Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4: different filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure

Solodovnikov, S.F.; Solodovnikova, Z.A.; Zolotova, E.S.; Kadyrova, Y.M.; Savina, A.A.; Stefanovich, S.Y.; Khaikina, E.G.

doi:10.1107/S205322961701378X

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Cs₃LiZn₂(WO₄)₄ and Rb₃Li₂Ga(MoO₄)₄: different filled derivatives of the cation-deficient Cs₆Zn₅(MoO₄)₈ structure

S. F. Solodovnikov, Z. A. Solodovnikova, E. S. Zolotova, Y. M. Kadyrova, A. A. Savina, S. Y. Stefanovich and E. G. Khaikina

Two new compounds, namely cubic tricaesium lithium dizinc tetrakis(tetraoxotungstate), Cs₃LiZn₂(WO₄)₄, and tetragonal trirubidium dilithium gallium tetrakis(tetraoxomolybdate), Rb₃Li₂Ga(MoO₄)₄, belong to the structural family of Cs₆Zn₅(MoO₄)₈ (space group I $\overline{4}$ 3d, Z = 4), with a partially incomplete (Zn_5/6□_1/6) position. In Cs₃LiZn₂(WO₄)₄, this position is fully statistically occupied by (Zn_2/3Li_1/3), and in Rb₃Li₂Ga(MoO₄)₄, the 2Li + Ga atoms are completely ordered in two distinct sites of the space group I $\overline{4}$ 2d (Z = 4). In the same way, the crystallographically equivalent A⁺ cations (A = Cs, Rb) in Cs₆Zn₅(MoO₄)₈, Cs₃LiZn₂(WO₄)₄ and isostructural A₃LiZn₂(MoO₄)₄ and Cs₃LiCo₂(MoO₄)₄ are divided into two sites in Rb₃Li₂Ga(MoO₄)₄, as in other isostructural A₃Li₂R(MoO₄)₄ compounds (AR = TlAl, RbAl, CsAl, CsGa, CsFe). In the title structures, the WO₄ and (Zn,Li)O₄ or LiO₄, GaO₄ and MoO₄ tetrahedra share corners to form open three-dimensional frameworks with the caesium or rubidium ions occupying cuboctahedral cavities. The tetrahedral frameworks are related to that of mayenite 12CaO·7Al₂O₃ and isotypic compounds. Comparison of isostructural Cs₃MZn₂(MoO₄)₄ (M = Li, Na, Ag) and Cs₆Zn₅(MoO₄)₈ shows a decrease of the cubic lattice parameter and an increase in thermal stability with the filling of the vacancies by Li⁺ in the Zn position of the Cs₆Zn₅(MoO₄)₈ structure, while filling of the cation vacancies by larger Na⁺ or Ag⁺ ions plays a destabilizing role. The series A₃Li₂R(MoO₄)₄ shows second harmonic generation effects compatible with that of β′-Gd₂(MoO₄)₃ and may be considered as nonlinear optical materials with a modest nonlinearity.

Keywords: triple tungstate; triple molybdate; tetrahedral framework; filling vacancies; crystal structure; structural family; crystal chemistry; thermal stability; second harmonic generation.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961701378X/ly3054sup1.cif Contains datablocks global, I, II
	Structure factor file (CIF format) https://doi.org/10.1107/S205322961701378X/ly3054Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S205322961701378X/ly3054IIsup3.hkl Contains datablock II
	Portable Document Format (PDF) file https://doi.org/10.1107/S205322961701378X/ly3054sup4.pdf Atomic coordinates

CCDC references: 1576374; 1576373

Computing details top

For both structures, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Tricaesium lithium dizinc tetrakis(tetraoxotungstate) (I) top

Crystal data top

Cs₃LiZn₂(WO₄)₄	Melting point: 1003 K
M_r = 1527.81	Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d	Cell parameters from 9302 reflections
Hall symbol: I -4bd 2c 3	θ = 4.1–29.9°
a = 12.2643 (1) Å	µ = 33.30 mm⁻¹
V = 1844.71 (3) Å³	T = 296 K
Z = 4	Fragment, colourless
F(000) = 2608	0.16 × 0.10 × 0.08 mm
D_x = 5.501 Mg m⁻³

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	453 independent reflections
Radiation source: fine-focus sealed tube	450 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 25 pixels mm^-1	θ_max = 29.9°, θ_min = 4.1°
φ and ω scans	h = −13→17
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −17→17
T_min = 0.076, T_max = 0.176	l = −15→17
9302 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.P)² + 21.4403P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.018	(Δ/σ)_max < 0.001
wR(F²) = 0.035	Δρ_max = 0.92 e Å⁻³
S = 1.39	Δρ_min = −0.84 e Å⁻³
453 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
21 parameters	Extinction coefficient: 0.00030 (3)
0 restraints	Absolute structure: Flack (1983), ??? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.033 (19)

