Deep hydration of an Li7–3xLa3Zr2MIIIxO12 solid-state electrolyte material: a case study on Al- and Ga-stabilized LLZO

Redhammer, G.J.; Tippelt, G.; Rettenwander, D.

doi:10.1107/S2053229621012250

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 78| Part 1| January 2022| Pages 1-6

https://doi.org/10.1107/S2053229621012250

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Deep hydration of an Li_7–3xLa₃Zr₂M^III_xO₁₂ solid-state electrolyte material: a case study on Al- and Ga-stabilized LLZO

Günther J. Redhammer,^a ^* Gerold Tippelt ^a and Daniel Rettenwander ^b

^aChemistry and Physics of Materials, University of Salzburg, Jakob Haringerstrasse 2A, 5020 Salzburg, Austria, and ^bDepartment of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, Norway
^*Correspondence e-mail: guenther.redhammer@sbg.ac.at

Edited by M. Gardiner, Australian National University, Australia (Received 16 July 2021; accepted 18 November 2021; online 6 December 2021)

Single crystals of an Li-stuffed, Al- and Ga-stabilized garnet-type solid-state electrolyte material, Li₇La₃Zr₂O₁₂ (LLZO), have been analysed using single-crystal X-ray diffraction to determine the pristine structural state immediately after synthesis via ceramic sintering techniques. Hydrothermal treatment at 150 °C for 28 d induces a phase transition in the Al-stabilized compound from the commonly observed cubic Ia $[\overline{3}]$ d structure to the acentric I $[\overline{4}]$ 3d subtype. Li^I ions at the interstitial octahedrally (4 + 2-fold) coordinated 48e site are most easily extracted and Al^III ions order onto the tetrahedral 12a site. Deep hydration induces a distinct depletion of Li^I at this site, while the second tetrahedral site, 12b, suffers only minor Li^I loss. Charge balance is maintained by the incorporation of H^I, which is bonded to an O atom. Hydration of Ga-stabilized LLZO induces similar effects, with complete depletion of Li^I at the 48e site. The Li^I/H^I exchange not only leads to a distinct increase in the unit-cell size, but also alters some bonding topology, which is discussed here.

Keywords: solid-state electrolyte; LLZO; hydrothermal degradation; crystal structure; structure analysis; garnet; lattice expansion.

CCDC references: 2122845; 2122844; 2122843; 2122842

1. Introduction

The garnet family, X₃Y₂Z₃O₁₂, has been well described mineralogically and crystallographically in recent decades (Novak & Gibbs, 1971 ), and is of interest to a range of scientists from the fields of geoscience and technology, due to its thermodynamic stability in a variety of geological environments and its flexible structure, which can host ∼60 different chemical elements as major and minor components (Geiger, 2013 ; Baxter et al., 2013 ). Furthermore, the so-called Li-stuffed garnets, e.g. Li₄La₃Zr₂Li₃O₁₂, or as sum formula, Li₇La₃Zr₂O₁₂ (LLZO), have raised particular interest as promising materials for use as solid-state electrolytes in all solid-state Li batteries due to their superior Li-ion conductivity (Cussen, 2010 ; Wang et al., 2020 ; Murugan et al., 2007 ; Samson et al., 2019 ). Pure end-member LLZO is tetragonal, has the space group I4₁/acd (Awaka et al., 2009 ) and has distinctly lower Li-ion conductivities. The high Li-ion conductivity is associated with the `standard' cubic garnet structure with Ia $[\overline{3}]$ d symmetry. The latter can be stabilized by various aliovalent substitutions, e.g. by small amounts of Al^III, which – in the first experiments – entered the structure as a contaminant from the corundum crucibles during synthesis (Geiger et al., 2011 ; Buschmann et al., 2011 ). The incorporation of Ga^III into LLZO also increases the Li-ion conductivity, but induces a reduction of the symmetry to I $[\overline{4}]$ 3d (Rettenwander et al., 2016 ; Wagner et al., 2016a ; Robben et al., 2016 ), i.e. the space group of hydrogarnet Ca₃Al₂(O₄H₄)₃ (Lager et al., 1987 ). A stabilization of the cubic structure for nominally pure LLZO is also possible by the uptake of H^I, which raises a question about LLZO stability in hydrous environments (Larraz et al., 2013 ). Several studies have investigated the role of Li^I/H^I exchange under different environmental conditions and found that LLZO-type materials are distinctly unstable in the presence of moisture (Ma et al., 2015 ; Galven et al., 2011 , 2012 , 2013 ; Larraz et al., 2015 ; Orera et al., 2016 ; Liu et al., 2019 ). Surfaces quickly degrade with the formation of LiOH and Li₂CO₃, and an increase in unit-cell parameters is observed as Li^I/H^I exchange progresses. Until now, only a few studies have systematically investigated the mechanisms behind this structural degradation. In recent studies, we have shown, using diffraction methods, that significant Li^I is especially lost from the interstitial sites of the structure in Al^III-, Ga^III- and Ta^V-substituted LLZOs during ageing at room temperature under high humidity (Hiebl et al., 2019 ; Redhammer et al., 2021a ,b ). In this article, we report on the deep hydration of Al- and Ga-substituted LLZO using hydrothermal treatment of single-crystalline material.

2. Experimental methodology

2.1. Synthesis and aging of material

Single crystals of Al- and Ga-stabilized LLZO were obtained using a solid-state ceramic sintering method, which has been described in detail elsewhere (Rettenwander et al., 2016; Wagner et al., 2016a). In brief, Li₂CO₃ (with an excess of 10%), La₂O₃, ZrO₂ and Al₂O₃ or Ga₂O₃ were carefully mixed in the required stoichiometric proportions for the nominal compositions Li_6.55La₃Zr₂Al_0.15O₁₂ (Al15-LLZO) and Li_5.8La₃Zr₂Ga_0.4O₁₂ (Ga40-LLZO). The mixtures were pressed into pellets and preheated at 850 °C for 4 h for decarbonatization. The samples were subsequently milled in a high-energy ball mill under alcohol using ZrO₂ balls, then dried, pelletized and sintered at 1230 °C for 6 h. This yielded a dense ceramic consisting of large individual crystallites of up to 150 µm. Structural refinements were carried out on the fresh LLZOs within 24 h of synthesis to assess the unaltered structural state. Parts of the pellets were crushed carefully and aged in a 45 ml Teflon-lined autoclave (25 mg sample and 250 ml distilled water) at 150 °C for a period of 28 d. The pH value of the liquid, in which the crystals were submerged, was measured after the experiment; the pH value was ∼13 for both compositions. The hydrated single LLZO crystallites were then filtered off and the remaining liquid was left to evaporate. The resulting precipitate was identified as Li₂CO₃ using powder diffraction (PXRD), i.e. proving that Li^I was extracted from the LLZO material.

2.2. Refinement

Information on data collection and refinement results is given in Table 1. Indexing the diffraction data for pristine Al-LLZO yields the space-group symmetry Ia $[\overline{3}]$ d. Refining the structure with framework cations and O atoms results in only two strong residual electron-density peaks at the 24d and 96h positions. Assuming that Li atoms occupy only these two positions, then there must be a distinct overpopulation at the 24d site. Thus, Al^III is assigned to the 24d site and its content was fixed using the chemical composition calculated from energy dispersive X-ray (EDX) analysis on a similar material synthesized using an identical experimental setup (Rettenwander et al., 2016). The Li content was allowed to refine freely.

Table 1
Experimental details

For all structures: Z = 8. Experiments were carried out at 298 K with Mo Kα radiation using a Bruker SMART APEX diffractometer. Absorption was corrected for by multi-scan methods (APEX2; Bruker, 2012 ). LLZO-Al15-pristine = fresh sample of Al-doped LLZO, measured directly after the end of the synthesis, LLZO-Al15-hydro-150C = Al-doped LLZO aged hydrothermally at 150 °C, LLZO-Ga40-pristine = fresh sample of Ga-doped LLZO, measured directly after the end of the synthesis and LLZO-Ga40-hydro-150C = Ga-doped LLZO aged hydrothermally at 150 °C.

	LLZO-Al15-pristine	LLZO-Al15-hydro-150C	LLZO-Ga40-pristine	LLZO-Ga40-hydro-150C
Crystal data
Chemical formula	Al_0.15La_2.95Li_5.73O₁₂Zr₂	Al_0.15H_5.52La_2.88Li_1.64O₁₂Zr_1.95	Ga_0.28La_2.94Li_6.44O_12.00Zr_2.00	Ga_0.26H_3.90La_2.96Li_1.99O₁₂Zr₂
M_r	827.89	790.95	847.67	821.46
Crystal system, space group	Cubic, Ia $[\overline{3}]$ d	Cubic, I $[\overline{4}]$ 3d	Cubic, I $[\overline{4}]$ 3d	Cubic, I $[\overline{4}]$ 3d
a (Å)	12.9637 (2)	13.0738 (2)	12.9669 (2)	13.06720 (12)
V (Å³)	2178.65 (10)	2234.63 (10)	2180.26 (10)	2231.25 (6)
μ (mm⁻¹)	13.24	12.61	13.88	13.57
Crystal size (mm)	0.12 × 0.11 × 0.07	0.13 × 0.12 × 0.08	0.13 × 0.13 × 0.10	0.12 × 0.11 × 0.09

Data collection
T_min, T_max	0.22, 0.39	0.21, 0.36	0.19, 0.25	0.21, 0.36
No. of measured, independent and observed [I > 2σ(I)] reflections	33130, 455, 441	34201, 819, 819	35033, 1054, 1045	35657, 918, 915
R_int	0.029	0.026	0.038	0.028
(sin θ/λ)_max (Å⁻¹)	0.840	0.804	0.884	0.838

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.032, 1.51	0.013, 0.029, 1.27	0.013, 0.026, 1.29	0.018, 0.037, 1.12
No. of reflections	455	819	1054	918
No. of parameters	25	44	48	43
No. of restraints	0	1	2	3
H-atom treatment	–	Only H-atom coordinates refined	–	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.44	0.58, −0.51	0.53, −0.65	0.54, −0.52
Absolute structure	–	Refined as an inversion twin	Refined as an inversion twin	Refined as an inversion twin
Absolute structure parameter	–	0.50 (3)	0.50 (4)	0.99944 (15)
Computer programs: APEX2 (Bruker, 2012), SIR2014 (Burla et al., 2012 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and WinGX (Farrugia, 2012).

For pristine Ga-stabilized LLZO, indexing of the diffraction data yields the space-group symmetry I $[\overline{4}]$ 3d. Three different sites are identified from residual electron-density maps for the Li^I ions: at Wykoff positions 12a, 12b and 48e. It is evident that Ga^III must be located at the 12a position, as the 12a site becomes distinctly overpopulated when refined with only Li^I. In subsequent refinements, both the Li1 and Li2 sites are assumed to be fully occupied and the electron density is modelled with Li + Ga = 1. The result is that Ga^III almost exclusively resides at the 12a position. Refinement of the anisotropic atomic displacement parameters (adps) is possible for all atoms using the same strategy as that applied by Wagner et al. (2016a,b ). The data of the hydrothermally treated Ga-LLZO sample can also be indexed using I $[\overline{4}]$ 3d symmetry when the model for untreated material is used as the starting point. The Li1 site is again assumed to be fully occupied and its electron density was modelled with Li + Ga = 1. This approach is considered valid as the resultant Ga^III content is similar (albeit slightly higher) to that obtained for the untreated sample. The Li2 and, in particular, the Li3 sites are distinctly depleted in Li and no anisotropic atomic displacement refinement is possible. Thus, the isotropic adps are adjusted and fixed to the U_eq value refined for the Li1 site; anisotropic adps could be obtained for Li1. Protons are located close to the O1 atom using residual electron-density maps. Fixing the U_eq value of hydrogen yields reliable occupation factors for this site and an almost charge-balanced chemical formula (with a slight surplus of 0.35 negative charges).

For deeply hydrated Al-LLZO, indexing of data yields a change in symmetry from Ia $[\overline{3}]$ d to acentric I $[\overline{4}]$ 3d. The structure of this compound is refined using the model of the Ga-stabilized LLZO, as described above for the La-, Zr- and the two O-atom positions. The electron densities at Li1 and Li2 were modelled first with only Li⁺ ions. In this case, the Li1 position is distinctly overpopulated, while the occupation of the Li2 position is low, and there is no indication that the Li3 position is occupied at all. Consequently, all Al^III is assigned to the Li1 site and its occupation is fixed to the value used in the unaltered sample, consistent with the assumption that no Al left the structure during hydration. Refinement of the anisotropic adps is not possible for the Li1 site, and the isotropic adp is very small, so the isotropic adp of Li1 was adjusted in such a way that it has a similar value to the U_eq value of the Li2 site (where anisotropic adp refinements were possible) and fixed as such in subsequent refinements. Two distinct residual electron-density peaks are identified in residual electron-density maps: one high (2.5 e Å⁻³), very close to the Zr-atom position, and another at ∼0.8 Å from the O1 atom. This latter (x, y, z) position is close to the proposed H-atom positions given by Larraz et al. (2013) and Orera et al. (2016). Hence, this residual density is assigned to the H atom, which is bonded to the O1 atom. Independent refinement of the x, y and z positions, and the occupation of the H atom is possible, whereas the isotropic adp had to be fixed. A residual density close to Zr can be explained by positional disorder at this site, similar to that reported for deeply hydrated Ta-substituted LLZO, which also transformed to the I $[\overline{4}]$ 3d structure. However, there is a marked decrease in the reliability factors associated with the refinements when Zr^IV disorder is applied, e.g. there is no sign of another site close to O2 that would allow for another H atom to be bonded to the O2 atom. Furthermore, no reliable residual electron-density peaks can be detected.

Two additional crystals were hydrated in the same way and both were then analysed; the results are consistent with those reported in the tables and below.

3. Results and discussion

In the pristine state, Al-LLZO shows the typical garnet structure with Ia $[\overline{3}]$ d symmetry. La^III occupies the eightfold-coordinated 24c site with two symmetrically independent La—O bond lengths (see Table 2). A slight deficit in the La^III ion site occupation is observed, which is in line with previous studies (Hiebl et al., 2019; Rettenwander et al., 2016; Wagner et al., 2016a,b). The Zr^IV ions are located at the 16a position with a regular sixfold oxygen coordination and a bond length of 2.076 (16) Å. As depicted in Fig. 1, the garnet structure comprises an integrated framework constructed of edge-sharing octahedral and dodecahedral sites, in which the Li atoms are located at both the regular 24d tetrahedral site (Li1) and at the interstitial 96h position (Li2), often denoted to have a distorted octahedral coordination [Li2—O distances range between 1.854 (15) and 2.646 (14) Å, with the average of the four smaller bond lengths being 2.085 Å]. Al^III substitutes into the 24d position and the four equivalent Li—O lengths are 1.9044 (17) Å; both the 24d and the 96h positions show distinct vacancies.

Table 2
Selected geometric parameters (Å)

LLZO-Al15-pristine
La1—O1ⁱ	2.5110 (17)	Li2—O1	1.854 (15)
La1—O1	2.5951 (17)	Li2—O1^vii	2.085 (14)
Zr1—O1ⁱⁱ	2.1076 (16)	Li2—O1^vi	2.159 (15)
Li1—Li2ⁱⁱⁱ	1.616 (14)	Li2—O1^viii	2.242 (14)
Li1—O1^iv	1.9044 (17)	Li2—Li2^viii	2.46 (2)
Li1—Li2^v	2.367 (14)	Li2—O1^ix	2.646 (14)
Li2—Li2^vi	0.79 (3)

LLZO-Al15-hydro-150C
La1—O1ⁱ	2.506 (3)	Zr1B—O2^xii	2.06 (3)
La1—O1	2.518 (3)	Zr1B—O2^iv	2.10 (3)
La1—O2^x	2.544 (3)	Zr1B—O1ⁱⁱ	2.14 (3)
La1—O2ⁱ	2.607 (3)	Zr1B—O1^xiv	2.19 (3)
Zr1A—O1^xi	2.007 (4)	Zr1B—O1^xi	2.36 (3)
Zr1A—O2^xii	2.217 (4)	Li1—O1^xv	1.998 (3)
Zr1B—O2^xiii	1.85 (3)	Li2—O2^xvi	1.976 (3)

LLZO-Ga40-pristine
La1—O2^xiii	2.4935 (19)	Li2—O2^xvi	1.9246 (19)
La1—O1ⁱ	2.5264 (19)	Li2—Li3^xviii	2.340 (9)
La1—O2ⁱ	2.587 (2)	Li3—O1	1.878 (14)
La1—O1^xvii	2.5975 (19)	Li3—O1^vii	2.075 (8)
Zr1—O2^xiii	2.0823 (18)	Li3—O2ⁱ	2.108 (9)
Zr1—O1ⁱⁱ	2.1346 (18)	Li3—O1^viii	2.229 (8)
Li1—Li3ⁱⁱⁱ	1.645 (8)	Li3—Li3^vii	2.513 (13)
Li1—O1^xv	1.8941 (18)	Li3—O2^vii	2.639 (8)

LLZO-Ga40-hydro-150C
La1—O1ⁱ	2.514 (3)	Li1—Li3ⁱⁱⁱ	1.5 (2)
La1—O1^xvii	2.525 (3)	Li1—O1^xv	1.987 (4)
La1—O2^xiii	2.539 (4)	Li2—O2^xvi	1.982 (4)
La1—O2ⁱ	2.603 (4)	Li2—Li3^xviii	3.2 (2)
Zr1—O1ⁱⁱ	2.031 (3)	Li3—O1^vii	2.4 (2)
Zr1—O2^xiii	2.187 (4)	Li3—Li3^viii	2.6 (4)
Symmetry codes: (i) z, x, y; (ii) x − $[{1\over 4}]$ , z − $[{1\over 4}]$ , y − $[{1\over 4}]$ ; (iii) −z + $[{3\over 4}]$ , y − $[{1\over 4}]$ , −x + $[{1\over 4}]$ ; (iv) z, −x, −y + $[{1\over 2}]$ ; (v) −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ , x; (vi) −x + $[{1\over 4}]$ , z − $[{1\over 4}]$ , y + $[{1\over 4}]$ ; (vii) y − $[{1\over 4}]$ , −x + $[{1\over 4}]$ , −z + $[{3\over 4}]$ ; (viii) −y + $[{1\over 4}]$ , x + $[{1\over 4}]$ , −z + $[{3\over 4}]$ ; (ix) y, −z + $[{1\over 2}]$ , x + $[{1\over 2}]$ ; (x) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (xi) z − $[{1\over 4}]$ , y − $[{1\over 4}]$ , x − $[{1\over 4}]$ ; (xii) −y + $[{1\over 2}]$ , z, −x; (xiii) −x, −y + $[{1\over 2}]$ , z; (xiv) y − $[{1\over 4}]$ , x − $[{1\over 4}]$ , z − $[{1\over 4}]$ ; (xv) −z + $[{3\over 4}]$ , −y + $[{1\over 4}]$ , x + $[{1\over 4}]$ ; (xvi) x + $[{3\over 4}]$ , −z + $[{1\over 4}]$ , −y + $[{3\over 4}]$ ; (xvii) x, −y, −z + $[{1\over 2}]$ ; (xviii) y + $[{3\over 4}]$ , −x + $[{1\over 4}]$ , −z + $[{3\over 4}]$ .

Figure 1
The crystal structure of Al-stabilized LLZO (space group Ia $[\overline{3}]$ d) in a polyhedral format. LaO₈ sites are in light blue and ZrO₆ octahedra in sea green, whereas the Li1 (orange) and Li2 sites (yellow) are shown as spheres only for clarity and to highlight their diffusion pathway.

