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Two new isotypic triple molybdates, namely tri­cesium lithium dicobalt tetra­kis­(tetra­oxo­molybdate), Cs3LiCo2(MoO4)4, and tri­rubidium lithium dizinc tetra­kis­(tetra­oxo­molybdate), Rb3LiZn2(MoO4)4, crystallize in the non-centrosymmetric cubic space group I\overline{4}3d and adopt the Cs6Zn5(MoO4)8 structure type. In the parent structure, the Zn positions have 5/6 occupancy, while they are fully occupied by statistically distributed M2+ and Li+ cations in the title compounds. In both structures, all corners of the (M2/3Li1/3)O4 tetra­hedra (M = Co and Zn), having point symmetry \overline{4}, are shared with the MoO4 tetra­hedra, which lie on threefold axes and share corners with three (M,Li)O4 tetra­hedra to form open mixed frameworks. Large alkaline cations occupy distorted cubocta­hedral cavities with \overline{4} symmetry. The mixed tetra­hedral frameworks in the structures are close to those of mayenite (12CaO·7Al2O3) and the related compounds 11CaO·7Al2O3·CaF2, wadalite (Ca6Al5Si2O16Cl3) and Na6Zn3(AsO4)4·3H2O, but the terminal vertices of the MoO4 tetra­hedra are directed in opposite directions along the threefold axes compared with the configurations of Al(Si)O4 or AsO4 tetra­hedra. The cation arrangements in Cs3LiCo2(MoO4)4, Rb3LiZn2(MoO4)4 and Cs6Zn5(MoO4)8 repeat the structure of Y3Au3Sb4, being stuffed derivatives of the Th3P4 type.

Supporting information

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Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105037121/iz1066sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105037121/iz1066Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270105037121/iz1066IIsup3.hkl
Contains datablock II

Comment top

Double molybdates of alkaline and bivalent ions formed in the systems A2MoO4–MMoO4 (A = Li, Na, K, Rb and Cs; M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and Ba) have been well known for at least three decades, and some of them, such as K4Zn(MoO4)3 and A2Pb(MoO4)2 (A = K, Rb and Cs), may be used as ferroelastic and other inorganic materials (Solodovnikov et al., 1994). Most of the studied [or 'The most frequently studied'?] structures of these molybdates, for example, Li2Ni2(MoO4)3 (Ozima & Sato, 1977), K2Zn2(MoO4)3 (Gicquel-Mayer & Perez, 1975), K2Ni(MoO4)2 (Klevtsova & Klevtsov, 1978) and Rb2Cu2(MoO4)3 (Solodovnikov & Solodovnikova, 1997), contain MO6 octahedra and MoO4 tetrahedra linked by the corners. Other O-atom coordinations of bivalent cations were found in the structures of Rb4Mn(MoO4)3 and Cs4Cu(MoO4)3 (Solodovnikov et al., 1988), with trigonal bipyramids around M2+ (M = Mn and Cu), and in K4Zn(MoO4)3 (Gicquel-Mayer et al., 1980) and Cs6Zn5(MoO4)8 (Solodovnikov et al., 1987; Mueller et al., 1987), with ZnO4 tetrahedra. The latter structure is unique among double salts with tetrahedral oxoanions and has an incomplete Zn position (site occupation factor = 5/6), leading to the formula Cs3(Zn5/6□1/6)3(MoO4)4, where □ denotes a cationic vacancy. The only triple molybdate known to date, which contains two monovalent cations along with a bivalent cation, viz. AgKCu3(MoO4)4 (Szillat & Mūller-Buschbaum, 1995), has a crystal structure very close to that of K2Cu3(MoO4)4 (Glinskaya et al., 1980), with highly distorted CuO6 octahedra. This paper presents the crystal structure determination of two new triple molybdates, Cs3LiCo2(MoO4)4, (I), and Rb3LiZn2(MoO4)4, (II), isolated upon studying the phase formation in the systems Cs2MoO4–Li2MoO4–CoMoO4 and Rb2MoO4–Li2MoO4–ZnMoO4.

