and observed [I > 2σ(I)] reflections	16946, 898, 871	51710, 10437, 9427	19496, 1358, 1293	56066, 10213, 7491
Rint	0.042	0.0453	0.067	0.089
(sin θ/λ)max (Å^−1)	0.626	0.625	0.624	0.627
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.015, 0.036, 1.08	0.041, 0.117, 1.08	0.033, 0.091, 1.19	0.061, 0.094, 1.03
No. of reflections	898	10437	1358	9888
No. of parameters	52	599	52	598
No. of restraints	18	423	18	0
Δρmax, Δρmin (e Å^−3)	0.62, −0.47	4.15, −1.82	0.75, −1.15	3.45, −2.48

Table 2
Crystal and refinement data for ZnAs-I and ZnAs-II

Chemical formula	[Zn(XeF2)6][AsF6]2 (ZnAs-I)	[Zn(XeF2)6][AsF6]2 at 0.15 GPa (ZnAs-II)
Phase	I	II
Temperature (K)	100	298
Mr	1459.01	1459.01
Crystal system, space group	Triclinic, P	Monoclinic, P2/n
a, b, c (Å)	9.1236 (7), 13.2086 (10), 10.3242 (9)	13.630 (2), 13.6939 (9), 14.1449 (8)
α, β, γ (°)	89.555 (3), 93.491 (3), 90.650 (3)	90, 90.497 (10), 90
V (Å^3)	1241.75 (17)	2640.0 (4)
Z	2	4
Radiation type	Mo Kα λ = 0.71073 Å	Synchrotron, λ = 0.1582 Å
μ (mm^−1)	11.85	0.83
Crystal size (mm)	0.40 × 0.20 × 0.20	0.25 × 0.22 × 0.05
Data Collection
No. of measured, independent and observed [I > 2σ(I)] reflections	42983, 8946, 8140	5517, 2927, 2267
Rint	0.089	0.036
(sin θ/λ)max (Å^−1)	0.625	0.625
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.052, 0.148, 1.17	0.062, 0.197, 1.08
No. of reflections	8946	2927
No. of parameters	304	307
No. of restraints	198	477
Δρmax, Δρmin (e Å^−3)	2.13, −1.79	1.77, −1.18

Table 3
Crystal and refinement data for CuSb and ZnSb at selected pressures

Chemical formula	[Cu(XeF2)6][SbF6]2 at 0.28 GPa	[Cu(XeF2)6][SbF6]2 at 1.93 GPa	[Zn(XeF2)6][SbF6]2 at 0.16 GPa	[Zn(XeF2)6][SbF6]2 at 2.78 GPa
Phase	I	I	I	I
Mr	1550.84	1550.84	1552.67	1552.67
Crystal system, space group	Trigonal, R	Trigonal, R	Trigonal, R	Trigonal, R
Temperature (K)	298	298	298	298
a, b, c (Å)	10.0084 (4), 10.0084 (4), 22.4492 (7)	9.6632 (7), 9.6632 (7), 21.6075 (11)	10.0363 (4), 10.0363 (4), 22.5388 (11)	9.5373 (10), 9.5373 (10), 21.292 (2)
α, β, γ (°)	90, 90, 120	90, 90, 120	90, 90, 120	90, 90, 120
V (Å^3)	1947.43 (17)	1747.34 (19)	1966.11 (18)	1677.3 (4)
Z	3	3	3	3
Radiation type	Synchrotron, λ = 0.2906 Å	Synchrotron, λ = 0.2906 Å	Synchrotron, λ = 0.2906 Å	Synchrotron, λ = 0.2906 Å
μ (mm^−1)	5.24	5.60	4.99	5.84
Crystal size (mm)	0.20 × 0.10 × 0.05	0.20 × 0.10 × 0.05	0.30 × 0.25 × 0.20	0.30 × 0.25 × 0.20
Data collection
No. of measured, independent and observed [I > 2σ(I)] reflections	1503, 692, 679	1185, 587, 548	1559, 808, 747	1179, 624, 407
Rint	0.030	0.017	0.022	0.031
(sin θ/λ)max (Å^−1)	0.624	0.624	0.625	0.624
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.058, 0.137, 1.17	0.060, 0.169, 1.16	0.059, 0.171, 1.10	0.081, 0.266, 1.06
No. of reflections	692	587	808	624
No. of parameters	52	51	52	51
No. of restraints	18	18	18	18
Δρmax, Δρmin(e Å^−3)	1.32, −2.09	1.29, −1.15	0.98, −1.51	2.50, −1.44

3. Results

3.1. [Cu(XeF₂)₆][SbF₆]₂ (CuSb) structures

3.1.1. CuSb-I

At 200 K, CuSb crystallizes in the space group R (the hexa­gonal setting was used throughout), with Z = 3 and Z′ = 0.167; we shall refer to this phase as CuSb-I [Figs. 1, 2(a) and 3(a)]. The structure consists of discrete [Cu(XeF₂)₆]²⁺ cations with six equivalent linear monodentate XeF₂ ligands bound to Cu1 through F1. The Xe1—F1 bond distance is slightly longer than the terminal Xe1—F2 distance at 2.087 (2) and 1.929 (3) Å, respectively, as is common for coordinating XeF₂ ligands (Tramšek & Žemva, 2006). The Cu atoms occupy the lattice points of the rhombohedral unit cell. This 3a site has (S₆) symmetry and all the Cu—F bond lengths [1.9877 (19) Å] are equal, with apparently no Jahn–Teller distortion. Xe1⋯F1 contacts of 3.442 (3) and 3.470 (2) Å are formed between ligands attached to the same Cu²⁺ centre. The octa­hedral [SbF₆]⁻ anions occupy the 6c sites and have crystallographic 3 (C₃) point symmetry.

Figure 2 The structures of layers in the CuSb and ZnAs phases, showing (a) CuSb-I, (b) CuSb-II, (c) ZnAs-I and (d) ZnAs-II. The figures are projected down the axis that best highlights their similarity to CdCl2. The colours in parts (a) and (b) are as in Fig. 1. In parts (c) and (d), Zn polyhedra are shown in blue and As in yellow. XeF2 ligands are shown in `stick' format.

Figure 3 The Xe contacts between intra­layer anions and XeF2 ligands in (a) CuSb-I, (b) CuSb-II Cu1, (c) CuSb-II Cu2, (d) CuSb-II Cu3, (e) ZnAs-I Zn1, (f) ZnAs-I Zn2, (g) ZnAs-II Zn1 and (h) ZnAs-II Zn2. Inter­layer and same-centre contacts have been omitted for clarity.

The packing in CuSb-I resembles that in CdCl₂ (Fig. S3). The Cd and Cl atoms occupy positions with the same fractional coordinates in CdCl₂ as Cu and Sb in CuSb-I, but the space group symmetry of CdCl₂ is reduced by the XeF₂ and fluoride ligands. Both structures consist of layers which are stacked along the c axes of the unit cells (Fig. 1). The layers [Fig. 2(a)] themselves are com­posed of a layer of cations sandwiched between two layers of anions. The direct chloride bridging of the CdCl₂ structure is replaced in CuSb-I by cation–anion inter­actions mediated by Xe⋯F contacts. The anions are located adjacent to triangular faces of the CuXe₆ octa­hedra, with pairs of F⋯Xe contacts made to two Xe atoms forming one edge of the octa­hedron [two F3⋯Xe1 contacts measuring 3.549 (4) and 3.571 (4) Å to one Xe1, and F3⋯Xe1 and F4⋯Xe1 contacts measuring 3.474 (3) and 3.694 (4) Å to the other; the sum of the van der Waals radii of Xe and F is 3.74 Å (Vogt & Alvarez, 2014)]. Substanti­ally shorter F2⋯Xe1 contacts measuring 3.182 (4) Å are formed to Xe atoms of the cations in the second coordination shell of the same layer, and these decorate the upper and lower surfaces of the layers [Fig. 1(b)].

The contacts between the layers com­prise short F2⋯Xe1 contacts measuring 3.211 (2) Å involving pairs of cations, and longer F4⋯Xe1 inter­actions [3.565 (4) Å] between cations and anions.

The mol­ecular electrostatic potential of XeF₂ shows a positive belt around the equator of the mol­ecule (Kirshenboim & Kozuch, 2016; Gomila & Frontera, 2020). The maximum value of the potential is not located perpendicular to the F—Xe—F axis, but instead there are two maxima, which are slightly displaced towards the F atoms. These lie between the accumulations of electron density associated with the Xe—F bonding and Xe-based lone pairs anti­cipated from the Valence Shell Electron Pair Repulsion (VSEPR) model. Theoretical models suggest that optimal contacts usually subtend angles between 60 and 75° to the primary Xe—F bonds (Gomila & Frontera, 2020). This is true for the shortest Xe1⋯F2 contacts [∠F2—Xe1⋯F2 = 75.39 (10) and 64.27 (11)°], as well as the longer contacts to F3 and F4 [69.63 (9) and 68.13 (12)°, respectively]. Other contacts are formed in directions which are nearly perpendicular to the Xe—F bonds, for example, the F1—Xe1⋯F3 and F4 contacts measuring 3.549 (4) and 3.565 (4) Å form angles of 82.89 (8) and 87.83 (11)° at Xe1.

3.1.2. CuSb-II

At 170 K, CuSb-I undergoes a transition to a triclinic phase, CuSb-II, in the space group P, with Z = 4 and Z′ = 2. No further structural transitions occur on cooling to 30 K. The increase in Z′ from 0.167 to 2 leads to a substantial increase in structural com­plexity [Figs. 2(b) and 3(b)–(d)]. The matrix relating the basis vectors of the unit cell of CuSb-I (a_I, etc.) to those of CuSb-II (a_II, etc.) is given in Equation (5).

The integrity of the sample is preserved across the transition, but the threefold axis of rotation, which was present along [001] in phase I becomes a twin law about [20] in phase II.

The asymmetric unit of CuSb-II contains one [Cu(XeF₂)₆]²⁺ cation on a general position (based on Cu1) and two more located on inversion centres (Cu2 and Cu3). Cu1 is bound to six crystallographically unique XeF₂ ligands based on Xe11 to Xe61, which bind to Cu1 through odd-numbered F atoms F11, F31,…F111; the terminal F atoms carry even-based labels, F21, F41,…F121. The labelling in the cations based on Cu2 and Cu3 is similar, except that the Xe and F labels extend to Xe32, F62, Xe33 and F63 as a result of the inversion symmetry. There are four [SbF₆]⁻ anions in general positions, based on Sb1–Sb4, respectively, carrying F14–F64 to F17–F67.

The averaged Jahn–Teller distortion of phase I is resolved into a static distortion in phase II. Around Cu1, atoms F11 and F91 are extended to distances of 2.100 (6) and 2.099 (7) Å, while the other Cu1—F bonds are between 1.920 (6) (Cu1—F51) and 2.004 (6) Å (Cu1—F71). Similarly, Cu2 exhibits elongated Cu2—F32 bonds [2.095 (6) Å] and shortened Cu2—F12 and Cu2—F52 bonds [1.924 (6) and 1.961 (6) Å, respectively]. Cu3 has long Cu3—F53 bonds [2.114 (6) Å] and short Cu3—F13 and Cu3—F33 bonds [1.931 (6) and 1.932 (6) Å, respectively]. The average Cu—F distance is 1.998 Å, which is very similar to that in CuSb-I. The effect of the Jahn–Teller distortion is propagated to the ligands, a long Cu—F bond leading to shorter (Cu)F—Xe bonds, which have an average length of 2.058 (4) Å com­pared to 2.106 (3) Å for the remainder.

CuSb-II is, like CuSb-I, based on the CdCl₂ structure. The layered packing arrangement is retained, but while the cation based on Cu1 remains in a similar orientation to phase I, Cu2 and Cu3 both undergo rotation within the layer [Figs. 2(b) and 3(b)–(d)]. The anions based on Sb1 and Sb3 have both undergone significant reorientation, while those based on Sb2 and Sb4 maintain more similar orientations to the phase I structure. An animation of the transition, calculated using symmetry mode analysis (ISODISTORT) (Campbell et al., 2006; Stokes et al., 2025) for a simplified structure consisting only of the [CuF₆]²⁺ and [SbF₆]⁻ octa­hedra is available in the supporting information (Movie_1). This demonstrates the large and small reorientations which have occurred in alternate columns consisting of cations and anions running along the c direction of phase II. The loss of alignment of the different com­ponents of the full structure can be seen by com­parison of Figs. 2(a) and 2(b).

The movie referred to in the previous paragraph was gen­er­a­ted by linear inter­polation along the irreducible representations which govern the transition, and it should not be inter­preted as depicting a mechanism. Nevertheless, the symmetry analysis does enable the transformation to be broken down into a formal sequence of symmetry-lowering steps, shown in Fig. 4 in the form of a Bärnighausen tree (Müller, 2013), which helps to unravel the com­plexity of CuSb-II. The first step, labelled Γ₂⁺Γ₃⁺, generates the unit cell with metrics equal to the primitive rhombohedral setting of CuSb-I, but with the space-group symmetry reduced to P as a result of tilting of the octa­hedra away from the rotoinversion axes. The second generates a metrically monoclinic cell through excitation of the F₁⁺ irreducible representation and leads to a doubling of the unit-cell volume. The effect is partially to reverse the tilting that occurred in the Γ₂⁺Γ₃⁺ step for some sites (those which become Cu1, Sb2 and Sb4 in phase II) and to accentuate it for the other sites, while retaining the translational symmetry along the [001] direction. This translational symmetry is broken in the third step, labelled Σ₁, by rotating alternate Cu2, Sb1 and Sb3 octa­hedra clockwise and anti­clockwise about axes parallel to [001]; small alternating displacements occur for the Cu1, Sb2 and Sb3 octa­hedra. The combined effect is to generate CuSb-II, increasing the volume by another factor of two.

Figure 4 Bärnighausen tree showing the group–subgroup relationship between CuSb-I and CuSb-II. See Fig. 10 and text for relationships between basis vectors. The unit-cell dimensions given do not include the effect of strain (see Table 4).

The reorientations of the cations and anions result in reorganization of the Xe⋯F contacts. A notable feature of the structure of CuSb-I is that the shortest inter­molecular Xe⋯F contacts (<3.3 Å) are formed by the cations to other cations in the second mol­ecular coordination sphere, `leap-frogging' the nearest-neighbour [SbF₆]⁻ anions, which all form contacts exceeding 3.4 Å [Fig. 1(b)]. In phase II, there are many short Xe⋯F contacts involving the [SbF₆]⁻ anions, for example, Xe11 and Xe33 have short intra­layer inter­actions of 3.168 (10) (F14) and 3.201 (8) Å (F64), respectively [Figs. 3(b) and 3(d)], with inter­layer contacts to F42 [3.309 (8) Å] and F61 [3.356 (9) Å]. Overall, the Xe⋯F contacts involving the anions span the range from 3.168 (10) (Xe11⋯F14) to 3.731 (8) Å (Xe21⋯F34), com­pared to a range from 3.474 (3) to 3.694 (4) Å in phase I.

The cation–cation contacts in phase II range between 3.063 (9) (Xe31⋯F101) and 3.697 (6) Å (Xe12⋯F52), com­pared to a range from 3.182 (4) to 3.470 (2) Å in phase I. The Xe⋯F contacts involving the anions generally shorten to a greater degree than those formed to cations: the maximum shortening exhibited by these contacts is 0.218 (6) Å for F12, com­pared to a maximum shortening of 0.306 (13) Å for the contacts to anions.

The inter­action angle ∠F—Xe⋯F is shown as a function of inter­action length for inter-ion contacts in Fig. 5. Points shown in blue correspond to phase I and those in red to phase II, the proliferation of the latter being a consequence of the lowering of symmetry. The distribution of square points in the plot makes clear the formation of short cation–anion contacts with optimal F—Xe⋯F angles in the range 60–75° over the course of the transition. By contrast, in phase I, the short cation–cation contacts (filled blue circles) all subtend optimal angles, but they are much more widely distributed in phase II, with some angles extending beyond 80° (filled red circles).

Figure 5 The inter­action angle (∠F⋯Xe—F) of contacts within the sum of the van der Waals radii of F and Xe as a function of inter­action distance for CuSb-I and CuSb-II. Inter­action angles are shown as the acute angle formed to the F—Xe—F axis. Phase I contacts are shown in blue and phase II contacts are shown in red. Cation–anion contacts are shown as empty squares and cation–cation contacts are shown as filled circles. Pseudo-equatorial contacts, those close to 90°, are shown inside the dashed lines at 80 and 90°. Inter­nal F⋯Xe—F inter­actions formed within the cations have been omitted.

In phase I, the number of contacts making angles between 80 and 90° is 12 (both blue squares in Fig. 5 corresponding to six cation–anion inter­actions as a result of the high symmetry). In phase II, there are 13 such contacts, but these are now distributed between the Xe atoms in three crystallographically distinct cations. The average number of contacts beyond the optimal range is therefore 12 per Cu centre in phase I, but only 4.3 per Cu centre in phase II.

The transition from phase I to II is thus characterized by a strengthening in the cation–anion contacts, which are both shorter and formed at more optimal angles in phase II. At the same time, the disordered Jahn–Teller distortion of phase I becomes ordered in phase II. But what drives the transition? Is it an enthalpic effect associated with more optimal contact formation or the result of the reduced effect of entropy at low tem­per­a­ture? This question can be addressed by examining the isostructural Zn analogue, ZnSb.

3.2. [Zn(XeF₂)₆][SbF₆]₂ (ZnSb)

3.2.1. ZnSb-I and ZnSb-II

ZnSb was, like CuSb, found in two phases, denoted ZnSb-I and ZnSb-II. ZnSb-I, which occurs above 160 K, is isostructural with CuSb-I. The Zn1—F1 bond length is 2.001 (5) Å. Minor differences in the inter­molecular contact distances are observed as a result of the difference in Cu—F and Zn—F bond lengths, though the ordering of inter-centre contacts remains the same as in CuSb-I.

ZnSb-II, which is formed at 160 K, is isostructural with CuSb-II. Zn²⁺ is Jahn–Teller inactive and the Zn—F bond lengths are more regularly distributed than in CuSb-II, ranging from 1.984 (6) to 2.021 (6) Å.

Both Cu²⁺ and Zn²⁺ have malleable coordination geometries (Gaazo et al., 1976; Thomas et al., 2023), and the principal significance of the results for ZnSb is that they clarify the role of changes in the geometry of the metal sites in the phase transitions. CuSb undergoes Jahn–Teller ordering on cooling, which causes the shape of the Cu coordination spheres to distort in phase II. By contrast, there are no significant changes in the Zn—F bond lengths over the course of the ZnSb-I→ZnSb-II transition (Table S3). Distortions in the shapes of the octa­hedra can be conveniently qu­anti­fied using continuous shape measures of the metal sites in ZnSb-II relative to that in ZnSb-I (Table S3) (Alvarez et al., 2002; Cirera et al., 2005). None of the values exceeds 0.06; indeed, the same is true for the other Zn-containing phases reported below. The transitions reported for the Zn system thus occur with minimal distortion to the coordination geometry and the transition seen in CuSb cannot be associated with the adoption of an ordered Jahn–Teller distortion in CuSb-II. The enthalpic effect of optimization of the cation–anion contacts is therefore the most likely driver for the phase transition.

3.3. High-pressure analysis of CuSb-I and ZnSb-I

The variation in unit-cell volume of CuSb-I and ZnSb-I between ambient pressure and 2.78 (5) GPa is shown in Fig. 6. The rhombohedral phase persisted for both com­pounds until diffraction quality had declined to a point where the patterns could not be indexed. Pressure therefore does not promote the symmetry-lowering transitions described above. The CuSb and ZnSb phase II structures have a smaller volume per formula unit than the phase I structures, and would be anti­cipated to be more stable at high pressure. It is possible that kinetic factors, such as the inhibition of ion rotation at high pressure, are the cause for the persistence of phase I.

Figure 6 The unit-cell volume as a function of pressure for CuSb-I and ZnSb-I. Cu data points are given as blue squares and Zn data points are given as red circles. Volume error bars lie fully within the data points but have been omitted for clarity. The trend line shows the second-order Birch–Murnaghan equation of state derived for the combined data sets.

The number of pressure points available for each com­pound is too limited to determine the equation-of-state parameters reliably, but as they exhibit very similar trends of volume versus pressure, an approximate average bulk modulus for the combined systems can be ob­tained. A second-order Birch–Murnaghan equation (Birch, 1947) yields an acceptable fit to the combined data, yielding a bulk modulus of 11.4 (6) GPa;, and the reference volume of the average Cu/Zn system refines to 1982 (10) ų. The value of the bulk modulus is similar to the hy­dro­gen-bonded monoclinic phase of L-histidine [11.6 (6) GPa] (Novelli et al., 2020) and L-alanine [13.1 (6) GPa] (Funnell et al., 2010), as well as FeF₃ [14 (1) GPa] (Jørgensen & Smith, 2006). The similarity of the trends depicted in Fig. 6 implies that the Jahn–Teller distortion present in CuSb plays little role in the com­pressibility mechanism.

3.4. [Zn(XeF₂)₆][AsF₆]₂ (ZnAs)

3.4.1. ZnAs-I

The phases found for the ZnAs system are distinct from those of the [SbF₆]⁻ salts described above. At ambient pressure between 100 and 200 K, the ZnAs-I phase forms in the space group P, with Z = 2 and Z′ = 1. The structure is shown in Figs. 2(c) and 3(e)–(f). This is isostructural to the recently reported triclinic [Cu(XeF₂)₆][RuF₆]₂ phase at 100 K (Mržljak et al., 2025).

There are two crystallographically independent Zn sites, both located on inversion centres, with Zn—F bond lengths between 1.974 (11) and 2.021 (11) Å. The [AsF₆]⁻ anions lie on general positions. The structure has the same CdCl₂ motif as the Sb-containing analogues [Fig. 2(c)].

Inspection of the unit-cell dimensions of ZnAs-I (Table 2) identifies it with the third phase in the Bärnighausen tree of Fig. 4, the inter­mediate following the F₁⁺ step in the symmetry pathway leading from MSb-I to MSb-II (M = Cu, Zn). As would be anti­cipated from the discussion in Section 3.1.2, the basis vectors of the unit cells of ZnSb-II and ZnAs-I are related such that the c axis length of ZnAs-I is approximately half of that found for ZnSb-II, whilst the a and b axes are similar.

In order to identify the differences between the com­plete structures of ZnSb-II and ZnAs-I, the structure of the former was transformed using the matrix (100, 010, 00) and atoms located within 0.8 Å were merged. The asymmetric unit of the transformed model is shown in blue in Fig. 7 and we shall refer to it as T-ZnSb-II.

Figure 7 Overlay of the asymmetric units of T-ZnSb-II (blue) and ZnAs-I (red). Both disorder com­ponents are shown for T-ZnSb-II.

Fig. 7 shows the overlay of the structures of T-ZnSb-II and ZnAs-I, demonstrating the relationship between them. The Zn and Sb/As positions in the two structures are the same. Zn1 in ZnAs-I derives from Zn1 in ZnSb-II and Zn2 derives from the superposition of Zn2 and Zn3 from ZnSb-II. The orientation of the cations centred on Zn2 in ZnAs-I is the same as those centred on Zn3 in ZnSb-II. At Zn1, one-third of the XeF₂ ligands overlay well; the positions of two-thirds of the ligating F atoms are in slightly different positions in the two phases, but the positions of the terminal F atoms are nevertheless similar. As1 sits close to the merged Sb1/Sb3 site of ZnSb-II, while the distinct Sb2/4 sites resolve into a single distinct orientation in ZnAs-I.

Therefore, the ZnAs-I structure can be considered as a modification of the half-c-axis averaged cell of ZnSb-II. The Zn1 site has rearranged ligand orientations in ZnAs-I and Zn2 is the result of adoption of the Zn3 site in ZnSb-II. Both anions have re-orientated, with the disorder in Sb1 being resolved in As1, and the anion based on As2 being a rotated form of that of Sb2. A simplified animation of the transition is shown in the file Movie_2 in the supporting information.

The difference in ion orientation between the systems changes the pattern of Xe⋯F contacts, shown projected onto the (20) planes in Figs. 3(e)–(f). The structure contains ap­proximately perpendicular contacts to Xe31, Xe12, Xe22 and Xe32. This results in a total of ten pseudo-equatorial contacts, across two centres, for an average of five per centre. This is similar to the 4.3 per centre seen in ZnSb-II, and significantly fewer than the 12 seen in ZnSb-I.

3.4.2. ZnAs-II

ZnAs-I did not exhibit any structural phase transitions between 100 and 200 K, and pressure was trialled as an additional thermodynamic variable to manipulate the structural behaviour.