The hydrothermally altered sample of Al-LLZO shows additional Bragg peaks of type k = odd and l = odd that obey Ia $[\overline{3}]$ d symmetry. Calculated precession images of the hk0 plane for unaltered and altered Al-LLZO are compared in Fig. 2, where some Bragg peaks that obey Ia $[\overline{3}]$ d symmetry are marked. Indexing of the observed data definitively yield the space-group symmetry I $[\overline{4}]$ 3d, in accordance with the findings of Larraz et al. (2013) and Orera et al. (2016) for Li^I/H^I-exchanged LLZO. The symmetry reduction is associated with several rearrangements in the structural architecture. The oxygen site at 96h in Ia $[\overline{3}]$ d splits into two different 48e positions, i.e. O1 and O2, in I $[\overline{4}]$ 3d, thus allowing for two different sets of Zr—O and four different La—O bond lengths. The Zr^IV ion shifts from (0, 0, 0) with site symmetry $[\overline{3}]$ (Ia $[\overline{3}]$ d) to the 16c position (x, x, x) with site symmetry 3 (I $[\overline{4}]$ 3d). Some positional disorder is observed at the Zr position, where around 20% of the Zr^IV is displaced to a general 48e position, with a Zr—Zr offset of ∼0.39 (3) Å. Free refinement of the site occupancies of these two Zr positions total 1.96 Zr^IV atoms per formula unit, i.e. very close to the expected value of 2.0. Whereas in Ia $[\overline{3}]$ d, the six Zr—O bond lengths are equivalent to a value of 2.1076 (16) Å. In the hydrothermally altered structure, Zr^IV is in a very distorted octahedral environment at 16c, with Zr1A—O1^xi bond lengths of 2.007 (4) Å (×3), and Zr1A—O2^xii of 2.217 (4) Å (×3) (see Table 2 for symmetry codes). For the general position, the Zr1B—O bonds range between 1.85 (3) and 2.36 (3) Å (Table 2). It is interesting to note that a similar behaviour was found during hydrothermal alteration of Li₆La₃ZrTaO₁₂ (LLZTO). Pristine LLZTO shows Ia $[\overline{3}]$ d space-group symmetry but deep hydration induces a symmetry reduction to I $[\overline{4}]$ 3d. A disorder at the Zr/Ta site is also observed in hydrated LLZTO similar to that in hydrated Al-stabilized LLZO in this study. It would appear that the symmetry reduction, induced by Li^I/H^I exchange, causes a large distortion of the O-atom environment around the 16c position and induces some positional disorder.

Figure 2
Reconstructed precession images of the hk0 plane of (a) a single crystal of Al-stabilized LLZO directly after synthesis with some selected Bragg reflections indexed and (b) a single crystal after hydrothermal alteration at 150 °C for 28 d. Note the presence of sharp superstructure reflections, which obey Ia $[\overline{3}]$ d symmetry. In part (b), the yellow encircled Bragg reflections are the same as in part (a), while the blue encircled reflections in the rectangular box correspond (from left to right) to the $[\overline {57}]$ 0, $[\overline {37}]$ 0, $[\overline {17}]$ 0,… Bragg reflections.

The regular 24d tetrahedral site of the Ia $[\overline{3}]$ d garnet structure splits into two different sites, 12a (Li1) and 12b (Li2), upon symmetry reduction to I $[\overline{4}]$ 3d. Al^III is ordered onto the 12a (Li1) site but a distinct number of vacancies are observed on both sites. While ∼4.5 apfu Li^I occupy the interstitial 96h position in the pristine state, this position (Li3 at 48e) is completely unoccupied in the deeply hydrated form, i.e. all the Li^I ions have vacated the interstitial octahedral site.

Recently, Redhammer et al. (2021b) observed a progressive increase of the tetrahedral site (24d and 12a) occupation in Al-stabilized LLZO during continuous Li^I/H^I exchange in a humid atmosphere and under mild hydrothermal conditions. The shift and ordering of Li^I from the interstitial site to the regular tetrahedral site, and the preference of Li^I and Al^III for the 12a position, are described as triggers for the symmetry reduction from Ia $[\overline{3}]$ d to I $[\overline{4}]$ 3d (Redhammer et al., 2021b). A study of the structure of the deeply hydrated samples here shows that, after complete recovery of Li^I from the interstitial site, the tetrahedral 12a and 12b sites also take part in the Li^I/H^I exchange. When compared to the data of Redhammer et al. (2021b), it is obvious that, in this study, more Li^I is extracted from the 12a site [∼1.4 to 0.64 (2) apfu], but there is only a moderate change in site occupation at 12b [∼1.1 to 0.82 (2) apfu]. As Li^I is extracted from the structure, H^I is incorporated and bonds with the O1 atom. The Li^I ions in the 12a tetrahedron are thus coordinated by four OH groups, with the O—H vector pointing towards the empty Li3 site (compare with Fig. 3). The proposed position of H^I is in line with that found by Orera et al. (2016) for pure undoped LLZO based on neutron diffraction on polycrystalline powders. Refinements indicate that the deeply hydrated Al-LLZO has a composition of La_2.88Zr_1.95Al_0.15Li_1.64H_5.52O₁₂. It is also worth noting that a significantly lower number of La^III ions are found at the 24d site, so it would appear that La^III also leaves the structure under hydrothermal conditions. This is in line with the observations of Redhammer et al. (2021a,b), who observed an instability of LLZO powders in highly humid air, with decomposition of LLZO, leading to the formation of lanthanite La₂(CO₃)₃·8H₂O within ∼30 d of exposure.

Figure 3
Polyhedral representations of part of the crystal structure of Ga-stabilized LLZO (space group I $[\overline{4}]$ 3d) in the (a) pristine and (b) hydrothermally altered state viewed on the (12, $[\overline 6]$ ,3) plane. LaO₈ sites are in light blue, ZrO₆ octahedra in green and Li1, Li2 and Li3 sites in orange, yellow and grey, respectively. The dashed grey bonds around the Li3 site are the two most distant. [Symmetry codes: (i) −z + $[{3\over 4}]$ , −y + $[{1\over 4}]$ , x − $[{3\over 4}]$ ; (ii) −z + 1, −x + $[{1\over 2}]$ , y; (iii) −x + 1, −y + $[{1\over 2}]$ , z; (iv) −x + $[{1\over 2}]$ , y, −z; (v) −x + $[{1\over 2}]$ , −y, z + $[{1\over 2}]$ ; (vi) −z + $[{3\over 4}]$ , −y + $[{1\over 4}]$ , x + $[{1\over 4}]$ .]

The Li^I/H^I exchange is accompanied by a large increase in the a unit-cell parameter from 12.9637 (2) to 13.0738 (2) Å, which is among the largest values yet recorded for hydrated LLZO, cf. 13.06245 (4) Å at 77 K for hydrated LLZO with an Li_2.3H_4.7La₃Zr₂O₁₂ composition (Orera et al., 2016) or 13.0530 (8) Å for Li_3.08H_3.52La₃Zr₂O₁₂Ta_0.4 (Yow et al., 2016 ). A replacement of stronger Li—O bonds by weaker O—H bonds and the creation of a large number of vacant sites, especially around the empty 48e (Li3) site, both require more space and are considered responsible for the lattice expansion.

Pristine unaltered Ga-stabilized LLZO shows I $[\overline{4}]$ 3d symmetry. A section of this crystal structure is illustrated in Fig. 3, together with that of the hydrothermally treated sample. Both the tetrahedrally coordinated 12a and 12b positions appear to be fully occupied, with the Ga^III ions ordered onto the 12a position. In contrast to the Li-stuffed garnets with Ia $[\overline{3}]$ d symmetry, the decreased number of vacancies at the regular tetrahedral sites are considered to be a characteristic feature of the I $[\overline{4}]$ 3d garnet structure. The 48e interstitial site [Li3 in Fig. 3(a)] is occupied by 3.71 Li^I apfu, equivalent to being ∼62% full. All of the tetrahedral faces of the fourfold oxygen coordination around the Li1 and Li2 sites are shared with neighbouring Li3 sites, with interatomic contacts of 1.645 (8) (Li1—Li3) and 2.340 (9) Å (Li2—Li3), thereby forming a three-dimensional network that is responsible for the good Li-ion conductivity in this compound. The dodecahedral site has a small number of vacancies, while the regular octahedral positions are fully occupied with Zr^IV, resulting in a composition of La_2.94Zr_2.00Ga_0.28Li_6.43O₁₂ for the unaltered Ga-stabilized LLZO material.

A smaller and larger set of La—O1/O2 bonds are observed at the dodecahedral site [2.4935 (19)–2.5264 (19) and 2.587 (2)–2.5975 (19) Å] and the octahedron is regular with two independent Zr—O bonds ranging between 2.0823 (18) and 2.1346 (18) Å. Therefore, the octahedra are much less distorted than those in the altered Al-LLZO with the same symmetry (Table 2). The Li1 (12a) site, which hosts Ga^III, is slightly smaller than the Li2 (12b) site, whereas the Li3 site, as in Al-LLZO, shows a very distorted 4 + 2-fold coordination, with bond lengths between 1.878 (4) and 2.639 (8) Å; the average of the four shorter bonds is 2.073 Å, i.e. slightly smaller than in the pristine Al-LLZO [see Fig. 3(a)].

As in Al-LLZO, hydrothermal treatment of Ga-LLZO induces Li^I/H^I exchange. Again, a large increase of the lattice parameter to 13.06720 (12) Å is close to the value in hydrated Al-LLZO, suggesting that values around 13.07 Å represent an upper limit for lattice-parameter increase due to hydration. From site-occupation refinements, very minor Li^I ions are found at the interstitial 48e position, i.e. this site is almost completely depleted. One key difference with Al-LLZO is that no Li^I is lost from the 12a position. It seems that Ga^III ions pin Li^I at this site. However, Li^I ions are extracted from the 12b site where the amount of Li^I is reduced from 1.49 apfu in the pristine to 0.50 apfu in the altered sample. Protons are again located close to the O1 atom [Fig. 3(b)], giving rise to a fully hydrated Li1(OH)₄ coordination around the 12a site. Some differences to Al-LLZO are, however, evident: there is no significant reduction in the La-site occupation and no residual electron density is observed close to the Zr^IV ions, i.e. there is no indication of disorder at the 16c position in altered Ga-LLZO. Nevertheless, the ZrO₆ octahedron is much more distorted in the altered sample, with Zr—O bond lengths ranging between 2.03 (3) and 2.187 (4) Å; the difference between the two independent Zr—O bonds increases with prolonged Li^I/H^I exchange. This was outlined by Redhammer et al. (2021b) and the data of this study fit the extrapolated trends observed there. A distinct alteration is also observed within the coordination sphere of the 24d site due to H^I incorporation. The most prominent effects include the reduction of the longer La1—O1^xvii distance by ∼0.073 Å, as well as changes in the three other La—O bond lengths. In addition, Li1—O1^xv and Li2—O2^xvi are extended in the altered sample (see Table 2).

Supporting information

CCDC references: 2122845; 2122844; 2122843; 2122842

Crystal structure: contains datablocks global, LLZO-Al15-pristine, LLZO-Al15-hydro-150C, LLZO-Ga40-pristine, LLZO-Ga40-hydro-150C. DOI: https://doi.org/10.1107/S2053229621012250/ep3020sup1.cif

Structure factors: contains datablock LLZO-Al15-pristine. DOI: https://doi.org/10.1107/S2053229621012250/ep3020LLZO-Al15-pristinesup2.hkl

Structure factors: contains datablock LLZO-Al15-hydro-150C. DOI: https://doi.org/10.1107/S2053229621012250/ep3020LLZO-Al15-hydro-150Csup3.hkl

Structure factors: contains datablock LLZO-Ga40-pristine. DOI: https://doi.org/10.1107/S2053229621012250/ep3020LLZO-Ga40-pristinesup4.hkl

Structure factors: contains datablock LLZO-Ga40-hydro-150C. DOI: https://doi.org/10.1107/S2053229621012250/ep3020LLZO-Ga40-hydro-150Csup5.hkl

Computing details top

For all structures, data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: APEX2 (Bruker, 2012); program(s) used to solve structure: SIR2014 (Burla et al., 2012); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

(LLZO-Al15-pristine) top

Crystal data top

Al_0.15La_2.95Li_5.73O₁₂Zr₂	D_x = 5.048 Mg m⁻³
M_r = 827.89	Mo Kα radiation, λ = 0.71073 Å
Cubic, Ia3d	Cell parameters from 33130 reflections
Hall symbol: -I 4bd 2c 3	θ = 3.9–36.6°
a = 12.9637 (2) Å	µ = 13.24 mm⁻¹
V = 2178.65 (10) Å³	T = 298 K
Z = 8	Cuboid, colorless
F(000) = 2906	0.12 × 0.11 × 0.07 mm

Data collection top

Bruker SMART APEX diffractometer	441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
rotation, ω–scans at 4 different φ positions	θ_max = 36.6°, θ_min = 3.9°
Absorption correction: multi-scan (APEX2; Bruker, 2012)	h = −21→21
T_min = 0.22, T_max = 0.39	k = −21→21
33130 measured reflections	l = −21→21
455 independent reflections

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0044P)² + 13.2478P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.016	(Δ/σ)_max = 0.001
wR(F²) = 0.032	Δρ_max = 0.71 e Å⁻³
S = 1.51	Δρ_min = −0.44 e Å⁻³
455 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
25 parameters	Extinction coefficient: 0.00041 (3)
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.125	0	0.25	0.00857 (8)	0.983 (3)
Zr1	0	0	0	0.00669 (12)
O1	0.09999 (13)	0.19604 (13)	0.28188 (13)	0.0117 (3)
Li1	0.375	0	0.25	0.022 (6)	0.47 (6)
Al1	0.375	0	0.25	0.022 (5)	0.05
Li2	0.0961 (10)	0.1880 (11)	0.4246 (11)	0.023 (4)*	0.36 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01087 (11)	0.00742 (9)	0.00742 (9)	0	0	0.00134 (7)
Zr1	0.00669 (12)	0.00669 (12)	0.00669 (12)	0.00008 (8)	0.00008 (8)	0.00008 (8)
O1	0.0092 (6)	0.0120 (7)	0.0140 (7)	−0.0016 (5)	0.0003 (5)	0.0004 (5)
Li1	0.009 (9)	0.029 (12)	0.029 (12)	0	0	0
Al1	0.009 (15)	0.029 (9)	0.029 (9)	0	0	0

Geometric parameters (Å, º) top

La1—O1ⁱ	2.5110 (17)	O1—Zr1^xv	2.1076 (16)
La1—O1ⁱⁱ	2.5110 (17)	O1—Li2^v	2.159 (15)
La1—O1ⁱⁱⁱ	2.5110 (17)	O1—Li2^xxii	2.242 (14)
La1—O1^iv	2.5110 (17)	O1—La1^xx	2.5110 (17)
La1—O1	2.5951 (17)	O1—Li2^x	2.646 (14)
La1—O1^v	2.5952 (17)	Li1—Li2^xi	1.616 (14)
La1—O1^vi	2.5952 (17)	Li1—Li2^viii	1.616 (14)
La1—O1^vii	2.5952 (17)	Li1—Li2ⁱ	1.616 (14)
La1—Li2^viii	2.992 (14)	Li1—Li2ⁱⁱⁱ	1.616 (14)
La1—Li2^ix	2.992 (14)	Li1—O1^viii	1.9044 (17)
La1—Li2^x	2.992 (14)	Li1—O1ⁱⁱⁱ	1.9044 (17)
La1—Li2^xi	2.992 (14)	Li1—O1^xi	1.9044 (17)
Zr1—O1^xii	2.1076 (16)	Li1—O1ⁱ	1.9044 (17)
Zr1—O1^vii	2.1076 (16)	Li1—Li2^xxiii	2.367 (14)
Zr1—O1^xiii	2.1076 (16)	Li1—Li2^xxiv	2.367 (14)
Zr1—O1ⁱⁱ	2.1076 (16)	Li1—Li2^xxv	2.367 (14)
Zr1—O1^xiv	2.1076 (16)	Li1—Li2^xxvi	2.367 (14)
Zr1—O1^xv	2.1076 (16)	Li2—Li2^v	0.79 (3)
Zr1—Li2^ix	2.906 (15)	Li2—Al1^xx	1.616 (14)
Zr1—Li2^xvi	2.906 (15)	Li2—Li1^xx	1.616 (14)
Zr1—Li2^xvii	2.906 (15)	Li2—O1^xxii	2.085 (14)
Zr1—Li2^xviii	2.906 (15)	Li2—O1^v	2.159 (15)
Zr1—Li2^xix	2.906 (15)	Li2—O1^xxi	2.242 (14)
Zr1—Li2^vi	2.906 (15)	Li2—Al1^xxvii	2.367 (14)
O1—Li2	1.854 (15)	Li2—Li1^xxvii	2.367 (14)
O1—Al1^xx	1.9044 (17)	Li2—Li2^xxii	2.46 (2)
O1—Li1^xx	1.9044 (17)	Li2—Li2^xxi	2.46 (2)
O1—Li2^xxi	2.085 (14)	Li2—O1^xxviii	2.646 (14)

