Li2GeMo3O8: a novel reduced molybdenum oxide containing Mo3O13 cluster units

Gall, P.; Gougeon, P.

doi:10.1107/S2056989016009750

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Volume 72| Part 7| July 2016| Pages 995-997

https://doi.org/10.1107/S2056989016009750

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Li₂GeMo₃O₈: a novel reduced molybdenum oxide containing Mo₃O₁₃ cluster units

Philippe Gall ^a and Patrick Gougeon ^a ^*

^aInstitut des Sciences, Chimiques de Rennes, UMR 6226 CNRS – INSA Rennes – Université de Rennes 1, Avenue du Général Leclerc, 35042 Rennes Cedex, France
^*Correspondence e-mail: patrick.gougeon@univ-rennes1.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 June 2016; accepted 15 June 2016; online 21 June 2016)

The crystal structure of the title compound, dilithium germanium trimolybdenum octaoxide, consists of distorted hexagonal-close-packed oxygen layers with stacking sequence ABAC along [001] that are held together by alternating lithium–germanium and molybdenum layers. The two Li⁺ and Ge⁴⁺ ions all have site symmetry 3m. and occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atom has a formal oxidation state of +3.3 and occupies an octahedral site (site symmetry .m.) and forms strongly bonded triangular cluster units [Mo—Mo distance = 2.4728 (8) Å] involving three MoO₆ octahedra that are each shared along two edges, constituting an Mo₃O₁₃ unit.

Keywords: crystal structure; reduced molybdenum oxide; triangular Mo₃ cluster; lithium; germanium.

CCDC reference: 1485831

1. Chemical context

Reduced molybdenum oxides containing the Mo₃O₁₃ cluster unit crystallize either in the hexagonal space group type P6₃mc (a ∼ 5.7–5.8 Å, c ∼ 10.0–10.2 Å) or in the trigonal space group types P3m1 (a ∼ 5.7–5.8 Å, c ∼ 4.9–5.3 Å) or R $[\overline{3}]$ m (a ∼ 5.8–5.9 Å, c ∼ 30.0–30.1 Å). Representatives of the first family are the ternary compounds M₂Mo₃O₈ (McCarroll et al., 1957 ) where M is a divalent metal such as Mg, Zn, Fe, Co, Ni, Zn and Cd as well as the quaternary compounds ScZnMo₃O₈ and Li₂MMo₃O₈ (M = Sn, In) (Gall et al., 2013a ,b ). The LiRMo₃O₈ series (R = Sc, Y, In, Sm, Gd, Tb, Dy, Ho, Er and Yb) (DeBenedittis & Katz, 1965 ; McCarroll, 1977 ) crystallize in the P3m1 space group and finally, LiZn₂Mo₃O₈ and Zn₃Mo₃O₈ (Torardi & McCarley, 1985 ) crystallize in space group R $[\overline{3}]$ m. The crystal structures of all these compounds consist of distorted hexagonal-close-packed oxygen layers with stacking sequences ABAC, ABAB and ABC for compounds crystallizing in the space groups P6₃mc, P3m1 and R $[\overline{3}]$ m, respectively. The oxygen layers are separated by alternating mixed-metal atom (Li, M, or R) layers and molybdenum layers. The metal atoms occupy both tetrahedral and octahedral sites in a ratio of 1:1 (M₂Mo₃O₈ and LiRMo₃O₈) or 2:1 (LiZn₂Mo₃O₈ and Zn₃Mo₃O₈) between two adjacent oxygen layers. The molybdenum atoms occupy three quarters of the octahedral sites and form strongly bonded triangular cluster units involving three MoO₆ octahedra that are each shared along two edges, the whole constituting an Mo₃O₁₃ unit. The Mo—Mo bonds within the trinuclear cluster units range from about 2.5 to 2.6 Å, and the number of electrons available for Mo–Mo bonding is six in M₂Mo₃O₈ and LiRMo₃O₈, seven in LiZn₂Mo₃O₈ and Li₂InMo₃O₈, and eight in Zn₃Mo₃O₈ and Li₂SnMo₃O₈. The energy-level diagram deduced from LCAO–MO calculations on the Mo₃O₁₃ unit shows three bonding orbitals (a1 and e), a non-bonding level (a1), and five anti-bonding orbitals (2e and a2) (Cotton, 1964 ). This explains why the compounds with seven electrons per Mo₃ cluster unit are paramagnetic with moments corresponding to one unpaired electron per Mo₃ cluster unit, and those with six and eight electrons per Mo₃ show temperature-independent paramagnetism.