A crystal of ZnAs, taken from the same sample as that used for the structure analysis of ZnAs-I, was exposed to a pressure of 0.15 (5) GPa. The structure belonged to the space group P2/n, with Z = 4 and Z′ = 1 (ZnAs-II). The question of whether this phase is the result of a transition or a rare ambient-pressure polymorph is difficult to answer definitively. We have not observed this phase for ZnAs at ambient pressure across a sampling of 11 crystals. It is generally good practice to confirm the identity of a phase before pressure is applied, but this was not possible in the case of ZnAs because of its extreme sensitivity to moisture in the air. While crystals can be mounted on a fibre from under oil and stabilized at low tem­per­a­ture, they decom­pose rapidly on removal from the cold nitro­gen flow of the low-tem­per­a­ture device. Screening of crystals in a closed carefully dried DAC in the absence of a pressure-transmitting medium was also unsuccessful as crystals always decom­posed under these conditions. Data were only collected at one pressure [0.15 (5) GPa], as the sample lost crystallinity after prolonged exposure to the medium.

ZnAs-II also possesses the CdCl₂ motif, with layers shown in Fig. 2(d) and the Xe⋯F anion contacts shown in Figs. 3(g)–(h). There are two cations and four anions in the asymmetric unit. Atoms are labelled in the same manner as previously, with suffixes 1 and 2 being bonded to Zn1 and Zn2, respectively, and F atoms with the suffixes 3, 4, 5 and 6 being bonded to As1, As2, As3 and As4. The Zn atoms lie on inversion centres. The Zn—F bond distances are between 1.966 (9) and 2.020 (12) Å. All the [AsF₆]⁻ anions reside on .2. special positions.

P2/n is not a subgroup of R and so ZnAs-II does not form part of the Bärnighausen tree shown in Fig. 4. Nevertheless, for the purposes of visualization of the relationship between the structure and ZnAs-II, the space group symmetry of the latter was artificially lowered to P and symmetry mode analysis carried out using ISODISTORT. An animation of the transition is shown in Movie_3 in the supporting information. By-and-large, similar comments apply to the relationship between these phases, as was the case between ZnSb-I and ZnAs-I, in that one set of cations and anions undergo more exaggerated tilting than the remainder. The difference is that an F₁⁺ mode now causes a pattern of alternating tilts which breaks the translational symmetry of the parent phase, doubling the lengths of the a and b axes but leaving the space group type unchanged as R. A Γ₂⁺Γ₃⁺ step converts the enlarged R-cell to its primitive setting with loss of the trigonal symmetry to give the model of ZnAs-II.

The above analysis shows that the basis vectors of ZnAs-II are related to those of ZnSb-I by the matrix

An overlay of the transformed structure of ZnSb-I with that of ZnAs-II is shown in Fig. 8. The Zn sites overlap well, with the match extending also to the XeF₂ ligands for Zn1. The cation based on Zn2 has undergone a reorientation, with each XeF₂ ligand having an effectively mirrored coordination. The four symmetry-related Sb1 atoms in the transformed cell of ZnSb-I sit on the same sites as the four symmetry-distinct As1–As4 sites of ZnAs-II. The anions based on As1, As2 and As4 have very similar orientations to those based on Sb1, with only minor tilt changes and distortions. That based on As3 has significantly reoriented, rotating by approximately 45° around the b axis.

Figure 8 Overlay of ZnSb-I (blue) and ZnAs-II (red).

The relationship between ZnAs-I and ZnAs-II can be analysed by again lowering the translational symmetry of ZnAs-I with the matrix (101/00/10), which yields a unit cell of dimensions a = 13.355, b = 13.209, c = 14.188 Å, α = 89.26, β = 97.08, γ = 89.90° and V = 2483.5 ų, which are similar to those of phase II. The movie generated from this analysis is available in the supporting information as Movie_4, which shows that lowering of symmetry during a transition of phase II to I occurs as the anions lose their alignment with the .2. axes of phase II.

Cation–anion contacts are shown in Figs. 3(g)–(h). Fig. 9 shows a plot of contact angle against distance in a similar manner to Fig. 5 for ZnAs-I (blue) and ZnAs-II (red). The majority of F⋯Xe—F angles formed by contacts from both anions (squares) and cations (filled circles) fall into the optimal 60–75° range. Cation–cation contacts tend to be shorter than cation–anion contacts, though there is significant overlap, and the inter­action angles are broadly the same. The shortest inter­molecular contact [between Xe22 and F46 at 3.08 (2) Å] occurs between a cation and an anion. There are 10 pseudo-equatorial contacts to F atoms across the two Zn centres, giving an average of five per centre. This is similar to the situation found for ZnSb-II.

Figure 9 The inter­action angle (∠F⋯Xe—F) of contacts within the sum of the van der Waals radii of F and Xe as a function of inter­action distance for ZnAs-I and ZnAs-II. Inter­action angles are shown as the acute angle formed to the F—Xe—F axis. Phase I contacts are shown in blue and phase II contacts are shown in red. Cation–anion contacts are shown as squares and cation–cation contacts are shown as circles. Pseudo-equatorial contacts, those close to 90°, are shown inside the dashed lines at 80 and 90°. Inter­actions formed within the cations have been omitted.

4. Conclusions

The aim of this work was to resolve the disordered Jahn–Teller distortion about the Cu centre in CuSb-I by changing the tem­per­a­ture and the applied pressure. Ordering was found to occur on reducing the tem­per­a­ture to 170 K, leading to a change in the space group from R to P and the formation of a new twinned phase, CuSb-II. The transition is displacive, leading to a more com­plex structure in which cations and anions are rotated and the XeF₂ ligands reoriented relative to the original phase. Symmetry mode analysis shows that the com­plexity of the transition can be broken down into three elemental distortions, which aids the inter­pretation of the transition. The shortest Xe⋯F contacts in CuSb-I were formed not between cations and the nearest-neighbour anions, but instead between cations. The transition leads to a marked shortening of the cation–anion contacts and a more general adoption of a contact geometry in which the F⋯Xe—F contact angle lies between 60 and 75°, a range identified as optimal for this class of inter­action (Gomila & Frontera, 2020).

As our recent work on the actinide com­plexes M(OR)₄, where M = Th, U or Np and R = mesityl, has shown (Shephard et al., 2022), parallel experiments on isostructural analogues can help to pinpoint the chemical driving forces for phase transitions. In the case of the materials studied here, the same transition as had been observed in CuSb was observed in the analogous Zn system ZnSb, which demonstrates that the transition is not a consequence of the onset of Jahn–Teller ordering, but is instead associated with the formation of more optimal inter­molecular inter­actions.

Both CuSb-I and ZnSb-I were shown to be stable to pressure, reaching a maximum of 2.78 (5) GPa for the Zn system.

We have, as part of this work, also determined the crystal structures of the [AsF₆]⁻-containing system ZnAs. This is somewhat less stable than the Sb-containing systems, and decom­poses slowly at room tem­per­a­ture. At low tem­per­a­ture, the structure of ZnAs is triclinic, but it appears to become monoclinic even at the very modest pressure of 0.15 GPa. Both structures are closely related to those of the Sb analogues ZnAs-I as an inter­mediate in the pathway observed in the Sb-containing analogues, and ZnAs-II through symmetry loss in an enlarged rhombohedral phase. Indeed, all the structures reported here can be inter­preted in terms of distortions of a CdCl₂ aristotype.

The relationships between the basis vectors of the different phases could be determined directly from the orientation matrices of the different phases if the transition was observed in situ, or from the symmetry mode analysis. These relationships, which are summarized in Fig. 10, enable key differences between phases to be identified by superposition of two phases in a common set of axes. The unit-cell dimensions ob­tained by application of the transformations shown in Fig. 10, starting from those of ZnSb-I at 200 K, are com­pared with the observed dimensions for each phase in Table 4; com­parison of pairs of dimensions provides a measure of the strain generated over the course of a transition.

Table 4
Comparison of the observed unit-cell dimensions for phases of ZnA (A = As, Sb) with ideal strain-free values calculated from the underlying relationships between the basis vectors shown in Fig. 10

Phase	Space group		a (Å)	b (Å)	c (Å)	α (°)	β (°)	γ (°)	V (Å^3)	T (K)	P (GPa)
ZnSb-I	R	obs.	10.078	10.078	22.442	90	90	120	1974.0	200	0
ZnSb-II	P	ideal	9.476	13.834	20.156	90	90	84.85	2631.7
		obs.	9.482	13.705	20.048	89.51	88.72	86.96	2600.7	160	0
ZnAs-I	P	ideal	9.476	13.834	10.078	90	90	84.85	1315.9
		obs.	9.124	13.209	10.324	89.56	93.49	90.65	1241.8	100	0
ZnAs-II	P2/n	ideal	13.834	13.833	13.833	93.53	93.52	93.52	2631.7
		obs.	13.63	13.694	14.145	90	90.5	90	2640.0	298	0.15

Figure 10 A summary of the transformation matrices relating basis vectors of phases described in this article. The transitions discussed in the text are shown in black, while those derived by combination of other matrices are shown in blue.

Supporting information

Computing details

Copper (II) bisantimonyhexafluoride hexaxenondifluoride (CuSbI_200K)

Crystal data

CuF12Xe6·2(F6Sb)	Dx = 3.949 Mg m^−3
Mr = 1550.84	Ag Kα radiation, λ = 0.56086 Å
Trigonal, R3	Cell parameters from 9614 reflections
a = 10.0302 (3) Å	θ = 2.3–20.5°
c = 22.4539 (9) Å	µ = 5.57 mm^−1
V = 1956.33 (13) Å^3	T = 200 K
Z = 3	Block, colourless
F(000) = 2013	0.40 × 0.30 × 0.10 mm

Data collection

Bruker APEX-II CCD diffractometer	871 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.042
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0762 before and 0.0498 after correction. The Ratio of minimum to maximum transmission is 0.7118. The λ/2 correction factor is Not present.	θmax = 20.5°, θmin = 2.3°
Tmin = 0.530, Tmax = 0.745	h = −12→12
16946 measured reflections	k = −12→12
898 independent reflections	l = −27→27

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + 12.0603P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max = 0.001
wR(F^2) = 0.036	Δρmax = 0.62 e Å^−3
S = 1.08	Δρmin = −0.47 e Å^−3
898 reflections	Extinction correction: SHELXL-2019/1 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
52 parameters	Extinction coefficient: 0.00055 (3)
18 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
Xe1	0.54499 (3)	0.52936 (2)	0.75102 (2)	0.03486 (9)
Sb1	1.000000	1.000000	0.74777 (2)	0.03765 (11)
Cu1	0.333333	0.666667	0.666667	0.02239 (17)
F1	0.3417 (2)	0.5071 (2)	0.71645 (9)	0.0430 (4)
F2	0.7310 (3)	0.5458 (3)	0.78319 (10)	0.0618 (6)
F3	0.8925 (4)	0.8285 (3)	0.69882 (13)	0.0873 (9)
F4	1.0714 (4)	0.8973 (4)	0.79455 (14)	0.1036 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Xe1	0.04024 (13)	0.04266 (14)	0.03180 (13)	0.02830 (10)	−0.00224 (7)	0.00269 (8)
Sb1	0.04279 (15)	0.04279 (15)	0.02736 (19)	0.02140 (8)	0.000	0.000
Cu1	0.0199 (2)	0.0199 (2)	0.0274 (4)	0.00996 (11)	0.000	0.000
F1	0.0349 (10)	0.0406 (10)	0.0510 (11)	0.0171 (8)	−0.0026 (8)	0.0098 (8)
F2	0.0539 (13)	0.0945 (19)	0.0567 (13)	0.0519 (14)	−0.0071 (10)	0.0101 (12)
F3	0.097 (2)	0.0666 (17)	0.0812 (19)	0.0282 (16)	−0.0160 (16)	−0.0255 (15)
F4	0.127 (3)	0.121 (3)	0.089 (2)	0.081 (3)	−0.012 (2)	0.034 (2)

Geometric parameters (Å, º)

Xe1—F1	2.0871 (19)	Sb1—F4^ii	1.848 (3)
Xe1—F2	1.929 (2)	Cu1—F1^iii	1.9877 (19)
Sb1—F3	1.864 (3)	Cu1—F1^iv	1.9876 (19)
Sb1—F3^i	1.864 (3)	Cu1—F1	1.9877 (19)
Sb1—F3^ii	1.864 (3)	Cu1—F1^v	1.9876 (19)
Sb1—F4^i	1.848 (3)	Cu1—F1^vi	1.9877 (19)
Sb1—F4	1.848 (3)	Cu1—F1^vii	1.9876 (19)
F2—Xe1—F1	178.93 (10)	F1^iii—Cu1—F1^vi	91.47 (8)
F3^i—Sb1—F3	88.77 (14)	F1^iii—Cu1—F1	91.47 (8)
F3^ii—Sb1—F3^i	88.77 (14)	F1—Cu1—F1^vi	91.47 (9)
F3^ii—Sb1—F3	88.77 (14)	F1^v—Cu1—F1^iv	91.47 (9)
F4^i—Sb1—F3^ii	88.81 (16)	F1^vii—Cu1—F1^vi	88.53 (9)
F4^ii—Sb1—F3^i	177.54 (16)	F1^vii—Cu1—F1^iv	91.47 (8)
F4^ii—Sb1—F3	88.81 (16)	F1^iv—Cu1—F1	88.53 (8)
F4^ii—Sb1—F3^ii	91.57 (16)	F1^v—Cu1—F1^iii	88.53 (9)
F4^i—Sb1—F3	177.54 (15)	F1^v—Cu1—F1^vi	88.53 (8)
F4—Sb1—F3^ii	177.54 (16)	F1^vii—Cu1—F1^iii	180.0
F4—Sb1—F3	91.57 (17)	F1^iv—Cu1—F1^vi	180.0
F4^i—Sb1—F3^i	91.57 (17)	F1^iv—Cu1—F1^iii	88.53 (9)
F4—Sb1—F3^i	88.81 (16)	F1^vii—Cu1—F1	88.53 (9)
F4^i—Sb1—F4	90.87 (17)	F1^v—Cu1—F1^vii	91.47 (9)
F4^i—Sb1—F4^ii	90.87 (17)	F1^v—Cu1—F1	180.00 (11)
F4^ii—Sb1—F4	90.87 (17)	Cu1—F1—Xe1	123.74 (9)

Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) −y+1, x−y+1, z; (iv) x−y+2/3, x+1/3, −z+4/3; (v) −x+2/3, −y+4/3, −z+4/3; (vi) −x+y, −x+1, z; (vii) y−1/3, −x+y+1/3, −z+4/3.

Copper (II) Hexakisxenondifluoride Bisantimonyhexafluoride (CuSbII_170K)

Crystal data

CuF12Xe6·2(F6Sb)	Z = 4
Mr = 1550.84	F(000) = 2684
Triclinic, P1	Dx = 3.985 Mg m^−3
a = 9.4864 (13) Å	Ag Kα radiation, λ = 0.56086 Å
b = 13.7227 (17) Å	Cell parameters from 9931 reflections
c = 19.880 (3) Å	θ = 2.2–23.6°
α = 89.503 (4)°	µ = 5.62 mm^−1
β = 88.661 (4)°	T = 170 K
γ = 87.490 (4)°	Block, colourless
V = 2584.7 (6) Å^3	0.40 × 0.30 × 0.10 mm

Data collection

Bruker Venture diffractometer	9427 reflections with I > 2σ(I)
φ and ω scans	θmax = 20.5°, θmin = 0.8°
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0934 before and 0.0572 after correction. The Ratio of minimum to maximum transmission is 0.6432. The λ/2 correction factor is Not present.	h = −11→11
Tmin = 0.479, Tmax = 0.745	k = −17→17
10437 measured reflections	l = −22→24
10437 independent reflections

Refinement

Refinement on F^2	423 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.041	Secondary atom site location: difference Fourier map
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 62.2747P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
10437 reflections	Δρmax = 4.15 e Å^−3
599 parameters	Δρmin = −1.82 e Å^−3

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.

Refinement. Refined as a 2-component twin (see above) Enhance rigid bond (RIGU) restaints were applied globally.

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

	x	y	z	Uiso*/Ueq
Cu1	0.51393 (12)	0.98903 (8)	0.24811 (5)	0.0189 (2)
Xe11	0.81092 (6)	1.02247 (4)	0.13305 (3)	0.02272 (14)
F11	0.6387 (7)	0.9458 (5)	0.1641 (3)	0.0355 (14)
F21	0.9754 (7)	1.0924 (5)	0.1032 (4)	0.0440 (17)
Xe21	0.51931 (7)	1.25379 (4)	0.26161 (3)	0.02615 (14)
F31	0.5178 (7)	1.1230 (4)	0.2092 (3)	0.0327 (13)
F41	0.5183 (9)	1.3764 (5)	0.3093 (4)	0.0479 (18)
Xe31	0.70655 (8)	0.97452 (5)	0.40109 (4)	0.03252 (16)
F51	0.6757 (7)	1.0157 (5)	0.3001 (3)	0.0368 (15)
F61	0.7448 (10)	0.9389 (6)	0.4919 (4)	0.060 (2)
Xe41	0.49769 (7)	0.73659 (4)	0.21696 (3)	0.02548 (14)
F71	0.5109 (7)	0.8521 (5)	0.2839 (3)	0.0343 (14)
F81	0.4855 (7)	0.6291 (4)	0.1545 (4)	0.0389 (16)
Xe51	0.29475 (6)	1.01057 (4)	0.10261 (3)	0.02289 (14)
F91	0.3907 (7)	1.0398 (5)	0.3307 (3)	0.0375 (15)
F101	0.0244 (9)	0.9280 (6)	0.3859 (5)	0.059 (2)
Xe61	0.20144 (8)	0.98324 (5)	0.35816 (4)	0.03070 (16)
F111	0.3473 (6)	0.9591 (4)	0.1996 (3)	0.0267 (12)
F121	0.2430 (8)	1.0565 (5)	0.0151 (3)	0.0377 (15)
Cu2	1.000000	0.500000	0.000000	0.0136 (3)
Xe12	0.73111 (6)	0.52241 (4)	−0.12313 (3)	0.02063 (13)
F12	0.9247 (6)	0.4651 (4)	−0.0851 (3)	0.0265 (12)
F22	0.5561 (6)	0.5751 (5)	−0.1593 (4)	0.0350 (14)
Xe22	0.96974 (7)	0.76372 (4)	0.02228 (3)	0.02473 (14)
F32	0.8824 (6)	0.6328 (4)	0.0017 (3)	0.0321 (14)
F42	1.0463 (8)	0.8889 (5)	0.0446 (5)	0.052 (2)
Xe32	0.76198 (7)	0.48231 (5)	0.14020 (3)	0.02630 (15)
F52	0.8413 (6)	0.4382 (4)	0.0456 (3)	0.0324 (14)
F62	0.6889 (7)	0.5247 (6)	0.2273 (3)	0.0484 (19)
Cu3	0.000000	0.500000	0.500000	0.0158 (3)
Xe13	0.26941 (6)	0.47559 (5)	0.61875 (3)	0.02215 (13)
F13	0.0863 (6)	0.5460 (4)	0.5802 (3)	0.0299 (13)
F23	0.4380 (7)	0.4107 (5)	0.6532 (3)	0.0377 (15)
Xe23	0.25074 (6)	0.51643 (5)	0.36146 (3)	0.02321 (14)
F33	0.1844 (7)	0.4750 (5)	0.4590 (3)	0.0374 (15)
F43	0.3113 (7)	0.5528 (5)	0.2719 (3)	0.0359 (14)
Xe33	0.01126 (7)	0.77076 (5)	0.50272 (4)	0.03018 (16)
F53	−0.0126 (7)	0.6405 (5)	0.4554 (3)	0.0355 (14)
F63	0.0371 (9)	0.8960 (5)	0.5455 (5)	0.062 (2)
Sb1	0.03470 (7)	1.26363 (5)	0.24868 (3)	0.02471 (15)
F14	−0.1153 (9)	1.1826 (7)	0.2390 (5)	0.063 (2)
F24	0.1881 (8)	1.3468 (5)	0.2567 (4)	0.0499 (18)
F34	0.1642 (9)	1.1626 (5)	0.2258 (4)	0.0530 (19)
F44	0.0226 (8)	1.3030 (5)	0.1587 (3)	0.0443 (16)
F54	−0.0929 (9)	1.3659 (6)	0.2720 (4)	0.060 (2)
F64	0.0518 (10)	1.2281 (6)	0.3384 (4)	0.058 (2)
Sb2	0.52023 (8)	1.25894 (6)	0.48773 (4)	0.03242 (17)
F15	0.6492 (10)	1.2909 (9)	0.5525 (5)	0.085 (3)
F25	0.3971 (9)	1.2282 (7)	0.4213 (4)	0.064 (2)
F35	0.6690 (8)	1.2534 (7)	0.4230 (5)	0.063 (2)
F45	0.4865 (10)	1.3916 (6)	0.4703 (6)	0.075 (3)
F55	0.3694 (8)	1.2624 (6)	0.5507 (4)	0.0490 (18)
F65	0.5578 (11)	1.1266 (6)	0.5072 (4)	0.065 (2)
Sb3	0.99635 (8)	0.73883 (6)	0.24643 (4)	0.03206 (17)
F16	0.9936 (9)	0.6035 (6)	0.2628 (5)	0.063 (2)
F26	1.0003 (11)	0.8723 (6)	0.2311 (6)	0.080 (3)
F36	1.1355 (9)	0.7480 (6)	0.3105 (4)	0.0523 (19)
F46	1.1386 (8)	0.7161 (7)	0.1815 (4)	0.062 (2)
F56	0.8577 (9)	0.7278 (9)	0.1811 (4)	0.075 (3)
F66	0.8525 (10)	0.7587 (8)	0.3116 (5)	0.074 (3)
Sb4	0.52979 (7)	1.24913 (5)	0.01619 (4)	0.02433 (15)
F17	0.5039 (8)	1.3844 (5)	0.0095 (4)	0.0453 (17)
F27	0.5556 (8)	1.1127 (5)	0.0248 (4)	0.0405 (16)
F37	0.4061 (8)	1.2320 (6)	−0.0543 (3)	0.0449 (17)
F47	0.3756 (8)	1.2456 (5)	0.0782 (3)	0.0406 (16)
F57	0.6545 (9)	1.2620 (6)	0.0880 (4)	0.0526 (19)
F67	0.6818 (8)	1.2499 (6)	−0.0452 (4)	0.052 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0219 (6)	0.0174 (5)	0.0175 (6)	−0.0024 (4)	−0.0011 (4)	−0.0007 (4)
Xe11	0.0226 (3)	0.0244 (3)	0.0209 (3)	0.0001 (2)	0.0007 (2)	−0.0012 (2)
F11	0.034 (3)	0.032 (3)	0.041 (4)	−0.010 (3)	0.008 (3)	−0.007 (3)
F21	0.036 (4)	0.045 (4)	0.051 (4)	−0.010 (3)	0.015 (3)	0.006 (3)
Xe21	0.0292 (3)	0.0183 (3)	0.0306 (3)	0.0026 (2)	−0.0016 (3)	−0.0010 (2)
F31	0.043 (4)	0.026 (3)	0.028 (3)	0.003 (3)	0.001 (3)	−0.003 (2)
F41	0.064 (5)	0.024 (3)	0.056 (5)	−0.001 (3)	−0.003 (4)	−0.012 (3)
Xe31	0.0353 (4)	0.0309 (3)	0.0318 (4)	0.0024 (3)	−0.0168 (3)	−0.0051 (3)
F51	0.034 (3)	0.048 (4)	0.030 (3)	−0.011 (3)	−0.008 (3)	0.002 (3)
F61	0.085 (6)	0.058 (5)	0.038 (4)	0.007 (4)	−0.033 (4)	0.001 (4)
Xe41	0.0268 (3)	0.0155 (3)	0.0344 (4)	−0.0020 (2)	−0.0040 (3)	0.0020 (2)
F71	0.047 (4)	0.030 (3)	0.026 (3)	0.000 (3)	−0.005 (3)	−0.001 (2)
F81	0.047 (4)	0.021 (3)	0.050 (4)	−0.007 (3)	−0.009 (3)	−0.007 (3)
Xe51	0.0233 (3)	0.0233 (3)	0.0222 (3)	0.0011 (2)	−0.0064 (2)	−0.0032 (2)
F91	0.036 (3)	0.042 (4)	0.035 (3)	−0.011 (3)	0.001 (3)	−0.005 (3)
F101	0.054 (5)	0.039 (4)	0.083 (6)	−0.007 (3)	0.035 (4)	−0.004 (4)
Xe61	0.0347 (4)	0.0282 (3)	0.0287 (3)	−0.0016 (3)	0.0109 (3)	−0.0017 (3)
F111	0.026 (3)	0.029 (3)	0.026 (3)	−0.005 (2)	−0.004 (2)	0.004 (2)
F121	0.051 (4)	0.036 (4)	0.025 (3)	0.010 (3)	−0.015 (3)	−0.002 (3)
Cu2	0.0141 (7)	0.0132 (7)	0.0136 (7)	0.0009 (5)	−0.0013 (5)	−0.0010 (5)
Xe12	0.0183 (3)	0.0226 (3)	0.0212 (3)	−0.0002 (2)	−0.0058 (2)	−0.0012 (2)
F12	0.022 (3)	0.033 (3)	0.024 (3)	0.005 (2)	−0.006 (2)	−0.005 (2)
F22	0.024 (3)	0.033 (3)	0.047 (4)	0.005 (2)	−0.015 (3)	−0.001 (3)
Xe22	0.0276 (3)	0.0165 (3)	0.0304 (3)	−0.0009 (2)	−0.0056 (2)	−0.0020 (2)
F32	0.028 (3)	0.023 (3)	0.046 (4)	−0.001 (2)	−0.008 (3)	−0.001 (3)
F42	0.052 (4)	0.021 (3)	0.085 (6)	−0.005 (3)	−0.018 (4)	−0.017 (3)
Xe32	0.0213 (3)	0.0356 (3)	0.0214 (3)	0.0016 (2)	0.0054 (2)	0.0001 (2)
F52	0.029 (3)	0.034 (3)	0.035 (3)	−0.009 (3)	0.009 (3)	−0.007 (3)
F62	0.031 (4)	0.089 (6)	0.024 (3)	0.007 (4)	0.005 (3)	−0.003 (3)
Cu3	0.0182 (7)	0.0170 (7)	0.0118 (7)	0.0028 (6)	−0.0007 (6)	−0.0001 (5)
Xe13	0.0201 (3)	0.0289 (3)	0.0177 (3)	−0.0007 (2)	−0.0045 (2)	−0.0018 (2)
F13	0.035 (3)	0.028 (3)	0.026 (3)	0.008 (2)	−0.007 (2)	−0.006 (2)
F23	0.027 (3)	0.050 (4)	0.035 (4)	0.011 (3)	−0.009 (3)	−0.003 (3)
Xe23	0.0216 (3)	0.0306 (3)	0.0172 (3)	−0.0004 (2)	0.0024 (2)	−0.0018 (2)
F33	0.028 (3)	0.062 (4)	0.021 (3)	0.008 (3)	0.003 (2)	0.008 (3)
F43	0.036 (3)	0.050 (4)	0.022 (3)	−0.003 (3)	0.004 (3)	0.001 (3)
Xe33	0.0290 (3)	0.0207 (3)	0.0411 (4)	−0.0003 (2)	−0.0047 (3)	−0.0039 (3)
F53	0.050 (4)	0.028 (3)	0.029 (3)	−0.001 (3)	−0.006 (3)	0.001 (2)
F63	0.066 (5)	0.028 (4)	0.093 (7)	−0.006 (4)	−0.010 (5)	−0.025 (4)
Sb1	0.0275 (3)	0.0223 (3)	0.0244 (3)	0.0005 (3)	−0.0023 (3)	−0.0030 (3)
F14	0.059 (5)	0.072 (5)	0.063 (5)	−0.043 (4)	0.008 (4)	−0.012 (4)
F24	0.051 (4)	0.043 (4)	0.058 (5)	−0.017 (3)	−0.012 (4)	−0.004 (3)
F34	0.061 (5)	0.037 (4)	0.059 (5)	0.021 (3)	0.005 (4)	−0.010 (3)
F44	0.057 (4)	0.048 (4)	0.029 (3)	−0.001 (3)	−0.004 (3)	0.002 (3)
F54	0.063 (5)	0.053 (5)	0.061 (5)	0.027 (4)	0.001 (4)	−0.017 (4)
F64	0.090 (6)	0.054 (5)	0.030 (4)	0.006 (4)	−0.005 (4)	0.008 (3)
Sb2	0.0287 (4)	0.0325 (4)	0.0356 (4)	0.0065 (3)	0.0001 (3)	−0.0076 (3)
F15	0.047 (5)	0.140 (9)	0.068 (6)	−0.011 (5)	−0.012 (4)	−0.048 (6)
F25	0.061 (5)	0.098 (7)	0.035 (4)	−0.025 (5)	−0.013 (4)	0.000 (4)
F35	0.038 (4)	0.089 (6)	0.061 (5)	0.010 (4)	0.015 (4)	−0.002 (5)
F45	0.063 (6)	0.028 (4)	0.131 (9)	0.002 (4)	0.022 (5)	0.005 (4)
F55	0.045 (4)	0.051 (4)	0.051 (4)	−0.004 (3)	0.016 (3)	−0.019 (3)
F65	0.092 (7)	0.043 (4)	0.056 (5)	0.036 (4)	0.010 (4)	0.003 (4)
Sb3	0.0256 (4)	0.0422 (4)	0.0279 (4)	0.0041 (3)	−0.0030 (3)	0.0047 (3)
F16	0.056 (5)	0.043 (4)	0.091 (7)	−0.008 (3)	−0.012 (4)	0.006 (4)
F26	0.089 (7)	0.043 (5)	0.106 (8)	0.011 (4)	−0.018 (6)	0.037 (5)
F36	0.056 (5)	0.053 (5)	0.048 (4)	0.006 (4)	−0.023 (4)	−0.005 (3)
F46	0.038 (4)	0.098 (7)	0.051 (5)	−0.007 (4)	0.012 (4)	−0.006 (4)
F56	0.036 (4)	0.150 (9)	0.040 (4)	−0.011 (5)	−0.015 (3)	0.012 (5)
F66	0.059 (5)	0.102 (7)	0.057 (5)	0.018 (5)	0.024 (4)	0.000 (5)
Sb4	0.0231 (3)	0.0217 (3)	0.0278 (4)	0.0016 (2)	0.0035 (3)	−0.0013 (3)
F17	0.055 (4)	0.020 (3)	0.061 (5)	0.002 (3)	0.009 (4)	0.003 (3)
F27	0.047 (4)	0.023 (3)	0.051 (4)	0.010 (3)	0.006 (3)	−0.003 (3)
F37	0.048 (4)	0.060 (5)	0.028 (3)	−0.013 (3)	−0.009 (3)	0.007 (3)
F47	0.048 (4)	0.036 (3)	0.036 (4)	0.004 (3)	0.022 (3)	−0.002 (3)
F57	0.061 (5)	0.048 (4)	0.051 (4)	−0.011 (4)	−0.025 (4)	0.002 (3)
F67	0.033 (4)	0.070 (5)	0.052 (4)	0.007 (3)	0.025 (3)	0.004 (4)