In the title structures, the Li+ and M2+ (M = Co and Zn) cations are statistically distributed in the 12a Wyckoff position (site symmetry 4), whereas the Cs and Mo atoms occupy the 12b (site symmetry 4) and 16c (site symmetry 3) positions, respectively. Atoms, O1 and O2 are in the special 16c and general 48e positions, respectively, forming tetrahedral environments around the M,Li position and Mo atoms. Among molybdates, tetrahedral coordination of Co2+ is found for the first time. Metal–oxygen distances in the (M2/3Li1/3)O4 tetrahedra (M = Co and Zn) are in a good agreement with the Co—O (1.967–1.980 Å) and Li—O (1.774–2.092 Å) bond lengths in βII-Li2CoSiO4 (Yamaguchi et al., 1979) and the Zn—O (1.858–2.038 Å) bond lengths in K4Zn(MoO4)3 (Gicquel-Mayer et al., 1980). In the Cs6Zn5(MoO4)8 structure (Solodovnikov et al., 1987; Mueller et al., 1987), the slightly increased Zn—O distances (1.98–2.00 Å) could be caused by the presence of vacancies in the Zn positions.

In the structures of (I) and (II), the (M2/3Li1/3)O4 tetrahedra (M = Co and Zn) share all corners with the MoO4 tetrahedra, which their three corners with the adjacent (M, Li)O4 tetrahedra to form open mixed frameworks (Fig. 1). Characteristic details of the frameworks are the eight-membered rings of alternating (M2/3Li1/3)O4 and MoO4 tetrahedra (1–8 in Fig. 2). Each (M2/3Li1/3)O4 tetrahedron takes part in four rings, whereas the MoO4 tetrahedron connects three rings. The eight-membered ring together with four terminal MoO4 tetrahedra (9–12 in Fig. 2) attached to the (M2/3Li1/3)O4 tetrahedra form a cage around the large cations Cs+ or Rb+, having a distorted 12-fold cuboctahedral coordination.

Both compounds adopt the Cs6Zn5(MoO4)8 structure type (Solodovnikov et al., 1987; Mueller et al., 1987). Thus, (I) and (II) may be considered as completely filled derivatives of the Cs6Zn5(MoO4)8 structure following the scheme 5Zn2+ + □ 4M2+ + 2Li+. It is interesting that the cation arrangements in these three compounds repeat the atomic arrangement of the Y3Au3Sb4 structure (Dwight, 1977), being in turn a stuffed derivative of the Th3P4 type.

The mixed tetrahedral frameworks in (I), (II) and Cs6Zn5(MoO4)8 are close to those of mayenite (12CaO·7 A l2O3; Bartl & Scheller, 1970) and the related compounds 11CaO·7 A l2O3·CaF2 (Williams, 1973), wadalite (Ca6Al5Si2O16Cl3; Tsukimura et al., 1993) and Na6Zn3(AsO4)4·3H2O (Grey et al., 1989). However, there is an important difference; the terminal vertices of the MoO4 tetrahedra are oppositely directed along the threefold axes compared with the Al(Si)O4 or AsO4 tetrahedra. The latter arrangement substantially changes the configuration of the tetrahedral cage around the out-of-framework ions, instead providing three new inner sites occupied by two Ca2+ or Na+ cations, and O2-, F- or Cl- anions or wer molecules.

Experimental top

Compounds (I) and (II) were revealed upon studying the systems Cs2MoO4–Li2MoO4–CoMoO4 and Rb2MoO4–Li2MoO4–ZnMoO4. Polycrystalline samples of the compounds were prepared by solid-state reactions from simple molybdates at 773 K for 150 h. Single crystals were grown by spontaneous crystallization of melted mixtures of Li2MoO4, Cs2MoO4, 2CoMoO4 and 2Cs2Mo2O7, and sintered Rb3LiZn2(MoO4)4 and 3Rb2Mo2O7, upon slow cooling at rates of 3 K h-1 in the ranges 873–673 K and 793–673 K, respectively. X-ray powder diffraction patterns of ground crystals of both compounds were consistent with their calculated powder diffractograms, experimental X-ray diffraction data for corresponding sintered samples and the powder pattern reported for Cs6Zn5(MoO4)8 (Solodovnikov et al., 1987). The crystals have the shapes of partly faceted fragments of a cubic habit with the maximum dimensions of 2 mm.