O1ⁱ—La1—O1ⁱⁱ	111.62 (8)	Li1^xx—O1—La1^xx	93.43 (7)
O1ⁱ—La1—O1ⁱⁱⁱ	71.83 (8)	Li2^xxi—O1—La1^xx	80.6 (4)
O1ⁱⁱ—La1—O1ⁱⁱⁱ	160.65 (7)	Zr1^xv—O1—La1^xx	103.01 (7)
O1ⁱ—La1—O1^iv	160.65 (7)	Li2^v—O1—La1^xx	164.2 (4)
O1ⁱⁱ—La1—O1^iv	71.83 (8)	Li2^xxii—O1—La1^xx	77.8 (4)
O1ⁱⁱⁱ—La1—O1^iv	111.62 (8)	Li2—O1—La1	96.1 (5)
O1ⁱ—La1—O1	68.90 (7)	Al1^xx—O1—La1	123.07 (7)
O1ⁱⁱ—La1—O1	73.03 (6)	Li1^xx—O1—La1	123.07 (7)
O1ⁱⁱⁱ—La1—O1	124.22 (3)	Li2^xxi—O1—La1	170.6 (4)
O1^iv—La1—O1	95.13 (5)	Zr1^xv—O1—La1	100.28 (6)
O1ⁱ—La1—O1^v	95.13 (5)	Li2^v—O1—La1	89.0 (4)
O1ⁱⁱ—La1—O1^v	124.22 (3)	Li2^xxii—O1—La1	85.3 (4)
O1ⁱⁱⁱ—La1—O1^v	73.03 (6)	La1^xx—O1—La1	102.03 (6)
O1^iv—La1—O1^v	68.90 (7)	Li2—O1—Li2^x	78.6 (7)
O1—La1—O1^v	72.77 (8)	Al1^xx—O1—Li2^x	60.1 (3)
O1ⁱ—La1—O1^vi	124.22 (3)	Li1^xx—O1—Li2^x	60.1 (3)
O1ⁱⁱ—La1—O1^vi	95.13 (5)	Li2^xxi—O1—Li2^x	102.4 (4)
O1ⁱⁱⁱ—La1—O1^vi	68.90 (7)	Zr1^xv—O1—Li2^x	169.9 (3)
O1^iv—La1—O1^vi	73.03 (6)	Li2^v—O1—Li2^x	94.4 (3)
O1—La1—O1^vi	165.64 (7)	Li2^xxii—O1—Li2^x	16.0 (6)
O1^v—La1—O1^vi	109.12 (7)	La1^xx—O1—Li2^x	79.2 (3)
O1ⁱ—La1—O1^vii	73.03 (6)	La1—O1—Li2^x	69.6 (3)
O1ⁱⁱ—La1—O1^vii	68.90 (7)	Li2^xi—Li1—Li2^viii	133.1 (10)
O1ⁱⁱⁱ—La1—O1^vii	95.13 (5)	Li2^xi—Li1—Li2ⁱ	99.1 (4)
O1^iv—La1—O1^vii	124.22 (3)	Li2^viii—Li1—Li2ⁱ	99.1 (4)
O1—La1—O1^vii	109.12 (7)	Li2^xi—Li1—Li2ⁱⁱⁱ	99.1 (4)
O1^v—La1—O1^vii	165.64 (7)	Li2^viii—Li1—Li2ⁱⁱⁱ	99.1 (4)
O1^vi—La1—O1^vii	72.77 (8)	Li2ⁱ—Li1—Li2ⁱⁱⁱ	133.1 (10)
O1ⁱ—La1—Li2^viii	43.4 (3)	Li2^xi—Li1—O1^viii	163.6 (5)
O1ⁱⁱ—La1—Li2^viii	147.5 (3)	Li2^viii—Li1—O1^viii	62.9 (5)
O1ⁱⁱⁱ—La1—Li2^viii	47.1 (3)	Li2ⁱ—Li1—O1^viii	78.7 (5)
O1^iv—La1—Li2^viii	124.3 (3)	Li2ⁱⁱⁱ—Li1—O1^viii	72.1 (5)
O1—La1—Li2^viii	77.2 (3)	Li2^xi—Li1—O1ⁱⁱⁱ	72.1 (5)
O1^v—La1—Li2^viii	56.0 (3)	Li2^viii—Li1—O1ⁱⁱⁱ	78.7 (5)
O1^vi—La1—Li2^viii	116.0 (3)	Li2ⁱ—Li1—O1ⁱⁱⁱ	163.6 (5)
O1^vii—La1—Li2^viii	110.0 (3)	Li2ⁱⁱⁱ—Li1—O1ⁱⁱⁱ	62.9 (5)
O1ⁱ—La1—Li2^ix	147.5 (3)	O1^viii—Li1—O1ⁱⁱⁱ	113.69 (5)
O1ⁱⁱ—La1—Li2^ix	43.4 (3)	Li2^xi—Li1—O1^xi	62.9 (5)
O1ⁱⁱⁱ—La1—Li2^ix	124.3 (3)	Li2^viii—Li1—O1^xi	163.6 (5)
O1^iv—La1—Li2^ix	47.1 (3)	Li2ⁱ—Li1—O1^xi	72.1 (5)
O1—La1—Li2^ix	110.0 (3)	Li2ⁱⁱⁱ—Li1—O1^xi	78.7 (5)
O1^v—La1—Li2^ix	116.0 (3)	O1^viii—Li1—O1^xi	101.32 (10)
O1^vi—La1—Li2^ix	56.0 (3)	O1ⁱⁱⁱ—Li1—O1^xi	113.69 (5)
O1^vii—La1—Li2^ix	77.2 (3)	Li2^xi—Li1—O1ⁱ	78.7 (5)
Li2^viii—La1—Li2^ix	168.0 (6)	Li2^viii—Li1—O1ⁱ	72.1 (5)
O1ⁱ—La1—Li2^x	124.3 (3)	Li2ⁱ—Li1—O1ⁱ	62.9 (5)
O1ⁱⁱ—La1—Li2^x	47.1 (3)	Li2ⁱⁱⁱ—Li1—O1ⁱ	163.6 (5)
O1ⁱⁱⁱ—La1—Li2^x	147.5 (3)	O1^viii—Li1—O1ⁱ	113.69 (6)
O1^iv—La1—Li2^x	43.4 (3)	O1ⁱⁱⁱ—Li1—O1ⁱ	101.32 (10)
O1—La1—Li2^x	56.0 (3)	O1^xi—Li1—O1ⁱ	113.69 (5)
O1^v—La1—Li2^x	77.2 (3)	Li2^xi—Li1—Li2^xxiii	7.0 (9)
O1^vi—La1—Li2^x	110.0 (3)	Li2^viii—Li1—Li2^xxiii	135.9 (7)
O1^vii—La1—Li2^x	116.0 (3)	Li2ⁱ—Li1—Li2^xxiii	92.1 (7)
Li2^viii—La1—Li2^x	122.0 (5)	Li2ⁱⁱⁱ—Li1—Li2^xxiii	103.8 (7)
Li2^ix—La1—Li2^x	59.4 (5)	O1^viii—Li1—Li2^xxiii	160.7 (4)
O1ⁱ—La1—Li2^xi	47.1 (3)	O1ⁱⁱⁱ—Li1—Li2^xxiii	79.0 (4)
O1ⁱⁱ—La1—Li2^xi	124.3 (3)	O1^xi—Li1—Li2^xxiii	59.6 (4)
O1ⁱⁱⁱ—La1—Li2^xi	43.4 (3)	O1ⁱ—Li1—Li2^xxiii	75.7 (3)
O1^iv—La1—Li2^xi	147.5 (3)	Li2^xi—Li1—Li2^xxiv	135.9 (7)
O1—La1—Li2^xi	116.0 (3)	Li2^viii—Li1—Li2^xxiv	7.0 (9)
O1^v—La1—Li2^xi	110.0 (3)	Li2ⁱ—Li1—Li2^xxiv	103.8 (7)
O1^vi—La1—Li2^xi	77.2 (3)	Li2ⁱⁱⁱ—Li1—Li2^xxiv	92.1 (7)
O1^vii—La1—Li2^xi	56.0 (3)	O1^viii—Li1—Li2^xxiv	59.6 (4)
Li2^viii—La1—Li2^xi	59.4 (5)	O1ⁱⁱⁱ—Li1—Li2^xxiv	75.7 (3)
Li2^ix—La1—Li2^xi	122.0 (5)	O1^xi—Li1—Li2^xxiv	160.7 (4)
Li2^x—La1—Li2^xi	168.0 (6)	O1ⁱ—Li1—Li2^xxiv	79.0 (4)
O1^xii—Zr1—O1^vii	180.00 (13)	Li2^xxiii—Li1—Li2^xxiv	139.6 (7)
O1^xii—Zr1—O1^xiii	86.55 (7)	Li2^xi—Li1—Li2^xxv	103.8 (7)
O1^vii—Zr1—O1^xiii	93.45 (7)	Li2^viii—Li1—Li2^xxv	92.1 (7)
O1^xii—Zr1—O1ⁱⁱ	93.45 (7)	Li2ⁱ—Li1—Li2^xxv	7.0 (9)
O1^vii—Zr1—O1ⁱⁱ	86.55 (7)	Li2ⁱⁱⁱ—Li1—Li2^xxv	135.9 (7)
O1^xiii—Zr1—O1ⁱⁱ	180.00 (13)	O1^viii—Li1—Li2^xxv	75.7 (4)
O1^xii—Zr1—O1^xiv	86.55 (7)	O1ⁱⁱⁱ—Li1—Li2^xxv	160.7 (4)
O1^vii—Zr1—O1^xiv	93.45 (7)	O1^xi—Li1—Li2^xxv	79.0 (4)
O1^xiii—Zr1—O1^xiv	86.55 (7)	O1ⁱ—Li1—Li2^xxv	59.6 (4)
O1ⁱⁱ—Zr1—O1^xiv	93.45 (7)	Li2^xxiii—Li1—Li2^xxv	96.8 (2)
O1^xii—Zr1—O1^xv	93.45 (7)	Li2^xxiv—Li1—Li2^xxv	96.8 (2)
O1^vii—Zr1—O1^xv	86.55 (7)	Li2^xi—Li1—Li2^xxvi	92.1 (7)
O1^xiii—Zr1—O1^xv	93.45 (7)	Li2^viii—Li1—Li2^xxvi	103.8 (7)
O1ⁱⁱ—Zr1—O1^xv	86.55 (7)	Li2ⁱ—Li1—Li2^xxvi	135.9 (7)
O1^xiv—Zr1—O1^xv	180.00 (9)	Li2ⁱⁱⁱ—Li1—Li2^xxvi	7.0 (9)
O1^xii—Zr1—Li2^ix	93.0 (3)	O1^viii—Li1—Li2^xxvi	79.0 (4)
O1^vii—Zr1—Li2^ix	87.0 (3)	O1ⁱⁱⁱ—Li1—Li2^xxvi	59.6 (4)
O1^xiii—Zr1—Li2^ix	134.2 (3)	O1^xi—Li1—Li2^xxvi	75.7 (3)
O1ⁱⁱ—Zr1—Li2^ix	45.8 (3)	O1ⁱ—Li1—Li2^xxvi	160.7 (4)
O1^xiv—Zr1—Li2^ix	47.8 (3)	Li2^xxiii—Li1—Li2^xxvi	96.8 (2)
O1^xv—Zr1—Li2^ix	132.2 (3)	Li2^xxiv—Li1—Li2^xxvi	96.8 (2)
O1^xii—Zr1—Li2^xvi	87.0 (3)	Li2^xxv—Li1—Li2^xxvi	139.6 (7)
O1^vii—Zr1—Li2^xvi	93.0 (3)	Li2^v—Li2—Al1^xx	158 (3)
O1^xiii—Zr1—Li2^xvi	45.8 (3)	Li2^v—Li2—Li1^xx	158 (3)
O1ⁱⁱ—Zr1—Li2^xvi	134.2 (3)	Al1^xx—Li2—Li1^xx	0
O1^xiv—Zr1—Li2^xvi	132.2 (3)	Li2^v—Li2—O1	101.9 (17)
O1^xv—Zr1—Li2^xvi	47.8 (3)	Al1^xx—Li2—O1	66.2 (5)
Li2^ix—Zr1—Li2^xvi	180.0 (7)	Li1^xx—Li2—O1	66.2 (5)
O1^xii—Zr1—Li2^xvii	134.2 (3)	Li2^v—Li2—O1^xxii	141 (3)
O1^vii—Zr1—Li2^xvii	45.8 (3)	Al1^xx—Li2—O1^xxii	60.4 (4)
O1^xiii—Zr1—Li2^xvii	47.8 (3)	Li1^xx—Li2—O1^xxii	60.4 (4)
O1ⁱⁱ—Zr1—Li2^xvii	132.2 (3)	O1—Li2—O1^xxii	108.0 (7)
O1^xiv—Zr1—Li2^xvii	93.0 (3)	Li2^v—Li2—O1^v	57.2 (15)
O1^xv—Zr1—Li2^xvii	87.0 (3)	Al1^xx—Li2—O1^v	140.1 (8)
Li2^ix—Zr1—Li2^xvii	119.82 (4)	Li1^xx—Li2—O1^v	140.1 (8)
Li2^xvi—Zr1—Li2^xvii	60.18 (4)	O1—Li2—O1^v	99.9 (6)
O1^xii—Zr1—Li2^xviii	45.8 (3)	O1^xxii—Li2—O1^v	92.6 (6)
O1^vii—Zr1—Li2^xviii	134.2 (3)	Li2^v—Li2—O1^xxi	112.5 (10)
O1^xiii—Zr1—Li2^xviii	132.2 (3)	Al1^xx—Li2—O1^xxi	56.4 (4)
O1ⁱⁱ—Zr1—Li2^xviii	47.8 (3)	Li1^xx—Li2—O1^xxi	56.4 (4)
O1^xiv—Zr1—Li2^xviii	87.0 (3)	O1—Li2—O1^xxi	101.8 (7)
O1^xv—Zr1—Li2^xviii	93.0 (3)	O1^xxii—Li2—O1^xxi	85.7 (5)
Li2^ix—Zr1—Li2^xviii	60.18 (4)	O1^v—Li2—O1^xxi	157.6 (7)
Li2^xvi—Zr1—Li2^xviii	119.82 (4)	Li2^v—Li2—Al1^xxvii	14.6 (19)
Li2^xvii—Zr1—Li2^xviii	180.0 (6)	Al1^xx—Li2—Al1^xxvii	170.3 (9)
O1^xii—Zr1—Li2^xix	47.8 (3)	Li1^xx—Li2—Al1^xxvii	170.3 (9)
O1^vii—Zr1—Li2^xix	132.2 (3)	O1—Li2—Al1^xxvii	114.1 (6)
O1^xiii—Zr1—Li2^xix	93.0 (3)	O1^xxii—Li2—Al1^xxvii	126.4 (7)
O1ⁱⁱ—Zr1—Li2^xix	87.0 (3)	O1^v—Li2—Al1^xxvii	49.5 (3)
O1^xiv—Zr1—Li2^xix	134.2 (3)	O1^xxi—Li2—Al1^xxvii	115.1 (6)
O1^xv—Zr1—Li2^xix	45.8 (3)	Li2^v—Li2—Li1^xxvii	14.6 (19)
Li2^ix—Zr1—Li2^xix	119.82 (4)	Al1^xx—Li2—Li1^xxvii	170.3
Li2^xvi—Zr1—Li2^xix	60.18 (4)	Li1^xx—Li2—Li1^xxvii	170.3 (9)
Li2^xvii—Zr1—Li2^xix	119.82 (4)	O1—Li2—Li1^xxvii	114.1 (6)
Li2^xviii—Zr1—Li2^xix	60.18 (4)	O1^xxii—Li2—Li1^xxvii	126.4 (7)
O1^xii—Zr1—Li2^vi	132.2 (3)	O1^v—Li2—Li1^xxvii	49.5 (3)
O1^vii—Zr1—Li2^vi	47.8 (3)	O1^xxi—Li2—Li1^xxvii	115.1 (6)
O1^xiii—Zr1—Li2^vi	87.0 (3)	Al1^xxvii—Li2—Li1^xxvii	0
O1ⁱⁱ—Zr1—Li2^vi	93.0 (3)	Li2^v—Li2—Li2^xxii	150.2 (6)
O1^xiv—Zr1—Li2^vi	45.8 (3)	Al1^xx—Li2—Li2^xxii	40.45 (19)
O1^xv—Zr1—Li2^vi	134.2 (3)	Li1^xx—Li2—Li2^xxii	40.45 (19)
Li2^ix—Zr1—Li2^vi	60.18 (4)	O1—Li2—Li2^xxii	60.7 (7)
Li2^xvi—Zr1—Li2^vi	119.82 (4)	O1^xxii—Li2—Li2^xxii	47.3 (4)
Li2^xvii—Zr1—Li2^vi	60.18 (4)	O1^v—Li2—Li2^xxii	99.7 (8)
Li2^xviii—Zr1—Li2^vi	119.82 (4)	O1^xxi—Li2—Li2^xxii	95.5 (4)
Li2^xix—Zr1—Li2^vi	180.0 (8)	Al1^xxvii—Li2—Li2^xxii	148.9 (8)
Li2—O1—Al1^xx	50.9 (4)	Li1^xxvii—Li2—Li2^xxii	148.9 (8)
Li2—O1—Li1^xx	50.9 (4)	Li2^v—Li2—Li2^xxi	118 (3)
Al1^xx—O1—Li1^xx	0	Al1^xx—Li2—Li2^xxi	40.45 (19)
Li2—O1—Li2^xxi	77.1 (6)	Li1^xx—Li2—Li2^xxi	40.45 (19)
Al1^xx—O1—Li2^xxi	47.5 (4)	O1—Li2—Li2^xxi	55.7 (7)
Li1^xx—O1—Li2^xxi	47.5 (4)	O1^xxii—Li2—Li2^xxi	99.8 (4)
Li2—O1—Zr1^xv	103.8 (4)	O1^v—Li2—Li2^xxi	155.1 (10)
Al1^xx—O1—Zr1^xv	129.08 (9)	O1^xxi—Li2—Li2^xxi	46.1 (4)
Li1^xx—O1—Zr1^xv	129.08 (9)	Al1^xxvii—Li2—Li2^xxi	130.9 (8)
Li2^xxi—O1—Zr1^xv	87.8 (4)	Li1^xxvii—Li2—Li2^xxi	130.9 (8)
Li2—O1—Li2^v	20.9 (7)	Li2^xxii—Li2—Li2^xxi	74.1 (6)
Al1^xx—O1—Li2^v	70.9 (4)	Li2^v—Li2—O1^xxviii	51.5 (9)
Li1^xx—O1—Li2^v	70.9 (4)	Al1^xx—Li2—O1^xxviii	130.2 (7)
Li2^xxi—O1—Li2^v	86.72 (8)	Li1^xx—Li2—O1^xxviii	130.2 (7)
Zr1^xv—O1—Li2^v	85.9 (4)	O1—Li2—O1^xxviii	146.7 (7)
Li2—O1—Li2^xxii	73.1 (6)	O1^xxii—Li2—O1^xxviii	105.0 (6)
Al1^xx—O1—Li2^xxii	45.0 (4)	O1^v—Li2—O1^xxviii	82.5 (5)
Li1^xx—O1—Li2^xxii	45.0 (4)	O1^xxi—Li2—O1^xxviii	76.4 (4)
Li2^xxi—O1—Li2^xxii	86.5 (6)	Al1^xxvii—Li2—O1^xxviii	44.2 (2)
Zr1^xv—O1—Li2^xxii	174.0 (4)	Li1^xxvii—Li2—O1^xxviii	44.2 (2)
Li2^v—O1—Li2^xxii	92.0 (7)	Li2^xxii—Li2—O1^xxviii	152.1 (9)
Li2—O1—La1^xx	144.1 (4)	Li2^xxi—Li2—O1^xxviii	114.5 (8)
Al1^xx—O1—La1^xx	93.43 (7)

Symmetry codes: (i) z, x, y; (ii) −z+1/4, −y+1/4, −x+1/4; (iii) z, −x, −y+1/2; (iv) −z+1/4, y−1/4, x+1/4; (v) −x+1/4, z−1/4, y+1/4; (vi) x, −y, −z+1/2; (vii) −x+1/4, −z+1/4, −y+1/4; (viii) −z+3/4, −y+1/4, x+1/4; (ix) z−1/2, −x, y; (x) z−1/2, x, −y+1/2; (xi) −z+3/4, y−1/4, −x+1/4; (xii) x−1/4, z−1/4, y−1/4; (xiii) z−1/4, y−1/4, x−1/4; (xiv) y−1/4, x−1/4, z−1/4; (xv) −y+1/4, −x+1/4, −z+1/4; (xvi) −z+1/2, x, −y; (xvii) y, z−1/2, −x; (xviii) −y, −z+1/2, x; (xix) −x, y, z−1/2; (xx) y, z, x; (xxi) −y+1/4, x+1/4, −z+3/4; (xxii) y−1/4, −x+1/4, −z+3/4; (xxiii) −y+1/2, z−1/2, x; (xxiv) −y+1/2, −z+1/2, −x+1/2; (xxv) y+1/4, −x+1/4, z−1/4; (xxvi) y+1/4, x−1/4, −z+3/4; (xxvii) −y+1/4, x−1/4, z+1/4; (xxviii) y, −z+1/2, x+1/2.