We present here the crystal structure of the new quaternary compound Li₂GeMo₃O₈ in which the Mo₃ cluster unit has eight electrons available for bonding.

2. Structural commentary

Li₂GeMo₃O₈ is isotypic with the Li₂MMo₃O₈ (M = Sn, In) compounds (Gall et al., 2013a,b). Its crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence ABAC along [001] that are held together by alternating lithium–germanium and molybdenum layers (Fig. 1). The Li⁺ and Ge⁴⁺ ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular cluster units involving three MoO₆ octahedra that are each shared along two edges, constituting an Mo₃O₁₃ unit (Fig. 2). The Mo—Mo distance within the Mo₃ triangle is 2.4728 (8) Å compared to 2.5036 (7) and 2.5455 (4) Å found in the tin and indium analogues, respectively. The Mo—O distances range from 2.004 (6) to 2.146 (3) Å (Table 1) while in Li₂InMo₃O₈ they range from 2.0212 (17) to 2.1241 (16) Å and in Li₂SnMo₃O₈ from 2.020 (6) to 2.122 (3) Å. The Li—O distances in the title structure range from 1.78 (2) to 2.012 (13) Å with average distances of 1.97 and 1.86 Å for the Li1 and Li2 sites, respectively. Both Li sites have site symmetry 3m.. For the Ge site, likewise with site symmetry 3m., the Ge—O distances are 3×1.883 (5) and 3×2.016 (5) Å. The average distance of 1.95 Å is close to the value of 1.92 Å calculated from the sum of the ionic radii of O²⁻ and Ge⁴⁺ in octahedral coordination according to Shannon & Prewitt (1969 ). The oxidation state of +4 for the Ge atoms was also confirmed from the Ge—O bond lengths by using the relationship of Brown & Wu (1976 ) {s = [d(Ge—O)/1.746]^−6.05} which leads to a value of +3.5 (1). The latter relationship applied to Mo—O bonds {s = [d(Mo—O)/1.882]⁻⁶} yield an oxidation state of +3.38 for the Mo atom, and thus 7.86 electrons per Mo₃ cluster unit, close to the expected value of 8. This is consistent with the chemical composition Li₂⁺Ge⁴⁺Mo₃^3.33+O₈²⁻.

Table 1
Selected bond lengths (Å)

Li1—O3	1.84 (2)	Ge1—O1^ix	2.016 (5)
Li1—O2ⁱ	2.012 (13)	Ge1—O1^x	2.016 (5)
Li1—O2ⁱⁱ	2.012 (13)	Ge1—O1^xi	2.016 (4)
Li1—O2ⁱⁱⁱ	2.012 (13)	Mo1—O4^xii	2.004 (6)
Li2—O4	1.78 (3)	Mo1—O1^xii	2.039 (4)
Li2—O1^iv	1.892 (6)	Mo1—O1^v	2.039 (4)
Li2—O1^v	1.892 (6)	Mo1—O3	2.076 (3)
Li2—O1^vi	1.892 (6)	Mo1—O2	2.146 (3)
Ge1—O2	1.883 (5)	Mo1—O2^xiii	2.146 (3)
Ge1—O2^vii	1.883 (5)	Mo1—Mo1^xiv	2.4728 (8)
Ge1—O2^viii	1.883 (5)
Symmetry codes: (i) $[x-y+1, x, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[y, -x+y+1, z+{\script{1\over 2}}]$ ; (iv) $[x-y, x-1, z-{\script{1\over 2}}]$ ; (v) $[y+1, -x+y+2, z-{\script{1\over 2}}]$ ; (vi) $[-x+3, -y+1, z-{\script{1\over 2}}]$ ; (vii) -x+y+2, -x+2, z; (viii) -y+2, x-y, z; (ix) -x+y+2, -x+2, z-1; (x) -y+2, x-y, z-1; (xi) x, y, z-1; (xii) $[-x+3, -y+2, z-{\script{1\over 2}}]$ ; (xiii) -y+2, x-y+1, z; (xiv) -x+y+2, -x+3, z.

