Li₃Al(MoO₄)₃, a lyonsite molybdate

Trilithium aluminium trimolybdate(VI), Li₃Al(MoO₄)₃, has been grown as single crystals from α-Al₂O₃ and MoO₃ in an Li₂MoO₄ flux at 998 K. This compound is an example of the well known lyonsite structure type, the general formula of which can be written as A₁₆B₁₂O₄₈. Because this structure can accomodate cationic mixing as well as cationic vacancies, a wide range of chemical compositions can adopt this structure type. This has led to instances in the literature where membership in the lyonsite family has been overlooked when assigning the structure type to novel compounds. In the title compound, there are two octa­hedral sites with substitutional disorder between Li⁺ and Al³⁺, as well as a trigonal prismatic site fully occupied by Li⁺. The (Li,Al)O₆ octa­hedra and LiO₆ trigonal prisms are linked to form hexa­gonal tunnels along the [100] axis. These polyhedra are connected by isolated MoO₄ tetra­hedra. Infinite chains of face-sharing (Li,Al)O₆ octa­hedra extend through the centers of the tunnels. A mixed Li/Al site, an Li, an Mo, and two O atoms are located on mirror planes.

S1. Comment

Although its namesake mineral, α-Cu₃Fe₄(VO₄)₆, was not structurally characterized until much later [Reference needed?], the lyonsite crystal structure was first observed in 1964 in NaCo_2.31(MoO₄)₃ (Ibers & Smith, 1964). An excellent review of this structure type was published recently (Smit et al., 2006). The general formula for the lyonsite family of compounds can be written as A₁₆B₁₂O₄₈ (or A₁₆(BO₄)₁₂ or A₄(BO₄)₃). The A cations, with octahedral and trigonal prismatic coordination environments, most commonly have formal oxidation states of +1, +2 or +3, though some examples have been found with cations in higher oxidation states, such as Ti⁴⁺ (Smit et al., 2008) and Nb⁵⁺ (Smit et al., 2006). The tetrahedral B cations in lyonsite consist exclusively of V⁵⁺, Mo⁶⁺ and W⁶⁺. Typically, there is a mixture of two cations on the A site, or sometimes cationic vacancies, in order to preserve overall electroneutrality.

The lyonsite crystal structure (Fig. 1) features isolated BO₄ tetrahedra which are interconnected by AO₆ octahedra and trigonal prisms. The octahedra and trigonal prisms form hexagonal tunnels in the [100] direction. The BO₄ tetrahedra line the interior of these tunnels, and infinite chains of face-sharing AO₆ octahedra extend through the center of the tunnels. The AO₆ octahedra in the hexagonal tunnels share edges to form columns, while the AO₆ trigonal prisms share edges to form zigzag sheets. When there are multiple A cations, the larger ones tend to be localized on the more geometrically accomodating trigonal prismatic site. Because the face-sharing octahedra in the infinite chains possess the shortest A···A interatomic distances, cationic vacancies, when present, are concentrated on this site to reduce coulombic repulsions.

The title compound crystallizes in space group Pnma of the orthorhombic system with the lyonsite structure type. Previously, only the unit-cell parameters of Li₃Al(MoO₄)₃ had been reported on the basis of indexing of powder X-ray diffraction data (Klevtsov, 1970). Here, we report the first high-quality single-crystal X-ray diffraction structure determination. The crystals were prepared by a high-temperature solution reaction where Li₂MoO₄ served as the flux. Alkali molybdates are commonly used as flux for the growth of single crystals of complex molybdenum-containing oxides (Bugaris & zur Loye, 2012).

In Li₃Al(MoO₄)₃ (Fig. 2), the B sites are occupied by Mo⁶⁺ cations tetrahedrally coordinated by oxide anions. The Mo—O bond distances in the title compound are in the range 1.7244 (17)–1.7937 (16) Å [average 1.766 (5) Å]. These interatomic distances are consistent with those for the isostructural compound, Li₃Ga(MoO₄)₃ (van der Lee et al., 2008), which are in the range 1.734 (2)–1.795 (2) Å. The O—Mo—O angles of 104.01 (12)–116.13 (12)° correspond to a nearly regular MoO₄ tetrahedron.