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	Occ. (<1)
Cs	0.8750	0.0000	0.2500	0.0280 (2)
W	0.40026 (2)	0.40026 (2)	0.40026 (2)	0.01296 (11)
Zn	0.3750	0.0000	0.2500	0.0154 (4)	0.67
Li	0.3750	0.0000	0.2500	0.0154 (4)	0.33
O1	0.3185 (4)	0.3185 (4)	0.3185 (4)	0.028 (2)
O2	0.5312 (4)	0.4081 (4)	0.3375 (4)	0.0238 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.0193 (4)	0.0324 (3)	0.0324 (3)	0.000	0.000	0.000
W	0.01296 (11)	0.01296 (11)	0.01296 (11)	0.00285 (8)	0.00285 (8)	0.00285 (8)
Zn	0.0084 (9)	0.0188 (6)	0.0188 (6)	0.000	0.000	0.000
Li	0.0084 (9)	0.0188 (6)	0.0188 (6)	0.000	0.000	0.000
O1	0.028 (2)	0.028 (2)	0.028 (2)	−0.002 (2)	−0.002 (2)	−0.002 (2)
O2	0.019 (2)	0.023 (2)	0.029 (3)	−0.0057 (19)	0.0084 (19)	0.000 (2)

Geometric parameters (Å, º) top

Cs—O2ⁱ	3.271 (5)	W—Cs^xvii	4.4711 (3)
Cs—O2ⁱⁱ	3.271 (5)	W—Cs^xviii	4.4711 (3)
Cs—O2ⁱⁱⁱ	3.271 (5)	W—Cs^xix	4.4711 (3)
Cs—O2^iv	3.271 (5)	Zn—O2^viii	1.935 (5)
Cs—O1^v	3.3604 (15)	Zn—O2^v	1.935 (5)
Cs—O1^vi	3.3604 (15)	Zn—O2^xx	1.935 (5)
Cs—O1^vii	3.3604 (15)	Zn—O2^xxi	1.935 (5)
Cs—O1^viii	3.3604 (15)	Zn—Cs^xxii	3.7552
Cs—O2^ix	3.367 (5)	Zn—Cs^xv	3.7552
Cs—O2^x	3.367 (5)	Zn—Cs^xvi	3.7552
Cs—O2^xi	3.367 (5)	Zn—Cs^x	3.7552
Cs—O2^xii	3.367 (5)	O1—Cs^xv	3.3604 (15)
W—O1	1.737 (9)	O1—Cs^viii	3.3604 (15)
W—O2^xiii	1.783 (4)	O1—Cs^xvi	3.3604 (15)
W—O2	1.783 (4)	O2—Li^viii	1.935 (5)
W—O2^xiv	1.783 (4)	O2—Zn^viii	1.935 (5)
W—Cs^viii	4.0359 (2)	O2—Cs^xv	3.271 (5)
W—Cs^xv	4.0359 (2)	O2—Cs^xix	3.367 (5)
W—Cs^xvi	4.0359 (2)