Figure 1
View of the crystal structure of Li₂GeMo₃O₈ in a projection approximately along [010]. Displacement ellipsoids are drawn at the 97% probability level.

Figure 2
The Mo₃O₁₃ cluster unit with its numbering scheme, with ellipsoids drawn at the 97% probability level. [Symmetry codes: (v) y + 1, −x + y+2, z − $[{1\over 2}]$ ; (xii) −x + 3, −y + 2, z − $[{1\over 2}]$ ; (xiii) −y + 2, x-y + 1, z; (xiv) −x + y+2, −x + 3, z.]

3. Database survey

The M₂Mo₃O₈ (Mg, Zn, Fe, Co, Ni, Zn and Cd) compounds containing triangular Mo₃ clusters were first synthesized by McCarroll et al. (1957). They presented the results of a structure determination on Zn₂Mo₃O₈ from photographic data (R = 0.118). Later, a refinement of the structure was accomplished by Ansell & Katz (1966 ) with an R factor of 0.069. Among the above compounds, it is interesting to note that Fe₂Mo₃O₈ is a mineral known as kamiokite (Kanazawa & Sasaki, 1986 ). Later, DeBenedittis & Katz (1965) reported the existence of the LiRMo₃O₈ (R = Sc and Y) compounds. Subsequently, McCarroll (1977) obtained isotypic compounds with R = In, Sm, Gd, Tb, Dy, Ho, Er, and Yb. In 1985, Torardi & McCarley (1985) described the new Mo₃ cluster compounds LiZn₂Mo₃O₈, Zn₃Mo₃O₈ and ScZnMo₃O₈ and, in 2013, Gall et al. (2013a,b), the quaternary compounds Li₂MMo₃O₈ (M = Sn and In).

4. Synthesis and crystallization

Single crystals of Li₂GeMo₃O₈ were obtained by heating a mixture of Li₂MoO₄, O₂, MoO₃ and Mo with the nominal composition Li₂GeMo₆O₁₂ at 1923 K for 72 h in a molybdenum crucible sealed under low argon pressure using an arc-welding system. The molybdate Li₂MoO₄ was synthesized by heating an equimolar ratio of MoO₃ (CERAC 99.95%) and Li₂CO₃ (CERAC 99.9%) in an alumina vessel at 873 K in air over 12 h. Before use, the Mo powder was heated under a hydrogen flow at 1273 K for 6 h. The composition of the final crystals thus obtained was determined after a complete X-ray structural study on one of them.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All atoms were refined with anisotropic displacement parameters, except for the Li atoms, which were refined isotropically.

Table 2
Experimental details

Crystal data
Chemical formula	Li₂GeMo₃O₈
M_r	502.29
Crystal system, space group	Hexagonal, P6₃mc
Temperature (K)	293
a, c (Å)	5.7268 (3), 9.9841 (6)
V (Å³)	283.57 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	11.74
Crystal size (mm)	0.21 × 0.13 × 0.07

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Analytical (de Meulenaar & Tompa, 1965 )
T_min, T_max	0.048, 0.157
No. of measured, independent and observed [I > 2σ(I)] reflections	4457, 522, 501
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.076, 1.10
No. of reflections	522
No. of parameters	31
No. of restraints	1
Δρ_max, Δρ_min (e Å⁻³)	1.43, −1.33
Absolute structure	Flack (1983 ), 247 Friedel pairs
Absolute structure parameter	0.01 (3)
Computer programs: COLLECT (Nonius, 1998 ), EVALCCD (Duisenberg et al., 2003 ), SIR97 (Altomare et al., 1999 ), SHELXL97 (Sheldrick, 2008 ) and DIAMOND (Bergerhoff, 1996 ).