Refinement top

In both structures, the contents of the M,Li positions (M = Co and Zn) were accepted as 2/3M + 1/3Li taking into account their complete occupations and electroneutrality requirements in accordance with X-ray diffraction data for corresponding sintered samples.

Structure description top

Double molybdates of alkaline and bivalent ions formed in the systems A2MoO4–MMoO4 (A = Li, Na, K, Rb and Cs; M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and Ba) have been well known for at least three decades, and some of them, such as K4Zn(MoO4)3 and A2Pb(MoO4)2 (A = K, Rb and Cs), may be used as ferroelastic and other inorganic materials (Solodovnikov et al., 1994). Most of the studied [or 'The most frequently studied'?] structures of these molybdates, for example, Li2Ni2(MoO4)3 (Ozima & Sato, 1977), K2Zn2(MoO4)3 (Gicquel-Mayer & Perez, 1975), K2Ni(MoO4)2 (Klevtsova & Klevtsov, 1978) and Rb2Cu2(MoO4)3 (Solodovnikov & Solodovnikova, 1997), contain MO6 octahedra and MoO4 tetrahedra linked by the corners. Other O-atom coordinations of bivalent cations were found in the structures of Rb4Mn(MoO4)3 and Cs4Cu(MoO4)3 (Solodovnikov et al., 1988), with trigonal bipyramids around M2+ (M = Mn and Cu), and in K4Zn(MoO4)3 (Gicquel-Mayer et al., 1980) and Cs6Zn5(MoO4)8 (Solodovnikov et al., 1987; Mueller et al., 1987), with ZnO4 tetrahedra. The latter structure is unique among double salts with tetrahedral oxoanions and has an incomplete Zn position (site occupation factor = 5/6), leading to the formula Cs3(Zn5/6□1/6)3(MoO4)4, where □ denotes a cationic vacancy. The only triple molybdate known to date, which contains two monovalent cations along with a bivalent cation, viz. AgKCu3(MoO4)4 (Szillat & Mūller-Buschbaum, 1995), has a crystal structure very close to that of K2Cu3(MoO4)4 (Glinskaya et al., 1980), with highly distorted CuO6 octahedra. This paper presents the crystal structure determination of two new triple molybdates, Cs3LiCo2(MoO4)4, (I), and Rb3LiZn2(MoO4)4, (II), isolated upon studying the phase formation in the systems Cs2MoO4–Li2MoO4–CoMoO4 and Rb2MoO4–Li2MoO4–ZnMoO4.

In the title structures, the Li+ and M2+ (M = Co and Zn) cations are statistically distributed in the 12a Wyckoff position (site symmetry 4), whereas the Cs and Mo atoms occupy the 12b (site symmetry 4) and 16c (site symmetry 3) positions, respectively. Atoms, O1 and O2 are in the special 16c and general 48e positions, respectively, forming tetrahedral environments around the M,Li position and Mo atoms. Among molybdates, tetrahedral coordination of Co2+ is found for the first time. Metal–oxygen distances in the (M2/3Li1/3)O4 tetrahedra (M = Co and Zn) are in a good agreement with the Co—O (1.967–1.980 Å) and Li—O (1.774–2.092 Å) bond lengths in βII-Li2CoSiO4 (Yamaguchi et al., 1979) and the Zn—O (1.858–2.038 Å) bond lengths in K4Zn(MoO4)3 (Gicquel-Mayer et al., 1980). In the Cs6Zn5(MoO4)8 structure (Solodovnikov et al., 1987; Mueller et al., 1987), the slightly increased Zn—O distances (1.98–2.00 Å) could be caused by the presence of vacancies in the Zn positions.

In the structures of (I) and (II), the (M2/3Li1/3)O4 tetrahedra (M = Co and Zn) share all corners with the MoO4 tetrahedra, which their three corners with the adjacent (M, Li)O4 tetrahedra to form open mixed frameworks (Fig. 1). Characteristic details of the frameworks are the eight-membered rings of alternating (M2/3Li1/3)O4 and MoO4 tetrahedra (1–8 in Fig. 2). Each (M2/3Li1/3)O4 tetrahedron takes part in four rings, whereas the MoO4 tetrahedron connects three rings. The eight-membered ring together with four terminal MoO4 tetrahedra (9–12 in Fig. 2) attached to the (M2/3Li1/3)O4 tetrahedra form a cage around the large cations Cs+ or Rb+, having a distorted 12-fold cuboctahedral coordination.