O2ⁱ—Cs—O2ⁱⁱ	129.41 (11)	O2—W—Cs^xv	52.48 (16)
O2ⁱ—Cs—O2ⁱⁱⁱ	74.35 (18)	O2^xiv—W—Cs^xv	125.97 (17)
O2ⁱⁱ—Cs—O2ⁱⁱⁱ	129.41 (11)	Cs^viii—W—Cs^xv	90.572 (7)
O2ⁱ—Cs—O2^iv	129.41 (11)	O1—W—Cs^xvi	55.141 (5)
O2ⁱⁱ—Cs—O2^iv	74.35 (18)	O2^xiii—W—Cs^xvi	52.48 (16)
O2ⁱⁱⁱ—Cs—O2^iv	129.41 (11)	O2—W—Cs^xvi	125.97 (17)
O2ⁱ—Cs—O1^v	169.94 (8)	O2^xiv—W—Cs^xvi	122.67 (17)
O2ⁱⁱ—Cs—O1^v	50.69 (16)	Cs^viii—W—Cs^xvi	90.572 (7)
O2ⁱⁱⁱ—Cs—O1^v	98.09 (14)	Cs^xv—W—Cs^xvi	90.572 (7)
O2^iv—Cs—O1^v	60.54 (9)	O1—W—Cs^xvii	132.209 (4)
O2ⁱ—Cs—O1^vi	60.54 (9)	O2^xiii—W—Cs^xvii	42.09 (17)
O2ⁱⁱ—Cs—O1^vi	169.94 (8)	O2—W—Cs^xvii	117.48 (16)
O2ⁱⁱⁱ—Cs—O1^vi	50.69 (16)	O2^xiv—W—Cs^xvii	70.83 (16)
O2^iv—Cs—O1^vi	98.09 (14)	Cs^viii—W—Cs^xvii	107.287 (1)
O1^v—Cs—O1^vi	119.92 (11)	Cs^xv—W—Cs^xvii	161.508 (4)
O2ⁱ—Cs—O1^vii	50.69 (16)	Cs^xvi—W—Cs^xvii	84.632 (1)
O2ⁱⁱ—Cs—O1^vii	98.09 (14)	O1—W—Cs^xviii	132.209 (4)
O2ⁱⁱⁱ—Cs—O1^vii	60.54 (9)	O2^xiii—W—Cs^xviii	117.48 (16)
O2^iv—Cs—O1^vii	169.94 (8)	O2—W—Cs^xviii	70.83 (16)
O1^v—Cs—O1^vii	119.92 (11)	O2^xiv—W—Cs^xviii	42.09 (17)
O1^vi—Cs—O1^vii	90.15 (19)	Cs^viii—W—Cs^xviii	84.632 (1)
O2ⁱ—Cs—O1^viii	98.09 (14)	Cs^xv—W—Cs^xviii	107.287 (1)
O2ⁱⁱ—Cs—O1^viii	60.54 (9)	Cs^xvi—W—Cs^xviii	161.508 (4)
O2ⁱⁱⁱ—Cs—O1^viii	169.94 (8)	Cs^xvii—W—Cs^xviii	79.803 (6)
O2^iv—Cs—O1^viii	50.69 (16)	O1—W—Cs^xix	132.209 (4)
O1^v—Cs—O1^viii	90.15 (19)	O2^xiii—W—Cs^xix	70.83 (16)
O1^vi—Cs—O1^viii	119.92 (11)	O2—W—Cs^xix	42.09 (17)
O1^vii—Cs—O1^viii	119.92 (11)	O2^xiv—W—Cs^xix	117.48 (16)
O2ⁱ—Cs—O2^ix	57.31 (15)	Cs^viii—W—Cs^xix	161.508 (4)
O2ⁱⁱ—Cs—O2^ix	119.97 (15)	Cs^xv—W—Cs^xix	84.632 (1)
O2ⁱⁱⁱ—Cs—O2^ix	110.35 (10)	Cs^xvi—W—Cs^xix	107.287 (1)
O2^iv—Cs—O2^ix	72.11 (8)	Cs^xvii—W—Cs^xix	79.803 (6)
O1^v—Cs—O2^ix	132.57 (9)	Cs^xviii—W—Cs^xix	79.803 (6)
O1^vi—Cs—O2^ix	62.27 (15)	O2^viii—Zn—O2^v	107.0 (3)
O1^vii—Cs—O2^ix	107.14 (17)	O2^viii—Zn—O2^xx	110.70 (15)
O1^viii—Cs—O2^ix	59.60 (8)	O2^v—Zn—O2^xx	110.70 (15)
O2ⁱ—Cs—O2^x	110.35 (10)	O2^viii—Zn—O2^xxi	110.70 (15)
O2ⁱⁱ—Cs—O2^x	72.11 (8)	O2^v—Zn—O2^xxi	110.70 (15)
O2ⁱⁱⁱ—Cs—O2^x	57.31 (15)	O2^xx—Zn—O2^xxi	107.0 (3)
O2^iv—Cs—O2^x	119.97 (15)	O2^viii—Zn—Cs^xxii	158.95 (15)
O1^v—Cs—O2^x	59.60 (8)	O2^v—Zn—Cs^xxii	63.40 (15)
O1^vi—Cs—O2^x	107.14 (17)	O2^xx—Zn—Cs^xxii	90.35 (14)
O1^vii—Cs—O2^x	62.27 (15)	O2^xxi—Zn—Cs^xxii	60.56 (14)
O1^viii—Cs—O2^x	132.57 (9)	O2^viii—Zn—Cs^xv	60.56 (14)
O2^ix—Cs—O2^x	166.13 (17)	O2^v—Zn—Cs^xv	90.35 (14)
O2ⁱ—Cs—O2^xi	119.97 (15)	O2^xx—Zn—Cs^xv	158.95 (15)
O2ⁱⁱ—Cs—O2^xi	110.35 (10)	O2^xxi—Zn—Cs^xv	63.40 (15)
O2ⁱⁱⁱ—Cs—O2^xi	72.11 (8)	Cs^xxii—Zn—Cs^xv	99.6
O2^iv—Cs—O2^xi	57.31 (15)	O2^viii—Zn—Cs^xvi	63.40 (15)
O1^v—Cs—O2^xi	62.27 (15)	O2^v—Zn—Cs^xvi	158.95 (15)
O1^vi—Cs—O2^xi	59.60 (8)	O2^xx—Zn—Cs^xvi	60.56 (14)
O1^vii—Cs—O2^xi	132.57 (9)	O2^xxi—Zn—Cs^xvi	90.35 (14)
O1^viii—Cs—O2^xi	107.14 (17)	Cs^xxii—Zn—Cs^xvi	131.8
O2^ix—Cs—O2^xi	90.84 (2)	Cs^xv—Zn—Cs^xvi	99.6
O2^x—Cs—O2^xi	90.84 (2)	O2^viii—Zn—Cs^x	90.35 (14)
O2ⁱ—Cs—O2^xii	72.11 (8)	O2^v—Zn—Cs^x	60.56 (14)
O2ⁱⁱ—Cs—O2^xii	57.31 (15)	O2^xx—Zn—Cs^x	63.40 (15)
O2ⁱⁱⁱ—Cs—O2^xii	119.97 (15)	O2^xxi—Zn—Cs^x	158.95 (15)
O2^iv—Cs—O2^xii	110.35 (10)	Cs^xxii—Zn—Cs^x	99.6
O1^v—Cs—O2^xii	107.14 (17)	Cs^xv—Zn—Cs^x	131.8
O1^vi—Cs—O2^xii	132.57 (9)	Cs^xvi—Zn—Cs^x	99.6
O1^vii—Cs—O2^xii	59.60 (8)	W—O1—Cs^xv	99.77 (15)
O1^viii—Cs—O2^xii	62.27 (15)	W—O1—Cs^viii	99.77 (15)
O2^ix—Cs—O2^xii	90.84 (2)	Cs^xv—O1—Cs^viii	117.18 (8)
O2^x—Cs—O2^xii	90.84 (2)	W—O1—Cs^xvi	99.77 (15)
O2^xi—Cs—O2^xii	166.13 (17)	Cs^xv—O1—Cs^xvi	117.18 (8)
O1—W—O2^xiii	107.59 (16)	Cs^viii—O1—Cs^xvi	117.18 (8)
O1—W—O2	107.59 (16)	W—O2—Li^viii	143.7 (3)
O2^xiii—W—O2	111.29 (14)	W—O2—Zn^viii	143.7 (3)
O1—W—O2^xiv	107.59 (16)	Li^viii—O2—Zn^viii	0.0
O2^xiii—W—O2^xiv	111.29 (14)	W—O2—Cs^xv	101.91 (19)
O2—W—O2^xiv	111.29 (14)	Li^viii—O2—Cs^xv	88.43 (16)
O1—W—Cs^viii	55.141 (5)	Zn^viii—O2—Cs^xv	88.43 (16)
O2^xiii—W—Cs^viii	125.97 (17)	W—O2—Cs^xix	117.1 (2)
O2—W—Cs^viii	122.67 (17)	Li^viii—O2—Cs^xix	85.68 (15)
O2^xiv—W—Cs^viii	52.48 (16)	Zn^viii—O2—Cs^xix	85.68 (15)
O1—W—Cs^xv	55.141 (5)	Cs^xv—O2—Cs^xix	119.54 (14)
O2^xiii—W—Cs^xv	122.67 (17)