(LLZO-Al15-hydro-150C) top

Crystal data top

Al_0.15H_5.52La_2.88Li_1.64O₁₂Zr_1.95	D_x = 4.707 Mg m⁻³
M_r = 790.95	Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d	Cell parameters from 34201 reflections
Hall symbol: I -4bd 2c 3	θ = 3.8–34.9°
a = 13.0738 (2) Å	µ = 12.61 mm⁻¹
V = 2234.63 (10) Å³	T = 298 K
Z = 8	Cuboid, colorless
F(000) = 2804.4	0.13 × 0.12 × 0.08 mm

Data collection top

Bruker SMART APEX diffractometer	819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
rotation, ω–scans at 4 different φ positions	θ_max = 34.9°, θ_min = 3.8°
Absorption correction: multi-scan (APEX2; Bruker, 2012)	h = −21→21
T_min = 0.21, T_max = 0.36	k = −21→21
34201 measured reflections	l = −21→21
819 independent reflections

Refinement top

Refinement on F²	Only H-atom coordinates refined
Least-squares matrix: full	w = 1/[σ²(F_o²) + 15.2822P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.013	(Δ/σ)_max = 0.001
wR(F²) = 0.029	Δρ_max = 0.57 e Å⁻³
S = 1.27	Δρ_min = −0.51 e Å⁻³
819 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
44 parameters	Extinction coefficient: 0.00083 (5)
1 restraint	Absolute structure: Refined as an inversion twin.
0 constraints	Absolute structure parameter: 0.50 (3)
Hydrogen site location: difference Fourier map

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.11936 (3)	0	0.25	0.01005 (9)	0.961 (10)
Zr1A	−0.01161 (12)	−0.01161 (12)	−0.01161 (12)	0.0069 (4)	0.79 (2)
Zr1B	−0.0073 (15)	0.006 (3)	0.013 (2)	0.024 (5)*	0.061 (6)
O1	0.0970 (2)	0.1899 (2)	0.2733 (3)	0.0132 (6)
O2	0.0335 (3)	0.4452 (3)	0.1429 (2)	0.0149 (7)
Li1	0.375	0	0.25	0.016*	0.62 (6)
Al1	0.375	0	0.25	0.016*	0.1
Li2	0.875	0	0.25	0.017 (9)	0.47 (9)
H1	0.098 (6)	0.180 (6)	0.323 (7)	0.025*	0.92 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00938 (13)	0.00852 (14)	0.01224 (15)	0	0	0.00403 (8)
Zr1A	0.0069 (4)	0.0069 (4)	0.0069 (4)	0.0000 (2)	0.0000 (2)	0.0000 (2)
O1	0.0112 (12)	0.0115 (13)	0.0169 (15)	0.0014 (9)	−0.0002 (10)	0.0028 (10)
O2	0.0193 (15)	0.0142 (13)	0.0110 (14)	0.0028 (10)	0.0005 (10)	0.0038 (10)
Li2	0.012 (14)	0.020 (12)	0.020 (12)	0	0	0

Geometric parameters (Å, º) top

La1—O1ⁱ	2.506 (3)	O1—Li1^viii	1.998 (3)
La1—O1ⁱⁱ	2.506 (3)	O1—Zr1A^vii	2.007 (4)
La1—O1	2.518 (3)	O1—Zr1B^xv	2.14 (3)
La1—O1ⁱⁱⁱ	2.518 (3)	O1—Zr1B^vii	2.19 (3)
La1—O2^iv	2.544 (3)	O1—Zr1B^xvi	2.36 (3)
La1—O2^v	2.544 (3)	O1—La1^viii	2.506 (3)
La1—O2ⁱ	2.607 (3)	O1—H1	0.66 (9)
La1—O2ⁱⁱ	2.607 (3)	O2—Zr1B^iv	1.85 (3)
La1—Li2^vi	3.1947 (4)	O2—Li2^xvii	1.976 (3)
La1—Li1	3.3422 (4)	O2—Zr1B^xviii	2.06 (3)
La1—Zr1A^vii	3.487 (2)	O2—Zr1B^xix	2.10 (3)
La1—H1	2.55 (8)	O2—Zr1A^iv	2.217 (4)
Zr1A—Zr1B^viii	0.39 (3)	O2—La1^iv	2.544 (3)
Zr1A—Zr1Bⁱ	0.39 (3)	O2—La1^viii	2.607 (3)
Zr1A—O1^ix	2.007 (4)	Li1—O1^xx	1.998 (3)
Zr1A—O1^x	2.007 (4)	Li1—O1ⁱⁱ	1.998 (3)
Zr1A—O1^xi	2.007 (4)	Li1—O1ⁱ	1.998 (3)
Zr1A—O2^xii	2.217 (4)	Li1—O1^xxi	1.998 (3)
Zr1A—O2^iv	2.217 (4)	Li1—La1^xxii	3.3422 (4)
Zr1A—O2ⁱⁱ	2.217 (4)	Li1—Zr1B^xxiii	3.54 (3)
Zr1A—La1^xi	3.487 (2)	Li1—Zr1B^xxiv	3.54 (3)
Zr1A—La1^ix	3.487 (2)	Li1—Zr1B^vii	3.54 (3)
Zr1A—La1^x	3.487 (2)	Li1—Zr1B^xii	3.54 (3)
Zr1A—Li1^xiii	3.5953 (5)	Li1—Zr1A^xxv	3.5953 (5)
Zr1B—Zr1B^viii	0.32 (5)	Li1—Zr1A^xxiii	3.5953 (5)
Zr1B—Zr1Bⁱ	0.32 (5)	Li2—O2^xxvi	1.976 (3)
Zr1B—O2^iv	1.85 (3)	Li2—O2^xxvii	1.976 (3)
Zr1B—O2^xii	2.06 (3)	Li2—O2^xvii	1.976 (3)
Zr1B—O2ⁱⁱ	2.10 (3)	Li2—O2^xxviii	1.976 (3)
Zr1B—O1^x	2.14 (3)	Li2—La1^xxix	3.1947 (4)
Zr1B—O1^xi	2.19 (3)	Li2—La1^xxii	3.1947 (4)
Zr1B—O1^ix	2.36 (3)	Li2—Zr1B^xxx	3.46 (3)
Zr1B—Li2^vi	3.47 (3)	Li2—Zr1B^xxii	3.46 (3)
Zr1B—La1^viii	3.49 (4)	Li2—Zr1B^xxix	3.46 (3)
Zr1B—Li1^xiv	3.54 (3)	Li2—Zr1B^xxxi	3.46 (3)
O1—Al1^viii	1.998 (3)

O1ⁱ—La1—O1ⁱⁱ	73.10 (16)	O1^xi—Zr1B—La1	94.1 (12)
O1ⁱ—La1—O1	68.42 (15)	O1^ix—Zr1B—La1	136.1 (13)
O1ⁱⁱ—La1—O1	123.66 (7)	Li2^vi—Zr1B—La1	54.4 (5)
O1ⁱ—La1—O1ⁱⁱⁱ	123.66 (7)	La1^viii—Zr1B—La1	69.7 (6)
O1ⁱⁱ—La1—O1ⁱⁱⁱ	68.42 (15)	Zr1B^viii—Zr1B—Li1^xiv	108 (10)
O1—La1—O1ⁱⁱⁱ	166.67 (15)	Zr1Bⁱ—Zr1B—Li1^xiv	160 (6)
O1ⁱ—La1—O2^iv	108.41 (9)	O2^iv—Zr1B—Li1^xiv	74.0 (10)
O1ⁱⁱ—La1—O2^iv	161.19 (8)	O2^xii—Zr1B—Li1^xiv	87.5 (13)
O1—La1—O2^iv	72.41 (10)	O2ⁱⁱ—Zr1B—Li1^xiv	163.1 (15)
O1ⁱⁱⁱ—La1—O2^iv	96.88 (11)	O1^x—Zr1B—Li1^xiv	30.1 (6)
O1ⁱ—La1—O2^v	161.19 (8)	O1^xi—Zr1B—Li1^xiv	97.9 (5)
O1ⁱⁱ—La1—O2^v	108.41 (9)	O1^ix—Zr1B—Li1^xiv	105.7 (10)
O1—La1—O2^v	96.88 (11)	Li2^vi—Zr1B—Li1^xiv	69.7 (5)
O1ⁱⁱⁱ—La1—O2^v	72.41 (10)	La1^viii—Zr1B—Li1^xiv	68.9 (7)
O2^iv—La1—O2^v	76.42 (15)	La1—Zr1B—Li1^xiv	118.2 (9)
O1ⁱ—La1—O2ⁱ	97.31 (11)	Al1^viii—O1—Li1^viii	0
O1ⁱⁱ—La1—O2ⁱ	71.54 (10)	Al1^viii—O1—Zr1A^vii	127.71 (18)
O1—La1—O2ⁱ	74.30 (10)	Li1^viii—O1—Zr1A^vii	127.71 (18)
O1ⁱⁱⁱ—La1—O2ⁱ	107.34 (10)	Al1^viii—O1—Zr1B^xv	117.5 (10)
O2^iv—La1—O2ⁱ	125.74 (7)	Li1^viii—O1—Zr1B^xv	117.5 (10)
O2^v—La1—O2ⁱ	66.49 (14)	Zr1A^vii—O1—Zr1B^xv	10.2 (9)
O1ⁱ—La1—O2ⁱⁱ	71.54 (10)	Al1^viii—O1—Zr1B^vii	121.3 (8)
O1ⁱⁱ—La1—O2ⁱⁱ	97.31 (11)	Li1^viii—O1—Zr1B^vii	121.3 (8)
O1—La1—O2ⁱⁱ	107.34 (10)	Zr1A^vii—O1—Zr1B^vii	9.5 (8)
O1ⁱⁱⁱ—La1—O2ⁱⁱ	74.30 (10)	Zr1B^xv—O1—Zr1B^vii	8.5 (11)
O2^iv—La1—O2ⁱⁱ	66.49 (14)	Al1^viii—O1—Zr1B^xvi	123.4 (5)
O2^v—La1—O2ⁱⁱ	125.74 (7)	Li1^viii—O1—Zr1B^xvi	123.4 (5)
O2ⁱ—La1—O2ⁱⁱ	166.47 (14)	Zr1A^vii—O1—Zr1B^xvi	4.3 (4)
O1ⁱ—La1—Li2^vi	143.45 (8)	Zr1B^xv—O1—Zr1B^xvi	6.0 (8)
O1ⁱⁱ—La1—Li2^vi	143.45 (8)	Zr1B^vii—O1—Zr1B^xvi	6.9 (12)
O1—La1—Li2^vi	83.33 (7)	Al1^viii—O1—La1^viii	95.15 (12)
O1ⁱⁱⁱ—La1—Li2^vi	83.33 (7)	Li1^viii—O1—La1^viii	95.15 (12)
O2^iv—La1—Li2^vi	38.21 (8)	Zr1A^vii—O1—La1^viii	100.61 (15)
O2^v—La1—Li2^vi	38.21 (8)	Zr1B^xv—O1—La1^viii	103.0 (8)
O2ⁱ—La1—Li2^vi	96.77 (7)	Zr1B^vii—O1—La1^viii	109.2 (8)
O2ⁱⁱ—La1—Li2^vi	96.77 (7)	Zr1B^xvi—O1—La1^viii	102.3 (8)
O1ⁱ—La1—Li1	36.55 (8)	Al1^viii—O1—La1	122.82 (15)
O1ⁱⁱ—La1—Li1	36.55 (8)	Li1^viii—O1—La1	122.82 (15)
O1—La1—Li1	96.67 (7)	Zr1A^vii—O1—La1	100.20 (13)
O1ⁱⁱⁱ—La1—Li1	96.67 (7)	Zr1B^xv—O1—La1	108.8 (8)
O2^iv—La1—Li1	141.79 (8)	Zr1B^vii—O1—La1	101.1 (7)
O2^v—La1—Li1	141.79 (8)	Zr1B^xvi—O1—La1	103.4 (8)
O2ⁱ—La1—Li1	83.23 (7)	La1^viii—O1—La1	105.71 (13)
O2ⁱⁱ—La1—Li1	83.23 (7)	Al1^viii—O1—H1	56 (7)
Li2^vi—La1—Li1	180	Li1^viii—O1—H1	56 (7)
O1ⁱ—La1—Zr1A^vii	34.45 (8)	Zr1A^vii—O1—H1	106 (7)
O1ⁱⁱ—La1—Zr1A^vii	96.17 (8)	Zr1B^xv—O1—H1	101 (7)
O1—La1—Zr1A^vii	34.50 (7)	Zr1B^vii—O1—H1	97 (7)
O1ⁱⁱⁱ—La1—Zr1A^vii	158.08 (7)	Zr1B^xvi—O1—H1	103 (7)
O2^iv—La1—Zr1A^vii	94.29 (8)	La1^viii—O1—H1	149 (7)
O2^v—La1—Zr1A^vii	128.79 (7)	La1—O1—H1	85 (7)
O2ⁱ—La1—Zr1A^vii	80.78 (8)	Zr1B^iv—O2—Li2^xvii	129.6 (7)
O2ⁱⁱ—La1—Zr1A^vii	93.16 (8)	Zr1B^iv—O2—Zr1B^xviii	7.3 (16)
Li2^vi—La1—Zr1A^vii	116.505 (14)	Li2^xvii—O2—Zr1B^xviii	130.6 (8)
Li1—La1—Zr1A^vii	63.495 (14)	Zr1B^iv—O2—Zr1B^xix	5.9 (9)
O1ⁱ—La1—H1	74.9 (17)	Li2^xvii—O2—Zr1B^xix	135.6 (10)
O1ⁱⁱ—La1—H1	116 (2)	Zr1B^xviii—O2—Zr1B^xix	8.8 (12)
O1—La1—H1	15 (2)	Zr1B^iv—O2—Zr1A^iv	4.1 (5)
O1ⁱⁱⁱ—La1—H1	160.1 (18)	Li2^xvii—O2—Zr1A^iv	125.57 (17)
O2^iv—La1—H1	82 (2)	Zr1B^xviii—O2—Zr1A^iv	9.7 (9)
O2^v—La1—H1	88.1 (17)	Zr1B^xix—O2—Zr1A^iv	10.0 (9)
O2ⁱ—La1—H1	60 (2)	Zr1B^iv—O2—La1^iv	105.3 (10)
O2ⁱⁱ—La1—H1	122 (2)	Li2^xvii—O2—La1^iv	89.03 (12)
Li2^vi—La1—H1	83.6 (18)	Zr1B^xviii—O2—La1^iv	97.9 (10)
Li1—La1—H1	96.4 (18)	Zr1B^xix—O2—La1^iv	104.4 (9)
Zr1A^vii—La1—H1	40.8 (17)	Zr1A^iv—O2—La1^iv	106.84 (13)
Zr1B^viii—Zr1A—Zr1Bⁱ	49 (4)	Zr1B^iv—O2—La1^viii	101.5 (11)
Zr1B^viii—Zr1A—O1^ix	105 (4)	Li2^xvii—O2—La1^viii	122.70 (14)
Zr1Bⁱ—Zr1A—O1^ix	113 (5)	Zr1B^xviii—O2—La1^viii	103.6 (8)
Zr1B^viii—Zr1A—O1^x	113 (5)	Zr1B^xix—O2—La1^viii	96.1 (9)
Zr1Bⁱ—Zr1A—O1^x	153 (3)	Zr1A^iv—O2—La1^viii	104.74 (13)
O1^ix—Zr1A—O1^x	89.46 (17)	La1^iv—O2—La1^viii	102.04 (12)
Zr1B^viii—Zr1A—O1^xi	153 (3)	O1^xx—Li1—O1ⁱⁱ	116.26 (11)
Zr1Bⁱ—Zr1A—O1^xi	105 (4)	O1^xx—Li1—O1ⁱ	116.26 (11)
O1^ix—Zr1A—O1^xi	89.46 (17)	O1ⁱⁱ—Li1—O1ⁱ	96.61 (19)
O1^x—Zr1A—O1^xi	89.46 (17)	O1^xx—Li1—O1^xxi	96.61 (19)
Zr1B^viii—Zr1A—O2^xii	20 (3)	O1ⁱⁱ—Li1—O1^xxi	116.26 (11)
Zr1Bⁱ—Zr1A—O2^xii	68 (4)	O1ⁱ—Li1—O1^xxi	116.26 (11)
O1^ix—Zr1A—O2^xii	94.57 (13)	O1^xx—Li1—La1	131.70 (10)
O1^x—Zr1A—O2^xii	96.47 (13)	O1ⁱⁱ—Li1—La1	48.30 (10)
O1^xi—Zr1A—O2^xii	172.9 (2)	O1ⁱ—Li1—La1	48.30 (10)
Zr1B^viii—Zr1A—O2^iv	68 (4)	O1^xxi—Li1—La1	131.70 (10)
Zr1Bⁱ—Zr1A—O2^iv	62 (4)	O1^xx—Li1—La1^xxii	48.30 (10)
O1^ix—Zr1A—O2^iv	172.9 (2)	O1ⁱⁱ—Li1—La1^xxii	131.70 (10)
O1^x—Zr1A—O2^iv	94.57 (13)	O1ⁱ—Li1—La1^xxii	131.70 (10)
O1^xi—Zr1A—O2^iv	96.47 (13)	O1^xxi—Li1—La1^xxii	48.30 (10)
O2^xii—Zr1A—O2^iv	79.14 (16)	La1—Li1—La1^xxii	180
Zr1B^viii—Zr1A—O2ⁱⁱ	62 (4)	O1^xx—Li1—Zr1B^xxiii	132.5 (5)
Zr1Bⁱ—Zr1A—O2ⁱⁱ	20 (3)	O1ⁱⁱ—Li1—Zr1B^xxiii	32.5 (5)
O1^ix—Zr1A—O2ⁱⁱ	96.47 (13)	O1ⁱ—Li1—Zr1B^xxiii	104.9 (5)
O1^x—Zr1A—O2ⁱⁱ	172.9 (2)	O1^xxi—Li1—Zr1B^xxiii	84.9 (5)
O1^xi—Zr1A—O2ⁱⁱ	94.57 (13)	La1—Li1—Zr1B^xxiii	63.8 (5)
O2^xii—Zr1A—O2ⁱⁱ	79.14 (16)	La1^xxii—Li1—Zr1B^xxiii	116.2 (5)
O2^iv—Zr1A—O2ⁱⁱ	79.14 (16)	O1^xx—Li1—Zr1B^xxiv	32.5 (5)
Zr1B^viii—Zr1A—La1^xi	150 (6)	O1ⁱⁱ—Li1—Zr1B^xxiv	84.9 (5)
Zr1Bⁱ—Zr1A—La1^xi	139 (6)	O1ⁱ—Li1—Zr1B^xxiv	132.5 (5)
O1^ix—Zr1A—La1^xi	95.88 (14)	O1^xxi—Li1—Zr1B^xxiv	104.9 (5)
O1^x—Zr1A—La1^xi	44.94 (11)	La1—Li1—Zr1B^xxiv	116.2 (5)
O1^xi—Zr1A—La1^xi	45.30 (10)	La1^xxii—Li1—Zr1B^xxiv	63.8 (5)
O2^xii—Zr1A—La1^xi	139.67 (9)	Zr1B^xxiii—Li1—Zr1B^xxiv	101.2 (4)
O2^iv—Zr1A—La1^xi	91.13 (9)	O1^xx—Li1—Zr1B^vii	84.9 (5)
O2ⁱⁱ—Zr1A—La1^xi	137.69 (9)	O1ⁱⁱ—Li1—Zr1B^vii	104.9 (5)
Zr1B^viii—Zr1A—La1^ix	139 (6)	O1ⁱ—Li1—Zr1B^vii	32.5 (5)
Zr1Bⁱ—Zr1A—La1^ix	110 (2)	O1^xxi—Li1—Zr1B^vii	132.5 (5)
O1^ix—Zr1A—La1^ix	45.30 (10)	La1—Li1—Zr1B^vii	63.8 (5)
O1^x—Zr1A—La1^ix	95.88 (14)	La1^xxii—Li1—Zr1B^vii	116.2 (5)
O1^xi—Zr1A—La1^ix	44.94 (11)	Zr1B^xxiii—Li1—Zr1B^vii	127.7 (9)
O2^xii—Zr1A—La1^ix	137.69 (9)	Zr1B^xxiv—Li1—Zr1B^vii	101.2 (4)
O2^iv—Zr1A—La1^ix	139.67 (9)	O1^xx—Li1—Zr1B^xii	104.9 (5)
O2ⁱⁱ—Zr1A—La1^ix	91.13 (9)	O1ⁱⁱ—Li1—Zr1B^xii	132.5 (5)
La1^xi—Zr1A—La1^ix	70.09 (5)	O1ⁱ—Li1—Zr1B^xii	84.9 (5)
Zr1B^viii—Zr1A—La1^x	110 (2)	O1^xxi—Li1—Zr1B^xii	32.5 (5)
Zr1Bⁱ—Zr1A—La1^x	150 (6)	La1—Li1—Zr1B^xii	116.2 (5)
O1^ix—Zr1A—La1^x	44.94 (11)	La1^xxii—Li1—Zr1B^xii	63.8 (5)
O1^x—Zr1A—La1^x	45.30 (10)	Zr1B^xxiii—Li1—Zr1B^xii	101.2 (4)
O1^xi—Zr1A—La1^x	95.88 (14)	Zr1B^xxiv—Li1—Zr1B^xii	127.7 (9)
O2^xii—Zr1A—La1^x	91.13 (9)	Zr1B^vii—Li1—Zr1B^xii	101.2 (4)
O2^iv—Zr1A—La1^x	137.69 (9)	O1^xx—Li1—Zr1A^xxv	26.21 (10)
O2ⁱⁱ—Zr1A—La1^x	139.67 (9)	O1ⁱⁱ—Li1—Zr1A^xxv	90.93 (10)
La1^xi—Zr1A—La1^x	70.09 (5)	O1ⁱ—Li1—Zr1A^xxv	130.14 (9)
La1^ix—Zr1A—La1^x	70.09 (5)	O1^xxi—Li1—Zr1A^xxv	103.67 (10)
Zr1B^viii—Zr1A—Li1^xiii	127 (3)	La1—Li1—Zr1A^xxv	119.79 (3)
Zr1Bⁱ—Zr1A—Li1^xiii	79 (4)	La1^xxii—Li1—Zr1A^xxv	60.21 (3)
O1^ix—Zr1A—Li1^xiii	100.02 (10)	Zr1B^xxiii—Li1—Zr1A^xxv	107.3 (5)
O1^x—Zr1A—Li1^xiii	113.16 (12)	Zr1B^xxiv—Li1—Zr1A^xxv	6.2 (5)
O1^xi—Zr1A—Li1^xiii	26.09 (10)	Zr1B^vii—Li1—Zr1A^xxv	98.1 (5)
O2^xii—Zr1A—Li1^xiii	146.86 (13)	Zr1B^xii—Li1—Zr1A^xxv	123.8 (5)
O2^iv—Zr1A—Li1^xiii	83.83 (9)	O1^xx—Li1—Zr1A^xxiii	130.14 (9)
O2ⁱⁱ—Zr1A—Li1^xiii	69.81 (9)	O1ⁱⁱ—Li1—Zr1A^xxiii	26.21 (10)
La1^xi—Zr1A—Li1^xiii	68.24 (3)	O1ⁱ—Li1—Zr1A^xxiii	103.67 (10)
La1^ix—Zr1A—Li1^xiii	56.29 (2)	O1^xxi—Li1—Zr1A^xxiii	90.93 (10)
La1^x—Zr1A—Li1^xiii	120.04 (7)	La1—Li1—Zr1A^xxiii	60.21 (3)
Zr1B^viii—Zr1B—Zr1Bⁱ	60.00 (6)	La1^xxii—Li1—Zr1A^xxiii	119.79 (3)
Zr1B^viii—Zr1B—O2^iv	138 (5)	Zr1B^xxiii—Li1—Zr1A^xxiii	6.2 (5)
Zr1Bⁱ—Zr1B—O2^iv	126 (9)	Zr1B^xxiv—Li1—Zr1A^xxiii	98.1 (5)
Zr1B^viii—Zr1B—O2^xii	47 (7)	Zr1B^vii—Li1—Zr1A^xxiii	123.8 (5)
Zr1Bⁱ—Zr1B—O2^xii	93 (9)	Zr1B^xii—Li1—Zr1A^xxiii	107.3 (5)
O2^iv—Zr1B—O2^xii	92.3 (15)	Zr1A^xxv—Li1—Zr1A^xxiii	104.29 (3)
Zr1B^viii—Zr1B—O2ⁱⁱ	78 (9)	O2^xxvi—Li2—O2^xxvii	111.48 (10)
Zr1Bⁱ—Zr1B—O2ⁱⁱ	36 (5)	O2^xxvi—Li2—O2^xvii	111.48 (10)
O2^iv—Zr1B—O2ⁱⁱ	90.9 (12)	O2^xxvii—Li2—O2^xvii	105.53 (19)
O2^xii—Zr1B—O2ⁱⁱ	85.5 (5)	O2^xxvi—Li2—O2^xxviii	105.53 (19)
Zr1B^viii—Zr1B—O1^x	95 (9)	O2^xxvii—Li2—O2^xxviii	111.48 (10)
Zr1Bⁱ—Zr1B—O1^x	130 (4)	O2^xvii—Li2—O2^xxviii	111.48 (10)
O2^iv—Zr1B—O1^x	101.9 (13)	O2^xxvi—Li2—La1^xxix	127.23 (9)
O2^xii—Zr1B—O1^x	97.3 (16)	O2^xxvii—Li2—La1^xxix	52.77 (9)
O2ⁱⁱ—Zr1B—O1^x	166.7 (19)	O2^xvii—Li2—La1^xxix	52.77 (9)
Zr1B^viii—Zr1B—O1^xi	119 (7)	O2^xxviii—Li2—La1^xxix	127.23 (9)
Zr1Bⁱ—Zr1B—O1^xi	77 (9)	O2^xxvi—Li2—La1^xxii	52.77 (9)
O2^iv—Zr1B—O1^xi	102.2 (13)	O2^xxvii—Li2—La1^xxii	127.23 (9)
O2^xii—Zr1B—O1^xi	165.4 (18)	O2^xvii—Li2—La1^xxii	127.23 (9)
O2ⁱⁱ—Zr1B—O1^xi	92.7 (16)	O2^xxviii—Li2—La1^xxii	52.77 (9)
O1^x—Zr1B—O1^xi	81.4 (6)	La1^xxix—Li2—La1^xxii	180
Zr1B^viii—Zr1B—O1^ix	44 (4)	O2^xxvi—Li2—Zr1B^xxx	125.3 (7)
Zr1Bⁱ—Zr1B—O1^ix	54 (7)	O2^xxvii—Li2—Zr1B^xxx	24.3 (5)
O2^iv—Zr1B—O1^ix	178.7 (12)	O2^xvii—Li2—Zr1B^xxx	112.0 (5)
O2^xii—Zr1B—O1^ix	89.0 (11)	O2^xxviii—Li2—Zr1B^xxx	87.6 (4)
O2ⁱⁱ—Zr1B—O1^ix	89.6 (12)	La1^xxix—Li2—Zr1B^xxx	63.6 (4)
O1^x—Zr1B—O1^ix	77.5 (10)	La1^xxii—Li2—Zr1B^xxx	116.4 (4)
O1^xi—Zr1B—O1^ix	76.6 (11)	O2^xxvi—Li2—Zr1B^xxii	24.3 (5)
Zr1B^viii—Zr1B—Li2^vi	164 (6)	O2^xxvii—Li2—Zr1B^xxii	87.6 (4)
Zr1Bⁱ—Zr1B—Li2^vi	126 (10)	O2^xvii—Li2—Zr1B^xxii	125.3 (7)
O2^iv—Zr1B—Li2^vi	26.1 (4)	O2^xxviii—Li2—Zr1B^xxii	112.0 (5)
O2^xii—Zr1B—Li2^vi	117.1 (14)	La1^xxix—Li2—Zr1B^xxii	116.4 (4)
O2ⁱⁱ—Zr1B—Li2^vi	100.0 (11)	La1^xxii—Li2—Zr1B^xxii	63.6 (4)
O1^x—Zr1B—Li2^vi	90.3 (7)	Zr1B^xxx—Li2—Zr1B^xxii	101.4 (3)
O1^xi—Zr1B—Li2^vi	77.4 (7)	O2^xxvi—Li2—Zr1B^xxix	87.6 (4)
O1^ix—Zr1B—Li2^vi	152.6 (9)	O2^xxvii—Li2—Zr1B^xxix	112.0 (5)
Zr1B^viii—Zr1B—La1^viii	93 (8)	O2^xvii—Li2—Zr1B^xxix	24.3 (5)
Zr1Bⁱ—Zr1B—La1^viii	125 (4)	O2^xxviii—Li2—Zr1B^xxix	125.3 (7)
O2^iv—Zr1B—La1^viii	47.1 (9)	La1^xxix—Li2—Zr1B^xxix	63.6 (4)
O2^xii—Zr1B—La1^viii	46.3 (8)	La1^xxii—Li2—Zr1B^xxix	116.4 (4)
O2ⁱⁱ—Zr1B—La1^viii	95.3 (9)	Zr1B^xxx—Li2—Zr1B^xxix	127.3 (8)
O1^x—Zr1B—La1^viii	95.9 (13)	Zr1B^xxii—Li2—Zr1B^xxix	101.4 (3)
O1^xi—Zr1B—La1^viii	148.2 (12)	O2^xxvi—Li2—Zr1B^xxxi	112.0 (5)
O1^ix—Zr1B—La1^viii	134.1 (12)	O2^xxvii—Li2—Zr1B^xxxi	125.3 (7)
Li2^vi—Zr1B—La1^viii	70.9 (7)	O2^xvii—Li2—Zr1B^xxxi	87.6 (4)
Zr1B^viii—Zr1B—La1	118 (6)	O2^xxviii—Li2—Zr1B^xxxi	24.3 (5)
Zr1Bⁱ—Zr1B—La1	82 (8)	La1^xxix—Li2—Zr1B^xxxi	116.4 (4)
O2^iv—Zr1B—La1	44.2 (7)	La1^xxii—Li2—Zr1B^xxxi	63.6 (4)
O2^xii—Zr1B—La1	95.2 (8)	Zr1B^xxx—Li2—Zr1B^xxxi	101.4 (3)
O2ⁱⁱ—Zr1B—La1	47.5 (6)	Zr1B^xxii—Li2—Zr1B^xxxi	127.3 (8)
O1^x—Zr1B—La1	144.4 (12)	Zr1B^xxix—Li2—Zr1B^xxxi	101.4 (3)