Both compounds adopt the Cs6Zn5(MoO4)8 structure type (Solodovnikov et al., 1987; Mueller et al., 1987). Thus, (I) and (II) may be considered as completely filled derivatives of the Cs6Zn5(MoO4)8 structure following the scheme 5Zn2+ + □ 4M2+ + 2Li+. It is interesting that the cation arrangements in these three compounds repeat the atomic arrangement of the Y3Au3Sb4 structure (Dwight, 1977), being in turn a stuffed derivative of the Th3P4 type.

The mixed tetrahedral frameworks in (I), (II) and Cs6Zn5(MoO4)8 are close to those of mayenite (12CaO·7 A l2O3; Bartl & Scheller, 1970) and the related compounds 11CaO·7 A l2O3·CaF2 (Williams, 1973), wadalite (Ca6Al5Si2O16Cl3; Tsukimura et al., 1993) and Na6Zn3(AsO4)4·3H2O (Grey et al., 1989). However, there is an important difference; the terminal vertices of the MoO4 tetrahedra are oppositely directed along the threefold axes compared with the Al(Si)O4 or AsO4 tetrahedra. The latter arrangement substantially changes the configuration of the tetrahedral cage around the out-of-framework ions, instead providing three new inner sites occupied by two Ca2+ or Na+ cations, and O2-, F- or Cl- anions or wer molecules.