Symmetry codes: (i) z+3/4, y−1/4, x−1/4; (ii) −z+1, x−1/2, −y+1/2; (iii) z+3/4, −y+1/4, −x+3/4; (iv) −z+1, −x+1/2, y; (v) −x+1, y−1/2, −z+1/2; (vi) y+3/4, −x+1/4, −z+3/4; (vii) y+3/4, x−1/4, z−1/4; (viii) −x+1, −y+1/2, z; (ix) y+1/2, −z+1/2, −x+1; (x) y+1/2, z−1/2, x−1/2; (xi) −y+5/4, x−3/4, −z+3/4; (xii) −y+5/4, −x+3/4, z−1/4; (xiii) y, z, x; (xiv) z, x, y; (xv) −y+1/2, z, −x+1; (xvi) z, −x+1, −y+1/2; (xvii) x−1/2, y+1/2, z+1/2; (xviii) y+1/2, z+1/2, x−1/2; (xix) z+1/2, x−1/2, y+1/2; (xx) x−1/4, −z+1/4, −y+3/4; (xxi) x−1/4, z−1/4, y−1/4; (xxii) z, x−1, y.

Tricaesium dilithium gallium tetrakis(tetraoxomolybdate) (II) top

Crystal data top

Rb₃Li₂Ga(MoO₄)₄	D_x = 3.888 Mg m⁻³
M_r = 979.77	Melting point: 833 K
Tetragonal, I42d	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4 2bw	Cell parameters from 9934 reflections
a = 11.8635 (3) Å	θ = 2.4–36.4°
c = 11.8932 (4) Å	µ = 13.25 mm⁻¹
V = 1673.88 (8) Å³	T = 296 K
Z = 4	Fragment, colourless
F(000) = 1776	0.08 × 0.07 × 0.07 mm

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	2024 independent reflections
Radiation source: fine-focus sealed tube	1907 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 25 pixels mm^-1	θ_max = 36.4°, θ_min = 2.4°
φ and ω scans	h = −19→10
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −19→19
T_min = 0.417, T_max = 0.457	l = −19→15
9934 measured reflections

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)] = 0.022	w = 1/[σ²(F_o²) + (0.0249P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.056	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 1.63 e Å⁻³
2024 reflections	Δρ_min = −0.84 e Å⁻³
60 parameters	Absolute structure: Flack (1983), ??? Friedel pairs
0 restraints	Absolute structure parameter: 0.004 (7)

Special details top

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

	x	y	z	U_iso*/U_eq
Rb1	0.0000	0.0000	0.0000	0.02889 (13)
Rb2	0.36464 (4)	0.2500	0.1250	0.02726 (9)
Mo	0.10403 (2)	0.14339 (2)	0.270940 (17)	0.01532 (5)
Ga	0.0000	0.0000	0.5000	0.01470 (10)
Li	−0.1246 (6)	0.2500	0.1250	0.0178 (13)
O1	0.1000 (2)	0.0759 (2)	0.41104 (19)	0.0234 (4)
O2	−0.02987 (18)	0.1486 (2)	0.2095 (2)	0.0250 (4)
O3	0.1896 (2)	0.0633 (2)	0.1856 (2)	0.0270 (5)
O4	0.1636 (2)	0.27782 (19)	0.2786 (2)	0.0262 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.0347 (2)	0.0347 (2)	0.0172 (2)	0.000	0.000	0.000
Rb2	0.02057 (18)	0.0273 (2)	0.0340 (2)	0.000	0.000	0.00513 (16)
Mo	0.01588 (9)	0.01733 (10)	0.01275 (8)	−0.00404 (8)	−0.00241 (7)	0.00295 (7)
Ga	0.01758 (15)	0.01758 (15)	0.0089 (2)	0.000	0.000	0.000
Li	0.017 (3)	0.020 (3)	0.017 (3)	0.000	0.000	0.000 (2)
O1	0.0237 (9)	0.0321 (11)	0.0145 (8)	−0.0028 (9)	0.0005 (8)	0.0083 (8)
O2	0.0205 (9)	0.0293 (11)	0.0251 (10)	−0.0003 (8)	−0.0065 (8)	0.0019 (9)
O3	0.0269 (11)	0.0292 (12)	0.0249 (11)	0.0005 (9)	0.0020 (9)	−0.0011 (9)
O4	0.0335 (12)	0.0232 (10)	0.0218 (10)	−0.0112 (9)	0.0004 (9)	−0.0011 (8)

