Symmetry reduction due to gallium substitution in the garnet Li6.43(2)Ga0.52(3)La2.67(4)Zr2O12.

Single-crystal structure refinements on lithium lanthanum zirconate (LLZO; Li7La3Zr2O12) substituted with gallium were successfully carried out in the cubic symmetry space group I [Formula: see text]3d. Gallium was found on two lithium sites as well as on the lanthanum position. Due to the structural distortion of the resulting Li6.43(2)Ga0.52(3)La2.67(4)Zr2O12 (Ga-LLZO) single crystals, a reduction of the LLZO cubic garnet symmetry from Ia[Formula: see text] d to I [Formula: see text]3d was necessary, which could hardly be analysed from X-ray powder diffraction data.

Chemical context

Garnets can be described with the ideal formula A 3 B 2(XO4)3 in space group Ia d, with different coordination polyhedra of the respective elements with oxygen, resulting in a distorted cube for A (e.g. Ca), an octa­hedron for B (e.g. Al) and a tetra­hedron for X (e.g. Si). The variability of the elements on the crystallographic sites (thereby keeping the high symmetry) gives rise to inter­esting material properties like ferrimagnetism (Geller, 1967 ▸). In recent years, garnet-type compounds containing Li have gained considerable inter­est as promising electrolyte materials for all-solid-state Li-ion batteries. The so-called ‘Li-stuffed’ garnets, which contain more Li than available on tetra­hedral sites (X), meaning that excess Li occupies other sites as well, show an increase in Li-ion mobility. An exhaustive overview of these compounds was recently given by Thangadurai et al. (2014 ▸). The garnet-type fast lithium ion conductor Li7La3Zr2O12, abbreviated as LLZO, is such an ‘Li-stuffed’ garnet. Awaka et al. (2009 ▸) described the crystal structure of pure LLZO at ambient conditions in space group I41/acd. Even a small amount of Al in the structure (Al-LLZO) stabilizes the cubic garnet symmetry described in space group Ia d by Geiger et al. (2011 ▸). These authors reported that Al could be found on two different tetra­hedral sites using 27Al MAS NMR spectroscopy but a final analysis was not possible due to the minor Al content. Rettenwander et al. (2014 ▸) reported on 71Ga MAS NMR spectroscopy measurements on gallium substituted Li7-3GaLa3Zr2O12 (Ga–LLZO) indicating a fourfold coordination of the gallium atoms. The authors excluded the presence of Ga at the 24d position (Ia d) and assumed that the local symmetry could be lower than indicated by diffraction methods. In principle, the following exchanges are possible: (i) 3 Li+ ↔ Ga3+ + 2 voids, which is the most probable one and yields a good explanation for the higher conductivity due to the higher lithium atom jump probability to empty positions as discussed (Rettenwander et al., 2014 ▸); (ii) La3+ ↔ Ga3+, a valence-neutral exchange which should lead to a dynamical disorder of the gallium atoms in order to lower the coordination number and shorten the Ga—O bond lengths for bond-valence balance, taking the different radii into account. The valence-neutral exchange should finally lead to higher displacement parameters of the atoms on the lanthanum position compared to that of the lighter zirconium atoms. (iii) Zr4+ ↔ Ga3+ + Li+, which needs slightly more lithium for charge balance and could therefore be of minor probability.