The A cationic sites in the title compound are occupied by a mixture of Li⁺ and Al³⁺ cations in a 3:1 ratio necessary to preserve charge electroneutrality. The trigonal prismatic sites are occupied completely by Li⁺ cations, while the octahedral sites are occupied by a mixture of Li⁺ and Al³⁺ cations. The edge-sharing AO₆ octahedra in the hexagonal tunnels contain 72.1 (2)% Li⁺, while the face-sharing AO₆ octahedra in the infinite chains contain 55.8 (5)% Li⁺. As the ionic radius of six-coordinate Al³⁺ is significantly smaller than that of six-coordinate Li⁺ (0.535 Å versus 0.76 Å; Shannon, 1976), it is to be expected that a higher percentage of Al³⁺ is found on the face-sharing octahedral site in order to alleviate coulombic repulsions. No Al³⁺ is found on the trigonal prismatic site, consistent with the fact that this latter site is more accomodating towards a larger cation, in this case Li⁺. A similar separation of large and small cations into trigonal prismatic and octahedral sites is observed in the 2H-perovskite related oxide structure type (zur Loye et al., 2012).

Other compounds belonging to the Li₃M³⁺(MoO₄)₃ family of compounds with the lyonsite structure type exhibit disorder of the Li⁺ and M³⁺ cations on the A sites. The edge-sharing AO₆ octahedral sites contain 70 (1), 69.2 (1), 66.67, 71.91 (17) and 75% of Li⁺, while the face-sharing AO₆ octahedral sites contain 56 (1), 61.7 (1), 66.67, 57.9 (3) and 58% of Li⁺, for M = V³⁺ (Mikhailova et al., 2010), Cr³⁺ (Sarapulova et al., 2009), Fe³⁺ (Klevtsova & Magarill, 1970), Ga³⁺ (van der Lee et al., 2008) and Sc³⁺ (Kolitsch & Tillmanns, 2003), respectively. With regard to the examples containing V³⁺, Cr³⁺, Fe³⁺ and Ga³⁺, the trigonal prismatic site is occupied entirely by Li⁺. For Li₃Sc(MoO₄)₃, the trigonal prismatic site contains 92% Li⁺ and 8% Sc³⁺. The appearance of Sc³⁺ on the trigonal prismatic site can be attributed to the larger ionic radius of six-coordinate Sc³⁺ (0.745 Å), which is approaching the size of six-coordinate Li⁺. The ionic radii of six-coordinate Cr³⁺ (0.615 Å), Ga³⁺ (0.62 Å), V³⁺ (0.64 Å) and Fe³⁺ (0.645 Å) are significantly smaller than that of Li⁺, so as in the title compound, none of these cations is found on the trigonal prismatic site.

In Li₃Al(MoO₄)₃, the Li/Al—O bond distances in the edge-sharing octahedra are in the range 2.003 (2)–2.143 (3) Å. For the face-sharing octahedra, the Li/Al—O interatomic distances are in the range 1.957 (2)–2.023 (3) Å. The bond lengths are shorter for the face-sharing octahedra because a higher concentration of the smaller Al³⁺ cation is found on those sites. Finally, the Li—O interatomic distances in the trigonal prisms are in the range 2.103 (5)–2.222 (6) Å.

The Li-ion conductivity of various Li-containing lyonsite materials has been investigated for their potential application as electrolyte materials in Li-ion batteries (Sebastian et al., 2003). It was determined that, although the lyonsite crystal structure is a three-dimensional framework, the conduction pathway of the Li⁺ ions is limited to the zigzag sheets of edge-sharing trigonal prisms. Therefore, it is to be expected that compounds with a greater concentration of Li⁺ on the trigonal prismatic sites would exhibit higher ionic conductivities. For example, the ionic conductivities measured for Li₃Cr(MoO₄)₃ and Li₃Fe(MoO₄)₃ were higher than those of the Li_2-2xMg_2+x(MoO₄)₃ series of compounds. In the Cr- and Fe-containing materials, the trigonal prismatic sites are fully occupied by Li⁺, whereas in the Mg-containing materials, the trigonal prismatic sites are occupied by a mixture of Li⁺ and Mg²⁺. It would be interesting to measure the ionic conductivity of the title compound, Li₃Al(MoO₄)₃, which contains only Li⁺ on the trigonal prismatic sites, in order to ascertain whether the ionic conductivity is comparable with or higher than the Cr- and Fe-containing materials.