Geometric parameters (Å, º) top

Rb1—O2ⁱ	3.073 (2)	Mo—O4	1.746 (2)
Rb1—O2	3.073 (2)	Mo—O2	1.750 (2)
Rb1—O2ⁱⁱ	3.073 (2)	Mo—O1	1.849 (2)
Rb1—O2ⁱⁱⁱ	3.073 (2)	Mo—Rb2^xiii	3.9327 (5)
Rb1—O3	3.240 (3)	Ga—O1ⁱⁱ	1.827 (2)
Rb1—O3ⁱⁱⁱ	3.240 (3)	Ga—O1^xiv	1.827 (2)
Rb1—O3ⁱ	3.240 (3)	Ga—O1	1.827 (2)
Rb1—O3ⁱⁱ	3.240 (3)	Ga—O1^xv	1.827 (2)
Rb1—O4^iv	3.291 (3)	Ga—Rb2^xvi	3.6858 (2)
Rb1—O4^v	3.291 (3)	Ga—Rb2^xvii	3.6858 (2)
Rb1—O4^vi	3.291 (3)	Ga—Rb2^xviii	3.6858 (2)
Rb1—O4^vii	3.291 (3)	Ga—Rb2^xiii	3.6858 (2)
Rb2—O4^iv	3.023 (3)	Li—O4^vii	1.925 (5)
Rb2—O4	3.023 (3)	Li—O4^xviii	1.925 (5)
Rb2—O1^viii	3.103 (2)	Li—O2^iv	1.929 (5)
Rb2—O1^ix	3.103 (2)	Li—O2	1.929 (5)
Rb2—O3	3.120 (2)	Li—Rb2ⁱ	3.592 (3)
Rb2—O3^iv	3.120 (2)	Li—Rb2^xviii	3.592 (3)
Rb2—O2^vi	3.274 (2)	Li—Rb1^xix	3.632 (3)
Rb2—O2^x	3.274 (2)	O1—Rb2^xiii	3.103 (2)
Rb2—O1^xi	3.304 (2)	O1—Rb2^xvi	3.304 (2)
Rb2—O1^xii	3.304 (2)	O2—Rb2^xviii	3.274 (2)
Rb2—O3^viii	3.338 (3)	O3—Rb2^xiii	3.338 (3)
Rb2—O3^ix	3.338 (3)	O4—Li^x	1.925 (5)
Mo—O3	1.721 (3)	O4—Rb1^xix	3.291 (3)