Structural commentary

The unit cell of the obtained single crystals could be well indexed using a body-centered cubic lattice with lattice parameter a = 12.9681 (15) Å. The space group determination with XPREP (Bruker, 2014 ▸) leads at once to the highest possible space group Ia d. However, a satisfactory structure solution or refinement with published structural data (Geiger et al., 2011 ▸) in this space group type was not possible. Consequently, structure solutions by charge flipping (Bruker, 2009 ▸) were tried in all possible subgroups of Ia d and the lowest R-values were obtained for the charge-flipping run in space group I 3d. Subsequent refinements lead to the present structure model and clearly indicate the substitution of Ga3+ on the former 24c La3+ site as well as 24d Li+ site in the aristotype in space group Ia d. The latter site splits into two sites due to the symmetry reduction as indicated by the Bärnighausen tree (Bärnig­hausen, 1980 ▸) given in Fig. 1 ▸. The deviation from six symmetry-equivalent Zr—O distances in LLZO (Ia d) results in a distortion of the ZrO6 octa­hedron with Zr—O distances of 3 × 2.095 (2) and 3 × 2.113 (2) Å in Ga–LLZO. Another significant reduction of the highest possible symmetry for LLZO is the distortion of the eightfold coordinate La position (Fig. 2 ▸), for which distances between 2.496 (2) and 2.595 (2) Å are found in Ga–LLZO. This distortion results from the splitting of the 96h position of the oxygen atom in Ia d into two 48e positions in I 3d (Fig. 1 ▸). Because the two lithium positions (Li22 and Li32) occupied by gallium are in principle identical to those positions of the higher symmetry structure (but with slightly shorter bond length due to the gallium substitution, viz. 4 × 1.916 (1) Å in LLZO and 4 × 1.908 (2) Å in Ga–LLZO), and the Li1 and Li2 positions are not occupied by gallium, the symmetry reduction is a confirmation of gallium atoms to be found also on the lanthanum position. This is also supported by the higher displacement parameter of the La site compared to the Zr site, as explained previously.

Figure 1

Bärnighausen tree (Bärnighausen, 1980 ▸) of the group–subgroup relation between cubic LLZO and the symmetry-reduced cubic Ga–LLZO.

Figure 2

Crystal structure of Li6.43(2)Ga0.52(3)La2.67(4)Zr2O12 (Ga–LLZO) with all possible atom positions between the ZrO6 octa­hedra (bottom) and the atom position specific coordination polyhedra (top). Displacement ellipsoids (top) are given at the 50% probability level.

Synthesis and crystallization

The synthesis was configured to yield a compound with nominal composition Li6.25Ga0.25La3Zr2O12. 2 g of a stoichiometric mixture of the pre-dried (30 h at 373 K in vacuum) educts Li2O (with an excess of 10%wt to compensate the lithium loss due to thermal treatment), La2O3, ZrO2 and Ga2O3 was weighted into a WC milling beaker (45 ml, 100 WC milling balls of 5 mm diameter, Fritsch, Germany) under inert conditions (glovebox) and high-energy ball-milled in a planetary ball mill (Pulverisette 7 premium line, Fritsch, Germany) under argon atmosphere for 8 h at a rotational speed of 10 s−1 as reported previously (Düvel et al., 2012 ▸) for Al-substituted LLZO. The obtained powder was pressed to a pellet using a uniaxial pressure of 0.8 GPa. A stack of three pellets was placed on a platinum ring seated on a corundum plate, covered with a corundum crucible and heated for 12 h at 1323 K in a muffle furnace before cooling to room-temperature. The middle pellet from the stack had smooth green color and showed visible grains. The surface of the pellet was grey and brittle and consisted mainly of lanthanum zirconates due to Li loss. From this pellet single crystals were extracted using a polarization microscope. Rietveld refinement of X-ray powder diffraction data of the green product shows a mixture of 96.8 (9)%wt cubic garnet-type Ga–LLZO and 3.2 (9)%wt Li2ZrO3 with a lattice parameter of a = 12.9738 (19) Å for its garnet-type structure. Energy dispersive X-ray analysis of the single crystal gave a tentative formula of Li6.5 (1)Ga0.5 (1)La2.8 (1)Zr2.0 (1)O12, in good agreement with the refined formula Li6.43 (2)Ga0.52 (3)La2.67 (4)Zr2O12 determined from single crystal X-ray diffraction data.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. Structure refinement was carried out as a two-component (merohedral) twin. Sites showing a statistical occupancy were constrained with respect to positions and anisotropic displacement parameters. An independent refinement of the anisotropic displacement parameters of Ga and Li on the Ga2/Li22 and Ga3/Li33 sites was not possible, although the reflection-to-parameter ratio is rather high. To ensure charge neutrality during the refinement of the Ga and Li occupancies on the Ga2/Li22 and Ga3/Li33 sites, the occupancies were restrained to exchange three Li atoms against one Ga atom.