Related literature

For related literature, see: Bugaris & zur Loye (2012); Ibers & Smith (1964); Klevtsov (1970); Klevtsova & Magarill (1970); Kolitsch & Tillmanns (2003); Lee et al. (2008); Loye et al. (2012); Mikhailova et al. (2010); Sarapulova et al. (2009); Sebastian et al. (2003); Shannon (1976); Smit et al. (2006, 2008).

S2. Experimental

Colorless prismatic crystals of Li₃Al(MoO₄)₃ were grown from a mixture of Li₂MoO₄ (Alfa Aesar, 99+%), α-Al₂O₃ (Alfa Aesar, 99.9%), and MoO₃ (Alfa Aesar, 99.95%). The Li₂MoO₄ was dried overnight at 423 K to remove any adsorbed water. The starting reagents α-Al₂O₃ (0.10196 g, 1 mmol), and MoO₃ (0.14394 g, 1 mmol), with Li₂MoO₄ (0.43455 g, 2.5 mmol) acting as both a source of Li and a flux, were ground together thoroughly using a mortar and pestle. The mixture was transferred to an alumina crucible, covered loosely and placed in a furnace. The mixture was heated at a rate of 200 K h^-1 to 998 K, where it was held for 12 h, before cooling at a rate of 2 K h^-1 to 773 K, at which point it was allowed to cool rapidly to room temperature. The excess lithium molybdate flux was removed by washing with hot water, aided by sonication, and colorless prismatic crystals of the title compound were isolated by vacuum filtration.

S3. Refinement

A model with substitutional disorder between Li and Al was proposed for this compound. Similar disorder was observed in the isostructural compounds Li₃M³⁺(MoO₄)₃ (M = V, Cr, Fe, Ga, Sc). The occupancies of the Li1/Al1 and Li2/Al2 crystallographic sites were constrained to 1.00, whereas restraints with an s.u. value of 0.001 were used for keeping the total number of Li atoms in the structural formula at 3.0 and the total number of Al atoms in the structural formula at 1.0, i.e. occupancy(Li1) + 0.5 × occupancy(Li2) = 1.0, and occupancy(Al1) + 0.5 × occupancy(Al2) = 0.5. There is no evidence in the refinement for the presence of Al on the trigonal prismatic site (100% Li).

The largest positive and negative residual electron densities of 0.804 and -0.763 e Å^-3 are located 0.76 and 0.58 Å, respectively, from atom Mo1.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2012); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures

	Fig. 1. Polyhedral representation of the lyonsite crystal structure type. In the electronic version of the paper, edge-sharing AO6 octahedra are shown in blue, face-sharing AO6 octahedra in brown, AO6 trigonal prisms in green and BO4 tetrahedra in gray.
	Fig. 2. Ball-and-stick representation of the crystal structure of Li3Al(MoO4)3, as viewed down [100]. In the electronic version of the paper, the blue spheres are Li^+ and Al^3+ cations [72.1 (2):27.9 (2)], the brown spheres are Li^+ and Al^3+ cations [55.8 (5):44.2 (4)], the green spheres are Li^+ cations, the gray spheres are Mo^6+ cations and the red spheres are O^2- anions.

Trilithium aluminium trimolybdate(VI)