Supporting information

CCDC reference: 1485831

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016009750/wm5299sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016009750/wm5299Isup2.hkl

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Dilithium germanium trimolybdenum octaoxide top

Crystal data top

Li₂GeMo₃O₈	D_x = 5.883 Mg m⁻³
M_r = 502.29	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃mc	Cell parameters from 4457 reflections
Hall symbol: P 6c -2c	θ = 4.1–35.0°
a = 5.7268 (3) Å	µ = 11.74 mm⁻¹
c = 9.9841 (6) Å	T = 293 K
V = 283.57 (3) Å³	Irregular block, black
Z = 2	0.21 × 0.13 × 0.07 mm
F(000) = 456

Data collection top

Nonius KappaCCD diffractometer	522 independent reflections
Radiation source: fine-focus sealed tube	501 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
φ scans (κ = 0) + additional ω scans	θ_max = 35.0°, θ_min = 4.1°
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	h = −7→9
T_min = 0.048, T_max = 0.157	k = −9→9
4457 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0515P)² + 0.3716P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.076	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 1.43 e Å⁻³
522 reflections	Δρ_min = −1.33 e Å⁻³
31 parameters	Absolute structure: Flack (1983), 247 Friedel pairs
1 restraint	Absolute structure parameter: 0.01 (3)

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.

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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
Li1	1.0000	1.0000	1.581 (2)	0.014 (3)*
Li2	1.3333	0.6667	1.490 (2)	0.014 (3)*
Ge1	1.3333	0.6667	1.09391 (9)	0.0076 (2)
Mo1	1.37881 (9)	1.18940 (4)	1.30891 (9)	0.00660 (13)
O1	1.4795 (4)	0.5205 (4)	1.9536 (5)	0.0081 (8)
O2	1.1704 (6)	0.8296 (6)	1.1906 (5)	0.0081 (8)
O3	1.0000	1.0000	1.3974 (7)	0.0110 (14)
O4	1.3333	0.6667	1.6680 (8)	0.0080 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0076 (3)	0.0076 (3)	0.0076 (4)	0.00381 (14)	0.000	0.000
Mo1	0.00622 (19)	0.00662 (16)	0.00683 (19)	0.00311 (10)	−0.00015 (18)	−0.00007 (9)
O1	0.0079 (13)	0.0079 (13)	0.0094 (18)	0.0045 (14)	0.0007 (8)	−0.0007 (8)
O2	0.0071 (12)	0.0071 (12)	0.010 (2)	0.0034 (13)	0.0017 (9)	−0.0017 (9)
O3	0.012 (2)	0.012 (2)	0.010 (3)	0.0058 (10)	0.000	0.000
O4	0.0102 (19)	0.0102 (19)	0.004 (3)	0.0051 (9)	0.000	0.000

Geometric parameters (Å, º) top

Li1—O3	1.84 (2)	Ge1—O1^xv	2.016 (5)
Li1—O2ⁱ	2.012 (13)	Ge1—O1^xvi	2.016 (4)
Li1—O2ⁱⁱ	2.012 (13)	Mo1—O4^xvii	2.004 (6)
Li1—O2ⁱⁱⁱ	2.012 (13)	Mo1—O1^xvii	2.039 (4)
Li1—Mo1ⁱ	2.949 (17)	Mo1—O1^viii	2.039 (4)
Li1—Mo1ⁱⁱⁱ	2.949 (17)	Mo1—O3	2.076 (3)
Li1—Mo1ⁱⁱ	2.949 (17)	Mo1—O2	2.146 (3)
Li1—Mo1^iv	3.305 (18)	Mo1—O2^v	2.146 (3)
Li1—Mo1^v	3.305 (18)	Mo1—Mo1^xviii	2.4728 (8)
Li1—Mo1	3.305 (18)	Mo1—Mo1^xix	2.4728 (8)
Li1—Li2	3.430 (9)	Mo1—Li1^xx	2.949 (17)
Li1—Li2^vi	3.430 (9)	O1—Li2^xxi	1.892 (6)
Li2—O4	1.78 (3)	O1—Ge1^xxii	2.016 (4)
Li2—O1^vii	1.892 (6)	O1—Mo1^xxiii	2.039 (4)
Li2—O1^viii	1.892 (6)	O1—Mo1^xxiv	2.039 (4)
Li2—O1^ix	1.892 (6)	O2—Li1^xx	2.012 (13)
Li2—Li1^x	3.430 (9)	O2—Mo1^iv	2.146 (3)
Li2—Li1^xi	3.430 (9)	O3—Mo1^iv	2.076 (3)
Ge1—O2	1.883 (5)	O3—Mo1^v	2.076 (3)
Ge1—O2^xii	1.883 (5)	O4—Mo1ⁱⁱⁱ	2.004 (5)
Ge1—O2^xiii	1.883 (5)	O4—Mo1^xxiv	2.004 (5)
Ge1—O1^xiv	2.016 (5)	O4—Mo1^xxiii	2.004 (5)