O2ⁱ—Rb1—O2	131.10 (6)	O2^vi—Rb2—O3^viii	127.65 (6)
O2ⁱ—Rb1—O2ⁱⁱ	131.10 (6)	O2^x—Rb2—O3^viii	57.12 (6)
O2—Rb1—O2ⁱⁱ	71.65 (9)	O1^xi—Rb2—O3^viii	61.64 (6)
O2ⁱ—Rb1—O2ⁱⁱⁱ	71.65 (9)	O1^xii—Rb2—O3^viii	107.20 (6)
O2—Rb1—O2ⁱⁱⁱ	131.10 (6)	O4^iv—Rb2—O3^ix	97.25 (6)
O2ⁱⁱ—Rb1—O2ⁱⁱⁱ	131.10 (6)	O4—Rb2—O3^ix	171.31 (6)
O2ⁱ—Rb1—O3	167.85 (6)	O1^viii—Rb2—O3^ix	57.29 (6)
O2—Rb1—O3	52.73 (6)	O1^ix—Rb2—O3^ix	53.12 (6)
O2ⁱⁱ—Rb1—O3	60.03 (6)	O3—Rb2—O3^ix	118.27 (6)
O2ⁱⁱⁱ—Rb1—O3	97.32 (6)	O3^iv—Rb2—O3^ix	117.80 (6)
O2ⁱ—Rb1—O3ⁱⁱⁱ	60.03 (6)	O2^vi—Rb2—O3^ix	57.12 (6)
O2—Rb1—O3ⁱⁱⁱ	167.85 (6)	O2^x—Rb2—O3^ix	127.65 (6)
O2ⁱⁱ—Rb1—O3ⁱⁱⁱ	97.32 (6)	O1^xi—Rb2—O3^ix	107.20 (6)
O2ⁱⁱⁱ—Rb1—O3ⁱⁱⁱ	52.73 (6)	O1^xii—Rb2—O3^ix	61.64 (6)
O3—Rb1—O3ⁱⁱⁱ	117.67 (5)	O3^viii—Rb2—O3^ix	90.15 (9)
O2ⁱ—Rb1—O3ⁱ	52.73 (6)	O3—Mo—O4	107.22 (12)
O2—Rb1—O3ⁱ	97.32 (6)	O3—Mo—O2	108.00 (12)
O2ⁱⁱ—Rb1—O3ⁱ	167.85 (6)	O4—Mo—O2	110.88 (11)
O2ⁱⁱⁱ—Rb1—O3ⁱ	60.03 (6)	O3—Mo—O1	107.90 (12)
O3—Rb1—O3ⁱ	117.67 (5)	O4—Mo—O1	111.04 (11)
O3ⁱⁱⁱ—Rb1—O3ⁱ	94.09 (9)	O2—Mo—O1	111.60 (11)
O2ⁱ—Rb1—O3ⁱⁱ	97.32 (6)	O3—Mo—Rb2	55.19 (8)
O2—Rb1—O3ⁱⁱ	60.03 (6)	O4—Mo—Rb2	52.06 (8)
O2ⁱⁱ—Rb1—O3ⁱⁱ	52.73 (6)	O2—Mo—Rb2	122.76 (8)
O2ⁱⁱⁱ—Rb1—O3ⁱⁱ	167.85 (6)	O1—Mo—Rb2	125.61 (7)
O3—Rb1—O3ⁱⁱ	94.09 (9)	O3—Mo—Rb1	56.73 (9)
O3ⁱⁱⁱ—Rb1—O3ⁱⁱ	117.67 (5)	O4—Mo—Rb1	125.25 (8)
O3ⁱ—Rb1—O3ⁱⁱ	117.67 (5)	O2—Mo—Rb1	51.29 (8)
O2ⁱ—Rb1—O4^iv	110.30 (6)	O1—Mo—Rb1	123.70 (8)
O2—Rb1—O4^iv	72.07 (6)	Rb2—Mo—Rb1	91.481 (5)
O2ⁱⁱ—Rb1—O4^iv	118.39 (6)	O3—Mo—Rb2^xiii	57.43 (9)
O2ⁱⁱⁱ—Rb1—O4^iv	59.04 (6)	O4—Mo—Rb2^xiii	124.99 (9)
O3—Rb1—O4^iv	58.35 (6)	O2—Mo—Rb2^xiii	124.13 (8)
O3ⁱⁱⁱ—Rb1—O4^iv	110.42 (6)	O1—Mo—Rb2^xiii	50.48 (7)
O3ⁱ—Rb1—O4^iv	60.68 (6)	Rb2—Mo—Rb2^xiii	93.783 (7)
O3ⁱⁱ—Rb1—O4^iv	131.72 (6)	Rb1—Mo—Rb2^xiii	91.893 (6)
O2ⁱ—Rb1—O4^v	59.04 (6)	O1ⁱⁱ—Ga—O1^xiv	109.60 (8)
O2—Rb1—O4^v	118.39 (6)	O1ⁱⁱ—Ga—O1	109.21 (15)
O2ⁱⁱ—Rb1—O4^v	72.07 (6)	O1^xiv—Ga—O1	109.60 (8)
O2ⁱⁱⁱ—Rb1—O4^v	110.30 (6)	O1ⁱⁱ—Ga—O1^xv	109.60 (8)
O3—Rb1—O4^v	131.72 (6)	O1^xiv—Ga—O1^xv	109.21 (15)
O3ⁱⁱⁱ—Rb1—O4^v	60.68 (6)	O1—Ga—O1^xv	109.60 (8)
O3ⁱ—Rb1—O4^v	110.42 (6)	O1ⁱⁱ—Ga—Rb2^xvi	155.93 (8)
O3ⁱⁱ—Rb1—O4^v	58.35 (6)	O1^xiv—Ga—Rb2^xvi	57.21 (8)
O4^iv—Rb1—O4^v	168.14 (9)	O1—Ga—Rb2^xvi	63.53 (8)
O2ⁱ—Rb1—O4^vi	118.39 (6)	O1^xv—Ga—Rb2^xvi	94.26 (7)
O2—Rb1—O4^vi	110.30 (6)	O1ⁱⁱ—Ga—Rb2^xvii	63.53 (8)
O2ⁱⁱ—Rb1—O4^vi	59.04 (6)	O1^xiv—Ga—Rb2^xvii	94.26 (7)
O2ⁱⁱⁱ—Rb1—O4^vi	72.07 (6)	O1—Ga—Rb2^xvii	155.93 (8)
O3—Rb1—O4^vi	60.68 (6)	O1^xv—Ga—Rb2^xvii	57.21 (8)
O3ⁱⁱⁱ—Rb1—O4^vi	58.35 (6)	Rb2^xvi—Ga—Rb2^xvii	132.425 (3)
O3ⁱ—Rb1—O4^vi	131.72 (6)	O1ⁱⁱ—Ga—Rb2^xviii	57.21 (8)
O3ⁱⁱ—Rb1—O4^vi	110.42 (6)	O1^xiv—Ga—Rb2^xviii	63.53 (8)
O4^iv—Rb1—O4^vi	90.612 (9)	O1—Ga—Rb2^xviii	94.26 (7)
O4^v—Rb1—O4^vi	90.612 (9)	O1^xv—Ga—Rb2^xviii	155.93 (8)
O2ⁱ—Rb1—O4^vii	72.07 (6)	Rb2^xvi—Ga—Rb2^xviii	99.363 (1)
O2—Rb1—O4^vii	59.04 (6)	Rb2^xvii—Ga—Rb2^xviii	99.363 (1)
O2ⁱⁱ—Rb1—O4^vii	110.30 (6)	O1ⁱⁱ—Ga—Rb2^xiii	94.26 (7)
O2ⁱⁱⁱ—Rb1—O4^vii	118.39 (6)	O1^xiv—Ga—Rb2^xiii	155.93 (8)
O3—Rb1—O4^vii	110.42 (6)	O1—Ga—Rb2^xiii	57.21 (8)