Crystal data

Li3Al(MoO4)3	F(000) = 976
Mr = 527.62	Dx = 3.903 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 4199 reflections
a = 5.0372 (10) Å	θ = 2.3–32.1°
b = 10.320 (2) Å	µ = 4.29 mm^−1
c = 17.272 (4) Å	T = 298 K
V = 897.8 (3) Å^3	Prism, colourless
Z = 4	0.07 × 0.07 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1606 independent reflections
Radiation source: fine-focus sealed tube	1414 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 32.1°, θmin = 2.3°
Absorption correction: numerical (SADABS; Sheldrick, 2008)	h = −7→7
Tmin = 0.661, Tmax = 0.746	k = −15→15
14109 measured reflections	l = −25→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0235P)^2 + 0.5382P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.048	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 0.80 e Å^−3
1606 reflections	Δρmin = −0.76 e Å^−3
99 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.00156 (18)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Li1	−0.2424 (3)	0.07138 (18)	0.52567 (10)	0.0143 (4)	0.721 (2)
Al1	−0.2424 (3)	0.07138 (18)	0.52567 (10)	0.0143 (4)	0.279 (2)
Li2	0.3952 (3)	0.2500	0.25035 (9)	0.0097 (4)	0.558 (5)
Al2	0.3952 (3)	0.2500	0.25035 (9)	0.0097 (4)	0.442 (4)
Li3	−0.2535 (12)	0.2500	0.6959 (4)	0.0249 (13)
Mo1	0.21939 (5)	0.2500	0.442175 (14)	0.01130 (7)
Mo2	−0.27972 (4)	−0.023570 (18)	0.343878 (10)	0.01200 (7)
O1	0.1429 (5)	0.2500	0.34148 (13)	0.0192 (5)
O2	0.4216 (4)	0.11598 (16)	0.46301 (9)	0.0212 (4)
O3	−0.0569 (5)	0.2500	0.50654 (13)	0.0240 (5)
O4	0.1446 (4)	0.12339 (15)	0.20699 (9)	0.0176 (3)
O5	−0.0798 (4)	0.01325 (17)	0.42573 (9)	0.0193 (3)
O6	−0.4391 (3)	0.11071 (16)	0.62544 (10)	0.0212 (3)
O7	−0.0816 (4)	−0.12129 (17)	0.28713 (10)	0.0242 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.0123 (8)	0.0180 (8)	0.0125 (8)	−0.0009 (6)	−0.0002 (6)	0.0039 (6)
Al1	0.0123 (8)	0.0180 (8)	0.0125 (8)	−0.0009 (6)	−0.0002 (6)	0.0039 (6)
Li2	0.0095 (8)	0.0097 (8)	0.0099 (7)	0.000	−0.0007 (6)	0.000
Al2	0.0095 (8)	0.0097 (8)	0.0099 (7)	0.000	−0.0007 (6)	0.000
Li3	0.024 (3)	0.027 (3)	0.024 (3)	0.000	−0.004 (2)	0.000
Mo1	0.01160 (12)	0.01323 (13)	0.00908 (12)	0.000	−0.00015 (8)	0.000
Mo2	0.01278 (10)	0.01106 (10)	0.01214 (10)	0.00103 (6)	−0.00103 (6)	0.00171 (6)
O1	0.0300 (13)	0.0135 (11)	0.0140 (10)	0.000	−0.0036 (9)	0.000
O2	0.0235 (9)	0.0216 (9)	0.0185 (8)	0.0028 (7)	−0.0018 (7)	0.0006 (6)
O3	0.0186 (12)	0.0364 (15)	0.0169 (11)	0.000	0.0002 (9)	0.000
O4	0.0245 (8)	0.0133 (7)	0.0150 (7)	0.0006 (7)	0.0004 (6)	−0.0015 (6)
O5	0.0167 (8)	0.0252 (9)	0.0161 (7)	−0.0001 (7)	0.0001 (6)	0.0013 (6)
O6	0.0239 (8)	0.0166 (8)	0.0230 (8)	−0.0045 (7)	−0.0059 (7)	0.0017 (6)
O7	0.0215 (9)	0.0261 (9)	0.0252 (9)	0.0064 (7)	−0.0017 (7)	−0.0057 (7)

Geometric parameters (Å, º)