Table 1

Experimental details

Crystal data
Chemical formula	Li6.43Ga0.52La2.67Zr2O12
M r	826.20
Crystal system, space group	Cubic, I 3d
Temperature (K)	301
a (Å)	12.9681 (15)
V (Å3)	2180.9 (8)
Z	8
Radiation type	Mo Kα
μ (mm−1)	13.41
Crystal size (mm)	0.25 × 0.15 × 0.13
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.495, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	472450, 3678, 3508
R int	0.046
(sin θ/λ)max (Å−1)	1.340
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.026, 0.056, 1.46
No. of reflections	3678
No. of parameters	50
No. of restraints	3
Δρmax, Δρmin (e Å−3)	2.08, −1.91
Absolute structure	Flack x determined using 1493 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.045 (9)

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), TOPAS (Bruker, 2009 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016001924/wm5261sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016001924/wm5261Isup2.hkl

CCDC reference: 1451178

Additional supporting information: crystallographic information; 3D view; checkCIF report

Li6.43Ga0.52La2.67Zr2O12	Mo Kα radiation, λ = 0.71073 Å
Mr = 826.20	Cell parameters from 9913 reflections
Cubic, I43d	θ = 3.1–72.3°
a = 12.9681 (15) Å	µ = 13.41 mm−1
V = 2180.9 (8) Å3	T = 301 K
Z = 8	Irregular, green
F(000) = 340	0.25 × 0.15 × 0.13 mm
Dx = 5.033 Mg m−3

Bruker APEXII CCD diffractometer	3508 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 72.3°, θmin = 2.2°
Tmin = 0.495, Tmax = 0.754	h = −34→34
472450 measured reflections	k = −34→34
3678 independent reflections	l = −34→34

Refinement on F2	w = 1/[σ2(Fo2) + (0.011P)2 + 8.6617P] where P = (Fo2 + 2Fc2)/3
Least-squares matrix: full	(Δ/σ)max = 0.049
R[F2 > 2σ(F2)] = 0.026	Δρmax = 2.08 e Å−3
wR(F2) = 0.056	Δρmin = −1.91 e Å−3
S = 1.46	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3678 reflections	Absolute structure: Flack x determined using 1493 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
50 parameters	Absolute structure parameter: 0.045 (9)
3 restraints

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

Refinement. Refined as a 2-component twin.

	x	y	z	Uiso*/Ueq	Occ. (<1)
La1	0.62292 (2)	0.0000	0.2500	0.00746 (2)	0.889 (4)
Ga1	0.62292 (2)	0.0000	0.2500	0.00746 (2)	0.111 (4)
Zr1	0.25005 (2)	0.25005 (2)	0.25005 (2)	0.00552 (4)
O1	0.19586 (18)	0.28163 (18)	0.10116 (16)	0.0118 (3)
O2	0.46910 (17)	0.55410 (17)	0.65064 (16)	0.0114 (2)
Li1	0.428 (3)	0.593 (2)	0.813 (2)	0.029 (5)	0.33333 (14)
Li2	0.642 (3)	0.178 (2)	0.065 (2)	0.029 (5)	0.33333 (14)
Ga2	0.3750	0.5000	0.7500	0.0061 (4)	0.0857 (12)
Li22	0.3750	0.5000	0.7500	0.0061 (4)	0.743 (4)
Ga3	0.2500	0.3750	0.0000	0.0110 (9)	0.0403 (12)
Li32	0.2500	0.3750	0.0000	0.0110 (9)	0.879 (4)