O3—Li1—O2ⁱ	122.9 (5)	Li1^x—Li2—Li1^xi	113.2 (5)
O3—Li1—O2ⁱⁱ	122.9 (5)	O2—Ge1—O2^xii	96.1 (2)
O2ⁱ—Li1—O2ⁱⁱ	93.3 (7)	O2—Ge1—O2^xiii	96.1 (2)
O3—Li1—O2ⁱⁱⁱ	122.9 (5)	O2^xii—Ge1—O2^xiii	96.1 (2)
O2ⁱ—Li1—O2ⁱⁱⁱ	93.3 (7)	O2—Ge1—O1^xiv	92.73 (17)
O2ⁱⁱ—Li1—O2ⁱⁱⁱ	93.3 (7)	O2^xii—Ge1—O1^xiv	166.8 (2)
O3—Li1—Mo1ⁱ	140.4 (3)	O2^xiii—Ge1—O1^xiv	92.73 (18)
O2ⁱ—Li1—Mo1ⁱ	46.7 (4)	O2—Ge1—O1^xv	92.73 (17)
O2ⁱⁱ—Li1—Mo1ⁱ	46.7 (4)	O2^xii—Ge1—O1^xv	92.73 (17)
O2ⁱⁱⁱ—Li1—Mo1ⁱ	96.7 (8)	O2^xiii—Ge1—O1^xv	166.8 (2)
O3—Li1—Mo1ⁱⁱⁱ	140.4 (3)	O1^xiv—Ge1—O1^xv	77.0 (2)
O2ⁱ—Li1—Mo1ⁱⁱⁱ	46.7 (4)	O2—Ge1—O1^xvi	166.8 (2)
O2ⁱⁱ—Li1—Mo1ⁱⁱⁱ	96.7 (8)	O2^xii—Ge1—O1^xvi	92.73 (17)
O2ⁱⁱⁱ—Li1—Mo1ⁱⁱⁱ	46.7 (4)	O2^xiii—Ge1—O1^xvi	92.73 (17)
Mo1ⁱ—Li1—Mo1ⁱⁱⁱ	67.0 (4)	O1^xiv—Ge1—O1^xvi	77.0 (2)
O3—Li1—Mo1ⁱⁱ	140.4 (3)	O1^xv—Ge1—O1^xvi	77.0 (2)
O2ⁱ—Li1—Mo1ⁱⁱ	96.7 (8)	O4^xvii—Mo1—O1^xvii	104.58 (15)
O2ⁱⁱ—Li1—Mo1ⁱⁱ	46.7 (4)	O4^xvii—Mo1—O1^viii	104.58 (15)
O2ⁱⁱⁱ—Li1—Mo1ⁱⁱ	46.7 (4)	O1^xvii—Mo1—O1^viii	76.0 (2)
Mo1ⁱ—Li1—Mo1ⁱⁱ	67.0 (4)	O4^xvii—Mo1—O3	160.6 (3)
Mo1ⁱⁱⁱ—Li1—Mo1ⁱⁱ	67.0 (4)	O1^xvii—Mo1—O3	90.60 (16)
O3—Li1—Mo1^iv	34.6 (2)	O1^viii—Mo1—O3	90.60 (16)
O2ⁱ—Li1—Mo1^iv	133.2 (4)	O4^xvii—Mo1—O2	87.53 (16)
O2ⁱⁱ—Li1—Mo1^iv	133.2 (4)	O1^xvii—Mo1—O2	167.40 (14)
O2ⁱⁱⁱ—Li1—Mo1^iv	88.2 (3)	O1^viii—Mo1—O2	97.8 (2)
Mo1ⁱ—Li1—Mo1^iv	175.1 (5)	O3—Mo1—O2	78.36 (18)
Mo1ⁱⁱⁱ—Li1—Mo1^iv	116.94 (6)	O4^xvii—Mo1—O2^v	87.53 (16)
Mo1ⁱⁱ—Li1—Mo1^iv	116.94 (6)	O1^xvii—Mo1—O2^v	97.8 (2)
O3—Li1—Mo1^v	34.6 (2)	O1^viii—Mo1—O2^v	167.40 (14)
O2ⁱ—Li1—Mo1^v	133.2 (4)	O3—Mo1—O2^v	78.36 (18)