Li1—O5	2.003 (2)	Li3—Li3^xii	3.136 (8)
Li1—O5^i	2.025 (2)	Li3—Li1^vi	3.471 (6)
Li1—O6	2.029 (2)	Mo1—O2	1.7550 (17)
Li1—O2^ii	2.061 (2)	Mo1—O2^vi	1.7550 (17)
Li1—O3	2.093 (2)	Mo1—O3	1.781 (3)
Li1—O2^i	2.143 (3)	Mo1—O1	1.781 (2)
Li1—Al1^i	2.987 (3)	Mo1—Li1^vi	3.2999 (17)
Li1—Li1^i	2.987 (3)	Mo1—Li1^viii	3.3647 (19)
Li1—Li1^iii	3.113 (3)	Mo1—Li1^i	3.3647 (19)
Li1—Al1^iii	3.113 (3)	Mo2—O7	1.7244 (17)
Li1—Mo2	3.2946 (18)	Mo2—O6^iii	1.7595 (17)
Li1—Mo1	3.2999 (17)	Mo2—O5	1.7770 (17)
Li2—O4^iv	1.957 (2)	Mo2—O4^vii	1.7937 (16)
Li2—O4^v	1.957 (2)	Mo2—Li1^iii	3.3337 (17)
Li2—O4^vi	1.965 (2)	Mo2—Li2^vii	3.3757 (10)
Li2—O4	1.965 (2)	O1—Al2^vii	2.018 (3)
Li2—O1^v	2.018 (3)	O1—Li2^vii	2.018 (3)
Li2—O1	2.023 (3)	O2—Al1^xiii	2.061 (2)
Li2—Al2^v	2.5186 (5)	O2—Li1^xiii	2.061 (2)
Li2—Li2^v	2.5186 (5)	O2—Al1^i	2.143 (3)
Li2—Li2^vii	2.5186 (5)	O2—Li1^i	2.143 (3)
Li2—Al2^vii	2.5186 (5)	O3—Al1^vi	2.093 (2)
Li2—Mo2^v	3.3756 (10)	O3—Li1^vi	2.093 (2)
Li2—Mo2^iv	3.3756 (10)	O4—Mo2^v	1.7936 (16)
Li3—O6	2.103 (5)	O4—Al2^vii	1.957 (2)
Li3—O6^vi	2.103 (5)	O4—Li2^vii	1.957 (2)
Li3—O7^viii	2.168 (5)	O5—Al1^i	2.025 (2)
Li3—O7^i	2.168 (5)	O5—Li1^i	2.025 (2)
Li3—O7^ix	2.222 (6)	O6—Mo2^iii	1.7595 (17)
Li3—O7^x	2.222 (6)	O7—Li3^i	2.168 (5)
Li3—Li3^xi	3.136 (8)	O7—Li3^xiv	2.222 (6)
O5—Li1—O5^i	84.27 (10)	O6—Li3—O6^vi	86.3 (3)
O5—Li1—O6	172.68 (12)	O6—Li3—O7^viii	147.5 (4)
O5^i—Li1—O6	97.21 (10)	O6^vi—Li3—O7^viii	90.32 (12)
O5—Li1—O2^ii	87.14 (9)	O6—Li3—O7^i	90.32 (12)
O5^i—Li1—O2^ii	166.42 (12)	O6^vi—Li3—O7^i	147.5 (4)
O6—Li1—O2^ii	90.03 (9)	O7^viii—Li3—O7^i	75.6 (2)
O5—Li1—O3	86.85 (10)	O6—Li3—O7^ix	130.8 (3)
O5^i—Li1—O3	95.01 (11)	O6^vi—Li3—O7^ix	80.53 (14)
O6—Li1—O3	100.13 (11)	O7^viii—Li3—O7^ix	80.15 (15)
O2^ii—Li1—O3	95.00 (11)	O7^i—Li3—O7^ix	124.2 (3)
O5—Li1—O2^i	88.90 (10)	O6—Li3—O7^x	80.53 (14)
O5^i—Li1—O2^i	84.87 (10)	O6^vi—Li3—O7^x	130.8 (3)
O6—Li1—O2^i	84.11 (9)	O7^viii—Li3—O7^x	124.2 (3)
O2^ii—Li1—O2^i	84.46 (9)	O7^i—Li3—O7^x	80.15 (15)
O3—Li1—O2^i	175.73 (12)	O7^ix—Li3—O7^x	73.4 (2)