Computing details top

For both compounds, data collection: SMART or APEX2? (Bruker, 2004); cell refinement: SMART or APEX2?; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the Cs3LiCo2(MoO4)4 structure.
[Figure 2] Fig. 2. The tetrahedral cage around the Cs atom in the Cs3LiCo2(MoO4)4 structure. An eight-membered ring is indicated by the tetrahedra labelled 1–8; attached tetrahedra are numbered 9–12.
(I) tricesium lithium dicobalt tetrakis(tetraoxomolybdate) top
Crystal data top
Cs3LiCo2(MoO4)4Dx = 4.231 Mg m3
Mr = 1163.34Mo Kα radiation, λ = 0.71073 Å
Cubic, I43dCell parameters from 2582 reflections
Hall symbol: I -4bd 2c 3θ = 4.1–29.0°
a = 12.2239 (2) ŵ = 10.40 mm1
V = 1826.54 (5) Å3T = 293 K
Z = 4Fragment, blue
F(000) = 20720.11 × 0.10 × 0.01 mm
Data collection top
Bruker-Nonius X8 APEX CCD
diffractometer
705 independent reflections
Radiation source: fine-focus sealed X-ray tube615 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
φ scans, frame data integrationθmax = 35.9°, θmin = 4.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1911
Tmin = 0.394, Tmax = 0.903k = 1919
8959 measured reflectionsl = 1912
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018 w = 1/[σ2(Fo2) + (0.0203P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.038(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.54 e Å3
705 reflectionsΔρmin = 0.61 e Å3
20 parametersAbsolute structure: Flack (1983), 303 Friedel pairs
0 restraintsAbsolute structure parameter: 0.002 (17)
Crystal data top
Cs3LiCo2(MoO4)4Z = 4
Mr = 1163.34Mo Kα radiation
Cubic, I43dµ = 10.40 mm1
a = 12.2239 (2) ÅT = 293 K
V = 1826.54 (5) Å30.11 × 0.10 × 0.01 mm
Data collection top
Bruker-Nonius X8 APEX CCD
diffractometer
705 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
615 reflections with I > 2σ(I)
Tmin = 0.394, Tmax = 0.903Rint = 0.038
8959 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.038Δρmax = 0.54 e Å3
S = 0.99Δρmin = 0.61 e Å3
705 reflectionsAbsolute structure: Flack (1983), 303 Friedel pairs
20 parametersAbsolute structure parameter: 0.002 (17)
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Cs0.87500.00000.25000.03197 (10)
Mo0.399978 (17)0.399978 (17)0.399978 (17)0.01762 (7)
Co0.62500.50000.25000.0216 (2)0.666667
Li0.62500.50000.25000.0216 (2)0.333333
O10.31880 (16)0.31880 (16)0.31880 (16)0.0305 (8)
O20.53058 (16)0.40826 (17)0.33772 (18)0.0293 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs0.02465 (17)0.03562 (13)0.03562 (13)0.0000.0000.000
Mo0.01762 (7)0.01762 (7)0.01762 (7)0.00285 (7)0.00285 (7)0.00285 (7)
Co0.0166 (4)0.0241 (3)0.0241 (3)0.0000.0000.000
Li0.0166 (4)0.0241 (3)0.0241 (3)0.0000.0000.000
O10.0305 (7)0.0305 (7)0.0305 (7)0.0018 (8)0.0018 (8)0.0018 (8)
O20.0221 (9)0.0328 (10)0.0329 (10)0.0009 (8)0.0099 (8)0.0025 (8)
Geometric parameters (Å, º) top
Cs—O2i3.262 (2)Mo—Csxvii4.4604 (2)
Cs—O2ii3.262 (2)Mo—Csxviii4.4604 (2)
Cs—O2iii3.262 (2)Mo—Csxix4.4604 (2)
Cs—O2iv3.262 (2)Co—O2xx1.9338 (19)
Cs—O1v3.350 (2)Co—O2xxi1.9338 (19)
Cs—O1vi3.350 (2)Co—O21.9338 (19)
Cs—O1vii3.350 (2)Co—O2xxii1.9338 (19)