	U11	U22	U33	U12	U13	U23
La1	0.00912 (4)	0.00656 (5)	0.00668 (5)	0.000	0.000	−0.00141 (3)
Ga1	0.00912 (4)	0.00656 (5)	0.00668 (5)	0.000	0.000	−0.00141 (3)
Zr1	0.00552 (4)	0.00552 (4)	0.00552 (4)	0.00021 (3)	0.00021 (3)	0.00021 (3)
O1	0.0129 (6)	0.0138 (6)	0.0087 (5)	0.0014 (5)	−0.0007 (5)	0.0006 (5)
O2	0.0131 (6)	0.0116 (6)	0.0096 (5)	0.0010 (5)	0.0000 (5)	−0.0013 (4)
Li1	0.051 (15)	0.015 (6)	0.022 (6)	−0.013 (9)	−0.013 (8)	0.006 (6)
Li2	0.051 (15)	0.015 (6)	0.022 (6)	−0.013 (9)	−0.013 (8)	0.006 (6)
Ga2	0.0078 (10)	0.0052 (6)	0.0052 (6)	0.000	0.000	0.000
Li22	0.0078 (10)	0.0052 (6)	0.0052 (6)	0.000	0.000	0.000
Ga3	0.0100 (14)	0.013 (2)	0.0100 (14)	0.000	0.000	0.000
Li32	0.0100 (14)	0.013 (2)	0.0100 (14)	0.000	0.000	0.000