O5—Li1—Al1^i	42.43 (7)	O6—Li3—Li3^xi	89.30 (15)
O5^i—Li1—Al1^i	41.85 (6)	O6^vi—Li3—Li3^xi	89.30 (15)
O6—Li1—Al1^i	138.60 (11)	O7^viii—Li3—Li3^xi	123.0 (3)
O2^ii—Li1—Al1^i	128.73 (11)	O7^i—Li3—Li3^xi	123.0 (3)
O3—Li1—Al1^i	91.28 (10)	O7^ix—Li3—Li3^xi	43.72 (19)
O2^i—Li1—Al1^i	85.78 (9)	O7^x—Li3—Li3^xi	43.72 (19)
O5—Li1—Li1^i	42.43 (7)	O6—Li3—Li3^xii	134.58 (13)
O5^i—Li1—Li1^i	41.85 (6)	O6^vi—Li3—Li3^xii	134.58 (13)
O6—Li1—Li1^i	138.60 (11)	O7^viii—Li3—Li3^xii	45.10 (8)
O2^ii—Li1—Li1^i	128.73 (11)	O7^i—Li3—Li3^xii	45.10 (8)
O3—Li1—Li1^i	91.28 (10)	O7^ix—Li3—Li3^xii	83.0 (3)
O2^i—Li1—Li1^i	85.78 (9)	O7^x—Li3—Li3^xii	83.0 (3)
O5—Li1—Li1^iii	87.35 (10)	Li3^xi—Li3—Li3^xii	106.9 (4)
O5^i—Li1—Li1^iii	125.59 (11)	O6—Li3—Li1^vi	83.1 (2)
O6—Li1—Li1^iii	85.97 (9)	O6^vi—Li3—Li1^vi	32.19 (12)
O2^ii—Li1—Li1^iii	43.24 (6)	O7^viii—Li3—Li1^vi	77.09 (15)
O3—Li1—Li1^iii	138.08 (12)	O7^i—Li3—Li1^vi	115.3 (3)
O2^i—Li1—Li1^iii	41.22 (6)	O7^ix—Li3—Li1^vi	106.81 (10)
Al1^i—Li1—Li1^iii	111.32 (11)	O7^x—Li3—Li1^vi	157.6 (3)
Li1^i—Li1—Li1^iii	111.32 (11)	Li3^xi—Li3—Li1^vi	121.18 (16)
O5—Li1—Al1^iii	87.35 (10)	Li3^xii—Li3—Li1^vi	119.46 (17)
O5^i—Li1—Al1^iii	125.59 (11)	O6—Li3—Li1	32.19 (12)
O6—Li1—Al1^iii	85.97 (9)	O6^vi—Li3—Li1	83.1 (2)
O2^ii—Li1—Al1^iii	43.24 (6)	O7^viii—Li3—Li1	115.3 (3)
O3—Li1—Al1^iii	138.08 (12)	O7^i—Li3—Li1	77.09 (15)
O2^i—Li1—Al1^iii	41.22 (6)	O7^ix—Li3—Li1	157.6 (3)
Al1^i—Li1—Al1^iii	111.32 (11)	O7^x—Li3—Li1	106.81 (10)
Li1^i—Li1—Al1^iii	111.32 (11)	Li3^xi—Li3—Li1	121.18 (16)
O5—Li1—Mo2	27.48 (6)	Li3^xii—Li3—Li1	119.46 (17)
O5^i—Li1—Mo2	108.21 (8)	Li1^vi—Li3—Li1	64.16 (13)
O6—Li1—Mo2	147.27 (9)	O2—Mo1—O2^vi	104.01 (12)
O2^ii—Li1—Mo2	61.25 (6)	O2—Mo1—O3	109.00 (7)
O3—Li1—Mo2	97.87 (8)	O2^vi—Mo1—O3	109.00 (7)
O2^i—Li1—Mo2	78.15 (7)	O2—Mo1—O1	109.01 (7)
Al1^i—Li1—Mo2	67.48 (6)	O2^vi—Mo1—O1	109.01 (7)
Li1^i—Li1—Mo2	67.48 (6)	O3—Mo1—O1	116.13 (12)
Li1^iii—Li1—Mo2	62.63 (6)	O2—Mo1—Li1	83.07 (7)
Al1^iii—Li1—Mo2	62.63 (6)	O2^vi—Mo1—Li1	139.45 (6)