Geometric parameters (Å, º)

Cu1—F51	1.920 (6)	Cu3—F13^ii	1.932 (6)
Cu1—F111	1.932 (6)	Cu3—F53	2.114 (6)
Cu1—F31	1.989 (6)	Cu3—F53^ii	2.114 (6)
Cu1—F71	2.004 (6)	Xe13—F23	1.933 (6)
Cu1—F91	2.099 (7)	Xe13—F13	2.108 (6)
Cu1—F11	2.100 (6)	Xe23—F43	1.926 (6)
Xe11—F21	1.945 (6)	Xe23—F33	2.106 (6)
Xe11—F11	2.062 (6)	Xe33—F63	1.951 (7)
Xe21—F41	1.938 (7)	Xe33—F53	2.051 (6)
Xe21—F31	2.084 (6)	Sb1—F64	1.853 (7)
Xe31—F61	1.905 (8)	Sb1—F14	1.858 (7)
Xe31—F51	2.104 (7)	Sb1—F34	1.864 (7)
Xe41—F81	1.946 (6)	Sb1—F54	1.867 (7)
Xe41—F71	2.088 (6)	Sb1—F44	1.869 (7)
Xe51—F121	1.913 (6)	Sb1—F24	1.899 (7)
Xe51—F111	2.110 (6)	Sb2—F25	1.848 (8)
F91—Xe61	2.047 (6)	Sb2—F15	1.864 (9)
F101—Xe61	1.939 (7)	Sb2—F45	1.865 (8)
Cu2—F12^i	1.924 (6)	Sb2—F65	1.874 (8)
Cu2—F12	1.924 (6)	Sb2—F55	1.878 (7)
Cu2—F52^i	1.961 (6)	Sb2—F35	1.887 (8)
Cu2—F52	1.961 (6)	Sb3—F26	1.857 (8)
Cu2—F32	2.095 (6)	Sb3—F46	1.863 (8)
Cu2—F32^i	2.095 (6)	Sb3—F36	1.865 (7)
Xe12—F22	1.933 (6)	Sb3—F66	1.872 (8)
Xe12—F12	2.119 (6)	Sb3—F56	1.881 (8)
Xe22—F42	1.952 (6)	Sb3—F16	1.883 (8)
Xe22—F32	2.059 (6)	Sb4—F17	1.865 (6)
Xe32—F62	1.935 (7)	Sb4—F67	1.867 (6)
Xe32—F52	2.093 (6)	Sb4—F37	1.871 (7)
Cu3—F33	1.931 (6)	Sb4—F27	1.884 (6)
Cu3—F33^ii	1.931 (6)	Sb4—F57	1.889 (7)
Cu3—F13	1.932 (6)	Sb4—F47	1.893 (6)
F51—Cu1—F111	177.2 (3)	F43—Xe23—F33	179.3 (3)
F51—Cu1—F31	89.4 (3)	Cu3—F33—Xe23	126.7 (3)
F111—Cu1—F31	92.7 (3)	F63—Xe33—F53	178.4 (4)
F51—Cu1—F71	91.7 (3)	Xe33—F53—Cu3	126.7 (3)
F111—Cu1—F71	86.3 (3)	F64—Sb1—F14	91.4 (4)
F31—Cu1—F71	177.9 (2)	F64—Sb1—F34	89.0 (4)
F51—Cu1—F91	86.8 (3)	F14—Sb1—F34	91.3 (4)
F111—Cu1—F91	91.3 (3)	F64—Sb1—F54	90.8 (4)
F31—Cu1—F91	91.1 (3)	F14—Sb1—F54	89.5 (4)
F71—Cu1—F91	90.7 (3)	F34—Sb1—F54	179.2 (4)
F51—Cu1—F11	92.7 (3)	F64—Sb1—F44	177.8 (4)
F111—Cu1—F11	89.3 (3)	F14—Sb1—F44	90.7 (4)
F31—Cu1—F11	86.0 (3)	F34—Sb1—F44	91.2 (4)
F71—Cu1—F11	92.2 (3)	F54—Sb1—F44	89.0 (4)
F91—Cu1—F11	177.1 (2)	F64—Sb1—F24	89.7 (4)
F21—Xe11—F11	178.8 (3)	F14—Sb1—F24	178.8 (4)
Xe11—F11—Cu1	121.4 (3)	F34—Sb1—F24	88.6 (4)
F41—Xe21—F31	179.0 (3)	F54—Sb1—F24	90.7 (4)
Cu1—F31—Xe21	127.2 (3)	F44—Sb1—F24	88.1 (3)
F61—Xe31—F51	176.9 (4)	F25—Sb2—F15	178.0 (4)
Cu1—F51—Xe31	125.8 (3)	F25—Sb2—F45	90.4 (5)
F81—Xe41—F71	179.9 (3)	F15—Sb2—F45	89.1 (5)
Cu1—F71—Xe41	119.5 (3)	F25—Sb2—F65	91.3 (5)
F121—Xe51—F111	178.8 (3)	F15—Sb2—F65	89.2 (5)
Xe61—F91—Cu1	123.2 (3)	F45—Sb2—F65	178.3 (5)
F101—Xe61—F91	178.6 (4)	F25—Sb2—F55	89.6 (4)
Cu1—F111—Xe51	126.1 (3)	F15—Sb2—F55	92.4 (4)
F12^i—Cu2—F12	180.0	F45—Sb2—F55	89.7 (4)
F12^i—Cu2—F52^i	89.1 (3)	F65—Sb2—F55	90.3 (4)
F12—Cu2—F52^i	90.9 (3)	F25—Sb2—F35	89.1 (4)
F12^i—Cu2—F52	90.9 (3)	F15—Sb2—F35	89.0 (4)
F12—Cu2—F52	89.1 (3)	F45—Sb2—F35	90.8 (4)
F52^i—Cu2—F52	180.0	F65—Sb2—F35	89.2 (4)
F12^i—Cu2—F32	87.9 (2)	F55—Sb2—F35	178.5 (4)
F12—Cu2—F32	92.1 (2)	F26—Sb3—F46	90.8 (5)
F52^i—Cu2—F32	91.1 (3)	F26—Sb3—F36	89.9 (4)
F52—Cu2—F32	88.9 (3)	F46—Sb3—F36	88.6 (4)
F12^i—Cu2—F32^i	92.1 (2)	F26—Sb3—F66	90.4 (5)
F12—Cu2—F32^i	87.9 (2)	F46—Sb3—F66	178.7 (5)
F52^i—Cu2—F32^i	88.9 (3)	F36—Sb3—F66	91.7 (4)
F52—Cu2—F32^i	91.1 (3)	F26—Sb3—F56	90.8 (5)
F32—Cu2—F32^i	180.00 (16)	F46—Sb3—F56	90.6 (4)
F22—Xe12—F12	179.0 (3)	F36—Sb3—F56	179.0 (4)
Cu2—F12—Xe12	124.4 (3)	F66—Sb3—F56	89.0 (4)
F42—Xe22—F32	177.6 (3)	F26—Sb3—F16	179.4 (5)
Xe22—F32—Cu2	122.8 (3)	F46—Sb3—F16	89.3 (4)
F62—Xe32—F52	179.3 (3)	F36—Sb3—F16	89.5 (4)
Cu2—F52—Xe32	122.8 (3)	F66—Sb3—F16	89.5 (5)
F33—Cu3—F33^ii	180.00 (16)	F56—Sb3—F16	89.8 (5)
F33—Cu3—F13	90.1 (3)	F17—Sb4—F67	91.2 (3)
F33^ii—Cu3—F13	89.9 (3)	F17—Sb4—F37	91.1 (4)
F33—Cu3—F13^ii	89.9 (3)	F67—Sb4—F37	90.2 (4)
F33^ii—Cu3—F13^ii	90.1 (3)	F17—Sb4—F27	178.9 (3)
F13—Cu3—F13^ii	180.0	F67—Sb4—F27	89.6 (3)
F33—Cu3—F53	90.6 (3)	F37—Sb4—F27	89.7 (3)
F33^ii—Cu3—F53	89.4 (3)	F17—Sb4—F57	90.7 (4)
F13—Cu3—F53	93.2 (3)	F67—Sb4—F57	90.2 (4)
F13^ii—Cu3—F53	86.8 (3)	F37—Sb4—F57	178.1 (3)
F33—Cu3—F53^ii	89.4 (3)	F27—Sb4—F57	88.4 (3)
F33^ii—Cu3—F53^ii	90.6 (3)	F17—Sb4—F47	89.9 (3)
F13—Cu3—F53^ii	86.8 (3)	F67—Sb4—F47	178.8 (3)
F13^ii—Cu3—F53^ii	93.2 (3)	F37—Sb4—F47	89.5 (3)
F53—Cu3—F53^ii	180.0 (4)	F27—Sb4—F47	89.3 (3)
F23—Xe13—F13	179.4 (3)	F57—Sb4—F47	90.1 (4)
Cu3—F13—Xe13	121.3 (3)

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

(CuSbII_30K)

Crystal data

CuF24Sb2Xe6	Z = 4
Mr = 1550.84	F(000) = 2684
Triclinic, P1	Dx = 4.112 Mg m^−3
a = 9.3636 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.5864 (11) Å	Cell parameters from 9976 reflections
c = 19.7151 (16) Å	θ = 2.5–26.4°
α = 89.348 (3)°	µ = 11.13 mm^−1
β = 88.430 (2)°	T = 30 K
γ = 87.758 (3)°	Block, colourless
V = 2505.1 (4) Å^3	0.50 × 0.30 × 0.30 mm

Data collection

Bruker D8 Venture diffractometer	9200 reflections with I > 2σ(I)
ω and phi scans	Rint = 0.090
Absorption correction: multi-scan TWINABS - Bruker AXS scaling for twinned crystals - Version 2012/1	θmax = 26.5°, θmin = 2.1°
Tmin = 0.002, Tmax = 0.020	h = −11→11
15982 measured reflections	k = −16→16
10164 independent reflections	l = 0→24

Refinement

Refinement on F^2	423 restraints
Least-squares matrix: full	Primary atom site location: From 170 K structure
R[F^2 > 2σ(F^2)] = 0.082	w = 1/[σ^2(Fo^2) + (0.1709P)^2 + 97.0281P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.251	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 4.38 e Å^−3
10164 reflections	Δρmin = −3.30 e Å^−3
598 parameters

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.

Refinement. Enhanced rigid body restraints were applied globally with default weights.

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

	x	y	z	Uiso*/Ueq
Cu1	0.5167 (2)	0.98286 (15)	0.24937 (10)	0.0196 (4)
Xe11	0.81876 (11)	1.02120 (8)	0.13224 (5)	0.0201 (3)
F11	0.6472 (11)	0.9409 (7)	0.1603 (5)	0.0212 (19)
F21	0.9854 (11)	1.0982 (7)	0.1050 (6)	0.027 (2)
Xe21	0.51942 (12)	1.24817 (8)	0.26188 (5)	0.0203 (3)
F31	0.5198 (11)	1.1151 (7)	0.2099 (5)	0.023 (2)
F41	0.5176 (11)	1.3741 (7)	0.3074 (5)	0.024 (2)
Xe31	0.69161 (12)	0.97192 (8)	0.40759 (6)	0.0216 (3)
F51	0.6731 (10)	1.0108 (7)	0.3037 (5)	0.0187 (18)
F61	0.7198 (12)	0.9370 (8)	0.5010 (5)	0.027 (2)
Xe41	0.50204 (11)	0.73292 (8)	0.21369 (5)	0.0203 (3)
F71	0.5168 (11)	0.8478 (7)	0.2843 (5)	0.0201 (19)
F81	0.4888 (11)	0.6288 (8)	0.1489 (5)	0.025 (2)
Xe51	0.29982 (11)	1.00778 (8)	0.10231 (5)	0.0199 (3)
F91	0.3821 (11)	1.0371 (7)	0.3339 (5)	0.023 (2)
F101	0.0008 (11)	0.9270 (7)	0.3728 (5)	0.023 (2)
Xe61	0.18720 (12)	0.98203 (8)	0.35338 (6)	0.0211 (3)
F111	0.3502 (11)	0.9536 (7)	0.2005 (5)	0.0216 (19)
F121	0.2517 (11)	1.0580 (8)	0.0137 (5)	0.028 (2)
Cu2	1.000000	0.500000	0.000000	0.0187 (6)
Xe12	0.73110 (11)	0.52582 (8)	−0.12429 (5)	0.0194 (3)
F12	0.9245 (11)	0.4680 (8)	−0.0851 (5)	0.024 (2)
F22	0.5546 (12)	0.5796 (8)	−0.1627 (6)	0.026 (2)
Xe22	0.96549 (11)	0.76614 (7)	0.02170 (5)	0.0202 (3)
F32	0.8708 (11)	0.6361 (7)	0.0051 (5)	0.023 (2)
F42	1.0506 (12)	0.8926 (8)	0.0400 (6)	0.030 (2)
Xe32	0.76296 (11)	0.47905 (8)	0.13985 (5)	0.0200 (3)
F52	0.8469 (11)	0.4314 (7)	0.0455 (5)	0.023 (2)
F62	0.6852 (11)	0.5239 (7)	0.2271 (5)	0.025 (2)
Cu3	0.000000	0.500000	0.500000	0.0190 (6)
Xe13	0.26676 (11)	0.47601 (8)	0.62009 (5)	0.0194 (2)
F13	0.0822 (11)	0.5483 (8)	0.5796 (5)	0.025 (2)
F23	0.4362 (12)	0.4088 (8)	0.6546 (6)	0.029 (2)
Xe23	0.25347 (12)	0.51409 (8)	0.36170 (5)	0.0198 (3)
F33	0.1891 (10)	0.4736 (8)	0.4614 (5)	0.024 (2)
F43	0.3133 (11)	0.5504 (8)	0.2707 (5)	0.025 (2)
Xe33	0.01366 (11)	0.77619 (8)	0.49821 (5)	0.0212 (3)
F53	−0.0109 (12)	0.6438 (7)	0.4522 (5)	0.026 (2)
F63	0.0388 (12)	0.9043 (8)	0.5395 (6)	0.030 (2)
Sb1	0.03508 (12)	1.26223 (8)	0.24970 (6)	0.0200 (3)
F14	−0.1169 (11)	1.1786 (8)	0.2400 (5)	0.025 (2)
F24	0.1885 (11)	1.3446 (7)	0.2587 (5)	0.023 (2)
F34	0.1653 (12)	1.1583 (8)	0.2261 (6)	0.030 (2)
F44	0.0245 (11)	1.3028 (8)	0.1582 (5)	0.025 (2)
F54	−0.0940 (11)	1.3663 (7)	0.2728 (5)	0.024 (2)
F64	0.0479 (13)	1.2252 (7)	0.3411 (5)	0.029 (2)
Sb2	0.52423 (12)	1.26612 (8)	0.48444 (6)	0.0214 (3)
F15	0.6507 (12)	1.3031 (9)	0.5499 (6)	0.033 (2)
F25	0.4022 (11)	1.2283 (8)	0.4165 (5)	0.025 (2)
F35	0.6755 (12)	1.2623 (8)	0.4198 (6)	0.031 (2)
F45	0.4849 (11)	1.4001 (7)	0.4639 (5)	0.025 (2)
F55	0.3720 (11)	1.2662 (8)	0.5474 (5)	0.024 (2)
F65	0.5684 (11)	1.1338 (8)	0.5089 (5)	0.026 (2)
Sb3	0.99778 (13)	0.72712 (8)	0.24482 (6)	0.0206 (3)
F16	0.9957 (12)	0.5905 (8)	0.2651 (6)	0.029 (2)
F26	1.0001 (12)	0.8631 (7)	0.2238 (6)	0.028 (2)
F36	1.1352 (12)	0.7428 (8)	0.3116 (6)	0.029 (2)
F46	1.1460 (11)	0.7034 (8)	0.1787 (5)	0.026 (2)
F56	0.8620 (10)	0.7101 (8)	0.1785 (5)	0.026 (2)
F66	0.8471 (12)	0.7488 (8)	0.3088 (6)	0.031 (2)
Sb4	0.53253 (12)	1.24863 (8)	0.01899 (6)	0.0202 (3)
F17	0.5063 (12)	1.3864 (7)	0.0141 (6)	0.026 (2)
F27	0.5604 (11)	1.1113 (7)	0.0267 (5)	0.023 (2)
F37	0.4098 (11)	1.2297 (8)	−0.0532 (6)	0.027 (2)
F47	0.3771 (12)	1.2426 (8)	0.0822 (5)	0.025 (2)
F57	0.6560 (11)	1.2613 (8)	0.0921 (5)	0.027 (2)
F67	0.6856 (11)	1.2525 (8)	−0.0433 (5)	0.028 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0260 (10)	0.0202 (10)	0.0126 (10)	−0.0032 (8)	0.0010 (8)	0.0032 (8)
Xe11	0.0260 (5)	0.0194 (5)	0.0148 (5)	−0.0021 (4)	0.0006 (4)	0.0029 (4)
F11	0.027 (5)	0.022 (5)	0.014 (4)	−0.004 (4)	−0.001 (4)	0.004 (4)
F21	0.030 (5)	0.020 (5)	0.031 (6)	−0.006 (4)	0.000 (4)	0.002 (4)
Xe21	0.0273 (5)	0.0180 (5)	0.0155 (5)	−0.0023 (4)	0.0001 (4)	0.0037 (4)
F31	0.037 (6)	0.016 (4)	0.014 (5)	−0.003 (4)	0.003 (4)	0.007 (3)
F41	0.029 (5)	0.019 (5)	0.023 (5)	0.000 (4)	0.003 (4)	−0.004 (4)
Xe31	0.0283 (6)	0.0196 (5)	0.0170 (5)	−0.0022 (4)	−0.0013 (4)	0.0025 (4)
F51	0.030 (5)	0.020 (5)	0.006 (4)	−0.004 (4)	0.002 (3)	0.004 (3)
F61	0.043 (6)	0.024 (5)	0.013 (5)	−0.003 (4)	−0.004 (4)	0.001 (4)
Xe41	0.0261 (5)	0.0175 (5)	0.0173 (5)	−0.0025 (4)	0.0002 (4)	0.0030 (4)
F71	0.034 (5)	0.015 (4)	0.011 (4)	−0.003 (3)	0.000 (4)	0.003 (3)
F81	0.027 (5)	0.026 (5)	0.022 (5)	−0.002 (4)	−0.004 (4)	−0.007 (4)
Xe51	0.0263 (5)	0.0184 (5)	0.0150 (5)	−0.0013 (4)	−0.0006 (4)	0.0026 (4)
F91	0.033 (5)	0.022 (5)	0.014 (5)	−0.004 (4)	0.000 (4)	0.010 (4)
F101	0.031 (5)	0.019 (5)	0.018 (5)	−0.007 (4)	0.005 (4)	0.009 (4)
Xe61	0.0278 (6)	0.0197 (5)	0.0157 (5)	−0.0020 (4)	0.0014 (4)	0.0032 (4)
F111	0.029 (5)	0.028 (5)	0.008 (4)	−0.002 (4)	0.004 (3)	0.003 (4)
F121	0.029 (5)	0.033 (6)	0.021 (5)	−0.001 (4)	−0.003 (4)	0.005 (4)
Cu2	0.0253 (14)	0.0167 (13)	0.0140 (14)	−0.0020 (10)	0.0022 (11)	0.0038 (11)
Xe12	0.0249 (5)	0.0187 (5)	0.0146 (5)	−0.0022 (4)	−0.0003 (4)	0.0025 (4)
F12	0.029 (5)	0.030 (5)	0.013 (5)	−0.001 (4)	0.001 (4)	−0.004 (4)
F22	0.033 (5)	0.021 (5)	0.026 (6)	−0.001 (4)	−0.006 (4)	0.007 (4)
Xe22	0.0260 (5)	0.0173 (5)	0.0173 (5)	−0.0017 (4)	−0.0004 (4)	0.0028 (4)
F32	0.026 (5)	0.022 (5)	0.023 (5)	−0.004 (4)	−0.005 (4)	−0.005 (4)
F42	0.033 (6)	0.022 (5)	0.035 (6)	−0.002 (4)	−0.008 (5)	0.002 (5)
Xe32	0.0255 (5)	0.0200 (5)	0.0144 (5)	−0.0017 (4)	0.0013 (4)	0.0033 (4)
F52	0.039 (6)	0.017 (4)	0.014 (4)	−0.005 (4)	−0.002 (4)	−0.002 (4)
F62	0.034 (6)	0.023 (5)	0.019 (5)	−0.004 (4)	0.000 (4)	0.004 (4)
Cu3	0.0264 (15)	0.0181 (14)	0.0124 (14)	−0.0012 (11)	0.0005 (11)	0.0024 (11)
Xe13	0.0251 (5)	0.0198 (5)	0.0133 (5)	−0.0019 (4)	−0.0001 (4)	0.0030 (4)
F13	0.033 (5)	0.026 (5)	0.017 (5)	−0.004 (4)	0.005 (4)	0.006 (4)
F23	0.034 (6)	0.027 (6)	0.026 (6)	0.006 (4)	−0.002 (4)	0.001 (4)
Xe23	0.0263 (5)	0.0194 (5)	0.0137 (5)	−0.0018 (4)	0.0002 (4)	0.0029 (4)
F33	0.019 (5)	0.034 (6)	0.018 (5)	0.000 (4)	0.004 (4)	0.006 (4)
F43	0.032 (5)	0.028 (5)	0.015 (5)	−0.002 (4)	0.008 (4)	0.013 (4)
Xe33	0.0273 (6)	0.0189 (5)	0.0173 (5)	−0.0015 (4)	0.0002 (4)	0.0032 (4)
F53	0.041 (6)	0.019 (5)	0.018 (5)	−0.002 (4)	0.001 (4)	0.005 (4)
F63	0.037 (6)	0.020 (5)	0.035 (6)	−0.003 (4)	−0.009 (5)	−0.004 (5)
Sb1	0.0263 (6)	0.0185 (6)	0.0153 (6)	−0.0018 (4)	−0.0003 (4)	0.0034 (4)
F14	0.032 (5)	0.028 (5)	0.014 (5)	−0.007 (4)	0.006 (4)	−0.002 (4)
F24	0.033 (5)	0.020 (4)	0.018 (5)	−0.003 (4)	−0.002 (4)	0.006 (4)
F34	0.032 (5)	0.022 (5)	0.037 (6)	0.001 (4)	−0.003 (4)	−0.001 (4)
F44	0.034 (6)	0.028 (5)	0.014 (5)	−0.003 (4)	0.001 (4)	0.004 (4)
F54	0.032 (5)	0.018 (4)	0.023 (5)	0.002 (4)	0.003 (4)	0.000 (4)
F64	0.055 (7)	0.016 (5)	0.017 (5)	−0.005 (4)	−0.008 (4)	0.006 (4)
Sb2	0.0270 (6)	0.0202 (6)	0.0171 (6)	−0.0017 (4)	0.0001 (4)	0.0005 (4)
F15	0.034 (5)	0.034 (6)	0.031 (6)	−0.001 (4)	−0.003 (4)	−0.005 (5)
F25	0.027 (5)	0.029 (5)	0.019 (5)	−0.004 (4)	−0.002 (4)	0.001 (4)
F35	0.029 (5)	0.031 (6)	0.032 (6)	0.004 (4)	−0.003 (4)	0.000 (4)
F45	0.035 (6)	0.016 (4)	0.025 (5)	0.001 (4)	0.003 (4)	0.004 (4)
F55	0.024 (5)	0.030 (5)	0.019 (5)	−0.004 (4)	0.006 (4)	0.006 (4)
F65	0.033 (5)	0.023 (5)	0.022 (5)	0.001 (4)	0.000 (4)	0.001 (4)
Sb3	0.0267 (6)	0.0203 (6)	0.0146 (6)	−0.0017 (4)	0.0008 (4)	0.0048 (4)
F16	0.035 (6)	0.022 (5)	0.031 (6)	−0.004 (4)	−0.004 (4)	0.012 (4)
F26	0.035 (6)	0.020 (5)	0.030 (6)	−0.004 (4)	0.004 (4)	0.006 (4)
F36	0.035 (5)	0.023 (5)	0.028 (5)	−0.003 (4)	−0.005 (4)	−0.001 (4)
F46	0.028 (5)	0.026 (5)	0.025 (5)	−0.001 (4)	−0.001 (4)	0.007 (4)
F56	0.020 (4)	0.033 (6)	0.024 (5)	−0.008 (4)	0.000 (4)	0.005 (4)
F66	0.030 (5)	0.034 (6)	0.027 (5)	−0.003 (4)	0.000 (4)	0.010 (4)
Sb4	0.0263 (6)	0.0179 (5)	0.0163 (6)	−0.0015 (4)	0.0008 (4)	0.0036 (4)
F17	0.039 (6)	0.013 (4)	0.026 (6)	0.000 (4)	−0.001 (4)	0.004 (4)
F27	0.031 (5)	0.025 (5)	0.015 (5)	−0.002 (4)	0.000 (4)	0.001 (4)
F37	0.029 (5)	0.027 (5)	0.024 (5)	−0.004 (4)	−0.005 (4)	0.007 (4)
F47	0.036 (5)	0.023 (5)	0.016 (5)	0.000 (4)	0.001 (4)	0.007 (4)
F57	0.025 (5)	0.037 (6)	0.018 (5)	−0.006 (4)	0.004 (4)	−0.001 (4)
F67	0.026 (5)	0.033 (6)	0.024 (5)	0.000 (4)	0.012 (4)	0.001 (4)