Symmetry codes: (i) z, x, y; (ii) z, −x, −y+1/2; (iii) x, −y, −z+1/2; (iv) −x, −y+1/2, z; (v) −x, y−1/2, −z+1/2; (vi) x−1, y, z; (vii) y+1/4, x+1/4, z+1/4; (viii) y, z, x; (ix) z−1/4, y−1/4, x−1/4; (x) x−1/4, z−1/4, y−1/4; (xi) y−1/4, x−1/4, z−1/4; (xii) −y+1/2, z, −x; (xiii) −y, z−1/2, −x+1/2; (xiv) z−1/2, −x+1/2, −y; (xv) x+1/4, z+1/4, y+1/4; (xvi) z+1/4, y+1/4, x+1/4; (xvii) −x+1, −y+1/2, z; (xviii) −z, −x+1/2, y; (xix) −y, −z+1/2, x; (xx) −z+3/4, −y+1/4, x+1/4; (xxi) −z+3/4, y−1/4, −x+1/4; (xxii) −x+3/4, z−1/4, −y+1/4; (xxiii) y+1/4, −x−1/4, −z+1/4; (xxiv) −y+1/2, −z, x+1/2; (xxv) −x+1/2, −y, z+1/2; (xxvi) x+3/4, z−1/4, y−1/4; (xxvii) −x+1, y−1/2, −z+1/2; (xxviii) x+3/4, −z+1/4, −y+3/4; (xxix) x+1, y, z; (xxx) x+1, −y, −z+1/2; (xxxi) −x+3/4, −z+1/4, y+1/4.

(LLZO-Ga40-pristine) top

Crystal data top

Ga_0.28La_2.94Li_6.44O_12.00Zr_2.00	D_x = 5.165 Mg m⁻³
M_r = 847.67	Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d	Cell parameters from 35033 reflections
Hall symbol: I -4bd 2c 3	θ = 3.9–38.9°
a = 12.9669 (2) Å	µ = 13.88 mm⁻¹
V = 2180.26 (10) Å³	T = 298 K
Z = 8	Cuboid, colorless
F(000) = 2974.7	0.13 × 0.13 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	1045 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
rotation, ω–scans at 4 different φ positions	θ_max = 38.9°, θ_min = 3.9°
Absorption correction: multi-scan (APEX2; Bruker, 2012)	h = −22→22
T_min = 0.19, T_max = 0.25	k = −22→22
35033 measured reflections	l = −22→22
1054 independent reflections

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.0079P)² + 2.531P] where P = (F_o² + 2F_c²)/3
Least-squares matrix: full	(Δ/σ)_max = 0.001
R[F² > 2σ(F²)] = 0.013	Δρ_max = 0.53 e Å⁻³
wR(F²) = 0.026	Δρ_min = −0.65 e Å⁻³
S = 1.29	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1054 reflections	Extinction coefficient: 0.00103 (4)
48 parameters	Absolute structure: Refined as an inversion twin.
2 restraints	Absolute structure parameter: 0.50 (4)
0 constraints

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.11966 (2)	0	0.25	0.00584 (5)	0.9814 (19)
Zr1	0.00014 (2)	0.00014 (2)	0.00014 (2)	0.00502 (8)
O1	0.09727 (14)	0.19681 (14)	0.27989 (14)	0.0087 (3)
O2	0.03322 (15)	0.44478 (16)	0.14725 (13)	0.0105 (3)
Li1	0.375	0	0.25	0.0038 (5)	0.818 (3)
Ga1	0.375	0	0.25	0.0038 (5)	0.182 (3)
Li2	0.875	0	0.25	0.021 (3)	0.995 (3)
Ga2	0.875	0	0.25	0.021 (3)	0.005 (3)
Li3	0.0971 (7)	0.1868 (6)	0.4268 (6)	0.014 (2)	0.62 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00591 (7)	0.00574 (8)	0.00587 (8)	0	0	0.00065 (5)
Zr1	0.00502 (8)	0.00502 (8)	0.00502 (8)	0.00015 (6)	0.00015 (6)	0.00015 (6)
O1	0.0079 (7)	0.0087 (7)	0.0095 (7)	−0.0008 (6)	0.0013 (5)	−0.0002 (6)
O2	0.0134 (8)	0.0122 (8)	0.0059 (7)	0.0021 (6)	−0.0003 (5)	0.0009 (6)
Li1	0.0043 (8)	0.0035 (6)	0.0035 (6)	0	0	0
Ga1	0.0043 (8)	0.0035 (6)	0.0035 (6)	0	0	0
Li2	0.013 (4)	0.025 (4)	0.025 (4)	0	0	0
Ga2	0.013 (4)	0.025 (4)	0.025 (4)	0	0	0
Li3	0.022 (4)	0.014 (4)	0.007 (3)	−0.005 (3)	0.004 (3)	0.001 (2)

Geometric parameters (Å, º) top

La1—O2ⁱ	2.4935 (19)	O2—Li3^xv	2.108 (9)
La1—O2ⁱⁱ	2.4935 (19)	O2—La1ⁱ	2.4936 (19)
La1—O1ⁱⁱⁱ	2.5264 (19)	O2—La1^xv	2.587 (2)
La1—O1^iv	2.5264 (19)	O2—Li3^xvi	2.639 (8)
La1—O2ⁱⁱⁱ	2.587 (2)	Li1—Li3^vii	1.645 (8)
La1—O2^iv	2.587 (2)	Li1—Li3^vi	1.645 (8)
La1—O1^v	2.5975 (19)	Li1—Li3ⁱⁱⁱ	1.645 (8)
La1—O1	2.5976 (19)	Li1—Li3^iv	1.645 (8)
La1—Li3^vi	3.037 (8)	Li1—O1^vi	1.8941 (18)
La1—Li3^vii	3.037 (8)	Li1—O1^iv	1.8941 (18)
La1—Ga2^viii	3.1725 (2)	Li1—O1ⁱⁱⁱ	1.8941 (18)
La1—Li2^viii	3.1725 (2)	Li1—O1^vii	1.8941 (18)
Zr1—O2^ix	2.0823 (18)	Li1—La1^xx	3.3109 (2)
Zr1—O2^iv	2.0823 (18)	Li2—O2^xxi	1.9246 (19)
Zr1—O2ⁱ	2.0823 (18)	Li2—O2^xxii	1.9246 (19)
Zr1—O1^x	2.1346 (18)	Li2—O2^xxiii	1.9246 (19)
Zr1—O1^xi	2.1346 (18)	Li2—O2^xix	1.9246 (19)
Zr1—O1^xii	2.1346 (18)	Li2—Li3^xxiv	2.340 (9)
Zr1—Li3^xiii	2.890 (8)	Li2—Li3^xxv	2.340 (9)
Zr1—Li3^v	2.890 (8)	Li2—Li3^xxvi	2.340 (9)
Zr1—Li3^xiv	2.890 (8)	Li2—Li3^xxvii	2.340 (9)
Zr1—Li3^x	3.140 (7)	Li2—La1^xx	3.1726 (2)
Zr1—Li3^xi	3.140 (7)	Li2—La1^xxviii	3.1726 (2)
Zr1—Li3^xii	3.140 (7)	Li3—Ga1^xv	1.645 (8)
O1—Ga1^xv	1.8941 (18)	Li3—Li1^xv	1.645 (8)
O1—Li1^xv	1.8941 (18)	Li3—O1^xviii	2.075 (8)
O1—Li3	1.909 (8)	Li3—O2ⁱⁱⁱ	2.108 (9)
O1—Li3^xvi	2.075 (8)	Li3—O1^xvi	2.229 (8)
O1—Zr1^xvii	2.1346 (18)	Li3—Ga2^xxix	2.340 (9)
O1—Li3^xviii	2.229 (8)	Li3—Li2^xxix	2.340 (9)
O1—La1^xv	2.5264 (19)	Li3—Li3^xvi	2.513 (13)
O2—Ga2^xix	1.9247 (19)	Li3—Li3^xviii	2.513 (13)
O2—Li2^xix	1.9247 (19)	Li3—O2^xviii	2.639 (8)
O2—Zr1ⁱ	2.0823 (18)	Li3—Zr1^v	2.890 (8)