La1—O1i	2.496 (2)	O2—Li2xxiii	2.09 (3)
La1—O1ii	2.496 (2)	O2—Zr1xxiv	2.113 (2)
La1—O2iii	2.520 (2)	O2—Li1	2.23 (4)
La1—O2iv	2.520 (2)	O2—La1xxv	2.520 (2)
La1—O2v	2.590 (2)	O2—Li2xxvi	2.54 (3)
La1—O2vi	2.590 (2)	O2—La1xxiii	2.590 (2)
La1—O1vii	2.595 (2)	O2—Li2xxvii	2.61 (4)
La1—O1viii	2.595 (2)	Li1—O2xxviii	1.91 (4)
Zr1—O1ix	2.095 (2)	Li1—O2xxii	2.04 (3)
Zr1—O1x	2.095 (2)	Li1—O1xxix	2.16 (3)
Zr1—O1	2.095 (2)	Li1—O1xxx	2.65 (3)
Zr1—O2xi	2.113 (2)	Li2—O1viii	1.90 (3)
Zr1—O2xii	2.113 (2)	Li2—O2vi	2.09 (3)
Zr1—O2xiii	2.113 (2)	Li2—O1xvi	2.22 (4)
O1—Li2xiv	1.90 (3)	Li2—O1xxxi	2.32 (3)
O1—Ga3	1.918 (2)	Li2—O2xxxii	2.54 (3)
O1—Li1xv	2.16 (3)	Li2—O2xxxiii	2.61 (4)
O1—Li2xvi	2.22 (4)	Li2—Li2xxxiv	2.68 (6)
O1—Li2xvii	2.32 (3)	Ga2—O2xxi	1.908 (2)
O1—La1xviii	2.496 (2)	Ga2—O2xxii	1.908 (2)
O1—La1xix	2.595 (2)	Ga2—O2xxviii	1.908 (2)
O1—Li1xx	2.65 (3)	Ga3—O1xxxv	1.918 (2)
O2—Ga2	1.908 (2)	Ga3—O1xxxvi	1.918 (2)
O2—Li1xxi	1.91 (4)	Ga3—O1xxxvii	1.918 (2)
O2—Li1xxii	2.04 (3)
O1i—La1—O1ii	73.18 (10)	La1xviii—O1—Li1xx	79.5 (6)
O1i—La1—O2iii	160.55 (5)	La1xix—O1—Li1xx	68.9 (8)
O1ii—La1—O2iii	111.27 (5)	Ga2—O2—Li1xxi	49.8 (10)
O1i—La1—O2iv	111.27 (5)	Ga2—O2—Li1xxii	48.0 (8)
O1ii—La1—O2iv	160.55 (5)	Li1xxi—O2—Li1xxii	77.4 (11)
O2iii—La1—O2iv	71.21 (10)	Ga2—O2—Li2xxiii	66.9 (11)
O1i—La1—O2v	73.18 (7)	Li1xxi—O2—Li2xxiii	18.2 (10)
O1ii—La1—O2v	95.73 (8)	Li1xxii—O2—Li2xxiii	85.1 (16)
O2iii—La1—O2v	123.67 (5)	Ga2—O2—Zr1xxiv	128.57 (12)
O2iv—La1—O2v	68.75 (9)	Li1xxi—O2—Zr1xxiv	104.4 (9)
O1i—La1—O2vi	95.73 (8)	Li1xxii—O2—Zr1xxiv	87.4 (8)
O1ii—La1—O2vi	73.18 (7)	Li2xxiii—O2—Zr1xxiv	88.5 (10)
O2iii—La1—O2vi	68.75 (9)	Ga2—O2—Li1	44.9 (8)
O2iv—La1—O2vi	123.67 (5)	Li1xxi—O2—Li1	72.9 (12)
O2v—La1—O2vi	166.44 (9)	Li1xxii—O2—Li1	85.9 (12)
O1i—La1—O1vii	125.03 (5)	Li2xxiii—O2—Li1	89.7 (13)
O1ii—La1—O1vii	68.53 (9)	Zr1xxiv—O2—Li1	173.2 (7)
O2iii—La1—O1vii	72.72 (6)	Ga2—O2—La1xxv	94.15 (8)
O2iv—La1—O1vii	94.96 (7)	Li1xxi—O2—La1xxv	143.6 (9)
O2v—La1—O1vii	73.07 (5)	Li1xxii—O2—La1xxv	80.5 (11)
O2vi—La1—O1vii	108.77 (5)	Li2xxiii—O2—La1xxv	161.0 (11)
O1i—La1—O1viii	68.53 (9)	Zr1xxiv—O2—La1xxv	103.05 (9)
O1ii—La1—O1viii	125.03 (5)	Li1—O2—La1xxv	77.0 (9)
O2iii—La1—O1viii	94.96 (7)	Ga2—O2—Li2xxvi	57.6 (8)
O2iv—La1—O1viii	72.72 (6)	Li1xxi—O2—Li2xxvi	76.3 (11)
O2v—La1—O1viii	108.77 (5)	Li1xxii—O2—Li2xxvi	99.9 (14)
O2vi—La1—O1viii	73.07 (5)	Li2xxiii—O2—Li2xxvi	91.0 (11)
O1vii—La1—O1viii	165.12 (9)	Zr1xxiv—O2—Li2xxvi	172.6 (9)
O1ix—Zr1—O1x	86.37 (10)	Li1—O2—Li2xxvi	14.0 (8)
O1ix—Zr1—O1	86.37 (10)	La1xxv—O2—Li2xxvi	79.4 (7)