O3ⁱⁱⁱ—Rb1—O4^vii	131.72 (6)	O1^xv—Ga—Rb2^xiii	63.53 (8)
O3ⁱ—Rb1—O4^vii	58.35 (6)	Rb2^xvi—Ga—Rb2^xiii	99.363 (1)
O3ⁱⁱ—Rb1—O4^vii	60.68 (6)	Rb2^xvii—Ga—Rb2^xiii	99.363 (1)
O4^iv—Rb1—O4^vii	90.612 (9)	Rb2^xviii—Ga—Rb2^xiii	132.425 (3)
O4^v—Rb1—O4^vii	90.612 (9)	O4^vii—Li—O4^xviii	106.1 (4)
O4^vi—Rb1—O4^vii	168.14 (9)	O4^vii—Li—O2^iv	111.85 (11)
O4^iv—Rb2—O4	75.77 (9)	O4^xviii—Li—O2^iv	109.18 (11)
O4^iv—Rb2—O1^viii	128.06 (6)	O4^vii—Li—O2	109.18 (11)
O4—Rb2—O1^viii	131.16 (6)	O4^xviii—Li—O2	111.85 (11)
O4^iv—Rb2—O1^ix	131.16 (6)	O2^iv—Li—O2	108.7 (4)
O4—Rb2—O1^ix	128.06 (6)	O4^vii—Li—Rb2ⁱ	57.30 (10)
O1^viii—Rb2—O1^ix	72.30 (8)	O4^xviii—Li—Rb2ⁱ	92.42 (17)
O4^iv—Rb2—O3	62.42 (7)	O2^iv—Li—Rb2ⁱ	64.78 (9)
O4—Rb2—O3	54.02 (6)	O2—Li—Rb2ⁱ	155.34 (13)
O1^viii—Rb2—O3	167.51 (6)	O4^vii—Li—Rb2^xviii	92.42 (17)
O1^ix—Rb2—O3	95.65 (6)	O4^xviii—Li—Rb2^xviii	57.30 (10)
O4^iv—Rb2—O3^iv	54.02 (6)	O2^iv—Li—Rb2^xviii	155.34 (13)
O4—Rb2—O3^iv	62.42 (7)	O2—Li—Rb2^xviii	64.78 (9)
O1^viii—Rb2—O3^iv	95.65 (6)	Rb2ⁱ—Li—Rb2^xviii	131.1 (2)
O1^ix—Rb2—O3^iv	167.51 (6)	O4^vii—Li—Rb1^xix	157.44 (16)
O3—Rb2—O3^iv	96.56 (10)	O4^xviii—Li—Rb1^xix	64.28 (10)
O4^iv—Rb2—O2^vi	60.77 (6)	O2^iv—Li—Rb1^xix	57.78 (10)
O4—Rb2—O2^vi	114.36 (6)	O2—Li—Rb1^xix	93.37 (17)
O1^viii—Rb2—O2^vi	114.41 (6)	Rb2ⁱ—Li—Rb1^xix	101.431 (6)
O1^ix—Rb2—O2^vi	70.39 (6)	Rb2^xviii—Li—Rb1^xix	97.986 (6)
O3—Rb2—O2^vi	62.67 (6)	O4^vii—Li—Rb1	64.28 (10)
O3^iv—Rb2—O2^vi	113.27 (6)	O4^xviii—Li—Rb1	157.44 (16)
O4^iv—Rb2—O2^x	114.36 (6)	O2^iv—Li—Rb1	93.37 (17)
O4—Rb2—O2^x	60.77 (6)	O2—Li—Rb1	57.78 (10)
O1^viii—Rb2—O2^x	70.39 (6)	Rb2ⁱ—Li—Rb1	97.986 (6)
O1^ix—Rb2—O2^x	114.41 (6)	Rb2^xviii—Li—Rb1	101.431 (6)
O3—Rb2—O2^x	113.27 (6)	Rb1^xix—Li—Rb1	132.0 (2)
O3^iv—Rb2—O2^x	62.67 (6)	Ga—O1—Mo	138.77 (14)
O2^vi—Rb2—O2^x	174.49 (9)	Ga—O1—Rb2^xiii	93.13 (9)
O4^iv—Rb2—O1^xi	119.82 (6)	Mo—O1—Rb2^xiii	102.15 (9)
O4—Rb2—O1^xi	72.73 (6)	Ga—O1—Rb2^xvi	86.82 (8)
O1^viii—Rb2—O1^xi	111.24 (5)	Mo—O1—Rb2^xvi	114.82 (10)
O1^ix—Rb2—O1^xi	55.43 (7)	Rb2^xiii—O1—Rb2^xvi	122.57 (7)
O3—Rb2—O1^xi	57.51 (6)	Mo—O2—Li	140.3 (2)
O3^iv—Rb2—O1^xi	134.93 (7)	Mo—O2—Rb1	102.33 (10)
O2^vi—Rb2—O1^xi	88.30 (5)	Li—O2—Rb1	90.14 (8)
O2^x—Rb2—O1^xi	92.40 (5)	Mo—O2—Rb2^xviii	118.13 (11)
O4^iv—Rb2—O1^xii	72.73 (6)	Li—O2—Rb2^xviii	83.02 (16)
O4—Rb2—O1^xii	119.82 (6)	Rb1—O2—Rb2^xviii	123.50 (7)
O1^viii—Rb2—O1^xii	55.43 (7)	Mo—O3—Rb2	97.88 (10)
O1^ix—Rb2—O1^xii	111.24 (5)	Mo—O3—Rb1	96.90 (10)
O3—Rb2—O1^xii	134.93 (7)	Rb2—O3—Rb1	117.97 (8)
O3^iv—Rb2—O1^xii	57.51 (6)	Mo—O3—Rb2^xiii	96.81 (10)
O2^vi—Rb2—O1^xii	92.40 (5)	Rb2—O3—Rb2^xiii	120.95 (8)
O2^x—Rb2—O1^xii	88.30 (5)	Rb1—O3—Rb2^xiii	116.42 (7)
O1^xi—Rb2—O1^xii	165.41 (8)	Mo—O4—Li^x	142.7 (2)
O4^iv—Rb2—O3^viii	171.31 (6)	Mo—O4—Rb2	100.83 (10)
O4—Rb2—O3^viii	97.25 (6)	Li^x—O4—Rb2	90.30 (9)
O1^viii—Rb2—O3^viii	53.12 (6)	Mo—O4—Rb1^xix	119.19 (11)
O1^ix—Rb2—O3^viii	57.29 (6)	Li^x—O4—Rb1^xix	83.92 (17)
O3—Rb2—O3^viii	117.80 (6)	Rb2—O4—Rb1^xix	119.37 (7)
O3^iv—Rb2—O3^viii	118.27 (6)