Geometric parameters (Å, º)

Cu1—F51	1.892 (10)	Cu3—F33^ii	1.930 (10)
Cu1—F111	1.912 (10)	Cu3—F53^ii	2.160 (10)
Cu1—F31	1.951 (10)	Cu3—F53	2.160 (10)
Cu1—F71	1.953 (10)	Xe13—F23	1.936 (11)
Cu1—F91	2.179 (11)	Xe13—F13	2.124 (11)
Cu1—F11	2.180 (10)	Xe23—F43	1.930 (10)
Xe11—F21	1.971 (10)	Xe23—F33	2.113 (10)
Xe11—F11	2.038 (10)	Xe33—F63	1.956 (10)
Xe21—F41	1.940 (10)	Xe33—F53	2.048 (10)
Xe21—F31	2.088 (10)	Sb1—F24	1.869 (10)
Xe31—F61	1.920 (10)	Sb1—F14	1.871 (10)
Xe31—F51	2.118 (9)	Sb1—F64	1.872 (10)
Xe41—F81	1.927 (10)	Sb1—F54	1.876 (10)
Xe41—F71	2.115 (9)	Sb1—F34	1.883 (11)
Xe51—F121	1.926 (11)	Sb1—F44	1.884 (10)
Xe51—F111	2.122 (10)	Sb2—F15	1.861 (11)
F91—Xe61	2.025 (10)	Sb2—F55	1.864 (10)
F101—Xe61	1.953 (10)	Sb2—F25	1.874 (10)
Cu2—F12^i	1.900 (10)	Sb2—F35	1.878 (12)
Cu2—F12	1.900 (10)	Sb2—F45	1.884 (10)
Cu2—F52^i	1.935 (10)	Sb2—F65	1.889 (10)
Cu2—F52	1.935 (10)	Sb3—F56	1.871 (10)
Cu2—F32	2.171 (10)	Sb3—F66	1.884 (12)
Cu2—F32^i	2.171 (10)	Sb3—F36	1.885 (11)
Xe12—F22	1.950 (10)	Sb3—F26	1.890 (10)
Xe12—F12	2.109 (10)	Sb3—F16	1.895 (10)
Xe22—F42	1.964 (11)	Sb3—F46	1.898 (11)
Xe22—F32	2.041 (10)	Sb4—F67	1.864 (10)
Xe32—F62	1.944 (11)	Sb4—F27	1.879 (10)
Xe32—F52	2.098 (10)	Sb4—F37	1.879 (10)
Cu3—F13	1.901 (11)	Sb4—F17	1.880 (10)
Cu3—F13^ii	1.901 (11)	Sb4—F57	1.886 (10)
Cu3—F33	1.930 (10)	Sb4—F47	1.894 (11)
F51—Cu1—F111	175.7 (4)	F43—Xe23—F33	179.6 (4)
F51—Cu1—F31	90.3 (4)	Cu3—F33—Xe23	124.2 (5)
F111—Cu1—F31	91.6 (4)	F63—Xe33—F53	178.3 (5)
F51—Cu1—F71	90.8 (4)	Xe33—F53—Cu3	126.6 (5)
F111—Cu1—F71	87.5 (4)	F24—Sb1—F14	179.2 (5)
F31—Cu1—F71	177.0 (4)	F24—Sb1—F64	90.0 (5)
F51—Cu1—F91	86.0 (4)	F14—Sb1—F64	90.2 (5)
F111—Cu1—F91	90.2 (4)	F24—Sb1—F54	90.4 (4)
F31—Cu1—F91	90.6 (4)	F14—Sb1—F54	90.3 (5)
F71—Cu1—F91	92.3 (4)	F64—Sb1—F54	90.6 (5)
F51—Cu1—F11	95.2 (4)	F24—Sb1—F34	89.3 (5)
F111—Cu1—F11	88.8 (4)	F14—Sb1—F34	89.9 (5)
F31—Cu1—F11	84.5 (4)	F64—Sb1—F34	89.7 (5)
F71—Cu1—F11	92.6 (4)	F54—Sb1—F34	179.6 (5)
F91—Cu1—F11	175.0 (4)	F24—Sb1—F44	88.6 (4)
F21—Xe11—F11	179.7 (4)	F14—Sb1—F44	91.2 (5)
Xe11—F11—Cu1	119.9 (5)	F64—Sb1—F44	178.4 (4)
F41—Xe21—F31	178.1 (4)	F54—Sb1—F44	88.8 (5)
Cu1—F31—Xe21	127.1 (5)	F34—Sb1—F44	91.0 (5)
F61—Xe31—F51	176.8 (4)	F15—Sb2—F55	91.9 (5)
Cu1—F51—Xe31	125.2 (5)	F15—Sb2—F25	178.1 (5)
F81—Xe41—F71	179.7 (4)	F55—Sb2—F25	90.0 (5)
Cu1—F71—Xe41	117.8 (5)	F15—Sb2—F35	89.5 (5)
F121—Xe51—F111	179.2 (4)	F55—Sb2—F35	178.2 (5)
Xe61—F91—Cu1	120.9 (5)	F25—Sb2—F35	88.6 (5)
F101—Xe61—F91	179.1 (4)	F15—Sb2—F45	89.5 (5)
Cu1—F111—Xe51	125.7 (5)	F55—Sb2—F45	90.8 (5)
F12^i—Cu2—F12	180.0	F25—Sb2—F45	90.7 (5)
F12^i—Cu2—F52^i	89.6 (4)	F35—Sb2—F45	90.5 (5)
F12—Cu2—F52^i	90.4 (4)	F15—Sb2—F65	87.7 (5)
F12^i—Cu2—F52	90.4 (4)	F55—Sb2—F65	88.8 (5)
F12—Cu2—F52	89.6 (4)	F25—Sb2—F65	92.1 (5)
F52^i—Cu2—F52	180.0	F35—Sb2—F65	90.1 (5)
F12^i—Cu2—F32	88.2 (4)	F45—Sb2—F65	177.1 (5)
F12—Cu2—F32	91.8 (4)	F56—Sb3—F66	88.8 (5)
F52^i—Cu2—F32	90.4 (4)	F56—Sb3—F36	179.4 (5)
F52—Cu2—F32	89.6 (4)	F66—Sb3—F36	91.4 (5)
F12^i—Cu2—F32^i	91.8 (4)	F56—Sb3—F26	90.3 (5)
F12—Cu2—F32^i	88.2 (4)	F66—Sb3—F26	91.1 (5)
F52^i—Cu2—F32^i	89.6 (4)	F36—Sb3—F26	90.3 (5)
F52—Cu2—F32^i	90.4 (4)	F56—Sb3—F16	89.4 (5)
F32—Cu2—F32^i	180.0	F66—Sb3—F16	89.2 (5)
F22—Xe12—F12	178.6 (4)	F36—Sb3—F16	90.0 (5)
Cu2—F12—Xe12	125.6 (5)	F26—Sb3—F16	179.5 (5)
F42—Xe22—F32	177.8 (5)	F56—Sb3—F46	89.7 (4)
Xe22—F32—Cu2	119.9 (5)	F66—Sb3—F46	178.4 (5)
F62—Xe32—F52	179.7 (4)	F36—Sb3—F46	90.1 (5)
Cu2—F52—Xe32	120.8 (5)	F26—Sb3—F46	89.5 (5)
F13—Cu3—F13^ii	180.0 (6)	F16—Sb3—F46	90.2 (5)
F13—Cu3—F33	89.8 (4)	F67—Sb4—F27	89.9 (5)
F13^ii—Cu3—F33	90.2 (4)	F67—Sb4—F37	89.1 (5)
F13—Cu3—F33^ii	90.2 (4)	F27—Sb4—F37	89.1 (4)
F13^ii—Cu3—F33^ii	89.8 (4)	F67—Sb4—F17	90.9 (5)
F33—Cu3—F33^ii	180.0	F27—Sb4—F17	178.2 (4)
F13—Cu3—F53^ii	87.0 (4)	F37—Sb4—F17	92.6 (5)
F13^ii—Cu3—F53^ii	93.0 (4)	F67—Sb4—F57	91.2 (5)
F33—Cu3—F53^ii	88.8 (4)	F27—Sb4—F57	88.3 (5)
F33^ii—Cu3—F53^ii	91.2 (4)	F37—Sb4—F57	177.4 (5)
F13—Cu3—F53	93.0 (4)	F17—Sb4—F57	90.0 (5)
F13^ii—Cu3—F53	87.0 (4)	F67—Sb4—F47	179.1 (5)
F33—Cu3—F53	91.2 (4)	F27—Sb4—F47	89.3 (4)
F33^ii—Cu3—F53	88.8 (4)	F37—Sb4—F47	90.7 (5)
F53^ii—Cu3—F53	180.0 (6)	F17—Sb4—F47	90.0 (5)
F23—Xe13—F13	178.5 (4)	F57—Sb4—F47	88.9 (4)
Cu3—F13—Xe13	120.2 (5)

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

(cusbi_0p28gpa)

Crystal data

CuF12Xe6·2(F6Sb)	Dx = 3.967 Mg m^−3
Mr = 1550.84	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1332 reflections
a = 10.0084 (4) Å	θ = 1.8–10.5°
c = 22.4492 (7) Å	µ = 5.24 mm^−1
V = 1947.43 (17) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2013	0.2 × 0.1 × 0.05 mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	679 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.030
Psi scans	θmax = 10.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→11
Tmin = 0.760, Tmax = 1.325	k = −5→5
1503 measured reflections	l = −27→27
692 independent reflections

Refinement

Refinement on F^2	18 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0909P)^2 + 9.3132P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.058	(Δ/σ)max = 0.001
wR(F^2) = 0.137	Δρmax = 1.32 e Å^−3
S = 1.17	Δρmin = −2.09 e Å^−3
692 reflections	Extinction correction: SHELXL-2019/2 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
52 parameters	Extinction coefficient: 0.269 (18)

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
Cu1	0.333333	0.666667	0.666667	0.0412 (6)
Xe1	0.54199 (10)	0.52710 (9)	0.75114 (2)	0.0570 (5)
F1	0.3382 (6)	0.5035 (6)	0.7157 (2)	0.0697 (14)
F2	0.7273 (8)	0.5442 (10)	0.7826 (3)	0.097 (2)
Sb1	1.000000	1.000000	0.74848 (4)	0.0577 (5)
F3	0.8910 (14)	0.8264 (11)	0.6996 (4)	0.133 (3)
F4	1.0718 (15)	0.8967 (16)	0.7949 (4)	0.153 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0370 (7)	0.0370 (7)	0.0497 (10)	0.0185 (3)	0.000	0.000
Xe1	0.0651 (6)	0.0674 (6)	0.0527 (6)	0.0438 (4)	−0.00295 (17)	0.00464 (19)
F1	0.059 (3)	0.066 (3)	0.082 (3)	0.029 (2)	−0.003 (2)	0.014 (3)
F2	0.080 (4)	0.138 (6)	0.092 (3)	0.069 (4)	−0.008 (3)	0.019 (4)
Sb1	0.0641 (6)	0.0641 (6)	0.0450 (6)	0.0320 (3)	0.000	0.000
F3	0.167 (10)	0.110 (7)	0.107 (4)	0.057 (7)	−0.011 (5)	−0.029 (5)
F4	0.163 (9)	0.177 (11)	0.151 (6)	0.109 (9)	−0.003 (7)	0.066 (7)

Geometric parameters (Å, º)

Cu1—F1^i	1.990 (5)	Xe1—F2	1.911 (6)
Cu1—F1	1.990 (5)	Sb1—F3	1.876 (9)
Cu1—F1^ii	1.990 (5)	Sb1—F3^vi	1.876 (9)
Cu1—F1^iii	1.990 (6)	Sb1—F3^vii	1.876 (9)
Cu1—F1^iv	1.990 (5)	Sb1—F4^vii	1.848 (8)
Cu1—F1^v	1.990 (6)	Sb1—F4^vi	1.848 (8)
Xe1—F1	2.090 (5)	Sb1—F4	1.848 (8)
F1^i—Cu1—F1^iii	92.4 (2)	Cu1—F1—Xe1	122.7 (3)
F1^iv—Cu1—F1^ii	87.6 (2)	F3^vi—Sb1—F3	89.2 (4)
F1^iv—Cu1—F1	92.4 (2)	F3—Sb1—F3^vii	89.2 (4)
F1^i—Cu1—F1^iv	180.0	F3^vi—Sb1—F3^vii	89.2 (4)
F1^i—Cu1—F1	87.6 (2)	F4^vi—Sb1—F3^vi	91.2 (5)
F1^iii—Cu1—F1^iv	87.6 (2)	F4^vi—Sb1—F3^vii	88.3 (5)
F1^ii—Cu1—F1	180.0	F4—Sb1—F3^vi	88.3 (5)
F1^i—Cu1—F1^v	87.6 (2)	F4—Sb1—F3^vii	177.5 (4)
F1^v—Cu1—F1^ii	87.6 (2)	F4^vii—Sb1—F3^vii	91.2 (5)
F1^iii—Cu1—F1^v	180.0	F4—Sb1—F3	91.2 (5)
F1^iii—Cu1—F1	87.6 (2)	F4^vii—Sb1—F3^vi	177.5 (4)
F1^iv—Cu1—F1^v	92.4 (2)	F4^vii—Sb1—F3	88.3 (5)
F1^v—Cu1—F1	92.4 (2)	F4^vi—Sb1—F3	177.5 (4)
F1^i—Cu1—F1^ii	92.4 (2)	F4^vi—Sb1—F4^vii	91.3 (5)
F1^iii—Cu1—F1^ii	92.4 (2)	F4^vii—Sb1—F4	91.3 (5)
F2—Xe1—F1	178.6 (3)	F4^vi—Sb1—F4	91.3 (5)

Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −x+2/3, −y+4/3, −z+4/3; (iii) y−1/3, −x+y+1/3, −z+4/3; (iv) −x+y, −x+1, z; (v) −y+1, x−y+1, z; (vi) −y+2, x−y+1, z; (vii) −x+y+1, −x+2, z.

(cusbi_1p03gpa)

Crystal data

CuF12Xe6·2(F6Sb)	Dx = 4.209 Mg m^−3
Mr = 1550.84	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1112 reflections
a = 9.8135 (6) Å	θ = 1.8–10.5°
c = 22.0081 (11) Å	µ = 5.24 mm^−1
V = 1835.52 (18) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2013	0.2 × 0.1 × 0.05 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	628 independent reflections
Radiation source: synchrotron	607 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.016
φ scans	θmax = 10.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −5→5
Tmin = 0.995, Tmax = 0.995	k = −12→11
1313 measured reflections	l = −27→27

Refinement

Refinement on F^2	18 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0897P)^2 + 19.8102P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.052	(Δ/σ)max = 0.001
wR(F^2) = 0.135	Δρmax = 1.08 e Å^−3
S = 1.12	Δρmin = −1.57 e Å^−3
628 reflections	Extinction correction: SHELXL-2019/2 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
52 parameters	Extinction coefficient: 0.041 (4)

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
Cu1	0.333333	0.666667	0.666667	0.0423 (7)
Xe1	0.53899 (12)	0.52438 (10)	0.75140 (2)	0.0524 (5)
F1	0.3289 (7)	0.4961 (8)	0.7171 (3)	0.0649 (16)
F2	0.7298 (9)	0.5438 (12)	0.7827 (3)	0.089 (2)
Sb1	1.000000	1.000000	0.74880 (4)	0.0471 (5)
F3	0.8930 (12)	0.8237 (10)	0.6985 (3)	0.102 (3)
F4	1.0762 (13)	0.8962 (13)	0.7967 (4)	0.110 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0380 (8)	0.0380 (8)	0.0511 (13)	0.0190 (4)	0.000	0.000
Xe1	0.0610 (6)	0.0629 (6)	0.0479 (6)	0.0420 (4)	−0.0028 (2)	0.0027 (2)
F1	0.051 (3)	0.063 (4)	0.076 (3)	0.025 (3)	−0.005 (3)	0.010 (3)
F2	0.074 (5)	0.134 (7)	0.082 (4)	0.069 (5)	−0.008 (4)	0.014 (4)
Sb1	0.0521 (6)	0.0521 (6)	0.0369 (6)	0.0261 (3)	0.000	0.000
F3	0.123 (7)	0.073 (5)	0.089 (4)	0.033 (5)	−0.002 (4)	−0.024 (4)
F4	0.131 (8)	0.134 (8)	0.095 (4)	0.089 (7)	0.003 (5)	0.044 (5)

Geometric parameters (Å, º)

Cu1—F1^i	1.990 (6)	Xe1—F2	1.914 (7)
Cu1—F1^ii	1.990 (6)	Sb1—F3^vi	1.872 (7)
Cu1—F1^iii	1.990 (6)	Sb1—F3	1.872 (8)
Cu1—F1^iv	1.990 (6)	Sb1—F3^vii	1.872 (7)
Cu1—F1	1.990 (6)	Sb1—F4^vi	1.864 (7)
Cu1—F1^v	1.990 (6)	Sb1—F4^vii	1.864 (8)
Xe1—F1	2.080 (6)	Sb1—F4	1.864 (7)
F1^i—Cu1—F1^iv	92.0 (3)	Cu1—F1—Xe1	119.1 (3)
F1—Cu1—F1^iii	92.0 (3)	F3—Sb1—F3^vi	88.6 (4)
F1—Cu1—F1^ii	180.0 (4)	F3^vi—Sb1—F3^vii	88.6 (4)
F1^i—Cu1—F1	88.0 (3)	F3—Sb1—F3^vii	88.6 (4)
F1^i—Cu1—F1^ii	92.0 (3)	F4^vii—Sb1—F3	177.6 (4)
F1^iv—Cu1—F1	88.0 (3)	F4^vii—Sb1—F3^vii	91.3 (5)
F1^iii—Cu1—F1^ii	88.0 (3)	F4—Sb1—F3	91.3 (5)
F1^i—Cu1—F1^v	180.0	F4—Sb1—F3^vii	89.0 (4)
F1^v—Cu1—F1^iii	92.0 (3)	F4^vi—Sb1—F3^vii	177.6 (4)
F1^iv—Cu1—F1^v	88.0 (3)	F4—Sb1—F3^vi	177.6 (4)
F1^iv—Cu1—F1^ii	92.0 (3)	F4^vi—Sb1—F3	89.0 (4)
F1—Cu1—F1^v	92.0 (3)	F4^vi—Sb1—F3^vi	91.3 (5)
F1^v—Cu1—F1^ii	88.0 (3)	F4^vii—Sb1—F3^vi	89.0 (4)
F1^i—Cu1—F1^iii	88.0 (3)	F4^vii—Sb1—F4^vi	91.1 (4)
F1^iv—Cu1—F1^iii	180.0	F4^vi—Sb1—F4	91.1 (4)
F2—Xe1—F1	178.3 (4)	F4^vii—Sb1—F4	91.1 (4)

Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −x+2/3, −y+4/3, −z+4/3; (iii) −y+1, x−y+1, z; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+y, −x+1, z; (vi) −x+y+1, −x+2, z; (vii) −y+2, x−y+1, z.