O5—Li1—Mo1	60.15 (7)	O3—Mo1—Li1	34.56 (4)
O5^i—Li1—Mo1	81.78 (7)	O1—Mo1—Li1	105.91 (8)
O6—Li1—Mo1	127.13 (9)	O2—Mo1—Li1^vi	139.45 (6)
O2^ii—Li1—Mo1	102.98 (8)	O2^vi—Mo1—Li1^vi	83.07 (7)
O3—Li1—Mo1	28.86 (7)	O3—Mo1—Li1^vi	34.56 (3)
O2^i—Li1—Mo1	147.24 (9)	O1—Mo1—Li1^vi	105.91 (8)
Al1^i—Li1—Mo1	64.49 (6)	Li1—Mo1—Li1^vi	67.92 (6)
Li1^i—Li1—Mo1	64.49 (6)	O2—Mo1—Li1^viii	136.30 (6)
Li1^iii—Li1—Mo1	136.68 (8)	O2^vi—Mo1—Li1^viii	33.83 (7)
Al1^iii—Li1—Mo1	136.68 (8)	O3—Mo1—Li1^viii	85.64 (3)
Mo2—Li1—Mo1	77.87 (4)	O1—Mo1—Li1^viii	99.71 (3)
O4^iv—Li2—O4^v	83.79 (11)	Li1—Mo1—Li1^viii	120.19 (3)
O4^iv—Li2—O4^vi	96.43 (8)	Li1^vi—Mo1—Li1^viii	53.24 (5)
O4^v—Li2—O4^vi	179.69 (8)	O2—Mo1—Li1^i	33.83 (7)
O4^iv—Li2—O4	179.69 (8)	O2^vi—Mo1—Li1^i	136.30 (6)
O4^v—Li2—O4	96.43 (8)	O3—Mo1—Li1^i	85.64 (3)
O4^vi—Li2—O4	83.36 (12)	O1—Mo1—Li1^i	99.71 (3)
O4^iv—Li2—O1^v	84.20 (9)	Li1—Mo1—Li1^i	53.24 (5)
O4^v—Li2—O1^v	84.20 (9)	Li1^vi—Mo1—Li1^i	120.18 (3)
O4^vi—Li2—O1^v	95.60 (10)	Li1^viii—Mo1—Li1^i	160.59 (6)
O4—Li2—O1^v	95.60 (10)	O7—Mo2—O6^iii	109.77 (8)
O4^iv—Li2—O1	96.34 (9)	O7—Mo2—O5	104.43 (8)
O4^v—Li2—O1	96.34 (9)	O6^iii—Mo2—O5	109.03 (8)
O4^vi—Li2—O1	83.85 (9)	O7—Mo2—O4^vii	109.81 (8)
O4—Li2—O1	83.85 (9)	O6^iii—Mo2—O4^vii	114.12 (8)
O1^v—Li2—O1	179.27 (15)	O5—Mo2—O4^vii	109.23 (8)
O4^iv—Li2—Al2^v	50.19 (6)	O7—Mo2—Li1	133.05 (7)
O4^v—Li2—Al2^v	50.19 (6)	O6^iii—Mo2—Li1	84.89 (6)
O4^vi—Li2—Al2^v	129.83 (8)	O5—Mo2—Li1	31.33 (6)
O4—Li2—Al2^v	129.83 (8)	O4^vii—Mo2—Li1	103.15 (6)
O1^v—Li2—Al2^v	51.53 (9)	O7—Mo2—Li1^iii	135.68 (7)
O1—Li2—Al2^v	129.20 (13)	O6^iii—Mo2—Li1^iii	30.63 (6)
O4^iv—Li2—Li2^v	50.19 (6)	O5—Mo2—Li1^iii	84.45 (6)
O4^v—Li2—Li2^v	50.19 (6)	O4^vii—Mo2—Li1^iii	107.62 (6)
O4^vi—Li2—Li2^v	129.83 (8)	Li1—Mo2—Li1^iii	56.02 (5)
O4—Li2—Li2^v	129.83 (8)	O7—Mo2—Li2^vii	93.67 (7)
O1^v—Li2—Li2^v	51.53 (9)	O6^iii—Mo2—Li2^vii	141.51 (6)
O1—Li2—Li2^v	129.20 (13)	O5—Mo2—Li2^vii	93.25 (6)
O4^iv—Li2—Li2^vii	130.08 (8)	O4^vii—Mo2—Li2^vii	27.40 (6)