O2ⁱ—La1—O2ⁱⁱ	74.68 (9)	Li3^xv—O2—La1ⁱ	161.4 (2)
O2ⁱ—La1—O1ⁱⁱⁱ	111.38 (5)	Ga2^xix—O2—La1^xv	124.19 (9)
O2ⁱⁱ—La1—O1ⁱⁱⁱ	160.56 (5)	Li2^xix—O2—La1^xv	124.19 (9)
O2ⁱ—La1—O1^iv	160.56 (5)	Zr1ⁱ—O2—La1^xv	100.00 (7)
O2ⁱⁱ—La1—O1^iv	111.38 (5)	Li3^xv—O2—La1^xv	90.4 (2)
O1ⁱⁱⁱ—La1—O1^iv	69.36 (8)	La1ⁱ—O2—La1^xv	102.82 (7)
O2ⁱ—La1—O2ⁱⁱⁱ	125.72 (4)	Ga2^xix—O2—Li3^xvi	59.26 (19)
O2ⁱⁱ—La1—O2ⁱⁱⁱ	68.66 (8)	Li2^xix—O2—Li3^xvi	59.26 (19)
O1ⁱⁱⁱ—La1—O2ⁱⁱⁱ	94.00 (6)	Zr1ⁱ—O2—Li3^xvi	170.9 (2)
O1^iv—La1—O2ⁱⁱⁱ	72.71 (6)	Li3^xv—O2—Li3^xvi	94.3 (2)
O2ⁱ—La1—O2^iv	68.66 (8)	La1ⁱ—O2—Li3^xvi	78.05 (18)
O2ⁱⁱ—La1—O2^iv	125.72 (4)	La1^xv—O2—Li3^xvi	71.06 (19)
O1ⁱⁱⁱ—La1—O2^iv	72.71 (6)	Li3^vii—Li1—Li3^vi	131.8 (5)
O1^iv—La1—O2^iv	94.00 (6)	Li3^vii—Li1—Li3ⁱⁱⁱ	99.6 (2)
O2ⁱⁱⁱ—La1—O2^iv	164.10 (8)	Li3^vi—Li1—Li3ⁱⁱⁱ	99.6 (2)
O2ⁱ—La1—O1^v	96.52 (6)	Li3^vii—Li1—Li3^iv	99.6 (2)
O2ⁱⁱ—La1—O1^v	73.06 (6)	Li3^vi—Li1—Li3^iv	99.6 (2)
O1ⁱⁱⁱ—La1—O1^v	122.80 (4)	Li3ⁱⁱⁱ—Li1—Li3^iv	131.8 (5)
O1^iv—La1—O1^v	69.03 (8)	Li3^vii—Li1—O1^vi	163.0 (3)
O2ⁱⁱⁱ—La1—O1^v	108.95 (5)	Li3^vi—Li1—O1^vi	64.8 (3)
O2^iv—La1—O1^v	72.92 (5)	Li3ⁱⁱⁱ—Li1—O1^vi	77.7 (3)
O2ⁱ—La1—O1	73.06 (6)	Li3^iv—Li1—O1^vi	71.4 (3)
O2ⁱⁱ—La1—O1	96.52 (6)	Li3^vii—Li1—O1^iv	71.4 (3)
O1ⁱⁱⁱ—La1—O1	69.03 (8)	Li3^vi—Li1—O1^iv	77.7 (3)
O1^iv—La1—O1	122.80 (4)	Li3ⁱⁱⁱ—Li1—O1^iv	163.0 (3)
O2ⁱⁱⁱ—La1—O1	72.92 (5)	Li3^iv—Li1—O1^iv	64.8 (3)
O2^iv—La1—O1	108.95 (5)	O1^vi—Li1—O1^iv	115.09 (6)
O1^v—La1—O1	167.16 (8)	Li3^vii—Li1—O1ⁱⁱⁱ	77.7 (3)
O2ⁱ—La1—Li3^vi	146.61 (16)	Li3^vi—Li1—O1ⁱⁱⁱ	71.4 (3)
O2ⁱⁱ—La1—Li3^vi	123.17 (17)	Li3ⁱⁱⁱ—Li1—O1ⁱⁱⁱ	64.8 (3)
O1ⁱⁱⁱ—La1—Li3^vi	42.58 (16)	Li3^iv—Li1—O1ⁱⁱⁱ	163.0 (3)
O1^iv—La1—Li3^vi	46.12 (15)	O1^vi—Li1—O1ⁱⁱⁱ	115.09 (6)
O2ⁱⁱⁱ—La1—Li3^vi	55.27 (17)	O1^iv—Li1—O1ⁱⁱⁱ	98.74 (12)
O2^iv—La1—Li3^vi	109.23 (16)	Li3^vii—Li1—O1^vii	64.8 (3)
O1^v—La1—Li3^vi	115.09 (16)	Li3^vi—Li1—O1^vii	163.0 (3)
O1—La1—Li3^vi	76.72 (16)	Li3ⁱⁱⁱ—Li1—O1^vii	71.4 (3)
O2ⁱ—La1—Li3^vii	123.17 (17)	Li3^iv—Li1—O1^vii	77.7 (3)
O2ⁱⁱ—La1—Li3^vii	146.61 (16)	O1^vi—Li1—O1^vii	98.74 (12)
O1ⁱⁱⁱ—La1—Li3^vii	46.12 (15)	O1^iv—Li1—O1^vii	115.09 (6)
O1^iv—La1—Li3^vii	42.58 (16)	O1ⁱⁱⁱ—Li1—O1^vii	115.09 (6)
O2ⁱⁱⁱ—La1—Li3^vii	109.23 (16)	Li3^vii—Li1—La1^xx	114.1 (3)
O2^iv—La1—Li3^vii	55.27 (17)	Li3^vi—Li1—La1^xx	114.1 (3)
O1^v—La1—Li3^vii	76.72 (15)	Li3ⁱⁱⁱ—Li1—La1^xx	65.9 (3)
O1—La1—Li3^vii	115.09 (16)	Li3^iv—Li1—La1^xx	65.9 (3)
Li3^vi—La1—Li3^vii	59.3 (3)	O1^vi—Li1—La1^xx	49.37 (6)
O2ⁱ—La1—Ga2^viii	37.34 (4)	O1^iv—Li1—La1^xx	130.63 (6)
O2ⁱⁱ—La1—Ga2^viii	37.34 (4)	O1ⁱⁱⁱ—Li1—La1^xx	130.63 (6)
O1ⁱⁱⁱ—La1—Ga2^viii	145.32 (4)	O1^vii—Li1—La1^xx	49.37 (6)
O1^iv—La1—Ga2^viii	145.32 (4)	Li3^vii—Li1—La1	65.9 (3)
O2ⁱⁱⁱ—La1—Ga2^viii	97.95 (4)	Li3^vi—Li1—La1	65.9 (3)
O2^iv—La1—Ga2^viii	97.95 (4)	Li3ⁱⁱⁱ—Li1—La1	114.1 (3)
O1^v—La1—Ga2^viii	83.58 (4)	Li3^iv—Li1—La1	114.1 (3)
O1—La1—Ga2^viii	83.58 (4)	O1^vi—Li1—La1	130.63 (6)
Li3^vi—La1—Ga2^viii	150.36 (16)	O1^iv—Li1—La1	49.37 (6)
Li3^vii—La1—Ga2^viii	150.36 (16)	O1ⁱⁱⁱ—Li1—La1	49.37 (6)
O2ⁱ—La1—Li2^viii	37.34 (4)	O1^vii—Li1—La1	130.63 (6)
O2ⁱⁱ—La1—Li2^viii	37.34 (4)	La1^xx—Li1—La1	180
O1ⁱⁱⁱ—La1—Li2^viii	145.32 (4)	O2^xxi—Li2—O2^xxii	112.48 (6)
O1^iv—La1—Li2^viii	145.32 (4)	O2^xxi—Li2—O2^xxiii	103.61 (12)
O2ⁱⁱⁱ—La1—Li2^viii	97.95 (4)	O2^xxii—Li2—O2^xxiii	112.48 (6)
O2^iv—La1—Li2^viii	97.95 (4)	O2^xxi—Li2—O2^xix	112.48 (6)
O1^v—La1—Li2^viii	83.58 (4)	O2^xxii—Li2—O2^xix	103.60 (12)
O1—La1—Li2^viii	83.58 (4)	O2^xxiii—Li2—O2^xix	112.48 (6)
Li3^vi—La1—Li2^viii	150.36 (16)	O2^xxi—Li2—Li3^xxiv	161.7 (2)
Li3^vii—La1—Li2^viii	150.36 (16)	O2^xxii—Li2—Li3^xxiv	79.8 (2)
Ga2^viii—La1—Li2^viii	0	O2^xxiii—Li2—Li3^xxiv	58.3 (2)
O2^ix—Zr1—O2^iv	86.98 (8)	O2^xix—Li2—Li3^xxiv	75.8 (2)
O2^ix—Zr1—O2ⁱ	86.98 (8)	O2^xxi—Li2—Li3^xxv	58.3 (2)
O2^iv—Zr1—O2ⁱ	86.98 (8)	O2^xxii—Li2—Li3^xxv	75.8 (2)
O2^ix—Zr1—O1^x	94.92 (8)	O2^xxiii—Li2—Li3^xxv	161.7 (2)
O2^iv—Zr1—O1^x	177.97 (8)	O2^xix—Li2—Li3^xxv	79.8 (2)
O2ⁱ—Zr1—O1^x	92.40 (7)	Li3^xxiv—Li2—Li3^xxv	140.0 (4)
O2^ix—Zr1—O1^xi	92.40 (7)	O2^xxi—Li2—Li3^xxvi	75.8 (2)
O2^iv—Zr1—O1^xi	94.92 (8)	O2^xxii—Li2—Li3^xxvi	161.7 (2)
O2ⁱ—Zr1—O1^xi	177.97 (8)	O2^xxiii—Li2—Li3^xxvi	79.8 (2)
O1^x—Zr1—O1^xi	85.72 (7)	O2^xix—Li2—Li3^xxvi	58.3 (2)
O2^ix—Zr1—O1^xii	177.97 (8)	Li3^xxiv—Li2—Li3^xxvi	96.73 (13)
O2^iv—Zr1—O1^xii	92.40 (7)	Li3^xxv—Li2—Li3^xxvi	96.73 (13)
O2ⁱ—Zr1—O1^xii	94.92 (8)	O2^xxi—Li2—Li3^xxvii	79.8 (2)
O1^x—Zr1—O1^xii	85.72 (7)	O2^xxii—Li2—Li3^xxvii	58.3 (2)
O1^xi—Zr1—O1^xii	85.72 (7)	O2^xxiii—Li2—Li3^xxvii	75.8 (2)
O2^ix—Zr1—Li3^xiii	46.76 (18)	O2^xix—Li2—Li3^xxvii	161.7 (2)
O2^iv—Zr1—Li3^xiii	94.45 (17)	Li3^xxiv—Li2—Li3^xxvii	96.73 (13)
O2ⁱ—Zr1—Li3^xiii	133.42 (18)	Li3^xxv—Li2—Li3^xxvii	96.73 (13)
O1^x—Zr1—Li3^xiii	87.38 (16)	Li3^xxvi—Li2—Li3^xxvii	140.0 (4)
O1^xi—Zr1—Li3^xiii	45.80 (18)	O2^xxi—Li2—La1^xx	51.80 (6)
O1^xii—Zr1—Li3^xiii	131.42 (18)	O2^xxii—Li2—La1^xx	128.20 (6)
O2^ix—Zr1—Li3^v	133.42 (18)	O2^xxiii—Li2—La1^xx	51.80 (6)
O2^iv—Zr1—Li3^v	46.76 (18)	O2^xix—Li2—La1^xx	128.20 (6)
O2ⁱ—Zr1—Li3^v	94.45 (17)	Li3^xxiv—Li2—La1^xx	110.0 (2)
O1^x—Zr1—Li3^v	131.42 (18)	Li3^xxv—Li2—La1^xx	110.0 (2)
O1^xi—Zr1—Li3^v	87.38 (16)	Li3^xxvi—Li2—La1^xx	70.0 (2)
O1^xii—Zr1—Li3^v	45.80 (18)	Li3^xxvii—Li2—La1^xx	70.0 (2)
Li3^xiii—Zr1—Li3^v	119.81 (2)	O2^xxi—Li2—La1^xxviii	128.20 (6)
O2^ix—Zr1—Li3^xiv	94.45 (17)	O2^xxii—Li2—La1^xxviii	51.80 (6)
O2^iv—Zr1—Li3^xiv	133.42 (18)	O2^xxiii—Li2—La1^xxviii	128.20 (6)
O2ⁱ—Zr1—Li3^xiv	46.76 (18)	O2^xix—Li2—La1^xxviii	51.80 (6)
O1^x—Zr1—Li3^xiv	45.80 (18)	Li3^xxiv—Li2—La1^xxviii	70.0 (2)
O1^xi—Zr1—Li3^xiv	131.42 (18)	Li3^xxv—Li2—La1^xxviii	70.0 (2)
O1^xii—Zr1—Li3^xiv	87.38 (16)	Li3^xxvi—Li2—La1^xxviii	110.0 (2)
Li3^xiii—Zr1—Li3^xiv	119.81 (2)	Li3^xxvii—Li2—La1^xxviii	110.0 (2)
Li3^v—Zr1—Li3^xiv	119.81 (2)	La1^xx—Li2—La1^xxviii	180
O2^ix—Zr1—Li3^x	59.62 (16)	Ga1^xv—Li3—Li1^xv	0
O2^iv—Zr1—Li3^x	145.12 (16)	Ga1^xv—Li3—O1	63.9 (3)
O2ⁱ—Zr1—Li3^x	81.85 (16)	Li1^xv—Li3—O1	63.9 (3)
O1^x—Zr1—Li3^x	36.53 (16)	Ga1^xv—Li3—O1^xviii	59.9 (3)
O1^xi—Zr1—Li3^x	96.18 (16)	Li1^xv—Li3—O1^xviii	59.9 (3)
O1^xii—Zr1—Li3^x	121.32 (16)	O1—Li3—O1^xviii	106.6 (4)
Li3^xiii—Zr1—Li3^x	70.8 (3)	Ga1^xv—Li3—O2ⁱⁱⁱ	138.8 (5)
Li3^v—Zr1—Li3^x	166.5 (3)	Li1^xv—Li3—O2ⁱⁱⁱ	138.8 (5)
Li3^xiv—Zr1—Li3^x	49.0 (3)	O1—Li3—O2ⁱⁱⁱ	100.0 (4)
O2^ix—Zr1—Li3^xi	81.85 (16)	O1^xviii—Li3—O2ⁱⁱⁱ	93.4 (3)
O2^iv—Zr1—Li3^xi	59.62 (16)	Ga1^xv—Li3—O1^xvi	56.1 (3)
O2ⁱ—Zr1—Li3^xi	145.12 (16)	Li1^xv—Li3—O1^xvi	56.1 (3)
O1^x—Zr1—Li3^xi	121.32 (16)	O1—Li3—O1^xvi	100.9 (4)
O1^xi—Zr1—Li3^xi	36.53 (16)	O1^xviii—Li3—O1^xvi	83.7 (3)
O1^xii—Zr1—Li3^xi	96.18 (16)	O2ⁱⁱⁱ—Li3—O1^xvi	158.8 (4)
Li3^xiii—Zr1—Li3^xi	49.0 (3)	Ga1^xv—Li3—Ga2^xxix	169.9 (5)
Li3^v—Zr1—Li3^xi	70.8 (3)	Li1^xv—Li3—Ga2^xxix	169.9 (5)
Li3^xiv—Zr1—Li3^xi	166.5 (3)	O1—Li3—Ga2^xxix	115.3 (4)
Li3^x—Zr1—Li3^xi	119.11 (5)	O1^xviii—Li3—Ga2^xxix	127.8 (4)
O2^ix—Zr1—Li3^xii	145.12 (16)	O2ⁱⁱⁱ—Li3—Ga2^xxix	50.9 (2)
O2^iv—Zr1—Li3^xii	81.85 (16)	O1^xvi—Li3—Ga2^xxix	115.7 (4)
O2ⁱ—Zr1—Li3^xii	59.62 (16)	Ga1^xv—Li3—Li2^xxix	169.9 (5)
O1^x—Zr1—Li3^xii	96.18 (16)	Li1^xv—Li3—Li2^xxix	169.9 (5)
O1^xi—Zr1—Li3^xii	121.32 (16)	O1—Li3—Li2^xxix	115.3 (4)
O1^xii—Zr1—Li3^xii	36.53 (16)	O1^xviii—Li3—Li2^xxix	127.8 (4)
Li3^xiii—Zr1—Li3^xii	166.5 (3)	O2ⁱⁱⁱ—Li3—Li2^xxix	50.9 (2)
Li3^v—Zr1—Li3^xii	49.0 (3)	O1^xvi—Li3—Li2^xxix	115.7 (4)
Li3^xiv—Zr1—Li3^xii	70.8 (3)	Ga2^xxix—Li3—Li2^xxix	0
Li3^x—Zr1—Li3^xii	119.11 (5)	Ga1^xv—Li3—Li3^xvi	40.21 (10)
Li3^xi—Zr1—Li3^xii	119.11 (5)	Li1^xv—Li3—Li3^xvi	40.21 (10)
Ga1^xv—O1—Li1^xv	0	O1—Li3—Li3^xvi	53.9 (3)
Ga1^xv—O1—Li3	51.3 (3)	O1^xviii—Li3—Li3^xvi	99.0 (3)
Li1^xv—O1—Li3	51.3 (3)	O2ⁱⁱⁱ—Li3—Li3^xvi	153.4 (5)
Ga1^xv—O1—Li3^xvi	48.7 (2)	O1^xvi—Li3—Li3^xvi	47.0 (2)
Li1^xv—O1—Li3^xvi	48.7 (2)	Ga2^xxix—Li3—Li3^xvi	130.4 (4)
Li3—O1—Li3^xvi	78.1 (3)	Li2^xxix—Li3—Li3^xvi	130.4 (4)
Ga1^xv—O1—Zr1^xvii	128.17 (10)	Ga1^xv—Li3—Li3^xviii	40.21 (10)
Li1^xv—O1—Zr1^xvii	128.17 (10)	Li1^xv—Li3—Li3^xviii	40.21 (10)
Li3—O1—Zr1^xvii	101.7 (3)	O1—Li3—Li3^xviii	58.7 (3)
Li3^xvi—O1—Zr1^xvii	86.7 (2)	O1^xviii—Li3—Li3^xviii	48.0 (2)
Ga1^xv—O1—Li3^xviii	46.1 (2)	O2ⁱⁱⁱ—Li3—Li3^xviii	98.6 (5)
Li1^xv—O1—Li3^xviii	46.1 (2)	O1^xvi—Li3—Li3^xviii	95.0 (2)
Li3—O1—Li3^xviii	74.3 (3)	Ga2^xxix—Li3—Li3^xviii	149.1 (5)
Li3^xvi—O1—Li3^xviii	88.4 (4)	Li2^xxix—Li3—Li3^xviii	149.1 (5)
Zr1^xvii—O1—Li3^xviii	174.3 (2)	Li3^xvi—Li3—Li3^xviii	73.4 (3)
Ga1^xv—O1—La1^xv	95.95 (7)	Ga1^xv—Li3—O2^xviii	130.3 (4)
Li1^xv—O1—La1^xv	95.95 (7)	Li1^xv—Li3—O2^xviii	130.3 (4)
Li3—O1—La1^xv	147.0 (3)	O1—Li3—O2^xviii	148.4 (4)
Li3^xvi—O1—La1^xv	82.0 (2)	O1^xviii—Li3—O2^xviii	104.4 (3)
Zr1^xvii—O1—La1^xv	103.10 (7)	O2ⁱⁱⁱ—Li3—O2^xviii	84.0 (3)
Li3^xviii—O1—La1^xv	79.11 (19)	O1^xvi—Li3—O2^xviii	76.5 (2)
Ga1^xv—O1—La1	121.96 (8)	Ga2^xxix—Li3—O2^xviii	44.98 (15)
Li1^xv—O1—La1	121.96 (8)	Li2^xxix—Li3—O2^xviii	44.98 (15)
Li3—O1—La1	94.7 (3)	Li3^xvi—Li3—O2^xviii	115.1 (4)
Li3^xvi—O1—La1	170.6 (2)	Li3^xviii—Li3—O2^xviii	152.2 (5)
Zr1^xvii—O1—La1	100.81 (7)	Ga1^xv—Li3—Zr1^v	102.6 (4)
Li3^xviii—O1—La1	83.8 (2)	Li1^xv—Li3—Zr1^v	102.6 (4)
La1^xv—O1—La1	101.62 (6)	O1—Li3—Zr1^v	112.6 (3)
Ga2^xix—O2—Li2^xix	0	O1^xviii—Li3—Zr1^v	47.50 (17)
Ga2^xix—O2—Zr1ⁱ	129.42 (11)	O2ⁱⁱⁱ—Li3—Zr1^v	46.02 (16)
Li2^xix—O2—Zr1ⁱ	129.42 (11)	O1^xvi—Li3—Zr1^v	126.1 (3)
Ga2^xix—O2—Li3^xv	70.8 (2)	Ga2^xxix—Li3—Zr1^v	87.0 (2)
Li2^xix—O2—Li3^xv	70.8 (2)	Li2^xxix—Li3—Zr1^v	87.0 (2)
Zr1ⁱ—O2—Li3^xv	87.2 (2)	Li3^xvi—Li3—Zr1^v	142.5 (4)
Ga2^xix—O2—La1ⁱ	90.85 (7)	Li3^xviii—Li3—Zr1^v	70.7 (3)
Li2^xix—O2—La1ⁱ	90.85 (7)	O2^xviii—Li3—Zr1^v	92.8 (2)
Zr1ⁱ—O2—La1ⁱ	103.05 (8)

Symmetry codes: (i) −x, −y+1/2, z; (ii) −x, y−1/2, −z+1/2; (iii) z, x, y; (iv) z, −x, −y+1/2; (v) x, −y, −z+1/2; (vi) −z+3/4, −y+1/4, x+1/4; (vii) −z+3/4, y−1/4, −x+1/4; (viii) x−1, y, z; (ix) −y+1/2, z, −x; (x) x−1/4, z−1/4, y−1/4; (xi) z−1/4, y−1/4, x−1/4; (xii) y−1/4, x−1/4, z−1/4; (xiii) −z+1/2, x, −y; (xiv) −y, −z+1/2, x; (xv) y, z, x; (xvi) −y+1/4, x+1/4, −z+3/4; (xvii) y+1/4, x+1/4, z+1/4; (xviii) y−1/4, −x+1/4, −z+3/4; (xix) −x+1, −y+1/2, z; (xx) −x+3/4, z−1/4, −y+1/4; (xxi) x+3/4, z−1/4, y−1/4; (xxii) −x+1, y−1/2, −z+1/2; (xxiii) x+3/4, −z+1/4, −y+3/4; (xxiv) y+3/4, −x+1/4, −z+3/4; (xxv) y+3/4, x−1/4, z−1/4; (xxvi) −y+1, −z+1/2, x; (xxvii) −y+1, z−1/2, −x+1/2; (xxviii) x+1, y, z; (xxix) −y+1/4, x−3/4, −z+3/4.