O2ⁱⁱ—Li1—Mo1^v	88.2 (3)	O2—Mo1—O2^v	86.0 (3)
O2ⁱⁱⁱ—Li1—Mo1^v	133.2 (4)	O4^xvii—Mo1—Mo1^xviii	51.91 (12)
Mo1ⁱ—Li1—Mo1^v	116.94 (6)	O1^xvii—Mo1—Mo1^xviii	52.67 (9)
Mo1ⁱⁱⁱ—Li1—Mo1^v	175.1 (5)	O1^viii—Mo1—Mo1^xviii	90.54 (10)
Mo1ⁱⁱ—Li1—Mo1^v	116.94 (6)	O3—Mo1—Mo1^xviii	141.60 (11)
Mo1^iv—Li1—Mo1^v	59.0 (4)	O2—Mo1—Mo1^xviii	139.30 (11)
O3—Li1—Mo1	34.6 (2)	O2^v—Mo1—Mo1^xviii	94.37 (14)
O2ⁱ—Li1—Mo1	88.2 (3)	O4^xvii—Mo1—Mo1^xix	51.91 (12)
O2ⁱⁱ—Li1—Mo1	133.2 (4)	O1^xvii—Mo1—Mo1^xix	90.54 (9)
O2ⁱⁱⁱ—Li1—Mo1	133.2 (4)	O1^viii—Mo1—Mo1^xix	52.67 (9)
Mo1ⁱ—Li1—Mo1	116.94 (6)	O3—Mo1—Mo1^xix	141.60 (11)
Mo1ⁱⁱⁱ—Li1—Mo1	116.94 (6)	O2—Mo1—Mo1^xix	94.37 (13)
Mo1ⁱⁱ—Li1—Mo1	175.1 (5)	O2^v—Mo1—Mo1^xix	139.30 (11)
Mo1^iv—Li1—Mo1	59.0 (4)	Mo1^xviii—Mo1—Mo1^xix	60.0
Mo1^v—Li1—Mo1	59.0 (4)	O4^xvii—Mo1—Li1^xx	85.0 (3)
O3—Li1—Li2	74.6 (5)	O1^xvii—Mo1—Li1^xx	139.97 (14)
O2ⁱ—Li1—Li2	74.9 (3)	O1^viii—Mo1—Li1^xx	139.97 (15)
O2ⁱⁱ—Li1—Li2	162.6 (10)	O3—Mo1—Li1^xx	75.6 (3)
O2ⁱⁱⁱ—Li1—Li2	74.9 (3)	O2—Mo1—Li1^xx	43.02 (16)
Mo1ⁱ—Li1—Li2	120.8 (5)	O2^v—Mo1—Li1^xx	43.02 (16)
Mo1ⁱⁱⁱ—Li1—Li2	65.8 (4)	Mo1^xviii—Mo1—Li1^xx	123.5 (2)
Mo1ⁱⁱ—Li1—Li2	120.8 (5)	Mo1^xix—Mo1—Li1^xx	123.5 (2)
Mo1^iv—Li1—Li2	60.5 (4)	O4^xvii—Mo1—Li1	169.2 (3)
Mo1^v—Li1—Li2	109.2 (7)	O1^xvii—Mo1—Li1	67.23 (18)
Mo1—Li1—Li2	60.5 (4)	O1^viii—Mo1—Li1	67.23 (18)
O3—Li1—Li2^vi	74.6 (5)	O3—Mo1—Li1	30.2 (3)
O2ⁱ—Li1—Li2^vi	162.6 (10)	O2—Mo1—Li1	100.31 (19)
O2ⁱⁱ—Li1—Li2^vi	74.9 (3)	O2^v—Mo1—Li1	100.31 (19)
O2ⁱⁱⁱ—Li1—Li2^vi	74.9 (3)	Mo1^xviii—Mo1—Li1	119.49 (18)