(cusbi_1p49gpa)

Crystal data

CuF12Xe6·2(F6Sb)	Dx = 4.340 Mg m^−3
Mr = 1550.84	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1015 reflections
a = 9.7178 (6) Å	θ = 1.8–10.5°
c = 21.7656 (11) Å	µ = 5.50 mm^−1
V = 1780.08 (19) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2013	0.2 × 0.1 × 0.05 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	624 independent reflections
Radiation source: synchrotron	584 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.011
φ scans	θmax = 10.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.995, Tmax = 0.995	k = −11→11
1339 measured reflections	l = −27→27

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0754P)^2 + 26.9204P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.126	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 0.98 e Å^−3
624 reflections	Δρmin = −1.29 e Å^−3

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
Cu1	0.333333	0.666667	0.666667	0.0441 (7)
Xe1	0.53780 (12)	0.52345 (10)	0.75148 (2)	0.0518 (4)
F1	0.3244 (8)	0.4925 (8)	0.7174 (3)	0.0631 (16)
F2	0.7323 (10)	0.5470 (12)	0.7828 (3)	0.088 (2)
Sb1	1.000000	1.000000	0.74886 (4)	0.0439 (4)
F3	0.8942 (12)	0.8210 (10)	0.6982 (3)	0.092 (3)
F4	1.0785 (12)	0.8976 (12)	0.7977 (3)	0.093 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0408 (9)	0.0408 (9)	0.0507 (13)	0.0204 (5)	0.000	0.000
Xe1	0.0613 (5)	0.0625 (5)	0.0460 (5)	0.0418 (4)	−0.0024 (2)	0.0017 (3)
F1	0.050 (3)	0.067 (4)	0.072 (3)	0.028 (3)	−0.003 (3)	0.009 (3)
F2	0.070 (5)	0.135 (7)	0.080 (4)	0.066 (5)	−0.009 (4)	0.010 (5)
Sb1	0.0492 (5)	0.0492 (5)	0.0334 (5)	0.0246 (2)	0.000	0.000
F3	0.109 (7)	0.071 (5)	0.078 (4)	0.032 (5)	−0.001 (4)	−0.027 (4)
F4	0.114 (7)	0.108 (7)	0.081 (4)	0.073 (6)	0.000 (4)	0.033 (4)

Geometric parameters (Å, º)

Cu1—F1^i	1.986 (6)	Xe1—F2	1.913 (7)
Cu1—F1^ii	1.986 (6)	Sb1—F3^vi	1.874 (7)
Cu1—F1	1.986 (6)	Sb1—F3^vii	1.874 (7)
Cu1—F1^iii	1.986 (6)	Sb1—F3	1.874 (7)
Cu1—F1^iv	1.986 (6)	Sb1—F4^vii	1.860 (7)
Cu1—F1^v	1.986 (6)	Sb1—F4^vi	1.860 (7)
Xe1—F1	2.078 (6)	Sb1—F4	1.860 (7)
F1^i—Cu1—F1^iii	92.1 (3)	Cu1—F1—Xe1	117.4 (3)
F1^iv—Cu1—F1	87.9 (3)	F3^vii—Sb1—F3^vi	88.9 (4)
F1^iv—Cu1—F1^ii	180.0	F3^vi—Sb1—F3	88.9 (4)
F1^i—Cu1—F1^iv	92.1 (3)	F3^vii—Sb1—F3	88.9 (4)
F1^i—Cu1—F1^ii	87.9 (3)	F4^vi—Sb1—F3^vii	89.3 (4)
F1^iii—Cu1—F1^iv	92.1 (3)	F4^vi—Sb1—F3	178.2 (4)
F1—Cu1—F1^ii	92.1 (3)	F4—Sb1—F3^vii	178.2 (4)
F1^i—Cu1—F1^v	87.9 (3)	F4—Sb1—F3	91.2 (4)
F1^v—Cu1—F1	92.1 (3)	F4^vii—Sb1—F3	89.3 (4)
F1^iii—Cu1—F1^v	180.0	F4—Sb1—F3^vi	89.3 (4)
F1^iii—Cu1—F1^ii	87.9 (3)	F4^vii—Sb1—F3^vii	91.2 (4)
F1^iv—Cu1—F1^v	87.9 (3)	F4^vii—Sb1—F3^vi	178.2 (4)
F1^v—Cu1—F1^ii	92.1 (3)	F4^vi—Sb1—F3^vi	91.2 (4)
F1^i—Cu1—F1	180.0	F4^vi—Sb1—F4^vii	90.6 (4)
F1^iii—Cu1—F1	87.9 (3)	F4^vii—Sb1—F4	90.6 (4)
F2—Xe1—F1	178.7 (4)	F4^vi—Sb1—F4	90.6 (4)

Symmetry codes: (i) −x+2/3, −y+4/3, −z+4/3; (ii) −x+y, −x+1, z; (iii) y−1/3, −x+y+1/3, −z+4/3; (iv) x−y+2/3, x+1/3, −z+4/3; (v) −y+1, x−y+1, z; (vi) −y+2, x−y+1, z; (vii) −x+y+1, −x+2, z.

(cusbi_1p93gpa)

Crystal data

CuF12Xe6·2(F6Sb)	Dx = 4.421 Mg m^−3
Mr = 1550.84	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1045 reflections
a = 9.6632 (6) Å	θ = 1.8–10.5°
c = 21.6075 (11) Å	µ = 5.60 mm^−1
V = 1747.34 (19) Å^3	T = 293 K
Z = 3	Sphere
F(000) = 2013	0.2 × 0.1 × 0.05 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	587 independent reflections
Radiation source: synchrotron	548 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.017
φ scans	θmax = 10.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.995, Tmax = 0.995	k = −11→11
1185 measured reflections	l = −26→26

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.060	w = 1/[σ^2(Fo^2) + (0.0995P)^2 + 35.3591P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.169	(Δ/σ)max < 0.001
S = 1.16	Δρmax = 1.29 e Å^−3
587 reflections	Δρmin = −1.15 e Å^−3

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
Cu1	0.333333	0.666667	0.666667	0.0460 (9)
Xe1	0.53692 (16)	0.52281 (14)	0.75156 (3)	0.0518 (5)
F1	0.3200 (10)	0.4889 (11)	0.7178 (3)	0.064 (2)
F2	0.7337 (13)	0.5473 (16)	0.7825 (4)	0.086 (3)
Sb1	1.000000	1.000000	0.74897 (5)	0.0425 (5)
F3	0.8946 (14)	0.8198 (13)	0.6981 (4)	0.086 (3)
F4	1.0800 (15)	0.8979 (14)	0.7983 (4)	0.088 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0427 (12)	0.0427 (12)	0.0526 (17)	0.0213 (6)	0.000	0.000
Xe1	0.0619 (8)	0.0632 (7)	0.0453 (7)	0.0424 (5)	−0.0023 (3)	0.0008 (3)
F1	0.052 (4)	0.069 (6)	0.069 (4)	0.029 (4)	0.000 (4)	0.012 (4)
F2	0.065 (6)	0.136 (9)	0.079 (5)	0.066 (6)	−0.008 (5)	0.013 (6)
Sb1	0.0477 (6)	0.0477 (6)	0.0320 (7)	0.0239 (3)	0.000	0.000
F3	0.093 (7)	0.077 (6)	0.073 (5)	0.030 (6)	−0.001 (5)	−0.025 (5)
F4	0.117 (9)	0.097 (8)	0.072 (5)	0.071 (7)	−0.005 (5)	0.025 (5)

Geometric parameters (Å, º)

Cu1—F1^i	1.992 (8)	Xe1—F2	1.916 (9)
Cu1—F1^ii	1.993 (8)	Sb1—F3^vi	1.871 (9)
Cu1—F1^iii	1.993 (9)	Sb1—F3	1.871 (9)
Cu1—F1	1.992 (8)	Sb1—F3^vii	1.871 (9)
Cu1—F1^iv	1.992 (9)	Sb1—F4^vi	1.863 (9)
Cu1—F1^v	1.993 (8)	Sb1—F4^vii	1.863 (9)
Xe1—F1	2.084 (9)	Sb1—F4	1.863 (9)
F1^i—Cu1—F1	87.8 (3)	Cu1—F1—Xe1	115.6 (4)
F1^iv—Cu1—F1^iii	180.0	F3—Sb1—F3^vi	89.0 (5)
F1^iv—Cu1—F1^ii	92.2 (3)	F3^vi—Sb1—F3^vii	89.0 (5)
F1^i—Cu1—F1^iv	92.2 (3)	F3—Sb1—F3^vii	89.0 (5)
F1^i—Cu1—F1^ii	92.2 (3)	F4^vii—Sb1—F3	178.3 (5)
F1—Cu1—F1^iv	87.8 (3)	F4^vii—Sb1—F3^vii	91.1 (5)
F1^iii—Cu1—F1^ii	87.8 (3)	F4—Sb1—F3	91.1 (5)
F1^i—Cu1—F1^v	180.0	F4—Sb1—F3^vii	89.3 (5)
F1^v—Cu1—F1^iii	92.2 (3)	F4^vi—Sb1—F3^vii	178.3 (5)
F1—Cu1—F1^v	92.2 (3)	F4—Sb1—F3^vi	178.3 (5)
F1—Cu1—F1^ii	180.0	F4^vi—Sb1—F3	89.3 (5)
F1^iv—Cu1—F1^v	87.8 (3)	F4^vi—Sb1—F3^vi	91.1 (5)
F1^v—Cu1—F1^ii	87.8 (3)	F4^vii—Sb1—F3^vi	89.3 (5)
F1^i—Cu1—F1^iii	87.8 (3)	F4^vii—Sb1—F4^vi	90.5 (5)
F1—Cu1—F1^iii	92.2 (3)	F4^vi—Sb1—F4	90.5 (5)
F2—Xe1—F1	178.3 (5)	F4^vii—Sb1—F4	90.5 (5)

Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −x+2/3, −y+4/3, −z+4/3; (iii) −y+1, x−y+1, z; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+y, −x+1, z; (vi) −x+y+1, −x+2, z; (vii) −y+2, x−y+1, z.

(ZnSbI_200K)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 3.918 Mg m^−3
Mr = 1552.67	Ag Kα radiation, λ = 0.56086 Å
Trigonal, R3:H	Cell parameters from 4862 reflections
a = 10.0781 (4) Å	θ = 2.3–20.5°
c = 22.4417 (13) Å	µ = 5.65 mm^−1
V = 1974.0 (2) Å^3	T = 200 K
Z = 3	Block, colourless
F(000) = 2016	0.30 × 0.25 × 0.20 mm

Data collection

Bruker Venture diffractometer	1293 reflections with I > 2σ(I)
Radiation source: Microsource	Rint = 0.067
ω scans	θmax = 20.5°, θmin = 2.0°
Absorption correction: multi-scan TWINABS	h = −12→6
Tmin = 0.484, Tmax = 0.745	k = 0→12
19496 measured reflections	l = 0→27
1358 independent reflections

Refinement

Refinement on F^2	52 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0279P)^2 + 30.2864P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.091	(Δ/σ)max < 0.001
S = 1.19	Δρmax = 0.75 e Å^−3
1358 reflections	Δρmin = −0.68 e Å^−3

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.

Refinement. Refined as a 2-component twin. The twin law was Transforms h1.1(1)->h1.2(2) -0.24617 0.37665 0.37702 0.24544 0.62298 -0.37695 -2.49236 -1.24747 -0.24581 This is a rotation of 115.7deg about (0 -1 1)

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

	x	y	z	Uiso*/Ueq
Xe1	0.21422 (7)	−0.13610 (7)	0.58440 (2)	0.0343 (3)
Sb1	0.333333	−0.333333	0.41881 (5)	0.0387 (3)
Zn1	0.000000	0.000000	0.500000	0.0226 (5)
F1	0.0124 (6)	−0.1579 (6)	0.5500 (3)	0.0416 (12)
F2	0.3996 (8)	−0.1202 (9)	0.6163 (3)	0.0613 (18)
F3	0.1624 (11)	−0.3974 (13)	0.4676 (4)	0.095 (3)
F4	0.5066 (12)	−0.2606 (14)	0.3719 (4)	0.105 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Xe1	0.0413 (4)	0.0412 (4)	0.0316 (4)	0.0291 (3)	−0.0024 (2)	0.0034 (2)
Sb1	0.0438 (4)	0.0438 (4)	0.0287 (6)	0.0219 (2)	0.000	0.000
Zn1	0.0196 (6)	0.0196 (6)	0.0287 (11)	0.0098 (3)	0.000	0.000
F1	0.036 (3)	0.039 (3)	0.053 (3)	0.021 (2)	−0.003 (2)	0.015 (2)
F2	0.057 (4)	0.096 (5)	0.053 (4)	0.055 (4)	−0.007 (3)	0.011 (4)
F3	0.064 (5)	0.123 (8)	0.089 (6)	0.042 (6)	0.028 (4)	0.011 (6)
F4	0.085 (7)	0.130 (9)	0.088 (6)	0.043 (6)	0.044 (5)	0.006 (6)

Geometric parameters (Å, º)

Xe1—F2	1.931 (6)	Sb1—F3^i	1.863 (8)
Xe1—F1	2.082 (5)	Zn1—F1	2.001 (5)
Sb1—F4^i	1.848 (8)	Zn1—F1^iii	2.001 (5)
Sb1—F4	1.848 (8)	Zn1—F1^iv	2.001 (5)
Sb1—F4^ii	1.848 (8)	Zn1—F1^v	2.001 (5)
Sb1—F3^ii	1.863 (8)	Zn1—F1^vi	2.001 (5)
Sb1—F3	1.863 (8)	Zn1—F1^vii	2.001 (5)
F2—Xe1—F1	178.9 (3)	F1—Zn1—F1^iii	88.4 (3)
F4^i—Sb1—F4	90.8 (5)	F1—Zn1—F1^iv	91.6 (3)
F4^i—Sb1—F4^ii	90.8 (5)	F1^iii—Zn1—F1^iv	180.0
F4—Sb1—F4^ii	90.8 (5)	F1—Zn1—F1^v	88.4 (3)
F4^i—Sb1—F3^ii	91.8 (5)	F1^iii—Zn1—F1^v	91.6 (3)
F4—Sb1—F3^ii	88.5 (5)	F1^iv—Zn1—F1^v	88.4 (3)
F4^ii—Sb1—F3^ii	177.3 (5)	F1—Zn1—F1^vi	180.0
F4^i—Sb1—F3	88.5 (5)	F1^iii—Zn1—F1^vi	91.6 (3)
F4—Sb1—F3	177.3 (5)	F1^iv—Zn1—F1^vi	88.4 (3)
F4^ii—Sb1—F3	91.8 (5)	F1^v—Zn1—F1^vi	91.6 (3)
F3^ii—Sb1—F3	89.0 (5)	F1—Zn1—F1^vii	91.6 (3)
F4^i—Sb1—F3^i	177.3 (5)	F1^iii—Zn1—F1^vii	88.4 (3)
F4—Sb1—F3^i	91.8 (5)	F1^iv—Zn1—F1^vii	91.6 (3)
F4^ii—Sb1—F3^i	88.5 (5)	F1^v—Zn1—F1^vii	180.0
F3^ii—Sb1—F3^i	89.0 (5)	F1^vi—Zn1—F1^vii	88.4 (3)
F3—Sb1—F3^i	89.0 (5)	Zn1—F1—Xe1	124.8 (3)

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

(znsbi_0p16gpa)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 3.934 Mg m^−3
Mr = 1552.67	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1181 reflections
a = 10.0363 (4) Å	θ = 1.7–10.5°
c = 22.5388 (11) Å	µ = 4.99 mm^−1
V = 1966.11 (15) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2016	0.3 × 0.25 × 0.2 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	808 independent reflections
Radiation source: synchrotron	747 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.022
φ scans	θmax = 10.5°, θmin = 1.7°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→9
Tmin = 0.995, Tmax = 0.995	k = −11→12
1559 measured reflections	l = −25→27

Refinement

Refinement on F^2	18 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1121P)^2 + 15.7467P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.059	(Δ/σ)max = 0.001
wR(F^2) = 0.171	Δρmax = 0.98 e Å^−3
S = 1.10	Δρmin = −1.51 e Å^−3
808 reflections	Extinction correction: SHELXL-2019/2 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
52 parameters	Extinction coefficient: 0.044 (5)

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
Zn1	0.000000	0.000000	0.500000	0.0543 (7)
Xe1	0.21028 (11)	−0.13883 (10)	0.58457 (3)	0.0697 (5)
F1	0.0085 (7)	−0.1612 (7)	0.5494 (3)	0.0787 (16)
F2	0.3948 (9)	−0.1231 (12)	0.6165 (4)	0.115 (3)
Sb1	0.333333	−0.333333	0.41803 (5)	0.0711 (6)
F3	0.1636 (14)	−0.3976 (16)	0.4681 (5)	0.157 (4)
F4	0.5097 (14)	−0.2599 (17)	0.3719 (6)	0.173 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0472 (8)	0.0472 (8)	0.0683 (14)	0.0236 (4)	0.000	0.000
Xe1	0.0779 (7)	0.0795 (7)	0.0686 (7)	0.0520 (4)	−0.0035 (2)	0.0064 (3)
F1	0.067 (3)	0.071 (4)	0.100 (4)	0.035 (3)	−0.006 (3)	0.016 (3)
F2	0.098 (5)	0.161 (8)	0.114 (5)	0.086 (6)	−0.013 (4)	0.019 (5)
Sb1	0.0758 (7)	0.0758 (7)	0.0617 (8)	0.0379 (3)	0.000	0.000
F3	0.141 (9)	0.185 (12)	0.144 (8)	0.080 (9)	0.050 (7)	0.020 (8)
F4	0.134 (9)	0.202 (14)	0.160 (10)	0.067 (9)	0.060 (8)	−0.009 (9)

Geometric parameters (Å, º)

Zn1—F1	2.000 (6)	Xe1—F2	1.919 (7)
Zn1—F1^i	2.000 (6)	Sb1—F3^vi	1.869 (10)
Zn1—F1^ii	2.000 (6)	Sb1—F3	1.869 (10)
Zn1—F1^iii	2.000 (6)	Sb1—F3^vii	1.869 (10)
Zn1—F1^iv	2.000 (6)	Sb1—F4^vii	1.859 (10)
Zn1—F1^v	2.000 (6)	Sb1—F4	1.859 (10)
Xe1—F1	2.080 (6)	Sb1—F4^vi	1.859 (10)
F1—Zn1—F1^iii	87.9 (3)	Zn1—F1—Xe1	123.9 (3)
F1^iv—Zn1—F1^ii	87.9 (3)	F3—Sb1—F3^vi	87.3 (6)
F1^iv—Zn1—F1^i	92.1 (3)	F3^vi—Sb1—F3^vii	87.3 (6)
F1—Zn1—F1^iv	92.1 (3)	F3—Sb1—F3^vii	87.3 (6)
F1—Zn1—F1^i	92.1 (3)	F4—Sb1—F3	176.3 (5)
F1^iii—Zn1—F1^iv	180.0	F4—Sb1—F3^vii	91.9 (6)
F1^ii—Zn1—F1^i	180.0	F4^vi—Sb1—F3	91.9 (6)
F1—Zn1—F1^v	180.0	F4^vi—Sb1—F3^vii	89.1 (6)
F1^v—Zn1—F1^ii	92.1 (3)	F4^vii—Sb1—F3^vii	176.3 (5)
F1^iii—Zn1—F1^v	92.1 (3)	F4^vi—Sb1—F3^vi	176.3 (5)
F1^iii—Zn1—F1^i	87.9 (3)	F4^vii—Sb1—F3	89.1 (6)
F1^iv—Zn1—F1^v	87.9 (3)	F4^vii—Sb1—F3^vi	91.9 (6)
F1^v—Zn1—F1^i	87.9 (3)	F4—Sb1—F3^vi	89.1 (6)
F1—Zn1—F1^ii	87.9 (3)	F4—Sb1—F4^vii	91.7 (6)
F1^iii—Zn1—F1^ii	92.1 (3)	F4^vii—Sb1—F4^vi	91.7 (6)
F2—Xe1—F1	178.6 (4)	F4—Sb1—F4^vi	91.7 (6)

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

(znsbi_0p69gpa)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 4.145 Mg m^−3
Mr = 1552.67	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 1103 reflections
a = 9.8581 (5) Å	θ = 1.7–10.5°
c = 22.1728 (15) Å	µ = 5.25 mm^−1
V = 1866.10 (19) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2016	0.3 × 0.25 × 0.2 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	768 independent reflections
Radiation source: synchrotron	693 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.014
φ scans	θmax = 10.4°, θmin = 1.7°
Absorption correction: for a sphere CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.995, Tmax = 0.995	k = −12→12
1475 measured reflections	l = −26→27

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σ^2(Fo^2) + (0.1129P)^2 + 17.1104P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.166	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 1.08 e Å^−3
768 reflections	Δρmin = −1.24 e Å^−3

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
Zn1	0.000000	0.000000	0.500000	0.0566 (7)
Xe1	0.20727 (12)	−0.14116 (11)	0.58481 (2)	0.0665 (4)
F1	0.0001 (7)	−0.1682 (7)	0.5503 (3)	0.0748 (16)
F2	0.3977 (9)	−0.1217 (12)	0.6162 (4)	0.110 (3)
Sb1	0.333333	−0.333333	0.41787 (5)	0.0606 (5)
F3	0.1578 (12)	−0.4013 (14)	0.4681 (4)	0.126 (3)
F4	0.5133 (12)	−0.2585 (14)	0.3708 (4)	0.132 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0503 (9)	0.0503 (9)	0.0692 (15)	0.0252 (4)	0.000	0.000
Xe1	0.0757 (6)	0.0773 (6)	0.0624 (6)	0.0503 (4)	−0.0031 (2)	0.0042 (3)
F1	0.062 (3)	0.068 (4)	0.093 (4)	0.032 (3)	−0.004 (3)	0.019 (3)
F2	0.086 (5)	0.166 (8)	0.104 (5)	0.081 (6)	−0.012 (4)	0.013 (5)
Sb1	0.0657 (6)	0.0657 (6)	0.0505 (7)	0.0328 (3)	0.000	0.000
F3	0.102 (6)	0.156 (9)	0.109 (6)	0.057 (7)	0.038 (5)	0.026 (6)
F4	0.101 (6)	0.158 (9)	0.121 (6)	0.054 (7)	0.046 (5)	−0.003 (6)

Geometric parameters (Å, º)

Zn1—F1^i	1.999 (6)	Xe1—F2	1.920 (7)
Zn1—F1^ii	1.999 (6)	Sb1—F3^vi	1.877 (9)
Zn1—F1^iii	1.999 (6)	Sb1—F3^vii	1.877 (9)
Zn1—F1^iv	1.999 (6)	Sb1—F3	1.877 (9)
Zn1—F1^v	1.999 (6)	Sb1—F4^vii	1.864 (8)
Zn1—F1	1.999 (6)	Sb1—F4^vi	1.864 (8)
Xe1—F1	2.069 (6)	Sb1—F4	1.864 (8)
F1^i—Zn1—F1^iv	91.9 (3)	Zn1—F1—Xe1	120.6 (3)
F1^v—Zn1—F1^iii	88.1 (3)	F3^vii—Sb1—F3^vi	88.4 (5)
F1^v—Zn1—F1^ii	91.9 (3)	F3^vi—Sb1—F3	88.4 (5)
F1^i—Zn1—F1^v	88.1 (3)	F3^vii—Sb1—F3	88.4 (5)
F1^i—Zn1—F1^ii	88.1 (3)	F4^vi—Sb1—F3^vii	91.0 (5)
F1^iv—Zn1—F1^v	180.0	F4^vi—Sb1—F3	88.9 (5)
F1^iii—Zn1—F1^ii	180.0	F4—Sb1—F3^vii	88.9 (5)
F1^i—Zn1—F1	180.0	F4—Sb1—F3	177.2 (5)
F1—Zn1—F1^iii	88.1 (3)	F4^vii—Sb1—F3	91.0 (5)
F1^iv—Zn1—F1	88.1 (3)	F4—Sb1—F3^vi	91.0 (5)
F1^iv—Zn1—F1^ii	88.1 (3)	F4^vii—Sb1—F3^vii	177.2 (5)
F1^v—Zn1—F1	91.9 (3)	F4^vii—Sb1—F3^vi	88.9 (5)
F1—Zn1—F1^ii	91.9 (3)	F4^vi—Sb1—F3^vi	177.2 (5)
F1^i—Zn1—F1^iii	91.9 (3)	F4^vi—Sb1—F4^vii	91.7 (5)
F1^iv—Zn1—F1^iii	91.9 (3)	F4^vii—Sb1—F4	91.7 (5)
F2—Xe1—F1	178.5 (4)	F4^vi—Sb1—F4	91.7 (5)