(LLZO-Ga40-hydro-150C) top

Crystal data top

Ga_0.26H_3.90La_2.96Li_1.99O₁₂Zr₂	D_x = 4.891 Mg m⁻³
M_r = 821.46	Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d	Cell parameters from 35657 reflections
Hall symbol: I -4bd 2c 3	θ = 3.8–36.6°
a = 13.06720 (12) Å	µ = 13.57 mm⁻¹
V = 2231.25 (6) Å³	T = 298 K
Z = 8	Cuboid, colorless
F(000) = 2901.2	0.12 × 0.11 × 0.09 mm

Data collection top

Bruker SMART APEX diffractometer	915 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
rotation, ω–scans at 4 different φ positions	θ_max = 36.6°, θ_min = 3.8°
Absorption correction: multi-scan (APEX2; Bruker, 2012)	h = −21→21
T_min = 0.21, T_max = 0.36	k = −21→21
35657 measured reflections	l = −21→21
918 independent reflections

Refinement top

Refinement on F²	Only H-atom coordinates refined
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0072P)² + 28.9201P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.018	(Δ/σ)_max < 0.001
wR(F²) = 0.037	Δρ_max = 0.54 e Å⁻³
S = 1.12	Δρ_min = −0.52 e Å⁻³
918 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.00055 (4)
3 restraints	Absolute structure: Refined as an inversion twin.
0 constraints	Absolute structure parameter: 0.99944 (15)
Hydrogen site location: difference Fourier map

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.11790 (3)	0	0.25	0.00993 (9)	0.986 (4)
Zr1	−0.01020 (3)	−0.01020 (3)	−0.01020 (3)	0.01011 (17)
O1	0.0963 (3)	0.1906 (3)	0.2735 (3)	0.0106 (6)
O2	0.0339 (3)	0.4448 (3)	0.1420 (3)	0.0138 (6)
Li1	0.375	0	0.25	0.0068 (7)	0.824 (3)
Ga1	0.375	0	0.25	0.0068 (7)	0.176 (3)
Li2	0.875	0	0.25	0.007*	0.34 (5)
Li3	0.070 (16)	0.283 (15)	0.457 (16)	0.01*	0.04 (3)
H1	0.104 (11)	0.183 (10)	0.321 (8)	0.025*	0.65 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00856 (14)	0.00800 (14)	0.01322 (16)	0	0	0.00411 (10)
Zr1	0.01011 (17)	0.01011 (17)	0.01011 (17)	−0.00033 (13)	−0.00033 (13)	−0.00033 (13)
O1	0.0076 (11)	0.0106 (13)	0.0135 (14)	−0.0005 (10)	−0.0005 (10)	0.0019 (10)
O2	0.0191 (15)	0.0128 (14)	0.0095 (13)	0.0025 (11)	0.0030 (10)	0.0032 (11)
Li1	0.0055 (13)	0.0075 (10)	0.0075 (10)	0	0	0
Ga1	0.0055 (13)	0.0075 (10)	0.0075 (10)	0	0	0

Geometric parameters (Å, º) top

La1—Li3ⁱ	2.5 (2)	O2—La1^xvi	2.603 (4)
La1—Li3ⁱⁱ	2.5 (2)	Li1—Li3ⁱⁱⁱ	1.5 (2)
La1—O1ⁱⁱⁱ	2.514 (3)	Li1—Li3ⁱⁱ	1.5 (2)
La1—O1^iv	2.514 (3)	Li1—Li3^iv	1.5 (2)
La1—O1^v	2.525 (3)	Li1—Li3ⁱ	1.5 (2)
La1—O1	2.525 (3)	Li1—O1ⁱ	1.987 (4)
La1—O2^vi	2.539 (4)	Li1—O1^iv	1.987 (4)
La1—O2^vii	2.539 (4)	Li1—O1ⁱⁱⁱ	1.987 (4)
La1—O2ⁱⁱⁱ	2.603 (4)	Li1—O1ⁱⁱ	1.987 (4)
La1—O2^iv	2.603 (4)	Li1—La1^xx	3.3596 (4)
La1—Li3^viii	2.7 (2)	Li1—Zr1^xxi	3.5997 (1)
La1—Li3^ix	2.7 (2)	Li1—Zr1^xxii	3.5997 (1)
Zr1—O1^x	2.031 (3)	Li2—O2^xxiii	1.982 (4)
Zr1—O1^xi	2.031 (3)	Li2—O2^xxiv	1.982 (4)
Zr1—O1^viii	2.031 (3)	Li2—O2^xxv	1.982 (4)
Zr1—O2^iv	2.187 (4)	Li2—O2^xix	1.982 (4)
Zr1—O2^xii	2.187 (4)	Li2—La1^xx	3.1740 (4)
Zr1—O2^vi	2.187 (4)	Li2—La1^xxvi	3.1740 (4)
Zr1—Li3^xiii	2.9 (2)	Li2—Li3^xxvii	3.2 (2)
Zr1—Li3^xiv	2.9 (2)	Li2—Li3^xxviii	3.2 (2)
Zr1—Li3^vii	2.9 (2)	Li2—Li3^xxix	3.2 (2)
Zr1—La1^xi	3.5178 (5)	Li2—Li3^xxx	3.2 (2)
Zr1—La1^xv	3.5178 (5)	Li3—O1^xviii	0.9 (2)
Zr1—La1^x	3.5178 (5)	Li3—Ga1^xvi	1.5 (2)
O1—Li3^ix	0.9 (2)	Li3—Li1^xvi	1.5 (2)
O1—Ga1^xvi	1.987 (4)	Li3—Li3^vi	2.0 (4)
O1—Li1^xvi	1.987 (4)	Li3—O1^ix	2.4 (2)
O1—Zr1^xvii	2.031 (3)	Li3—La1^xxxi	2.5 (2)
O1—Li3^xviii	2.4 (2)	Li3—Li3^xviii	2.6 (4)
O1—La1^xvi	2.514 (3)	Li3—Li3^ix	2.6 (4)
O2—Li2^xix	1.982 (4)	Li3—La1^xviii	2.7 (2)
O2—Zr1^vi	2.187 (4)	Li3—Zr1^xxxii	2.9 (2)
O2—La1^vi	2.539 (4)	Li3—Li2^xxxiii	3.2 (2)

Li3ⁱ—La1—Li3ⁱⁱ	48 (9)	Li3ⁱⁱ—Li1—Li3ⁱ	86 (10)
Li3ⁱ—La1—O1ⁱⁱⁱ	57 (5)	Li3^iv—Li1—Li3ⁱ	122 (10)
Li3ⁱⁱ—La1—O1ⁱⁱⁱ	20 (5)	Li3ⁱⁱⁱ—Li1—O1ⁱ	24 (8)
Li3ⁱ—La1—O1^iv	20 (5)	Li3ⁱⁱ—Li1—O1ⁱ	140 (8)
Li3ⁱⁱ—La1—O1^iv	57 (5)	Li3^iv—Li1—O1ⁱ	87 (8)
O1ⁱⁱⁱ—La1—O1^iv	72.06 (16)	Li3ⁱ—Li1—O1ⁱ	102 (8)
Li3ⁱ—La1—O1^v	89 (5)	Li3ⁱⁱⁱ—Li1—O1^iv	140 (8)
Li3ⁱⁱ—La1—O1^v	103 (5)	Li3ⁱⁱ—Li1—O1^iv	87 (8)
O1ⁱⁱⁱ—La1—O1^v	123.13 (7)	Li3^iv—Li1—O1^iv	102 (8)
O1^iv—La1—O1^v	68.54 (15)	Li3ⁱ—Li1—O1^iv	24 (8)
Li3ⁱ—La1—O1	103 (5)	O1ⁱ—Li1—O1^iv	116.47 (11)
Li3ⁱⁱ—La1—O1	89 (5)	Li3ⁱⁱⁱ—Li1—O1ⁱⁱⁱ	102 (8)
O1ⁱⁱⁱ—La1—O1	68.54 (15)	Li3ⁱⁱ—Li1—O1ⁱⁱⁱ	24 (8)
O1^iv—La1—O1	123.13 (7)	Li3^iv—Li1—O1ⁱⁱⁱ	140 (8)
O1^v—La1—O1	167.17 (15)	Li3ⁱ—Li1—O1ⁱⁱⁱ	87 (8)
Li3ⁱ—La1—O2^vi	165 (5)	O1ⁱ—Li1—O1ⁱⁱⁱ	116.47 (11)
Li3ⁱⁱ—La1—O2^vi	118 (5)	O1^iv—Li1—O1ⁱⁱⁱ	96.2 (2)
O1ⁱⁱⁱ—La1—O2^vi	108.54 (10)	Li3ⁱⁱⁱ—Li1—O1ⁱⁱ	87 (8)
O1^iv—La1—O2^vi	161.05 (10)	Li3ⁱⁱ—Li1—O1ⁱⁱ	102 (8)
O1^v—La1—O2^vi	97.21 (12)	Li3^iv—Li1—O1ⁱⁱ	24 (8)
O1—La1—O2^vi	72.54 (11)	Li3ⁱ—Li1—O1ⁱⁱ	140 (8)
Li3ⁱ—La1—O2^vii	118 (5)	O1ⁱ—Li1—O1ⁱⁱ	96.2 (2)
Li3ⁱⁱ—La1—O2^vii	165 (5)	O1^iv—Li1—O1ⁱⁱ	116.47 (11)
O1ⁱⁱⁱ—La1—O2^vii	161.05 (10)	O1ⁱⁱⁱ—Li1—O1ⁱⁱ	116.47 (11)
O1^iv—La1—O2^vii	108.54 (10)	Li3ⁱⁱⁱ—Li1—La1	137 (8)
O1^v—La1—O2^vii	72.54 (11)	Li3ⁱⁱ—Li1—La1	43 (8)
O1—La1—O2^vii	97.21 (12)	Li3^iv—Li1—La1	137 (8)
O2^vi—La1—O2^vii	77.23 (18)	Li3ⁱ—Li1—La1	43 (8)
Li3ⁱ—La1—O2ⁱⁱⁱ	64 (5)	O1ⁱ—Li1—La1	131.89 (10)
Li3ⁱⁱ—La1—O2ⁱⁱⁱ	102 (5)	O1^iv—Li1—La1	48.11 (10)
O1ⁱⁱⁱ—La1—O2ⁱⁱⁱ	96.82 (12)	O1ⁱⁱⁱ—Li1—La1	48.11 (10)
O1^iv—La1—O2ⁱⁱⁱ	71.66 (11)	O1ⁱⁱ—Li1—La1	131.89 (10)
O1^v—La1—O2ⁱⁱⁱ	107.49 (10)	Li3ⁱⁱⁱ—Li1—La1^xx	43 (8)
O1—La1—O2ⁱⁱⁱ	74.13 (11)	Li3ⁱⁱ—Li1—La1^xx	137 (8)
O2^vi—La1—O2ⁱⁱⁱ	126.12 (8)	Li3^iv—Li1—La1^xx	43 (8)
O2^vii—La1—O2ⁱⁱⁱ	66.40 (16)	Li3ⁱ—Li1—La1^xx	137 (8)
Li3ⁱ—La1—O2^iv	102 (5)	O1ⁱ—Li1—La1^xx	48.11 (10)
Li3ⁱⁱ—La1—O2^iv	64 (5)	O1^iv—Li1—La1^xx	131.89 (10)
O1ⁱⁱⁱ—La1—O2^iv	71.66 (11)	O1ⁱⁱⁱ—Li1—La1^xx	131.89 (10)
O1^iv—La1—O2^iv	96.82 (12)	O1ⁱⁱ—Li1—La1^xx	48.11 (10)
O1^v—La1—O2^iv	74.13 (11)	La1—Li1—La1^xx	180
O1—La1—O2^iv	107.49 (10)	Li3ⁱⁱⁱ—Li1—Zr1^xxi	50 (8)
O2^vi—La1—O2^iv	66.40 (16)	Li3ⁱⁱ—Li1—Zr1^xxi	152 (8)
O2^vii—La1—O2^iv	126.12 (8)	Li3^iv—Li1—Zr1^xxi	85 (8)
O2ⁱⁱⁱ—La1—O2^iv	166.09 (15)	Li3ⁱ—Li1—Zr1^xxi	80 (8)
Li3ⁱ—La1—Li3^viii	108 (9)	O1ⁱ—Li1—Zr1^xxi	26.66 (10)
Li3ⁱⁱ—La1—Li3^viii	117 (2)	O1^iv—Li1—Zr1^xxi	90.62 (10)
O1ⁱⁱⁱ—La1—Li3^viii	136 (5)	O1ⁱⁱⁱ—Li1—Zr1^xxi	130.13 (10)
O1^iv—La1—Li3^viii	88 (4)	O1ⁱⁱ—Li1—Zr1^xxi	103.79 (10)
O1^v—La1—Li3^viii	19 (4)	La1—Li1—Zr1^xxi	119.390 (8)
O1—La1—Li3^viii	148 (4)	La1^xx—Li1—Zr1^xxi	60.610 (8)
O2^vi—La1—Li3^viii	79 (4)	Li3ⁱⁱⁱ—Li1—Zr1^xxii	152 (8)
O2^vii—La1—Li3^viii	63 (5)	Li3ⁱⁱ—Li1—Zr1^xxii	85 (8)
O2ⁱⁱⁱ—La1—Li3^viii	114 (4)	Li3^iv—Li1—Zr1^xxii	80 (8)
O2^iv—La1—Li3^viii	72 (4)	Li3ⁱ—Li1—Zr1^xxii	50 (8)
Li3ⁱ—La1—Li3^ix	117 (2)	O1ⁱ—Li1—Zr1^xxii	130.13 (10)
Li3ⁱⁱ—La1—Li3^ix	108 (9)	O1^iv—Li1—Zr1^xxii	26.66 (10)
O1ⁱⁱⁱ—La1—Li3^ix	88 (4)	O1ⁱⁱⁱ—Li1—Zr1^xxii	103.79 (10)
O1^iv—La1—Li3^ix	136 (5)	O1ⁱⁱ—Li1—Zr1^xxii	90.62 (10)
O1^v—La1—Li3^ix	148 (4)	La1—Li1—Zr1^xxii	60.610 (8)
O1—La1—Li3^ix	19 (4)	La1^xx—Li1—Zr1^xxii	119.390 (8)
O2^vi—La1—Li3^ix	63 (5)	Zr1^xxi—Li1—Zr1^xxii	103.936 (7)
O2^vii—La1—Li3^ix	79 (4)	O2^xxiii—Li2—O2^xxiv	111.13 (11)
O2ⁱⁱⁱ—La1—Li3^ix	72 (4)	O2^xxiii—Li2—O2^xxv	106.2 (2)
O2^iv—La1—Li3^ix	114 (4)	O2^xxiv—Li2—O2^xxv	111.13 (11)
Li3^viii—La1—Li3^ix	131 (9)	O2^xxiii—Li2—O2^xix	111.13 (11)
O1^x—Zr1—O1^xi	88.64 (15)	O2^xxiv—Li2—O2^xix	106.2 (2)
O1^x—Zr1—O1^viii	88.64 (15)	O2^xxv—Li2—O2^xix	111.13 (11)
O1^xi—Zr1—O1^viii	88.64 (15)	O2^xxiii—Li2—La1^xx	53.10 (10)
O1^x—Zr1—O2^iv	173.91 (17)	O2^xxiv—Li2—La1^xx	126.90 (10)
O1^xi—Zr1—O2^iv	96.82 (14)	O2^xxv—Li2—La1^xx	53.10 (10)
O1^viii—Zr1—O2^iv	94.15 (14)	O2^xix—Li2—La1^xx	126.90 (10)
O1^x—Zr1—O2^xii	96.82 (14)	O2^xxiii—Li2—La1^xxvi	126.90 (10)
O1^xi—Zr1—O2^xii	94.15 (14)	O2^xxiv—Li2—La1^xxvi	53.10 (10)
O1^viii—Zr1—O2^xii	173.91 (17)	O2^xxv—Li2—La1^xxvi	126.90 (10)
O2^iv—Zr1—O2^xii	80.15 (16)	O2^xix—Li2—La1^xxvi	53.10 (10)
O1^x—Zr1—O2^vi	94.15 (14)	La1^xx—Li2—La1^xxvi	180
O1^xi—Zr1—O2^vi	173.91 (17)	O2^xxiii—Li2—Li3^xxvii	169 (4)
O1^viii—Zr1—O2^vi	96.82 (14)	O2^xxiv—Li2—Li3^xxvii	76 (4)
O2^iv—Zr1—O2^vi	80.15 (16)	O2^xxv—Li2—Li3^xxvii	78 (4)
O2^xii—Zr1—O2^vi	80.15 (16)	O2^xix—Li2—Li3^xxvii	58 (4)
O1^x—Zr1—Li3^xiii	89 (4)	La1^xx—Li2—Li3^xxvii	130 (4)
O1^xi—Zr1—Li3^xiii	3 (4)	La1^xxvi—Li2—Li3^xxvii	50 (4)
O1^viii—Zr1—Li3^xiii	92 (4)	O2^xxiii—Li2—Li3^xxviii	58 (4)
O2^iv—Zr1—Li3^xiii	96 (4)	O2^xxiv—Li2—Li3^xxviii	169 (4)
O2^xii—Zr1—Li3^xiii	91 (4)	O2^xxv—Li2—Li3^xxviii	76 (4)
O2^vi—Zr1—Li3^xiii	171 (4)	O2^xix—Li2—Li3^xxviii	78 (4)
O1^x—Zr1—Li3^xiv	3 (4)	La1^xx—Li2—Li3^xxviii	50 (4)
O1^xi—Zr1—Li3^xiv	92 (4)	La1^xxvi—Li2—Li3^xxviii	130 (4)
O1^viii—Zr1—Li3^xiv	89 (4)	Li3^xxvii—Li2—Li3^xxviii	115 (4)
O2^iv—Zr1—Li3^xiv	171 (4)	O2^xxiii—Li2—Li3^xxix	76 (4)
O2^xii—Zr1—Li3^xiv	96 (4)	O2^xxiv—Li2—Li3^xxix	78 (4)
O2^vi—Zr1—Li3^xiv	91 (4)	O2^xxv—Li2—Li3^xxix	58 (4)
Li3^xiii—Zr1—Li3^xiv	92 (6)	O2^xix—Li2—Li3^xxix	169 (4)
O1^x—Zr1—Li3^vii	92 (4)	La1^xx—Li2—Li3^xxix	50 (4)
O1^xi—Zr1—Li3^vii	89 (4)	La1^xxvi—Li2—Li3^xxix	130 (4)
O1^viii—Zr1—Li3^vii	3 (4)	Li3^xxvii—Li2—Li3^xxix	115 (4)
O2^iv—Zr1—Li3^vii	91 (4)	Li3^xxviii—Li2—Li3^xxix	99 (7)
O2^xii—Zr1—Li3^vii	171 (4)	O2^xxiii—Li2—Li3^xxx	78 (4)
O2^vi—Zr1—Li3^vii	96 (4)	O2^xxiv—Li2—Li3^xxx	58 (4)
Li3^xiii—Zr1—Li3^vii	92 (6)	O2^xxv—Li2—Li3^xxx	169 (4)
Li3^xiv—Zr1—Li3^vii	92 (6)	O2^xix—Li2—Li3^xxx	76 (4)
O1^x—Zr1—La1^xi	94.85 (10)	La1^xx—Li2—Li3^xxx	130 (4)
O1^xi—Zr1—La1^xi	44.88 (10)	La1^xxvi—Li2—Li3^xxx	50 (4)
O1^viii—Zr1—La1^xi	44.58 (10)	Li3^xxvii—Li2—Li3^xxx	99 (7)
O2^iv—Zr1—La1^xi	90.93 (10)	Li3^xxviii—Li2—Li3^xxx	115 (4)
O2^xii—Zr1—La1^xi	136.97 (10)	Li3^xxix—Li2—Li3^xxx	115 (4)
O2^vi—Zr1—La1^xi	139.95 (10)	O1^xviii—Li3—Ga1^xvi	113 (10)
Li3^xiii—Zr1—La1^xi	48 (4)	O1^xviii—Li3—Li1^xvi	113 (10)
Li3^xiv—Zr1—La1^xi	97 (4)	Ga1^xvi—Li3—Li1^xvi	0
Li3^vii—Zr1—La1^xi	45 (4)	O1^xviii—Li3—Li3^vi	106 (10)
O1^x—Zr1—La1^xv	44.58 (10)	Ga1^xvi—Li3—Li3^vi	47 (8)
O1^xi—Zr1—La1^xv	94.85 (10)	Li1^xvi—Li3—Li3^vi	47 (8)
O1^viii—Zr1—La1^xv	44.88 (10)	O1^xviii—Li3—O1^ix	122 (10)
O2^iv—Zr1—La1^xv	136.97 (10)	Ga1^xvi—Li3—O1^ix	56 (7)
O2^xii—Zr1—La1^xv	139.95 (10)	Li1^xvi—Li3—O1^ix	56 (7)
O2^vi—Zr1—La1^xv	90.93 (10)	Li3^vi—Li3—O1^ix	20 (7)
Li3^xiii—Zr1—La1^xv	97 (4)	O1^xviii—Li3—La1^xxxi	81 (10)
Li3^xiv—Zr1—La1^xv	45 (4)	Ga1^xvi—Li3—La1^xxxi	113 (10)
Li3^vii—Zr1—La1^xv	48 (4)	Li1^xvi—Li3—La1^xxxi	113 (10)
La1^xi—Zr1—La1^xv	69.360 (12)	Li3^vi—Li3—La1^xxxi	66 (5)
O1^x—Zr1—La1^x	44.88 (10)	O1^ix—Li3—La1^xxxi	62 (5)
O1^xi—Zr1—La1^x	44.58 (10)	O1^xviii—Li3—Li3^xviii	89 (10)
O1^viii—Zr1—La1^x	94.85 (10)	Ga1^xvi—Li3—Li3^xviii	29 (5)
O2^iv—Zr1—La1^x	139.95 (10)	Li1^xvi—Li3—Li3^xviii	29 (5)
O2^xii—Zr1—La1^x	90.93 (10)	Li3^vi—Li3—Li3^xviii	67 (5)
O2^vi—Zr1—La1^x	136.97 (10)	O1^ix—Li3—Li3^xviii	81 (5)
Li3^xiii—Zr1—La1^x	45 (4)	La1^xxxi—Li3—Li3^xviii	127 (9)
Li3^xiv—Zr1—La1^x	48 (4)	O1^xviii—Li3—Li3^ix	135 (10)
Li3^vii—Zr1—La1^x	97 (4)	Ga1^xvi—Li3—Li3^ix	29 (5)
La1^xi—Zr1—La1^x	69.360 (12)	Li1^xvi—Li3—Li3^ix	29 (5)
La1^xv—Zr1—La1^x	69.360 (12)	Li3^vi—Li3—Li3^ix	67 (5)
Li3^ix—O1—Ga1^xvi	43 (10)	O1^ix—Li3—Li3^ix	66 (5)
Li3^ix—O1—Li1^xvi	43 (10)	La1^xxxi—Li3—Li3^ix	127 (9)
Ga1^xvi—O1—Li1^xvi	0	Li3^xviii—Li3—Li3^ix	46 (10)
Li3^ix—O1—Zr1^xvii	170 (10)	O1^xviii—Li3—La1^xviii	71 (10)
Ga1^xvi—O1—Zr1^xvii	127.29 (18)	Ga1^xvi—Li3—La1^xviii	145 (10)
Li1^xvi—O1—Zr1^xvii	127.29 (18)	Li1^xvi—Li3—La1^xviii	145 (10)
Li3^ix—O1—Li3^xviii	54 (10)	Li3^vi—Li3—La1^xviii	168 (4)
Ga1^xvi—O1—Li3^xviii	38 (5)	O1^ix—Li3—La1^xviii	153 (9)
Li1^xvi—O1—Li3^xviii	38 (5)	La1^xxxi—Li3—La1^xviii	102 (7)
Zr1^xvii—O1—Li3^xviii	117 (5)	Li3^xviii—Li3—La1^xviii	124 (10)
Li3^ix—O1—La1^xvi	79 (10)	Li3^ix—Li3—La1^xviii	124 (10)
Ga1^xvi—O1—La1^xvi	95.85 (13)	O1^xviii—Li3—Zr1^xxxii	7 (10)
Li1^xvi—O1—La1^xvi	95.85 (13)	Ga1^xvi—Li3—Zr1^xxxii	106 (10)
Zr1^xvii—O1—La1^xvi	100.89 (14)	Li1^xvi—Li3—Zr1^xxxii	106 (10)
Li3^xviii—O1—La1^xvi	61 (5)	Li3^vi—Li3—Zr1^xxxii	99 (10)
Li3^ix—O1—La1	89 (10)	O1^ix—Li3—Zr1^xxxii	116 (8)
Ga1^xvi—O1—La1	122.52 (15)	La1^xxxi—Li3—Zr1^xxxii	81 (5)
Li1^xvi—O1—La1	122.52 (15)	Li3^xviii—Li3—Zr1^xxxii	84 (8)
Zr1^xvii—O1—La1	100.55 (13)	Li3^ix—Li3—Zr1^xxxii	129 (10)
Li3^xviii—O1—La1	142 (5)	La1^xviii—Li3—Zr1^xxxii	78 (5)
La1^xvi—O1—La1	105.20 (13)	O1^xviii—Li3—Li2^xxxiii	133 (10)
Li2^xix—O2—Zr1^vi	126.18 (19)	Ga1^xvi—Li3—Li2^xxxiii	113 (10)
Li2^xix—O2—La1^vi	88.28 (13)	Li1^xvi—Li3—Li2^xxxiii	113 (10)
Zr1^vi—O2—La1^vi	106.46 (15)	Li3^vi—Li3—Li2^xxxiii	113 (10)
Li2^xix—O2—La1^xvi	123.00 (16)	O1^ix—Li3—Li2^xxxiii	93 (6)
Zr1^vi—O2—La1^xvi	104.36 (15)	La1^xxxi—Li3—Li2^xxxiii	90 (6)
La1^vi—O2—La1^xvi	102.25 (13)	Li3^xviii—Li3—Li2^xxxiii	131 (10)
Li3ⁱⁱⁱ—Li1—Li3ⁱⁱ	122 (10)	Li3^ix—Li3—Li2^xxxiii	87 (8)
Li3ⁱⁱⁱ—Li1—Li3^iv	86 (10)	La1^xviii—Li3—Li2^xxxiii	65 (4)
Li3ⁱⁱ—Li1—Li3^iv	122 (10)	Zr1^xxxii—Li3—Li2^xxxiii	140 (7)
Li3ⁱⁱⁱ—Li1—Li3ⁱ	122 (10)