O1x—Zr1—O1	86.37 (10)	Ga2—O2—La1xxiii	122.63 (10)
O1ix—Zr1—O2xi	93.51 (9)	Li1xxi—O2—La1xxiii	95.8 (10)
O1x—Zr1—O2xi	179.59 (11)	Li1xxii—O2—La1xxiii	170.6 (8)
O1—Zr1—O2xi	94.02 (9)	Li2xxiii—O2—La1xxiii	90.4 (8)
O1ix—Zr1—O2xii	94.02 (9)	Zr1xxiv—O2—La1xxiii	100.77 (8)
O1x—Zr1—O2xii	93.51 (9)	Li1—O2—La1xxiii	85.8 (7)
O1—Zr1—O2xii	179.59 (11)	La1xxv—O2—La1xxiii	101.98 (8)
O2xi—Zr1—O2xii	86.10 (9)	Li2xxvi—O2—La1xxiii	71.8 (9)
O1ix—Zr1—O2xiii	179.59 (11)	Ga2—O2—Li2xxvii	56.1 (7)
O1x—Zr1—O2xiii	94.02 (9)	Li1xxi—O2—Li2xxvii	83.4 (14)
O1—Zr1—O2xiii	93.51 (9)	Li1xxii—O2—Li2xxvii	8.2 (9)
O2xi—Zr1—O2xiii	86.10 (9)	Li2xxiii—O2—Li2xxvii	89.2 (9)
O2xii—Zr1—O2xiii	86.10 (9)	Zr1xxiv—O2—Li2xxvii	80.4 (7)
Li2xiv—O1—Ga3	55.1 (12)	Li1—O2—Li2xxvii	93.0 (11)
Li2xiv—O1—Zr1	100.2 (12)	La1xxv—O2—Li2xxvii	78.2 (6)
Ga3—O1—Zr1	129.12 (12)	Li2xxvi—O2—Li2xxvii	107.0 (12)
Li2xiv—O1—Li1xv	17.3 (11)	La1xxiii—O2—Li2xxvii	178.8 (7)
Ga3—O1—Li1xv	71.3 (8)	O2xxviii—Li1—O2xxii	108.5 (14)
Zr1—O1—Li1xv	84.8 (8)	O2xxviii—Li1—O1xxix	98.6 (18)
Li2xiv—O1—Li2xvi	80.8 (13)	O2xxii—Li1—O1xxix	93.9 (12)
Ga3—O1—Li2xvi	50.0 (9)	O2xxviii—Li1—O2	101.2 (12)
Zr1—O1—Li2xvi	85.8 (9)	O2xxii—Li1—O2	86.8 (14)
Li1xv—O1—Li2xvi	87.3 (14)	O1xxix—Li1—O2	158.9 (18)
Li2xiv—O1—Li2xvii	78.1 (15)	O2xxviii—Li1—O1xxx	144.7 (15)
Ga3—O1—Li2xvii	48.2 (10)	O2xxii—Li1—O1xxx	106.5 (15)
Zr1—O1—Li2xvii	177.3 (10)	O1xxix—Li1—O1xxx	83.1 (9)
Li1xv—O1—Li2xvii	93.8 (10)	O2—Li1—O1xxx	76.4 (12)
Li2xvi—O1—Li2xvii	91.8 (16)	O1viii—Li2—O2vi	101.0 (12)
Li2xiv—O1—La1xviii	147.5 (13)	O1viii—Li2—O1xvi	102.1 (17)
Ga3—O1—La1xviii	92.55 (8)	O2vi—Li2—O1xvi	91.1 (12)
Zr1—O1—La1xviii	103.48 (9)	O1viii—Li2—O1xxxi	98.5 (14)
Li1xv—O1—La1xviii	163.4 (9)	O2vi—Li2—O1xxxi	160.3 (14)
Li2xvi—O1—La1xviii	79.1 (7)	O1xvi—Li2—O1xxxi	82.0 (13)
Li2xvii—O1—La1xviii	77.3 (7)	O1viii—Li2—O2xxxii	151.8 (19)
Li2xiv—O1—La1xix	94.7 (9)	O2vi—Li2—O2xxxii	86.9 (13)
Ga3—O1—La1xix	123.13 (10)	O1xvi—Li2—O2xxxii	104.8 (10)
Zr1—O1—La1xix	100.26 (9)	O1viii—Li2—O2xxxiii	84.1 (12)
Li1xv—O1—La1xix	89.9 (10)	O2vi—Li2—O2xxxiii	85.2 (14)
Li2xvi—O1—La1xix	173.1 (9)	O1xvi—Li2—O2xxxiii	173.3 (16)
Li2xvii—O1—La1xix	82.1 (10)	O1xxxi—Li2—O2xxxiii	99.7 (11)
La1xviii—O1—La1xix	102.50 (8)	O2xxxii—Li2—O2xxxiii	69.5 (10)
Li2xiv—O1—Li1xx	81.4 (12)	O2xxi—Ga2—O2xxii	114.14 (7)
Ga3—O1—Li1xx	60.5 (8)	O2xxi—Ga2—O2xxviii	100.49 (13)
Zr1—O1—Li1xx	169.2 (8)	O2xxii—Ga2—O2xxviii	114.14 (7)
Li1xv—O1—Li1xx	95.1 (9)	O1—Ga3—O1xxxv	113.48 (7)
Li2xvi—O1—Li1xx	105.0 (14)	O1—Ga3—O1xxxvi	101.73 (14)
Li2xvii—O1—Li1xx	13.3 (11)	O1xxxv—Ga3—O1xxxvi	113.48 (7)