O4^v—Li2—Li2^vii	130.08 (8)	Li1—Mo2—Li2^vii	101.30 (4)
O4^vi—Li2—Li2^vii	49.90 (6)	Li1^iii—Mo2—Li2^vii	129.65 (4)
O4—Li2—Li2^vii	49.90 (6)	Mo1—O1—Al2^vii	154.31 (16)
O1^v—Li2—Li2^vii	127.92 (13)	Mo1—O1—Li2^vii	154.31 (16)
O1—Li2—Li2^vii	51.35 (9)	Mo1—O1—Li2	128.58 (15)
Al2^v—Li2—Li2^vii	179.45 (15)	Al2^vii—O1—Li2	77.11 (8)
Li2^v—Li2—Li2^vii	179.45 (15)	Li2^vii—O1—Li2	77.11 (8)
O4^iv—Li2—Al2^vii	130.08 (8)	Mo1—O2—Al1^xiii	139.49 (11)
O4^v—Li2—Al2^vii	130.08 (8)	Mo1—O2—Li1^xiii	139.49 (11)
O4^vi—Li2—Al2^vii	49.90 (6)	Mo1—O2—Al1^i	119.03 (10)
O4—Li2—Al2^vii	49.90 (6)	Al1^xiii—O2—Al1^i	95.54 (9)
O1^v—Li2—Al2^vii	127.92 (13)	Li1^xiii—O2—Al1^i	95.54 (9)
O1—Li2—Al2^vii	51.35 (9)	Mo1—O2—Li1^i	119.03 (10)
Al2^v—Li2—Al2^vii	179.45 (15)	Al1^xiii—O2—Li1^i	95.54 (9)
Li2^v—Li2—Al2^vii	179.45 (15)	Li1^xiii—O2—Li1^i	95.54 (9)
O4^iv—Li2—Mo2^v	155.18 (8)	Mo1—O3—Al1^vi	116.58 (8)
O4^v—Li2—Mo2^v	77.92 (5)	Mo1—O3—Li1^vi	116.58 (8)
O4^vi—Li2—Mo2^v	101.81 (7)	Mo1—O3—Li1	116.58 (8)
O4—Li2—Mo2^v	24.84 (5)	Al1^vi—O3—Li1	123.45 (16)
O1^v—Li2—Mo2^v	77.43 (5)	Li1^vi—O3—Li1	123.45 (16)
O1—Li2—Mo2^v	102.19 (5)	Mo2^v—O4—Al2^vii	152.31 (11)
Al2^v—Li2—Mo2^v	104.99 (5)	Mo2^v—O4—Li2^vii	152.31 (11)
Li2^v—Li2—Mo2^v	104.99 (5)	Mo2^v—O4—Li2	127.76 (10)
Li2^vii—Li2—Mo2^v	74.73 (4)	Al2^vii—O4—Li2	79.92 (6)
Al2^vii—Li2—Mo2^v	74.73 (4)	Li2^vii—O4—Li2	79.92 (6)
O4^iv—Li2—Mo2^iv	77.92 (5)	Mo2—O5—Li1	121.19 (11)
O4^v—Li2—Mo2^iv	155.18 (8)	Mo2—O5—Al1^i	133.77 (11)
O4^vi—Li2—Mo2^iv	24.84 (5)	Li1—O5—Al1^i	95.73 (10)
O4—Li2—Mo2^iv	101.81 (7)	Mo2—O5—Li1^i	133.77 (11)
O1^v—Li2—Mo2^iv	77.43 (5)	Li1—O5—Li1^i	95.73 (10)
O1—Li2—Mo2^iv	102.19 (5)	Mo2^iii—O6—Li1	123.14 (10)
Al2^v—Li2—Mo2^iv	104.99 (5)	Mo2^iii—O6—Li3	122.2 (2)
Li2^v—Li2—Mo2^iv	104.99 (5)	Li1—O6—Li3	114.3 (2)
Li2^vii—Li2—Mo2^iv	74.73 (4)	Mo2—O7—Li3^i	137.1 (2)
Al2^vii—Li2—Mo2^iv	74.73 (4)	Mo2—O7—Li3^xiv	122.43 (18)
Mo2^v—Li2—Mo2^iv	113.51 (5)	Li3^i—O7—Li3^xiv	91.18 (18)

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