Symmetry codes: (i) −z+3/4, −y+1/4, x+1/4; (ii) −z+3/4, y−1/4, −x+1/4; (iii) z, x, y; (iv) z, −x, −y+1/2; (v) x, −y, −z+1/2; (vi) −x, −y+1/2, z; (vii) −x, y−1/2, −z+1/2; (viii) y−1/4, x−1/4, z−1/4; (ix) y−1/4, −x+1/4, −z+3/4; (x) x−1/4, z−1/4, y−1/4; (xi) z−1/4, y−1/4, x−1/4; (xii) −y+1/2, z, −x; (xiii) −z+1/2, −x, y−1/2; (xiv) y−1/2, −z+1/2, −x; (xv) −y−1/4, x−1/4, −z+1/4; (xvi) y, z, x; (xvii) y+1/4, x+1/4, z+1/4; (xviii) −y+1/4, x+1/4, −z+3/4; (xix) −x+1, −y+1/2, z; (xx) −x+3/4, z−1/4, −y+1/4; (xxi) −x+1/2, −y, z+1/2; (xxii) y+1/4, −x−1/4, −z+1/4; (xxiii) x+3/4, z−1/4, y−1/4; (xxiv) −x+1, y−1/2, −z+1/2; (xxv) x+3/4, −z+1/4, −y+3/4; (xxvi) x+1, y, z; (xxvii) y+3/4, −x+1/4, −z+3/4; (xxviii) −y+1, −z+1/2, x; (xxix) −y+1, z−1/2, −x+1/2; (xxx) y+3/4, x−1/4, z−1/4; (xxxi) z−1/4, −y+1/4, −x+3/4; (xxxii) −x, y+1/2, −z+1/2; (xxxiii) −y+1/4, x−3/4, −z+3/4.

Selected geometric parameters (Å) top

LLZO-Al15-pristine
La1—O1ⁱ	2.5110 (17)	Li2—O1	1.854 (15)
La1—O1	2.5951 (17)	Li2—O1^vii	2.085 (14)
Zr1—O1ⁱⁱ	2.1076 (16)	Li2—O1^vi	2.159 (15)
Li1—Li2ⁱⁱⁱ	1.616 (14)	Li2—O1^viii	2.242 (14)
Li1—O1^iv	1.9044 (17)	Li2—Li2^viii	2.46 (2)
Li1—Li2^v	2.367 (14)	Li2—O1^ix	2.646 (14)
Li2—Li2^vi	0.79 (3)

LLZO-Al15-hydro-150C
La1—O1ⁱ	2.506 (3)	Zr1B—O2^xii	2.06 (3)
La1—O1	2.518 (3)	Zr1B—O2^iv	2.10 (3)
La1—O2^x	2.544 (3)	Zr1B—O1ⁱⁱ	2.14 (3)
La1—O2ⁱ	2.607 (3)	Zr1B—O1^xiv	2.19 (3)
Zr1A—O1^xi	2.007 (4)	Zr1B—O1^xi	2.36 (3)
Zr1A—O2^xii	2.217 (4)	Li1—O1^xv	1.998 (3)
Zr1B—O2^xiii	1.85 (3)	Li2—O2^xvi	1.976 (3)

LLZO-Ga40-pristine
La1—O2^xiii	2.4935 (19)	Li2—O2^xvi	1.9246 (19)
La1—O1ⁱ	2.5264 (19)	Li2—Li3^xviii	2.340 (9)
La1—O2ⁱ	2.587 (2)	Li3—O1	1.878 (14)
La1—O1^xvii	2.5975 (19)	Li3—O1^vii	2.075 (8)
Zr1—O2^xiii	2.0823 (18)	Li3—O2ⁱ	2.108 (9)
Zr1—O1ⁱⁱ	2.1346 (18)	Li3—O1^viii	2.229 (8)
Li1—Li3ⁱⁱⁱ	1.645 (8)	Li3—Li3^vii	2.513 (13)
Li1—O1^xv	1.8941 (18)	Li3—O2^vii	2.639 (8)

LLZO-Ga40-hydro-150C
La1—O1ⁱ	2.514 (3)	Li1—Li3ⁱⁱⁱ	1.5 (2)
La1—O1^xvii	2.525 (3)	Li1—O1^xv	1.987 (4)
La1—O2^xiii	2.539 (4)	Li2—O2^xvi	1.982 (4)
La1—O2ⁱ	2.603 (4)	Li2—Li3^xviii	3.2 (2)
Zr1—O1ⁱⁱ	2.031 (3)	Li3—O1^vii	2.4 (2)
Zr1—O2^xiii	2.187 (4)	Li3—Li3^viii	2.6 (4)

Symmetry codes: (i) z, x, y; (ii) x-1/4, z-1/4, y-1/4; (iii) -z+3/4, y-1/4, -x+1/4; (iv) z, -x, -y+1/2; (v) -y+1/2, z-1/2, x; (vi) -x+1/4, z-1/4, y+1/4; (vii) y-1/4, -x+1/4, -z+3/4; (viii) -y+1/4, x+1/4, -z+3/4; (ix) y, -z+1/2, x+1/2; (x) -x, y-1/2, -z+1/2; (xi) z-1/4, y-1/4, x-1/4; (xii) -y+1/2, z, -x; (xiii) -x, -y+1/2, z; (xiv) y-1/4, x-1/4, z-1/4; (xv) -z+3/4, -y+1/4, x+1/4; (xvi) x+3/4, -z+1/4, -y+3/4; (xvii) x, -y, -z+1/2; (xviii) y+3/4, -x+1/4, -z+3/4.

References

Awaka, J., Kijima, N., Hayakawa, H. & Akimoto, J. (2009). J. Solid State Chem. 182, 2046–2052. Web of Science CrossRef ICSD CAS Google Scholar
Baxter, E. F., Caddick, M. J. & Ague, J. J. (2013). Elements, 9, 415–419. Web of Science CrossRef CAS Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Mallamo, M., Mazzone, A., Polidori, G. & Spagna, R. (2012). J. Appl. Cryst. 45, 357–361. Web of Science CrossRef CAS IUCr Journals Google Scholar
Buschmann, H., Dölle, J., Berendts, S., Kuhn, A., Bottke, P., Wilkening, M., Heitjans, P., Senyshyn, A., Ehrenberg, H., Lotnyk, A., Duppel, V., Kienle, L. & Janek, J. (2011). Phys. Chem. Chem. Phys. 13, 19378–19392. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Cussen, E. (2010). Functional Oxides, edited by D. W. Bruce, D. O'Hare & R. I. Walton, pp. 119–202: London: John Wiley & Sons Ltd. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Galven, C., Dittmer, J., Suard, E., Le Berre, F. & Crosnier-Lopez, M.-P. (2012). Chem. Mater. 24, 3335–3345. CrossRef CAS Google Scholar
Galven, C., Fourquet, J.-L., Crosnier-Lopez, M.-P. & Le Berre, F. (2011). Chem. Mater. 23, 1892–1900. Web of Science CrossRef ICSD CAS Google Scholar
Galven, C., Suard, E., Mounier, D., Crosnier-Lopez, M.-P. & Le Berre, F. (2013). J. Mater. Res. 28, 2147–2153. Web of Science CrossRef CAS Google Scholar
Geiger, C. A. (2013). Elements, 9, 447–452. Web of Science CrossRef CAS Google Scholar
Geiger, C. A., Alekseev, E., Lazic, B., Fisch, M., Armbruster, T., Langner, R., Fechtelkord, M., Kim, N., Pettke, T. & Weppner, W. (2011). Inorg. Chem. 50, 1089–1097. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Hiebl, C., Young, D., Wagner, R., Wilkening, H. M. R., Redhammer, G. J. & Rettenwander, D. (2019). J. Phys. Chem. C, 123, 1094–1098. Web of Science CrossRef CAS Google Scholar
Lager, G. A., Armbruster, T. & Faber, J. (1987). Am. Mineral. 72, 756–765. CAS Google Scholar
Larraz, G., Orera, A. & Sanjuán, M. L. (2013). J. Mater. Chem. A, 1, 11419–11428. Web of Science CrossRef CAS Google Scholar
Larraz, G., Orera, A., Sanz, J., Sobrados, I., Diez-Gómez, V. & Sanjuán, M. L. (2015). J. Mater. Chem. A, 3, 5683–5691. Web of Science CrossRef CAS Google Scholar
Liu, X., Chen, Y., Hood, Z. D., Ma, C., Yu, S., Sharafi, A., Wang, H., An, K., Sakamoto, J., Siegel, D. J., Cheng, Y., Jalarvo, N. H. & Chi, M. (2019). Energy Environ. Sci. 12, 945–951. Web of Science CrossRef CAS Google Scholar
Ma, C., Rangasamy, E., Liang, C., Sakamoto, J., More, K. L. & Chi, M. (2015). Angew. Chem. Int. Ed. 54, 129–133. Web of Science CrossRef CAS Google Scholar
Murugan, R., Thangadurai, V. & Weppner, W. (2007). Angew. Chem. Int. Ed. 46, 7778–7781. Web of Science CrossRef CAS Google Scholar
Novak, G. A. & Gibbs, G. V. (1971). Am. Mineral. 56, 791–825. CAS Google Scholar
Orera, A., Larraz, G., Rodríguez-Velamazán, J. A., Campo, J. & Sanjuán, M. L. (2016). Inorg. Chem. 55, 1324–1332. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Redhammer, G. J., Badami, P., Meven, M., Ganschow, S., Berendts, S., Tippelt, G. & Rettenwander, D. (2021a). Appl. Mater. Interfaces, 13, 350–359. Web of Science CrossRef CAS Google Scholar
Redhammer, G. J., Tippelt, G., Portenkirchner, A. & Rettenwander, D. (2021b). Crystals, 11, 721. Web of Science CrossRef ICSD Google Scholar
Rettenwander, D., Redhammer, G., Preishuber-Pflügl, F., Cheng, L., Miara, L., Wagner, R., Welzl, A., Suard, E., Doeff, M. M., Wilkening, M., Fleig, J. & Amthauer, G. (2016). Chem. Mater. 28, 2384–2392. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Robben, L., Merzlyakova, E., Heitjans, P. & Gesing, T. M. (2016). Acta Cryst. E72, 287–289. Web of Science CrossRef ICSD IUCr Journals Google Scholar
Samson, A. J., Hofstetter, K., Bag, S. & Thangadurai, V. (2019). Energy Environ. Sci. 12, 2957–2975. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Wagner, R., Redhammer, G. J., Rettenwander, D., Senyshyn, A., Schmidt, W., Wilkening, M. & Amthauer, G. (2016a). Chem. Mater. 28, 1861–1871. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Wagner, R., Redhammer, G. J., Rettenwander, D., Tippelt, G., Welzl, A., Taibl, S., Fleig, J., Franz, A., Lottermoser, W. & Amthauer, G. (2016b). Chem. Mater. 28, 5943–5951. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Wang, C., Fu, K., Kammampata, S. P., McOwen, D. W., Samson, A. J., Zhang, L., Hitz, G. T., Nolan, A. M., Wachsman, E. D., Mo, Y., Thangadurai, V. & Hu, L. (2020). Chem. Rev. 120, 4257–4300. Web of Science CrossRef CAS PubMed Google Scholar
Yow, Z. F., Oh, Y. L., Gu, W. Y., Rao, R. P. & Adams, S. (2016). Solid State Ionics, 292, 122–129. Web of Science CrossRef CAS Google Scholar

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Volume 78| Part 1| January 2022| Pages 1-6

https://doi.org/10.1107/S2053229621012250

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