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

(znsbi_1p49gpa)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 4.366 Mg m^−3
Mr = 1552.67	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 766 reflections
a = 9.6971 (6) Å	θ = 1.7–10.4°
c = 21.7552 (16) Å	µ = 5.53 mm^−1
V = 1771.6 (2) Å^3	T = 293 K
Z = 3	Sphere
F(000) = 2016	0.3 × 0.25 × 0.2 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	679 independent reflections
Radiation source: synchrotron	559 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.018
φ scans	θmax = 10.5°, θmin = 1.7°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→9
Tmin = 0.995, Tmax = 0.995	k = −10→11
1308 measured reflections	l = −25→26

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0965P)^2 + 29.5631P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.168	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 1.24 e Å^−3
679 reflections	Δρmin = −1.17 e Å^−3

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
Zn1	0.000000	0.000000	0.500000	0.0564 (9)
Xe1	0.20501 (15)	−0.14279 (13)	0.58497 (3)	0.0607 (5)
F1	−0.0080 (10)	−0.1737 (10)	0.5505 (4)	0.071 (2)
F2	0.3996 (13)	−0.1203 (16)	0.6165 (5)	0.105 (4)
Sb1	0.333333	−0.333333	0.41781 (6)	0.0507 (5)
F3	0.1527 (13)	−0.4065 (15)	0.4688 (4)	0.104 (3)
F4	0.5153 (13)	−0.2549 (15)	0.3699 (5)	0.106 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0497 (12)	0.0497 (12)	0.070 (2)	0.0248 (6)	0.000	0.000
Xe1	0.0707 (7)	0.0706 (7)	0.0567 (7)	0.0471 (5)	−0.0029 (3)	0.0020 (3)
F1	0.053 (4)	0.067 (5)	0.091 (5)	0.028 (4)	0.002 (4)	0.026 (4)
F2	0.093 (7)	0.157 (11)	0.097 (7)	0.085 (8)	−0.017 (6)	0.005 (7)
Sb1	0.0547 (6)	0.0547 (6)	0.0427 (8)	0.0274 (3)	0.000	0.000
F3	0.085 (7)	0.124 (9)	0.090 (7)	0.041 (7)	0.029 (5)	0.022 (6)
F4	0.079 (7)	0.121 (9)	0.102 (7)	0.039 (7)	0.034 (5)	0.000 (6)

Geometric parameters (Å, º)

Zn1—F1^i	1.980 (8)	Xe1—F2	1.915 (9)
Zn1—F1	1.980 (8)	Sb1—F3	1.886 (10)
Zn1—F1^ii	1.980 (8)	Sb1—F3^vi	1.886 (10)
Zn1—F1^iii	1.980 (8)	Sb1—F3^vii	1.886 (10)
Zn1—F1^iv	1.980 (8)	Sb1—F4^vii	1.854 (9)
Zn1—F1^v	1.980 (8)	Sb1—F4	1.854 (9)
Xe1—F1	2.073 (8)	Sb1—F4^vi	1.854 (9)
F1^i—Zn1—F1^iii	180.0	Zn1—F1—Xe1	117.7 (4)
F1^iv—Zn1—F1^ii	180.0	F3^vi—Sb1—F3	89.0 (5)
F1^iv—Zn1—F1	87.8 (4)	F3—Sb1—F3^vii	89.0 (5)
F1^i—Zn1—F1^iv	92.2 (4)	F3^vi—Sb1—F3^vii	89.0 (5)
F1^i—Zn1—F1	87.8 (4)	F4—Sb1—F3^vi	88.8 (5)
F1^iii—Zn1—F1^iv	87.8 (4)	F4—Sb1—F3^vii	90.8 (5)
F1^ii—Zn1—F1	92.2 (4)	F4^vi—Sb1—F3^vi	177.7 (5)
F1^i—Zn1—F1^v	92.2 (4)	F4^vi—Sb1—F3^vii	88.8 (5)
F1^v—Zn1—F1^ii	87.8 (4)	F4^vii—Sb1—F3^vii	177.7 (5)
F1^iii—Zn1—F1^v	87.8 (4)	F4^vi—Sb1—F3	90.8 (5)
F1^iii—Zn1—F1	92.2 (4)	F4^vii—Sb1—F3^vi	90.8 (5)
F1^iv—Zn1—F1^v	92.2 (4)	F4^vii—Sb1—F3	88.8 (5)
F1^v—Zn1—F1	180.0	F4—Sb1—F3	177.7 (5)
F1^i—Zn1—F1^ii	87.8 (4)	F4—Sb1—F4^vii	91.5 (5)
F1^iii—Zn1—F1^ii	92.2 (4)	F4^vii—Sb1—F4^vi	91.5 (5)
F2—Xe1—F1	178.5 (5)	F4—Sb1—F4^vi	91.5 (5)

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

(znsbi_2p21gpa)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 4.533 Mg m^−3
Mr = 1552.67	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 582 reflections
a = 9.5895 (8) Å	θ = 2.1–10.4°
c = 21.426 (2) Å	µ = 5.74 mm^−1
V = 1706.3 (3) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2016	0.3 × 0.25 × 0.2 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	687 independent reflections
Radiation source: synchrotron	440 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.032
φ scans	θmax = 10.5°, θmin = 1.7°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→8
Tmin = 0.995, Tmax = 0.995	k = −10→11
1296 measured reflections	l = −24→26

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.073	w = 1/[σ^2(Fo^2) + (0.1018P)^2 + 56.8415P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.223	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 2.36 e Å^−3
687 reflections	Δρmin = −1.22 e Å^−3

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
Zn1	0.000000	0.000000	0.500000	0.0605 (17)
Xe1	0.2032 (2)	−0.1441 (2)	0.58487 (6)	0.0603 (7)
F1	−0.0118 (15)	−0.1758 (15)	0.5513 (6)	0.070 (4)
F2	0.4022 (18)	−0.119 (2)	0.6162 (7)	0.095 (5)
Sb1	0.333333	−0.333333	0.41764 (9)	0.0470 (7)
F3	0.1546 (19)	−0.405 (2)	0.4692 (7)	0.097 (5)
F4	0.5162 (17)	−0.2546 (19)	0.3681 (7)	0.087 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.056 (2)	0.056 (2)	0.070 (4)	0.0278 (12)	0.000	0.000
Xe1	0.0734 (11)	0.0726 (11)	0.0523 (10)	0.0496 (9)	−0.0030 (6)	0.0000 (6)
F1	0.050 (7)	0.068 (8)	0.081 (8)	0.021 (6)	−0.005 (6)	0.018 (7)
F2	0.081 (10)	0.125 (13)	0.096 (10)	0.066 (10)	−0.010 (8)	0.022 (9)
Sb1	0.0519 (10)	0.0519 (10)	0.0371 (12)	0.0260 (5)	0.000	0.000
F3	0.089 (11)	0.108 (13)	0.090 (11)	0.047 (10)	0.024 (8)	0.034 (9)
F4	0.071 (9)	0.097 (11)	0.087 (10)	0.038 (9)	0.028 (7)	0.011 (8)

Geometric parameters (Å, º)

Zn1—F1^i	1.968 (12)	Xe1—F2	1.921 (14)
Zn1—F1^ii	1.968 (12)	Sb1—F3^vi	1.858 (14)
Zn1—F1^iii	1.968 (12)	Sb1—F3	1.858 (14)
Zn1—F1^iv	1.968 (12)	Sb1—F3^vii	1.858 (14)
Zn1—F1	1.968 (12)	Sb1—F4^vii	1.857 (13)
Zn1—F1^v	1.968 (12)	Sb1—F4	1.857 (13)
Xe1—F1	2.058 (12)	Sb1—F4^vi	1.857 (13)
F1^i—Zn1—F1^iv	180.0	Zn1—F1—Xe1	116.4 (6)
F1—Zn1—F1^iii	88.2 (6)	F3—Sb1—F3^vi	88.3 (7)
F1—Zn1—F1^ii	180.0	F3^vi—Sb1—F3^vii	88.3 (7)
F1^i—Zn1—F1	88.2 (6)	F3—Sb1—F3^vii	88.3 (7)
F1^i—Zn1—F1^ii	91.8 (6)	F4—Sb1—F3	177.6 (7)
F1^iv—Zn1—F1	91.8 (6)	F4—Sb1—F3^vii	91.8 (7)
F1^iii—Zn1—F1^ii	91.8 (6)	F4^vi—Sb1—F3	91.8 (7)
F1^i—Zn1—F1^v	88.2 (6)	F4^vi—Sb1—F3^vii	89.3 (7)
F1^v—Zn1—F1^iii	180.0	F4^vii—Sb1—F3^vii	177.6 (7)
F1^iv—Zn1—F1^v	91.8 (6)	F4^vi—Sb1—F3^vi	177.6 (7)
F1^iv—Zn1—F1^ii	88.2 (6)	F4^vii—Sb1—F3	89.3 (7)
F1—Zn1—F1^v	91.8 (6)	F4^vii—Sb1—F3^vi	91.8 (7)
F1^v—Zn1—F1^ii	88.2 (6)	F4—Sb1—F3^vi	89.3 (7)
F1^i—Zn1—F1^iii	91.8 (6)	F4—Sb1—F4^vii	90.6 (7)
F1^iv—Zn1—F1^iii	88.2 (6)	F4^vii—Sb1—F4^vi	90.6 (7)
F2—Xe1—F1	178.8 (7)	F4—Sb1—F4^vi	90.6 (7)

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

(znsbi_2p78gpa)

Crystal data

F12Xe6Zn·2(F6Sb)	Dx = 4.611 Mg m^−3
Mr = 1552.67	Synchrotron radiation, λ = 0.2906 Å
Trigonal, R3	Cell parameters from 535 reflections
a = 9.5373 (10) Å	θ = 1.8–10.4°
c = 21.292 (2) Å	µ = 5.84 mm^−1
V = 1677.3 (3) Å^3	T = 293 K
Z = 3	Block, colourless
F(000) = 2016	0.3 × 0.25 × 0.2 × 0.40 (radius) mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	624 independent reflections
Radiation source: synchrotron	407 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.031
φ scans	θmax = 10.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→11
Tmin = 0.995, Tmax = 0.995	k = −11→11
1179 measured reflections	l = −24→26

Refinement

Refinement on F^2	51 parameters
Least-squares matrix: full	18 restraints
R[F^2 > 2σ(F^2)] = 0.081	w = 1/[σ^2(Fo^2) + (0.1402P)^2 + 88.9358P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.266	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 2.50 e Å^−3
624 reflections	Δρmin = −1.44 e Å^−3

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
Zn1	0.000000	0.000000	0.500000	0.066 (2)
Xe1	0.2024 (3)	−0.1444 (3)	0.58490 (7)	0.0667 (9)
F1	−0.0166 (18)	−0.1800 (19)	0.5522 (8)	0.078 (5)
F2	0.403 (2)	−0.118 (3)	0.6158 (9)	0.105 (6)
Sb1	0.333333	−0.333333	0.41760 (10)	0.0502 (9)
F3	0.154 (2)	−0.406 (2)	0.4702 (8)	0.090 (5)
F4	0.5163 (19)	−0.257 (2)	0.3677 (7)	0.081 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.061 (3)	0.061 (3)	0.078 (5)	0.0303 (14)	0.000	0.000
Xe1	0.0844 (15)	0.0819 (14)	0.0533 (12)	0.0561 (11)	−0.0027 (8)	0.0004 (7)
F1	0.063 (9)	0.084 (11)	0.090 (11)	0.039 (8)	−0.004 (8)	0.022 (8)
F2	0.096 (13)	0.167 (19)	0.080 (11)	0.087 (14)	−0.012 (9)	0.010 (11)
Sb1	0.0575 (12)	0.0575 (12)	0.0357 (14)	0.0287 (6)	0.000	0.000
F3	0.078 (11)	0.111 (14)	0.081 (12)	0.047 (10)	0.019 (8)	0.024 (10)
F4	0.067 (10)	0.100 (13)	0.070 (10)	0.039 (9)	0.014 (7)	0.006 (9)

Geometric parameters (Å, º)

Zn1—F1^i	1.984 (14)	Xe1—F2	1.920 (16)
Zn1—F1	1.984 (14)	Sb1—F3^vi	1.866 (15)
Zn1—F1^ii	1.984 (14)	Sb1—F3	1.866 (15)
Zn1—F1^iii	1.984 (14)	Sb1—F3^vii	1.866 (16)
Zn1—F1^iv	1.984 (14)	Sb1—F4^vii	1.853 (15)
Zn1—F1^v	1.984 (14)	Sb1—F4	1.853 (15)
Xe1—F1	2.062 (15)	Sb1—F4^vi	1.853 (15)
F1^i—Zn1—F1^iii	180.0	Zn1—F1—Xe1	114.3 (7)
F1^iv—Zn1—F1^ii	180.0	F3—Sb1—F3^vi	87.7 (8)
F1^iv—Zn1—F1	88.3 (7)	F3^vi—Sb1—F3^vii	87.7 (8)
F1^i—Zn1—F1^iv	91.7 (7)	F3—Sb1—F3^vii	87.7 (8)
F1^i—Zn1—F1	88.4 (7)	F4—Sb1—F3	177.9 (8)
F1^iii—Zn1—F1^iv	88.3 (7)	F4—Sb1—F3^vii	90.3 (7)
F1^ii—Zn1—F1	91.7 (7)	F4^vi—Sb1—F3	90.3 (7)
F1^i—Zn1—F1^v	91.7 (7)	F4^vi—Sb1—F3^vii	91.6 (8)
F1^v—Zn1—F1^ii	88.3 (7)	F4^vii—Sb1—F3^vii	178.0 (7)
F1^iii—Zn1—F1^v	88.3 (7)	F4^vi—Sb1—F3^vi	177.9 (7)
F1^iii—Zn1—F1	91.7 (7)	F4^vii—Sb1—F3	91.6 (8)
F1^iv—Zn1—F1^v	91.7 (7)	F4^vii—Sb1—F3^vi	90.3 (7)
F1^v—Zn1—F1	180.0	F4—Sb1—F3^vi	91.6 (8)
F1^i—Zn1—F1^ii	88.3 (7)	F4—Sb1—F4^vii	90.4 (7)
F1^iii—Zn1—F1^ii	91.7 (7)	F4^vii—Sb1—F4^vi	90.4 (7)
F2—Xe1—F1	178.3 (8)	F4—Sb1—F4^vi	90.4 (7)

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

(ZnAsI_100K)

Crystal data

F12Xe6Zn·2(AsF6)	Z = 2
Mr = 1459.01	F(000) = 1272
Triclinic, P1	Dx = 3.902 Mg m^−3
a = 9.1236 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.2086 (10) Å	Cell parameters from 4056 reflections
c = 10.3242 (9) Å	θ = 2.7–26.4°
α = 89.555 (3)°	µ = 11.85 mm^−1
β = 93.491 (3)°	T = 113 K
γ = 90.650 (3)°	Block, colourless
V = 1241.75 (17) Å^3	0.40 × 0.20 × 0.20 mm

Data collection

Bruker D8 Venture diffractometer	8140 reflections with I > 2σ(I)
ω and phi scans	Rint = 0.089
Absorption correction: multi-scan TWINABS - Bruker AXS scaling for twinned crystals - Version 2012/1	θmax = 26.4°, θmin = 2.2°
Tmin = 0.460, Tmax = 0.745	h = −11→11
8946 measured reflections	k = 0→16
8946 independent reflections	l = −12→12

Refinement

Refinement on F^2	198 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0197P)^2 + 61.049P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.052	(Δ/σ)max = 0.001
wR(F^2) = 0.148	Δρmax = 2.13 e Å^−3
S = 1.17	Δρmin = −1.79 e Å^−3
8946 reflections	Extinction correction: SHELXL-2019/2 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
304 parameters	Extinction coefficient: 0.0069 (6)

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.

Refinement. Refined as a 3-component twin.

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

	x	y	z	Uiso*/Ueq
Zn1	0.500000	1.000000	1.500000	0.0123 (6)
Xe11	0.80059 (13)	1.02924 (9)	1.28286 (11)	0.0149 (3)
F11	0.6462 (14)	0.9479 (9)	1.3846 (13)	0.028 (3)
F21	0.9441 (14)	1.1032 (9)	1.1875 (12)	0.028 (3)
Xe21	0.45287 (12)	0.73577 (8)	1.43458 (11)	0.0137 (3)
F31	0.3699 (11)	0.8816 (8)	1.4492 (11)	0.015 (2)
F41	0.5303 (13)	0.6000 (8)	1.4196 (12)	0.024 (3)
Xe31	0.29022 (14)	1.04815 (10)	1.18425 (12)	0.0189 (3)
F51	0.4148 (15)	1.0855 (10)	1.3521 (12)	0.031 (3)
F61	0.1746 (15)	1.0176 (11)	1.0239 (12)	0.033 (3)
Zn2	1.000000	0.500000	1.000000	0.0132 (6)
Xe12	1.30299 (13)	0.45362 (9)	1.23631 (11)	0.0161 (3)
F12	1.1226 (12)	0.5374 (9)	1.1626 (11)	0.019 (2)
F22	1.4707 (13)	0.3775 (10)	1.3036 (12)	0.027 (3)
Xe22	1.00720 (13)	0.76688 (9)	1.07115 (12)	0.0162 (3)
F32	0.9918 (13)	0.6460 (8)	0.9421 (11)	0.020 (2)
F42	1.0288 (15)	0.8803 (9)	1.1895 (13)	0.030 (3)
Xe32	1.21516 (13)	0.51546 (9)	0.71038 (11)	0.0148 (3)
F52	1.1752 (12)	0.4721 (9)	0.9017 (10)	0.019 (2)
F62	1.2554 (13)	0.5535 (9)	0.5342 (11)	0.022 (3)
As1	0.9564 (2)	0.74145 (15)	0.5060 (2)	0.0174 (4)
F13	0.8148 (15)	0.7403 (10)	0.3887 (15)	0.039 (3)
F23	0.8347 (15)	0.7585 (11)	0.6245 (15)	0.038 (3)
F33	0.9721 (14)	0.8700 (8)	0.4856 (13)	0.028 (3)
F43	1.1009 (14)	0.7432 (9)	0.6213 (11)	0.024 (3)
F53	1.0772 (14)	0.7206 (10)	0.3868 (12)	0.028 (3)
F63	0.9407 (14)	0.6118 (9)	0.5284 (13)	0.027 (3)
As2	1.4865 (2)	0.75422 (18)	1.0386 (2)	0.0248 (5)
F14	1.4176 (18)	0.8359 (16)	0.9201 (16)	0.065 (5)
F24	1.3480 (16)	0.7876 (14)	1.1359 (14)	0.049 (4)
F34	1.5889 (18)	0.8517 (12)	1.1042 (16)	0.050 (4)
F44	1.5563 (19)	0.6742 (12)	1.1559 (14)	0.049 (4)
F54	1.6240 (17)	0.7274 (10)	0.9424 (13)	0.038 (3)
F64	1.383 (3)	0.6583 (17)	0.9742 (17)	0.098 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0121 (14)	0.0127 (14)	0.0123 (14)	−0.0001 (11)	0.0017 (11)	−0.0001 (11)
Xe11	0.0142 (6)	0.0170 (6)	0.0137 (6)	−0.0004 (4)	0.0022 (4)	−0.0016 (5)
F11	0.034 (7)	0.017 (6)	0.036 (7)	−0.002 (5)	0.022 (6)	−0.002 (5)
F21	0.025 (7)	0.031 (7)	0.029 (7)	−0.011 (5)	0.012 (5)	0.004 (5)
Xe21	0.0160 (6)	0.0107 (5)	0.0144 (6)	−0.0001 (4)	0.0014 (4)	−0.0012 (4)
F31	0.007 (5)	0.016 (5)	0.022 (6)	0.001 (4)	−0.002 (4)	−0.004 (4)
F41	0.029 (7)	0.013 (5)	0.032 (7)	0.002 (5)	0.013 (5)	0.004 (5)
Xe31	0.0185 (6)	0.0215 (6)	0.0161 (6)	−0.0011 (5)	−0.0039 (5)	0.0023 (5)
F51	0.043 (8)	0.028 (7)	0.019 (6)	−0.001 (6)	−0.017 (6)	0.007 (5)
F61	0.034 (7)	0.044 (8)	0.020 (7)	−0.003 (6)	−0.008 (5)	−0.004 (6)
Zn2	0.0124 (15)	0.0145 (15)	0.0126 (15)	0.0018 (12)	0.0006 (11)	−0.0010 (12)
Xe12	0.0154 (6)	0.0204 (6)	0.0121 (6)	−0.0008 (5)	−0.0028 (4)	−0.0005 (5)
F12	0.011 (5)	0.023 (6)	0.023 (6)	−0.002 (4)	−0.004 (4)	0.001 (5)
F22	0.018 (6)	0.034 (7)	0.028 (7)	0.009 (5)	−0.004 (5)	0.002 (6)
Xe22	0.0198 (6)	0.0115 (5)	0.0174 (6)	0.0006 (4)	0.0012 (4)	0.0013 (4)
F32	0.028 (6)	0.017 (6)	0.016 (6)	0.003 (5)	−0.001 (5)	0.000 (4)
F42	0.039 (8)	0.019 (6)	0.031 (7)	−0.001 (5)	−0.002 (6)	−0.011 (5)
Xe32	0.0145 (6)	0.0155 (6)	0.0146 (6)	0.0012 (4)	0.0037 (4)	0.0019 (5)
F52	0.021 (6)	0.025 (6)	0.013 (5)	0.003 (5)	0.010 (4)	0.003 (5)
F62	0.021 (6)	0.024 (6)	0.022 (6)	−0.002 (5)	0.005 (5)	0.005 (5)
As1	0.0153 (10)	0.0143 (10)	0.0220 (11)	0.0001 (8)	−0.0027 (8)	0.0002 (8)
F13	0.026 (7)	0.029 (7)	0.058 (9)	0.001 (6)	−0.016 (6)	−0.004 (7)
F23	0.030 (7)	0.037 (8)	0.048 (8)	0.007 (6)	0.017 (6)	0.002 (6)
F33	0.036 (7)	0.008 (5)	0.038 (7)	−0.003 (5)	−0.015 (6)	0.008 (5)
F43	0.031 (6)	0.020 (6)	0.020 (6)	−0.002 (5)	−0.014 (5)	−0.003 (5)
F53	0.027 (6)	0.033 (7)	0.023 (6)	0.002 (5)	0.004 (5)	0.006 (5)
F63	0.027 (7)	0.015 (6)	0.038 (7)	−0.003 (5)	0.001 (5)	−0.001 (5)
As2	0.0234 (11)	0.0333 (12)	0.0173 (11)	−0.0036 (9)	−0.0021 (8)	0.0002 (9)
F14	0.035 (9)	0.116 (15)	0.042 (9)	0.016 (9)	−0.002 (7)	0.044 (10)
F24	0.026 (7)	0.095 (13)	0.026 (7)	0.011 (7)	−0.001 (6)	−0.002 (8)
F34	0.052 (9)	0.050 (9)	0.049 (9)	−0.011 (7)	0.001 (7)	−0.028 (7)
F44	0.072 (11)	0.051 (9)	0.026 (7)	0.027 (8)	0.018 (7)	0.010 (7)
F54	0.062 (9)	0.028 (7)	0.026 (7)	0.012 (6)	0.011 (6)	0.004 (6)
F64	0.150 (19)	0.106 (14)	0.038 (10)	−0.111 (15)	0.012 (10)	−0.024 (9)

Geometric parameters (Å, º)