Mo1ⁱ—Li1—Li2^vi	120.8 (5)	Mo1^xix—Mo1—Li1	119.49 (18)
Mo1ⁱⁱⁱ—Li1—Li2^vi	120.8 (5)	Li1^xx—Mo1—Li1	105.78 (5)
Mo1ⁱⁱ—Li1—Li2^vi	65.8 (4)	Li2^xxi—O1—Ge1^xxii	124.9 (8)
Mo1^iv—Li1—Li2^vi	60.5 (4)	Li2^xxi—O1—Mo1^xxiii	119.4 (6)
Mo1^v—Li1—Li2^vi	60.5 (4)	Ge1^xxii—O1—Mo1^xxiii	103.46 (15)
Mo1—Li1—Li2^vi	109.2 (7)	Li2^xxi—O1—Mo1^xxiv	119.4 (6)
Li2—Li1—Li2^vi	113.2 (5)	Ge1^xxii—O1—Mo1^xxiv	103.46 (15)
O4—Li2—O1^vii	101.1 (7)	Mo1^xxiii—O1—Mo1^xxiv	74.66 (17)
O4—Li2—O1^viii	101.1 (7)	Ge1—O2—Li1^xx	116.3 (6)
O1^vii—Li2—O1^viii	116.4 (5)	Ge1—O2—Mo1	125.62 (15)
O4—Li2—O1^ix	101.1 (7)	Li1^xx—O2—Mo1	90.3 (4)
O1^vii—Li2—O1^ix	116.4 (5)	Ge1—O2—Mo1^iv	125.62 (15)
O1^viii—Li2—O1^ix	116.4 (5)	Li1^xx—O2—Mo1^iv	90.3 (4)
O4—Li2—Li1	74.6 (5)	Mo1—O2—Mo1^iv	98.6 (2)
O1^vii—Li2—Li1	65.0 (2)	Li1—O3—Mo1^iv	115.18 (19)
O1^viii—Li2—Li1	65.0 (2)	Li1—O3—Mo1	115.18 (19)
O1^ix—Li2—Li1	175.6 (12)	Mo1^iv—O3—Mo1	103.2 (2)
O4—Li2—Li1^x	74.6 (5)	Li1—O3—Mo1^v	115.18 (19)
O1^vii—Li2—Li1^x	175.6 (12)	Mo1^iv—O3—Mo1^v	103.2 (2)
O1^viii—Li2—Li1^x	65.0 (2)	Mo1—O3—Mo1^v	103.2 (2)
O1^ix—Li2—Li1^x	65.0 (2)	Li2—O4—Mo1ⁱⁱⁱ	134.58 (16)
Li1—Li2—Li1^x	113.2 (5)	Li2—O4—Mo1^xxiv	134.58 (16)
O4—Li2—Li1^xi	74.6 (5)	Mo1ⁱⁱⁱ—O4—Mo1^xxiv	76.2 (2)
O1^vii—Li2—Li1^xi	65.0 (2)	Li2—O4—Mo1^xxiii	134.58 (16)
O1^viii—Li2—Li1^xi	175.6 (12)	Mo1ⁱⁱⁱ—O4—Mo1^xxiii	76.2 (2)
O1^ix—Li2—Li1^xi	65.0 (2)	Mo1^xxiv—O4—Mo1^xxiii	76.2 (2)
Li1—Li2—Li1^xi	113.2 (5)

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

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