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

Selected interatomic distances (Å) for Cs₃LiZn₂(WO₄)₄ and Rb₃Li₂Ga(MoO₄)₄ top

Cs₃LiZn2(WO₄)₄		Rb₃Li₂Ga(MoO₄)₄
W–tetrahedron		Mo–tetrahedron
W—O1	1.737 (9)	Mo—O3	1.721 (3)
W—O2	1.783 (4) (×3)	Mo—O4	1.746 (2)
<W—O>	1.772	Mo—O2	1.750 (2)
		Mo—O1	1.849 (2)
		<Mo—O>	1.767

(Zn_2/3Li_1/3)–tetrahedron		Ga–tetrahedron
(Zn_2/3Li_1/3)–O2	1.935 (5) (×4)	Ga—O1	1.827 (2) (×4)
		Li–tetrahedron
		Li—O4	1.925 (5) (×2)
		Li—O2	1.929 (5) (×2)
		<Li—O>	1.927

Cs–cuboctahedron		Rb(1)–cuboctahedron
Cs—O2	3.271 (5) (×4)	Rb1—O2	3.073 (2) (×4)
Cs—O1	3.3604 (15) (×4)	Rb1—O3	3.240 (3) (×4)
Cs—O2'	3.367 (5) (×4)	Rb1—O4	3.291 (3) (×4)
<Cs—O>	3.333	<Rb1—O>	3.201

		Rb2–cuboctahedron
		Rb2—O4	3.023 (3) (×2)
		Rb2—O1	3.103 (2) (×2)
		Rb2—O3	3.120 (2) (×2)
		Rb2—O2	3.274 (2) (×2)
		Rb2—O1'	3.304 (2) (×2)
		Rb2—O3'	3.338 (3) (×2)
		<Rb2—O>	3.194

The lattice parameters (Å) of single crystals and melting points (K) of compounds of the Cs₆Zn₅(MoO₄)₈ family (our data) top

Compound	a	M.p.	Compound	a	c	M.p.
Cs₆Zn₅(MoO₄)₈	12.2568 (2)	923	Tl₃Li₂Al(MoO₄)₄	11.7632 (2)**	11.7837 (4)	–
Rb₃LiZn₂(MoO₄)₄	11.9018 (14)	853	Rb₃Li₂Al(MoO₄)₄	11.8948 (4)	11.7981 (6)	873
Cs₃LiZn₂(MoO₄)₄	12.2100 (1)	1003	Rb₃Li₂Ga(MoO₄)₄	11.8635 (3)	11.8932 (4)	833
Cs₃LiCo₂(MoO₄)₄	12.2239 (2)	1013*	Cs₃Li₂Al(MoO₄)₄	12.2168 (2)	12.0951 (3)	983
Cs₃LiZn₂(WO₄)₄	12.2643 (1)	1003	Cs₃Li₂Ga(MoO₄)₄	12.1957 (6)	12.1709 (5)	923
Cs₃NaZn₂(MoO₄)₄	12.3134 (1)	783	Cs₃Li₂Fe(MoO₄)₄	12.1967 (3)**	12.2391 (5)	883
Cs₃AgZn₂(MoO₄)₄	12.321 (2)**	803	–	–	–	–

Notes: (*) compound decomposes in the solid phase into Cs₂Co₂(MoO₄)₃ and CsLiMoO₄; (**) PXRD data.

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