Zn1—F11	1.974 (11)	Xe12—F22	1.931 (11)
Zn1—F11^i	1.974 (11)	Xe12—F12	2.095 (11)
Zn1—F31	2.006 (10)	Xe22—F42	1.941 (12)
Zn1—F31^i	2.006 (10)	Xe22—F32	2.086 (11)
Zn1—F51^i	2.015 (11)	Xe32—F62	1.939 (11)
Zn1—F51	2.015 (11)	Xe32—F52	2.104 (10)
Xe11—F21	1.936 (11)	As1—F33	1.714 (11)
Xe11—F11	2.091 (11)	As1—F13	1.716 (13)
Xe21—F41	1.946 (11)	As1—F23	1.719 (13)
Xe21—F31	2.088 (10)	As1—F43	1.721 (11)
Xe31—F61	1.951 (12)	As1—F53	1.727 (13)
Xe31—F51	2.074 (12)	As1—F63	1.731 (12)
Zn2—F52^ii	1.985 (10)	As2—F64	1.686 (16)
Zn2—F52	1.985 (10)	As2—F54	1.689 (14)
Zn2—F32	2.015 (11)	As2—F44	1.700 (14)
Zn2—F32^ii	2.015 (11)	As2—F34	1.703 (15)
Zn2—F12	2.021 (11)	As2—F14	1.720 (15)
Zn2—F12^ii	2.021 (11)	As2—F24	1.725 (15)
F11—Zn1—F11^i	180.0	F22—Xe12—F12	179.4 (5)
F11—Zn1—F31	88.5 (5)	Zn2—F12—Xe12	123.6 (6)
F11^i—Zn1—F31	91.5 (5)	F42—Xe22—F32	177.9 (5)
F11—Zn1—F31^i	91.5 (5)	Zn2—F32—Xe22	123.1 (5)
F11^i—Zn1—F31^i	88.5 (5)	F62—Xe32—F52	178.8 (5)
F31—Zn1—F31^i	180.0	Zn2—F52—Xe32	128.2 (6)
F11—Zn1—F51^i	90.7 (6)	F33—As1—F13	89.1 (6)
F11^i—Zn1—F51^i	89.3 (6)	F33—As1—F23	90.4 (7)
F31—Zn1—F51^i	87.7 (5)	F13—As1—F23	90.7 (7)
F31^i—Zn1—F51^i	92.3 (5)	F33—As1—F43	90.5 (6)
F11—Zn1—F51	89.3 (6)	F13—As1—F43	178.8 (7)
F11^i—Zn1—F51	90.7 (6)	F23—As1—F43	90.4 (7)
F31—Zn1—F51	92.3 (5)	F33—As1—F53	91.2 (6)
F31^i—Zn1—F51	87.7 (5)	F13—As1—F53	88.9 (7)
F51^i—Zn1—F51	180.0	F23—As1—F53	178.3 (6)
F21—Xe11—F11	179.3 (5)	F43—As1—F53	90.0 (6)
Zn1—F11—Xe11	128.5 (6)	F33—As1—F63	179.4 (6)
F41—Xe21—F31	179.6 (5)	F13—As1—F63	91.3 (6)
Zn1—F31—Xe21	121.7 (5)	F23—As1—F63	89.2 (6)
F61—Xe31—F51	178.0 (6)	F43—As1—F63	89.1 (6)
Zn1—F51—Xe31	131.8 (7)	F53—As1—F63	89.2 (6)
F52^ii—Zn2—F52	180.0	F64—As2—F54	91.0 (10)
F52^ii—Zn2—F32	86.8 (5)	F64—As2—F44	89.6 (11)
F52—Zn2—F32	93.2 (5)	F54—As2—F44	91.2 (7)
F52^ii—Zn2—F32^ii	93.1 (5)	F64—As2—F34	179.3 (11)
F52—Zn2—F32^ii	86.8 (5)	F54—As2—F34	89.6 (8)
F32—Zn2—F32^ii	180.0 (7)	F44—As2—F34	90.6 (9)
F52^ii—Zn2—F12	87.1 (5)	F64—As2—F14	90.9 (11)
F52—Zn2—F12	92.9 (5)	F54—As2—F14	88.5 (7)
F32—Zn2—F12	91.2 (5)	F44—As2—F14	179.4 (10)
F32^ii—Zn2—F12	88.8 (5)	F34—As2—F14	88.8 (10)
F52^ii—Zn2—F12^ii	92.9 (5)	F64—As2—F24	91.1 (10)
F52—Zn2—F12^ii	87.1 (5)	F54—As2—F24	177.3 (8)
F32—Zn2—F12^ii	88.8 (5)	F44—As2—F24	90.5 (7)
F32^ii—Zn2—F12^ii	91.2 (5)	F34—As2—F24	88.3 (8)
F12—Zn2—F12^ii	180.0	F14—As2—F24	89.8 (8)

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

(ZnAsII_0p15GPa)

Crystal data

F12Xe6Zn·2(AsF6)	F(000) = 2544
Mr = 1459.01	Dx = 3.671 Mg m^−3
Monoclinic, P2/n	Synchrotron radiation, λ = 0.1582 Å
a = 13.630 (2) Å	Cell parameters from 1703 reflections
b = 13.6939 (9) Å	θ = 1.5–6.5°
c = 14.1449 (8) Å	µ = 0.83 mm^−1
β = 90.497 (10)°	T = 298 K
V = 2640.0 (4) Å^3	Block, colourless
Z = 4	0.25 × 0.22 × 0.05 mm

Data collection

Esperanto-CrysAlisPro-abstract goniometer imported esperanto images diffractometer	2927 independent reflections
Radiation source: synchrotron	2267 reflections with I > 2σ(I)
Detector resolution: 5.8140 pixels mm^-1	Rint = 0.036
ω scans	θmax = 5.7°, θmin = 1.5°
Absorption correction: multi-scan The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments.	h = −13→13
Tmin = 0.819, Tmax = 1.176	k = −16→17
5517 measured reflections	l = −17→17

Refinement

Refinement on F^2	477 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.1146P)^2 + 10.326P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.197	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 1.77 e Å^−3
2927 reflections	Δρmin = −1.18 e Å^−3
307 parameters

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
Zn1	−0.500000	0.500000	0.000000	0.0562 (11)
Xe11	−0.23553 (14)	0.54130 (9)	−0.02232 (9)	0.0691 (5)
F11	−0.3598 (14)	0.4762 (9)	0.0364 (9)	0.083 (5)
F21	−0.1182 (18)	0.5983 (12)	−0.0754 (13)	0.113 (7)
Xe21	−0.52856 (14)	0.52935 (9)	−0.25664 (7)	0.0733 (6)
F31	−0.4629 (17)	0.4804 (13)	−0.1327 (8)	0.108 (6)
F41	−0.5903 (18)	0.5673 (11)	−0.3714 (9)	0.104 (6)
Xe31	−0.45228 (15)	0.23557 (8)	−0.02065 (12)	0.0896 (7)
F51	−0.5251 (17)	0.3570 (9)	0.0249 (14)	0.118 (8)
F61	−0.393 (2)	0.1139 (12)	−0.0516 (18)	0.154 (8)
Zn2	0.000000	1.000000	0.000000	0.0495 (10)
Xe12	−0.26072 (13)	0.93453 (8)	0.02885 (9)	0.0667 (5)
F12	−0.1237 (16)	0.9328 (10)	−0.0347 (11)	0.095 (5)
F22	−0.3908 (19)	0.9362 (13)	0.0826 (13)	0.118 (7)
Xe22	0.05186 (14)	0.73970 (7)	0.01971 (8)	0.0769 (6)
F32	0.0692 (13)	0.8784 (7)	−0.0340 (8)	0.089 (5)
F42	0.0366 (19)	0.6103 (9)	0.0674 (10)	0.117 (6)
Xe32	−0.02278 (14)	0.97719 (9)	−0.25840 (7)	0.0709 (6)
F52	0.0142 (14)	1.0464 (8)	−0.1327 (7)	0.082 (5)
F62	−0.0552 (19)	0.9134 (13)	−0.3752 (9)	0.114 (7)
As1	−0.250000	0.75484 (19)	−0.250000	0.0861 (14)
F13	−0.250000	0.8778 (12)	−0.250000	0.110 (7)
F23	−0.125 (2)	0.7555 (10)	−0.2371 (15)	0.118 (6)
F33	−0.250000	0.6280 (12)	−0.250000	0.096 (6)
F43	−0.269 (2)	0.7539 (11)	−0.1262 (11)	0.119 (7)
As2	0.250000	0.7837 (2)	−0.250000	0.0963 (17)
F14	0.250000	0.9087 (7)	−0.250000	0.165 (10)
F24	0.2585 (18)	0.7833 (8)	−0.1292 (5)	0.199 (10)
F34	0.1243 (5)	0.7835 (8)	−0.2426 (17)	0.148 (7)
F44	0.250000	0.6584 (7)	−0.250000	0.171 (10)
As3	−0.250000	0.7138 (2)	0.250000	0.0953 (18)
F15	−0.250000	0.8306 (6)	0.250000	0.136 (8)
F25	−0.1460 (14)	0.7139 (11)	0.1742 (16)	0.186 (9)
F35	−0.3301 (16)	0.7137 (11)	0.1490 (13)	0.185 (8)
F45	−0.250000	0.5982 (6)	0.250000	0.131 (8)
As4	−0.250000	1.2957 (5)	−0.250000	0.122 (3)
F16	−0.250000	1.4213 (9)	−0.250000	0.175 (11)
F26	−0.1236 (7)	1.2954 (12)	−0.2540 (16)	0.203 (10)
F36	−0.250000	1.1712 (9)	−0.250000	0.173 (10)
F46	−0.2440 (19)	1.2998 (17)	−0.1296 (7)	0.148 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.063 (4)	0.0594 (13)	0.0464 (12)	0.0058 (12)	0.0077 (18)	0.0030 (10)
Xe11	0.0552 (16)	0.0823 (7)	0.0698 (7)	0.0059 (5)	−0.0056 (9)	0.0005 (5)
F11	0.065 (15)	0.097 (8)	0.086 (7)	0.002 (6)	0.008 (9)	0.020 (6)
F21	0.079 (18)	0.129 (10)	0.131 (11)	−0.007 (9)	0.011 (13)	0.034 (9)
Xe21	0.0824 (18)	0.0940 (8)	0.0436 (5)	−0.0023 (7)	0.0033 (8)	−0.0028 (5)
F31	0.106 (18)	0.164 (12)	0.053 (5)	0.046 (10)	0.005 (8)	0.003 (6)
F41	0.128 (19)	0.122 (10)	0.061 (5)	0.022 (9)	−0.010 (9)	0.020 (6)
Xe31	0.0992 (17)	0.0531 (6)	0.1166 (11)	0.0015 (5)	0.0154 (12)	0.0073 (6)
F51	0.103 (19)	0.081 (7)	0.171 (15)	−0.012 (7)	0.044 (16)	−0.001 (8)
F61	0.17 (2)	0.081 (8)	0.208 (16)	0.036 (9)	0.017 (17)	−0.003 (10)
Zn2	0.055 (3)	0.0474 (11)	0.0465 (11)	−0.0039 (10)	0.0073 (16)	−0.0043 (9)
Xe12	0.0570 (15)	0.0760 (7)	0.0672 (7)	−0.0030 (5)	0.0053 (9)	−0.0043 (5)
F12	0.077 (14)	0.110 (8)	0.097 (8)	−0.027 (7)	0.005 (10)	−0.021 (7)
F22	0.083 (19)	0.153 (12)	0.117 (10)	0.001 (10)	0.032 (13)	−0.022 (9)
Xe22	0.1051 (17)	0.0542 (6)	0.0715 (7)	0.0113 (5)	0.0008 (9)	−0.0014 (4)
F32	0.116 (13)	0.057 (5)	0.094 (7)	0.016 (5)	0.032 (9)	−0.004 (5)
F42	0.180 (19)	0.066 (6)	0.106 (8)	0.012 (7)	0.012 (12)	0.021 (6)
Xe32	0.0817 (17)	0.0844 (7)	0.0469 (5)	−0.0029 (6)	0.0085 (8)	−0.0027 (4)
F52	0.114 (15)	0.082 (6)	0.051 (4)	−0.024 (6)	0.010 (7)	−0.001 (4)
F62	0.13 (2)	0.148 (12)	0.067 (6)	−0.012 (11)	−0.013 (10)	−0.030 (7)
As1	0.105 (4)	0.0579 (14)	0.095 (2)	0.000	−0.002 (3)	0.000
F13	0.122 (19)	0.063 (8)	0.144 (14)	0.000	−0.013 (16)	0.000
F23	0.104 (16)	0.093 (8)	0.156 (14)	0.005 (7)	−0.005 (14)	0.008 (8)
F33	0.128 (19)	0.071 (8)	0.091 (9)	0.000	0.003 (13)	0.000
F43	0.15 (2)	0.103 (9)	0.108 (9)	−0.004 (10)	0.004 (13)	−0.018 (7)
As2	0.096 (5)	0.0761 (18)	0.117 (3)	0.000	0.029 (3)	0.000
F14	0.10 (2)	0.130 (14)	0.26 (2)	0.000	−0.04 (2)	0.000
F24	0.19 (3)	0.240 (19)	0.165 (15)	0.02 (2)	−0.020 (16)	−0.007 (12)
F34	0.111 (18)	0.124 (11)	0.210 (17)	0.000 (9)	0.009 (14)	−0.005 (13)
F44	0.13 (2)	0.122 (14)	0.26 (2)	0.000	0.00 (2)	0.000
As3	0.130 (6)	0.0769 (18)	0.0783 (17)	0.000	−0.006 (3)	0.000
F15	0.19 (3)	0.108 (12)	0.110 (12)	0.000	−0.024 (17)	0.000
F25	0.17 (2)	0.201 (17)	0.187 (16)	−0.011 (14)	0.054 (17)	−0.012 (15)
F35	0.22 (2)	0.142 (14)	0.189 (16)	0.035 (14)	−0.097 (19)	−0.014 (12)
F45	0.12 (2)	0.107 (12)	0.167 (17)	0.000	−0.042 (18)	0.000
As4	0.078 (8)	0.209 (5)	0.080 (2)	0.000	0.007 (4)	0.000
F16	0.15 (3)	0.213 (19)	0.161 (18)	0.000	−0.03 (2)	0.000
F26	0.08 (2)	0.37 (2)	0.155 (17)	0.008 (14)	−0.005 (17)	−0.01 (2)
F36	0.14 (3)	0.266 (19)	0.108 (13)	0.000	−0.02 (2)	0.000
F46	0.08 (2)	0.265 (18)	0.100 (9)	−0.033 (15)	−0.019 (13)	−0.013 (10)

Geometric parameters (Å, º)

Zn1—F31^i	1.966 (9)	As1—F13	1.684 (17)
Zn1—F31	1.966 (9)	As1—F23^iii	1.71 (3)
Zn1—F11	2.00 (2)	As1—F23	1.71 (3)
Zn1—F11^i	2.00 (2)	As1—F33	1.737 (16)
Zn1—F51^i	2.020 (12)	As1—F43	1.773 (15)
Zn1—F51	2.020 (12)	As1—F43^iii	1.773 (14)
Xe11—F21	1.937 (18)	As2—F24^iv	1.711 (7)
Xe11—F11	2.093 (14)	As2—F24	1.711 (7)
Xe21—F41	1.896 (17)	As2—F14	1.712 (9)
Xe21—F31	2.074 (16)	As2—F44	1.716 (9)
Xe31—F61	1.904 (15)	As2—F34	1.717 (6)
Xe31—F51	2.043 (15)	As2—F34^iv	1.717 (6)
Zn2—F32	1.975 (10)	As3—F45	1.583 (8)
Zn2—F32^ii	1.975 (10)	As3—F15	1.600 (8)
Zn2—F12^ii	1.98 (2)	As3—F25	1.785 (8)
Zn2—F12	1.98 (2)	As3—F25^v	1.785 (8)
Zn2—F52	1.992 (9)	As3—F35	1.790 (8)
Zn2—F52^ii	1.992 (9)	As3—F35^v	1.790 (8)
Xe12—F22	1.94 (2)	As4—F36	1.704 (10)
Xe12—F12	2.079 (18)	As4—F46^iii	1.705 (10)
Xe22—F42	1.908 (12)	As4—F46	1.705 (10)
Xe22—F32	2.060 (10)	As4—F16	1.721 (10)
Xe32—F62	1.917 (15)	As4—F26	1.725 (10)
Xe32—F52	2.073 (11)	As4—F26^iii	1.725 (10)
F31^i—Zn1—F31	180.0	F33—As1—F43	89.6 (5)
F31^i—Zn1—F11	91.7 (8)	F13—As1—F43^iii	90.4 (5)
F31—Zn1—F11	88.3 (8)	F23^iii—As1—F43^iii	92.9 (12)
F31^i—Zn1—F11^i	88.3 (8)	F23—As1—F43^iii	87.1 (12)
F31—Zn1—F11^i	91.7 (8)	F33—As1—F43^iii	89.6 (5)
F11—Zn1—F11^i	180.0	F43—As1—F43^iii	179.1 (10)
F31^i—Zn1—F51^i	94.5 (7)	F24^iv—As2—F24	179.6 (7)
F31—Zn1—F51^i	85.5 (7)	F24^iv—As2—F14	90.2 (4)
F11—Zn1—F51^i	92.3 (8)	F24—As2—F14	90.2 (4)
F11^i—Zn1—F51^i	87.7 (8)	F24^iv—As2—F44	89.8 (4)
F31^i—Zn1—F51	85.5 (7)	F24—As2—F44	89.8 (4)
F31—Zn1—F51	94.5 (7)	F14—As2—F44	180.0
F11—Zn1—F51	87.7 (8)	F24^iv—As2—F34	90.1 (4)
F11^i—Zn1—F51	92.3 (8)	F24—As2—F34	89.9 (4)
F51^i—Zn1—F51	180.0	F14—As2—F34	90.1 (3)
F21—Xe11—F11	178.3 (8)	F44—As2—F34	89.9 (3)
Zn1—F11—Xe11	127.1 (6)	F24^iv—As2—F34^iv	89.9 (4)
F41—Xe21—F31	177.0 (8)	F24—As2—F34^iv	90.1 (4)
Zn1—F31—Xe21	130.5 (9)	F14—As2—F34^iv	90.1 (3)
F61—Xe31—F51	173.0 (8)	F44—As2—F34^iv	89.9 (3)
Zn1—F51—Xe31	130.6 (8)	F34—As2—F34^iv	179.8 (8)
F32—Zn2—F32^ii	180.0	F45—As3—F15	180.0
F32—Zn2—F12^ii	92.6 (7)	F45—As3—F25	90.0 (5)
F32^ii—Zn2—F12^ii	87.4 (7)	F15—As3—F25	90.0 (5)
F32—Zn2—F12	87.4 (7)	F45—As3—F25^v	90.0 (5)
F32^ii—Zn2—F12	92.6 (7)	F15—As3—F25^v	90.0 (5)
F12^ii—Zn2—F12	180.0	F25—As3—F25^v	179.9 (9)
F32—Zn2—F52	89.4 (5)	F45—As3—F35	90.0 (5)
F32^ii—Zn2—F52	90.6 (5)	F15—As3—F35	90.0 (5)
F12^ii—Zn2—F52	89.8 (7)	F25—As3—F35	90.2 (7)
F12—Zn2—F52	90.2 (7)	F25^v—As3—F35	89.8 (7)
F32—Zn2—F52^ii	90.6 (5)	F45—As3—F35^v	90.0 (5)
F32^ii—Zn2—F52^ii	89.4 (5)	F15—As3—F35^v	90.0 (5)
F12^ii—Zn2—F52^ii	90.2 (7)	F25—As3—F35^v	89.8 (7)
F12—Zn2—F52^ii	89.8 (7)	F25^v—As3—F35^v	90.2 (7)
F52—Zn2—F52^ii	180.0	F35—As3—F35^v	179.9 (9)
F22—Xe12—F12	177.5 (9)	F36—As4—F46^iii	91.9 (8)
Zn2—F12—Xe12	130.8 (6)	F36—As4—F46	91.9 (8)
F42—Xe22—F32	179.0 (5)	F46^iii—As4—F46	176.2 (17)
Zn2—F32—Xe22	129.1 (6)	F36—As4—F16	180.0
F62—Xe32—F52	179.2 (9)	F46^iii—As4—F16	88.1 (8)
Zn2—F52—Xe32	129.6 (5)	F46—As4—F16	88.1 (8)
F13—As1—F23^iii	89.7 (5)	F36—As4—F26	89.9 (5)
F13—As1—F23	89.7 (5)	F46^iii—As4—F26	90.4 (9)
F23^iii—As1—F23	179.4 (10)	F46—As4—F26	89.6 (9)
F13—As1—F33	180.0	F16—As4—F26	90.1 (5)
F23^iii—As1—F33	90.3 (5)	F36—As4—F26^iii	89.9 (5)
F23—As1—F33	90.3 (5)	F46^iii—As4—F26^iii	89.6 (9)
F13—As1—F43	90.4 (5)	F46—As4—F26^iii	90.4 (9)
F23^iii—As1—F43	87.1 (12)	F16—As4—F26^iii	90.1 (5)
F23—As1—F43	92.9 (12)	F26—As4—F26^iii	179.7 (10)

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

(ZnSbII_160K)

Crystal data

F12Xe6Zn·2(F6Sb)	Z = 4
Mr = 1552.63	F(000) = 2688
Triclinic, P1	Dx = 3.963 Mg m^−3
a = 9.4869 (10) Å	Ag Kα radiation, λ = 0.56086 Å
b = 13.7005 (16) Å	Cell parameters from 6296 reflections
c = 20.057 (2) Å	θ = 2.3–20.5°
α = 89.469 (3)°	µ = 5.63 mm^−1
β = 88.697 (3)°	T = 160 K
γ = 86.951 (3)°	Block, colourless
V = 2602.4 (5) Å^3	0.30 × 0.25 × 0.20 mm

Data collection

Bruker Venture diffractometer	7491 reflections with I > 2.0σ(I)
Mirrors monochromator	Rint = 0.089
φ & ω scans	θmax = 20.6°, θmin = 0.8°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −11→11
Tmin = 0.14, Tmax = 0.32	k = −17→17
56066 measured reflections	l = 0→25
10213 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: From Cu analogue
R[F^2 > 2σ(F^2)] = 0.061	Weighting scheme based on measured s.u.'s Method = SQRT(W) = 1/(Data with the key SIGMA(/FO/) in list 6)
wR(F^2) = 0.094	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 3.45 e Å^−3
9888 reflections	Δρmin = −2.48 e Å^−3
598 parameters

Special details

Refinement. The sample consisted of multiple domains. Of 5111 reflectiuon used for indexing, 3194 could be indexed with a principal domain (Cell_Now). In addition to this: Domain 2: Rotated from first domain by 179.9 degrees about reciprocal axis 1.000 0.102 0.023 and real axis 1.000 0.012 -0.004 Twin law to convert hkl from first to 0.998 0.024 -0.007 this domain (SHELXL TWIN matrix): 0.204 -0.998 0.001 0.046 -0.003 -1.000 504 reflections within tolerance assigned to domain 2, 361 of them exclusively; 1556 reflections not yet assigned to a domain —————————————————————————— Domain 3: Rotated from first domain by 123.9 degrees about reciprocal axis 1.000 0.305 -0.801 and real axis 1.000 0.111 -0.189 Twin law to convert hkl from first to 0.738 0.356 -0.191 this domain (SHELXL TWIN matrix): -0.020 -0.491 -0.593 -1.397 1.007 -0.362 442 reflections within tolerance assigned to domain 3, 327 of them exclusively; 1229 reflections not yet assigned to a domain —————————————————————————— Domain 4 Rotated from first domain by 179.9 degrees about reciprocal axis 1.000 0.083 0.044 and real axis 1.000 0.003 0.001 Twin law to convert hkl from first to 0.999 0.005 0.002 this domain (SHELXL TWIN matrix): 0.167 -1.000 -0.001 0.087 0.003 -1.000 1020 reflections within tolerance assigned to domain 4, 290 of them exclusively; 939 reflections not yet assigned to a domain —————————————————————————— Domain 5: Rotated from first domain by 178.0 degrees about reciprocal axis -0.503 0.869 1.000 and real axis 1.000 -0.794 -0.415 Twin law to convert hkl from first to -0.375 -0.484 -0.271 this domain (SHELXL TWIN matrix): -1.106 -0.140 0.435 -1.196 1.015 -0.484 874 reflections within tolerance assigned to domain 5, 270 of them exclusively; 669 reflections not yet assigned to a domain —————————————————————————— Domain 6 Rotated from first domain by 159.1 degrees about reciprocal axis 0.084 -0.862 1.000 and real axis -0.258 1.000 -0.539 Twin law to convert hkl from first to -0.921 0.037 0.193 this domain (SHELXL TWIN matrix): -0.623 0.249 -0.595 -0.235 -1.411 -0.196 701 reflections within tolerance assigned to domain 6, 131 of them exclusively; 538 reflections not yet assigned to a domain —————————————————————————— Domain 7: Rotated from first domain by 179.1 degrees about reciprocal axis 0.492 0.963 1.000 and real axis 1.000 0.980 0.484 Twin law to convert hkl from first to -0.488 0.505 0.245 this domain (SHELXL TWIN matrix): 0.990 -0.022 0.492 1.066 1.014 -0.489 838 reflections within tolerance assigned to domain 7, 147 of them exclusively; 391 reflections not yet assigned to a domain —————————————————————————— Domain 8: Rotated from first domain by 180.0 degrees about reciprocal axis 0.003 -0.018 1.000 and real axis -0.022 -0.050 1.000 Twin law to convert hkl from first to -1.000 0.000 0.006 this domain (SHELXL TWIN matrix): 0.000 -0.998 -0.037 -0.044 -0.101 0.998 1280 reflections within tolerance assigned to domain 8, 67 of them exclusively; 324 reflections not yet assigned to a domain 324 reflections are left unindexed in this procedure. The small contributions made by the minor domains measnt that integration of all domains was unsuccessful, and the diffraction data were integrated with the first two domains only. Systematic errors were correction using TWINABS, which outputs two .hkl files for analysis, and HKLF 4 format file, where intensities have been 'detwinned' and an HKLF 5 format file where indices for the indices of overallped data are given explicitly. Refinement of the structure against the HKLF 5 data set in XL gave R1 = 0.0932 for 8267 Fo > 4sig(Fo) and 0.1238 for all 10606 data Refinement of the structure against the HKLF 4 data set gave: R1 = 0.0805 for 7793 Fo > 4sig(Fo) and 0.1030 for all 10205 data The HKLF 4 data set was used for further analysis but suffered from many outliers with Fo^{2 > Fc}2, as expected as the twinning was only partially accounted for during refinement. Refinement was switched to CRYSTALS and a statistical weighting scheme applied with a robust-resitant modifier as described by Prince & Nicholson [Acta Cryst. (1983) A39, 407-410] as a means for down-weighting data bady affected by unmodelled overlap. This procedure gave acceptable refinement indices, and a more linear normal probablity plot with slope = 0.989, intercept 0.08, correlation coefficent 0.995. The justification for using this weighting scheme is that the data were known to be contaminated with intensities for multiple minor domains of the sample and it was not possible to treat this effectively during integration. The reason for the poor quality of the sample is that it had undergone a phase transition from R-3 to P-1. The three fold symmetry of the parent phase is present in Domain 3 above. Reflections are selected by the following conditions :- Minimum value of SQRTW is 0.100E-04 Minimum value of RATIO is -3.00

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

	x	y	z	Uiso*/Ueq
Xe11	0.80642 (6)	0.02413 (4)	0.13228 (3)	0.0267
Xe21	0.52313 (7)	0.25564 (4)	0.26300 (3)	0.0303
Xe31	0.71989 (7)	−0.02622 (5)	0.39880 (3)	0.0345
Xe41	0.49611 (7)	−0.26359 (4)	0.21572 (3)	0.0301
Xe51	0.28861 (6)	0.01081 (4)	0.10253 (3)	0.0266
Xe61	0.21420 (7)	−0.02061 (5)	0.36168 (3)	0.0324
Zn1	0.51589 (11)	−0.01011 (7)	0.24732 (5)	0.0233
F71	0.5111 (6)	−0.1486 (4)	0.2821 (3)	0.0374
F11	0.6351 (6)	−0.0524 (4)	0.1670 (3)	0.0363
F61	0.7604 (8)	−0.0631 (5)	0.4905 (3)	0.0568
F81	0.4834 (7)	−0.3705 (4)	0.1538 (3)	0.0445
F41	0.5222 (7)	0.3780 (4)	0.3109 (3)	0.0503
F21	0.9652 (6)	0.0945 (4)	0.0990 (3)	0.0465
F51	0.6845 (6)	0.0140 (4)	0.3005 (3)	0.0411
F91	0.3973 (6)	0.0394 (4)	0.3262 (3)	0.0374
F101	0.0441 (7)	−0.0771 (5)	0.3968 (4)	0.0571
F31	0.5217 (6)	0.1262 (4)	0.2093 (3)	0.0388
F111	0.3426 (6)	−0.0388 (4)	0.1977 (3)	0.0346
F121	0.2360 (6)	0.0571 (4)	0.0141 (3)	0.0407
Xe32	0.76022 (7)	0.48121 (5)	0.13967 (3)	0.0330
Xe12	0.73119 (6)	0.52170 (4)	−0.12507 (3)	0.0257
Xe22	0.97008 (6)	0.76139 (4)	0.02372 (3)	0.0271
Zn2	1.0000	0.5000	0.0000	0.0184
F12	0.9213 (5)	0.4644 (4)	−0.0879 (3)	0.0325
F22	0.5561 (5)	0.5760 (4)	−0.1615 (3)	0.0370
F32	0.8888 (5)	0.6286 (4)	0.0006 (3)	0.0369
F42	1.0413 (6)	0.8866 (4)	0.0493 (4)	0.0542
F52	0.8384 (6)	0.4371 (4)	0.0474 (3)	0.0392
F62	0.6875 (7)	0.5241 (6)	0.2256 (3)	0.0647
Xe23	0.74616 (6)	0.48224 (5)	0.63883 (3)	0.0304
Xe33	0.99154 (7)	0.23320 (4)	0.49019 (4)	0.0333
Xe13	0.72906 (7)	0.52705 (5)	0.37959 (3)	0.0298
Zn3	1.0000	0.5000	0.5000	0.0194
F13	0.9089 (6)	0.4537 (4)	0.4175 (3)	0.0417
F23	0.5618 (6)	0.5949 (5)	0.3455 (3)	0.0446
F63	0.9649 (7)	0.1090 (4)	0.4478 (4)	0.0623
F43	0.6857 (6)	0.4458 (5)	0.7280 (3)	0.0419
F33	0.8105 (6)	0.5232 (5)	0.5426 (3)	0.0475
F53	1.0161 (6)	0.3651 (4)	0.5390 (3)	0.0394
Sb1	0.03682 (7)	0.26208 (5)	0.24714 (3)	0.0299
F14	−0.1116 (8)	0.1817 (6)	0.2364 (4)	0.0840
F34	0.1653 (8)	0.1606 (5)	0.2246 (4)	0.0652
F45	0.0536 (9)	0.2266 (6)	0.3359 (3)	0.0715
F54	−0.0895 (8)	0.3644 (6)	0.2710 (4)	0.0719
F64	0.0251 (7)	0.3035 (5)	0.1578 (3)	0.0546
F24	0.1870 (7)	0.3454 (5)	0.2565 (4)	0.0627
Sb2	0.48000 (8)	0.74672 (5)	0.51207 (4)	0.0374
F25	0.6041 (8)	0.7711 (7)	0.5798 (4)	0.0758
F44	0.3509 (8)	0.7223 (8)	0.4458 (4)	0.1032
F65	0.4516 (9)	0.8802 (5)	0.4944 (4)	0.0774
F35	0.3334 (7)	0.7541 (6)	0.5756 (4)	0.0680
F55	0.6294 (7)	0.7406 (5)	0.4506 (4)	0.0587
F15	0.5055 (8)	0.6149 (5)	0.5279 (5)	0.0839
Sb3	0.99582 (8)	0.74496 (6)	0.24756 (4)	0.0375
F16	0.9933 (9)	0.6108 (6)	0.2586 (5)	0.0830
F26	1.0008 (9)	0.8792 (5)	0.2373 (5)	0.0932
F36	1.1375 (7)	0.7488 (5)	0.3099 (3)	0.0597
F46	1.1325 (8)	0.7286 (7)	0.1809 (4)	0.0868
F56	0.8567 (7)	0.7410 (7)	0.1835 (4)	0.0804
F66	0.8581 (9)	0.7625 (7)	0.3145 (4)	0.0883
Sb4	0.52780 (7)	0.24791 (5)	0.01580 (4)	0.0301
F17	0.5048 (7)	0.3838 (4)	0.0089 (3)	0.0513
F27	0.5537 (6)	0.1110 (4)	0.0245 (3)	0.0443
F37	0.4062 (7)	0.2324 (5)	−0.0548 (3)	0.0496
F47	0.3735 (7)	0.2458 (4)	0.0772 (3)	0.0476
F57	0.6514 (7)	0.2594 (5)	0.0871 (4)	0.0598
F67	0.6804 (7)	0.2479 (5)	−0.0459 (4)	0.0586

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Xe11	0.0293 (3)	0.0285 (3)	0.0222 (3)	−0.0005 (2)	0.0011 (3)	−0.0019 (2)
Xe21	0.0372 (3)	0.0190 (3)	0.0345 (4)	0.0004 (3)	−0.0023 (3)	−0.0011 (3)
Xe31	0.0385 (4)	0.0340 (3)	0.0311 (4)	0.0042 (3)	−0.0130 (3)	−0.0086 (3)
Xe41	0.0339 (3)	0.0185 (3)	0.0381 (4)	−0.0038 (2)	−0.0053 (3)	0.0027 (3)
Xe51	0.0291 (3)	0.0257 (3)	0.0252 (3)	0.0008 (2)	−0.0062 (3)	−0.0040 (2)
Xe61	0.0356 (3)	0.0306 (3)	0.0306 (4)	−0.0003 (3)	0.0080 (3)	−0.0027 (3)
Zn1	0.0324 (6)	0.0228 (5)	0.0153 (5)	−0.0049 (4)	−0.0022 (5)	−0.0019 (4)
F71	0.055 (4)	0.022 (3)	0.037 (3)	−0.008 (3)	−0.011 (3)	0.006 (2)
F11	0.052 (4)	0.027 (3)	0.031 (3)	−0.007 (3)	0.016 (3)	−0.013 (2)
F61	0.080 (5)	0.053 (4)	0.037 (4)	0.007 (4)	−0.031 (4)	−0.005 (3)
F81	0.061 (4)	0.024 (3)	0.049 (4)	−0.006 (3)	−0.014 (3)	−0.010 (3)
F41	0.062 (4)	0.033 (3)	0.057 (4)	−0.006 (3)	−0.003 (4)	−0.014 (3)
F21	0.040 (3)	0.043 (4)	0.056 (4)	−0.005 (3)	0.019 (3)	0.007 (3)
F51	0.038 (3)	0.048 (4)	0.040 (4)	−0.018 (3)	−0.010 (3)	0.002 (3)
F91	0.044 (3)	0.031 (3)	0.038 (3)	−0.014 (3)	0.010 (3)	−0.007 (3)
F101	0.054 (4)	0.044 (4)	0.072 (5)	−0.009 (3)	0.026 (4)	−0.002 (4)
F31	0.054 (4)	0.024 (3)	0.038 (3)	−0.006 (3)	0.000 (3)	0.004 (3)
F111	0.039 (3)	0.031 (3)	0.035 (3)	−0.008 (2)	−0.006 (3)	0.002 (3)
F121	0.059 (4)	0.044 (4)	0.019 (3)	0.005 (3)	−0.015 (3)	−0.001 (3)
Xe32	0.0293 (3)	0.0421 (4)	0.0269 (3)	0.0013 (3)	0.0065 (3)	−0.0014 (3)
Xe12	0.0265 (3)	0.0261 (3)	0.0249 (3)	−0.0023 (2)	−0.0079 (3)	−0.0017 (2)
Xe22	0.0323 (3)	0.0180 (3)	0.0312 (3)	0.0002 (2)	−0.0052 (3)	−0.0050 (2)
Zn2	0.0262 (7)	0.0173 (7)	0.0117 (6)	0.0000 (6)	−0.0011 (6)	−0.0035 (5)
F12	0.025 (3)	0.044 (3)	0.029 (3)	0.006 (2)	−0.008 (2)	−0.006 (3)
F22	0.029 (3)	0.041 (3)	0.041 (4)	0.000 (2)	−0.006 (3)	0.005 (3)
F32	0.029 (3)	0.028 (3)	0.053 (4)	0.009 (2)	−0.017 (3)	−0.010 (3)
F42	0.046 (4)	0.022 (3)	0.095 (6)	−0.004 (3)	−0.016 (4)	−0.014 (3)
F52	0.036 (3)	0.049 (4)	0.033 (3)	−0.011 (3)	0.001 (3)	−0.010 (3)
F62	0.047 (4)	0.113 (6)	0.031 (4)	0.015 (4)	0.004 (3)	−0.006 (4)
Xe23	0.0298 (3)	0.0374 (4)	0.0236 (3)	−0.0010 (3)	0.0035 (3)	−0.0026 (3)
Xe33	0.0376 (4)	0.0217 (3)	0.0409 (4)	−0.0017 (3)	−0.0067 (3)	−0.0044 (3)
Xe13	0.0313 (3)	0.0345 (3)	0.0243 (3)	−0.0040 (3)	−0.0079 (3)	−0.0009 (3)
Zn3	0.0286 (7)	0.0196 (7)	0.0098 (6)	0.0017 (6)	−0.0016 (6)	−0.0023 (5)
F13	0.042 (3)	0.041 (3)	0.041 (4)	0.009 (3)	−0.014 (3)	−0.012 (3)
F23	0.029 (3)	0.068 (4)	0.036 (3)	0.007 (3)	−0.005 (3)	−0.005 (3)
F63	0.065 (5)	0.032 (4)	0.091 (6)	−0.009 (3)	−0.013 (4)	−0.025 (4)
F43	0.045 (4)	0.062 (4)	0.019 (3)	−0.010 (3)	0.003 (3)	−0.002 (3)
F33	0.035 (3)	0.075 (5)	0.031 (3)	0.008 (3)	0.005 (3)	0.009 (3)
F53	0.062 (4)	0.022 (3)	0.034 (3)	0.003 (3)	−0.014 (3)	0.003 (2)
Sb1	0.0358 (4)	0.0269 (3)	0.0271 (4)	−0.0008 (3)	−0.0014 (3)	−0.0062 (3)
F14	0.073 (5)	0.104 (7)	0.080 (6)	−0.055 (5)	0.019 (5)	−0.023 (5)
F34	0.072 (5)	0.048 (4)	0.072 (5)	0.031 (4)	−0.004 (4)	−0.013 (4)
F45	0.109 (7)	0.069 (5)	0.036 (4)	0.001 (5)	−0.005 (4)	0.004 (4)
F54	0.078 (5)	0.075 (5)	0.059 (5)	0.037 (4)	−0.003 (4)	−0.012 (4)
F64	0.071 (5)	0.059 (4)	0.035 (4)	−0.012 (4)	−0.011 (4)	0.007 (3)
F24	0.067 (5)	0.058 (5)	0.067 (5)	−0.022 (4)	−0.012 (4)	−0.008 (4)
Sb2	0.0370 (4)	0.0342 (4)	0.0404 (4)	0.0044 (3)	0.0006 (3)	−0.0086 (3)
F25	0.069 (5)	0.115 (7)	0.045 (4)	−0.015 (5)	−0.013 (4)	−0.009 (5)
F44	0.058 (5)	0.182 (10)	0.071 (6)	−0.001 (6)	−0.016 (5)	−0.052 (6)
F65	0.095 (6)	0.052 (5)	0.081 (6)	0.032 (4)	0.021 (5)	0.000 (4)
F35	0.043 (4)	0.085 (6)	0.073 (5)	0.014 (4)	0.016 (4)	0.008 (5)
F55	0.044 (4)	0.063 (5)	0.069 (5)	−0.002 (3)	0.020 (4)	−0.019 (4)
F15	0.085 (6)	0.031 (4)	0.134 (8)	−0.004 (4)	0.026 (6)	0.001 (5)
Sb3	0.0377 (4)	0.0436 (4)	0.0310 (4)	0.0020 (3)	−0.0035 (3)	0.0020 (3)
F16	0.098 (7)	0.055 (5)	0.099 (7)	−0.023 (4)	−0.015 (6)	−0.005 (5)
F26	0.113 (7)	0.043 (5)	0.122 (8)	0.008 (4)	−0.022 (6)	0.030 (5)
F36	0.073 (5)	0.058 (4)	0.048 (4)	0.006 (4)	−0.032 (4)	−0.009 (4)
F46	0.049 (5)	0.160 (9)	0.053 (5)	−0.020 (5)	0.001 (4)	−0.001 (6)
F56	0.048 (5)	0.134 (8)	0.057 (5)	0.008 (5)	−0.008 (4)	0.003 (5)
F66	0.073 (6)	0.115 (7)	0.074 (6)	0.009 (5)	0.035 (5)	−0.002 (5)
Sb4	0.0312 (3)	0.0239 (3)	0.0348 (4)	0.0012 (3)	0.0021 (3)	−0.0030 (3)
F17	0.064 (4)	0.028 (3)	0.060 (4)	0.002 (3)	0.008 (4)	0.012 (3)
F27	0.046 (4)	0.023 (3)	0.063 (4)	0.005 (3)	−0.006 (3)	−0.004 (3)
F37	0.056 (4)	0.058 (4)	0.035 (4)	−0.004 (3)	−0.020 (3)	0.000 (3)
F47	0.052 (4)	0.043 (4)	0.047 (4)	−0.003 (3)	0.010 (3)	−0.005 (3)
F57	0.058 (4)	0.055 (4)	0.068 (5)	−0.012 (3)	−0.014 (4)	0.005 (4)
F67	0.045 (4)	0.065 (5)	0.062 (5)	0.011 (3)	0.038 (4)	0.007 (4)

Geometric parameters (Å, º)

Xe11—F11	2.084 (5)	Xe33—F53	2.089 (6)
Xe11—F21	1.934 (5)	Xe13—F13	2.088 (5)
Xe21—F41	1.940 (6)	Xe13—F23	1.932 (6)
Xe21—F31	2.084 (6)	Zn3—F13^ii	2.007 (6)
Xe31—F61	1.945 (6)	Zn3—F53^ii	2.000 (5)
Xe31—F51	2.072 (6)	Zn3—F33^ii	1.984 (6)
Xe41—F71	2.085 (6)	Zn3—F13	2.007 (6)
Xe41—F81	1.939 (6)	Zn3—F33	1.984 (6)
Xe51—F111	2.086 (5)	Zn3—F53	2.000 (5)
Xe51—F121	1.946 (5)	Sb1—F14	1.851 (7)
Xe61—F91	2.070 (5)	Sb1—F34	1.852 (6)
Xe61—F101	1.942 (6)	Sb1—F45	1.850 (7)
Zn1—F71	2.018 (5)	Sb1—F54	1.855 (7)
Zn1—F11	2.018 (5)	Sb1—F64	1.879 (6)
Zn1—F51	1.986 (5)	Sb1—F24	1.886 (6)
Zn1—F91	2.021 (6)	Sb2—F25	1.862 (7)
Zn1—F31	2.013 (5)	Sb2—F44	1.872 (8)
Zn1—F111	2.000 (5)	Sb2—F65	1.867 (7)
Xe32—F52	2.062 (6)	Sb2—F35	1.865 (7)
Xe32—F62	1.927 (7)	Sb2—F55	1.856 (6)
Xe12—F12	2.079 (5)	Sb2—F15	1.834 (7)
Xe12—F22	1.940 (5)	Sb3—F16	1.851 (7)
Xe22—F32	2.074 (5)	Sb3—F26	1.852 (7)
Xe22—F42	1.954 (6)	Sb3—F36	1.859 (6)
Zn2—F52^i	2.013 (5)	Sb3—F46	1.848 (8)
Zn2—F12^i	2.005 (5)	Sb3—F56	1.866 (7)
Zn2—F32^i	2.004 (5)	Sb3—F66	1.860 (8)
Zn2—F12	2.005 (5)	Sb4—F17	1.867 (6)
Zn2—F32	2.004 (5)	Sb4—F27	1.885 (5)
Zn2—F52	2.013 (5)	Sb4—F37	1.868 (6)
Xe23—F43	1.935 (5)	Sb4—F47	1.892 (6)
Xe23—F33	2.093 (6)	Sb4—F57	1.882 (7)
Xe33—F63	1.940 (6)	Sb4—F67	1.883 (6)
F11—Xe11—F21	179.3 (3)	F33—Zn3—F53	90.8 (3)
F41—Xe21—F31	178.5 (3)	Xe13—F13—Zn3	121.3 (3)
F61—Xe31—F51	177.9 (3)	Xe23—F33—Zn3	127.4 (3)
F71—Xe41—F81	179.6 (2)	Xe33—F53—Zn3	127.5 (3)
F111—Xe51—F121	179.3 (2)	F14—Sb1—F34	90.6 (4)
F91—Xe61—F101	178.8 (3)	F14—Sb1—F45	92.0 (4)
F71—Zn1—F11	92.0 (2)	F34—Sb1—F45	89.2 (3)
F71—Zn1—F51	91.6 (2)	F14—Sb1—F54	90.2 (4)
F11—Zn1—F51	92.4 (3)	F34—Sb1—F54	178.9 (3)
F71—Zn1—F91	90.9 (2)	F45—Sb1—F54	90.0 (3)
F11—Zn1—F91	177.1 (2)	F14—Sb1—F64	90.7 (3)
F51—Zn1—F91	87.3 (3)	F34—Sb1—F64	91.6 (3)
F71—Zn1—F31	178.0 (2)	F45—Sb1—F64	177.2 (3)
F11—Zn1—F31	86.2 (2)	F54—Sb1—F64	89.1 (3)
F51—Zn1—F31	89.4 (2)	F14—Sb1—F24	178.8 (4)
F91—Zn1—F31	90.9 (2)	F34—Sb1—F24	89.7 (3)
F71—Zn1—F111	86.0 (2)	F45—Sb1—F24	89.1 (3)
F11—Zn1—F111	89.4 (2)	F54—Sb1—F24	89.4 (4)
F51—Zn1—F111	177.0 (2)	F64—Sb1—F24	88.2 (3)
F91—Zn1—F111	91.0 (2)	F25—Sb2—F44	178.3 (4)
F31—Zn1—F111	93.1 (2)	F25—Sb2—F65	91.2 (4)
Xe41—F71—Zn1	119.9 (3)	F44—Sb2—F65	88.9 (4)
Xe11—F11—Zn1	122.8 (3)	F25—Sb2—F35	88.2 (4)
Xe31—F51—Zn1	127.3 (3)	F44—Sb2—F35	90.1 (4)
Xe61—F91—Zn1	125.3 (3)	F65—Sb2—F35	90.1 (3)
Xe21—F31—Zn1	126.7 (3)	F25—Sb2—F55	90.1 (3)
Xe51—F111—Zn1	127.0 (3)	F44—Sb2—F55	91.6 (4)
F52—Xe32—F62	179.3 (3)	F65—Sb2—F55	89.7 (3)
F12—Xe12—F22	178.7 (2)	F35—Sb2—F55	178.4 (3)
F32—Xe22—F42	177.3 (3)	F25—Sb2—F15	90.0 (4)
F52^i—Zn2—F12^i	89.7 (2)	F44—Sb2—F15	89.9 (5)
F52^i—Zn2—F32^i	89.9 (2)	F65—Sb2—F15	178.8 (4)
F12^i—Zn2—F32^i	91.7 (2)	F35—Sb2—F15	90.1 (4)
F52^i—Zn2—F12	90.3 (2)	F55—Sb2—F15	90.2 (3)
F12^i—Zn2—F12	179.99	F16—Sb3—F26	179.1 (4)
F32^i—Zn2—F12	88.3 (2)	F16—Sb3—F36	90.0 (3)
F52^i—Zn2—F32	90.1 (2)	F26—Sb3—F36	89.1 (4)
F12^i—Zn2—F32	88.3 (2)	F16—Sb3—F46	90.2 (4)
F32^i—Zn2—F32	179.99	F26—Sb3—F46	89.6 (4)
F12—Zn2—F32	91.7 (2)	F36—Sb3—F46	89.3 (3)
F52^i—Zn2—F52	179.99	F16—Sb3—F56	90.1 (4)
F12^i—Zn2—F52	90.3 (2)	F26—Sb3—F56	90.7 (4)
F32^i—Zn2—F52	90.1 (2)	F36—Sb3—F56	178.7 (3)
F12—Zn2—F52	89.7 (2)	F46—Sb3—F56	89.4 (3)
F32—Zn2—F52	89.9 (2)	F16—Sb3—F66	90.3 (4)
Xe12—F12—Zn2	124.6 (3)	F26—Sb3—F66	89.9 (4)
Xe22—F32—Zn2	124.7 (2)	F36—Sb3—F66	90.7 (4)
Xe32—F52—Zn2	123.1 (3)	F46—Sb3—F66	179.5 (4)
F43—Xe23—F33	179.4 (3)	F56—Sb3—F66	90.5 (4)
F63—Xe33—F53	177.8 (3)	F17—Sb4—F27	178.7 (3)
F13—Xe13—F23	179.4 (3)	F17—Sb4—F37	91.2 (3)
F13^ii—Zn3—F53^ii	92.4 (2)	F27—Sb4—F37	90.1 (3)
F13^ii—Zn3—F33^ii	89.6 (3)	F17—Sb4—F47	90.5 (3)
F53^ii—Zn3—F33^ii	90.8 (3)	F27—Sb4—F47	89.4 (3)
F13^ii—Zn3—F13	179.99	F37—Sb4—F47	90.3 (3)
F53^ii—Zn3—F13	87.6 (2)	F17—Sb4—F57	90.6 (3)
F33^ii—Zn3—F13	90.4 (3)	F27—Sb4—F57	88.1 (3)
F13^ii—Zn3—F33	90.4 (3)	F37—Sb4—F57	178.3 (3)
F53^ii—Zn3—F33	89.2 (3)	F47—Sb4—F57	89.8 (3)
F33^ii—Zn3—F33	179.99	F17—Sb4—F67	90.4 (3)
F13—Zn3—F33	89.6 (3)	F27—Sb4—F67	89.7 (3)
F13^ii—Zn3—F53	87.6 (2)	F37—Sb4—F67	89.1 (3)
F53^ii—Zn3—F53	179.99	F47—Sb4—F67	179.0 (3)
F33^ii—Zn3—F53	89.2 (3)	F57—Sb4—F67	90.8 (3)
F13—Zn3—F53	92.4 (2)

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