Cs—O1viii3.350 (2)Co—Csxv3.7428
Cs—O2ix3.361 (2)Co—Csxvii3.7428
Cs—O2x3.361 (2)Co—Csxviii3.7428
Cs—O2xi3.361 (2)Co—Csxxiii3.7428
Cs—O2xii3.361 (2)O1—Csxv3.350 (2)
Mo—O11.719 (4)O1—Csviii3.350 (2)
Mo—O2xiii1.7715 (18)O1—Csxvi3.350 (2)
Mo—O2xiv1.7715 (18)O2—Liviii1.9338 (19)
Mo—O21.7715 (18)O2—Coviii1.9338 (19)
Mo—Csviii4.0192 (2)O2—Csxv3.262 (2)
Mo—Csxv4.0192 (2)O2—Csxvii3.361 (2)
Mo—Csxvi4.0192 (2)
O2i—Cs—O2ii129.44 (4)O1—Mo—Csxv55.211 (4)
O2i—Cs—O2iii74.31 (7)O2xiii—Mo—Csxv122.71 (7)
O2ii—Cs—O2iii129.44 (4)O2xiv—Mo—Csxv126.13 (7)
O2i—Cs—O2iv129.44 (4)O2—Mo—Csxv52.60 (8)
O2ii—Cs—O2iv74.31 (7)Csviii—Mo—Csxv90.670 (6)
O2iii—Cs—O2iv129.44 (4)O1—Mo—Csxvi55.211 (4)
O2i—Cs—O1v169.84 (3)O2xiii—Mo—Csxvi52.60 (8)
O2ii—Cs—O1v50.46 (7)O2xiv—Mo—Csxvi122.71 (7)
O2iii—Cs—O1v98.21 (5)O2—Mo—Csxvi126.13 (7)
O2iv—Cs—O1v60.63 (4)Csviii—Mo—Csxvi90.670 (6)
O2i—Cs—O1vi60.63 (4)Csxv—Mo—Csxvi90.670 (6)
O2ii—Cs—O1vi169.84 (3)O1—Mo—Csxvii132.266 (3)
O2iii—Cs—O1vi50.46 (7)O2xiii—Mo—Csxvii70.65 (7)
O2iv—Cs—O1vi98.21 (5)O2xiv—Mo—Csxvii117.26 (8)
O1v—Cs—O1vi120.00 (4)O2—Mo—Csxvii42.03 (8)
O2i—Cs—O1vii50.46 (7)Csviii—Mo—Csxvii161.457 (3)
O2ii—Cs—O1vii98.21 (5)Csxv—Mo—Csxvii84.618 (1)
O2iii—Cs—O1vii60.63 (4)Csxvi—Mo—Csxvii107.272 (1)
O2iv—Cs—O1vii169.84 (3)O1—Mo—Csxviii132.266 (3)
O1v—Cs—O1vii120.00 (4)O2xiii—Mo—Csxviii117.26 (8)
O1vi—Cs—O1vii90.01 (8)O2xiv—Mo—Csxviii42.03 (8)
O2i—Cs—O1viii98.21 (5)O2—Mo—Csxviii70.65 (7)
O2ii—Cs—O1viii60.63 (4)Csviii—Mo—Csxviii84.618 (1)
O2iii—Cs—O1viii169.84 (3)Csxv—Mo—Csxviii107.272 (1)
O2iv—Cs—O1viii50.46 (7)Csxvi—Mo—Csxviii161.457 (3)
O1v—Cs—O1viii90.01 (8)Csxvii—Mo—Csxviii79.716 (5)
O1vi—Cs—O1viii120.00 (4)O1—Mo—Csxix132.266 (3)
O1vii—Cs—O1viii120.00 (4)O2xiii—Mo—Csxix42.03 (8)
O2i—Cs—O2ix57.46 (6)O2xiv—Mo—Csxix70.65 (7)
O2ii—Cs—O2ix120.13 (6)O2—Mo—Csxix117.26 (8)
O2iii—Cs—O2ix110.18 (4)Csviii—Mo—Csxix107.272 (1)
O2iv—Cs—O2ix71.99 (4)Csxv—Mo—Csxix161.457 (3)
O1v—Cs—O2ix132.54 (3)Csxvi—Mo—Csxix84.618 (1)
O1vi—Cs—O2ix62.29 (6)Csxvii—Mo—Csxix79.716 (5)
O1vii—Cs—O2ix107.09 (7)Csxviii—Mo—Csxix79.716 (5)
O1viii—Cs—O2ix59.67 (4)O2xx—Co—O2xxi106.71 (13)
O2i—Cs—O2x110.18 (4)O2xx—Co—O2110.87 (6)
O2ii—Cs—O2x71.99 (4)O2xxi—Co—O2110.87 (6)
O2iii—Cs—O2x57.46 (6)O2xx—Co—O2xxii110.87 (6)
O2iv—Cs—O2x120.13 (6)O2xxi—Co—O2xxii110.87 (6)
O1v—Cs—O2x59.67 (4)O2—Co—O2xxii106.71 (13)
O1vi—Cs—O2x107.09 (7)O2xx—Co—Csxv158.93 (7)
O1vii—Cs—O2x62.29 (6)O2xxi—Co—Csxv63.52 (7)
O1viii—Cs—O2x132.54 (3)O2—Co—Csxv60.61 (7)
O2ix—Cs—O2x166.10 (7)O2xxii—Co—Csxv90.20 (6)
O2i—Cs—O2xi120.13 (6)O2xx—Co—Csxvii60.61 (7)
O2ii—Cs—O2xi110.18 (4)O2xxi—Co—Csxvii90.20 (6)
O2iii—Cs—O2xi71.99 (4)O2—Co—Csxvii63.52 (7)
O2iv—Cs—O2xi57.46 (6)O2xxii—Co—Csxvii158.93 (7)
O1v—Cs—O2xi62.29 (6)Csxv—Co—Csxvii99.6
O1vi—Cs—O2xi59.67 (4)O2xx—Co—Csxviii63.52 (7)
O1vii—Cs—O2xi132.54 (3)O2xxi—Co—Csxviii158.93 (7)
O1viii—Cs—O2xi107.09 (7)O2—Co—Csxviii90.20 (6)
O2ix—Cs—O2xi90.839 (9)O2xxii—Co—Csxviii60.61 (7)
O2x—Cs—O2xi90.839 (9)Csxv—Co—Csxviii131.8
O2i—Cs—O2xii71.99 (4)Csxvii—Co—Csxviii99.6
O2ii—Cs—O2xii57.46 (6)O2xx—Co—Csxxiii90.20 (6)
O2iii—Cs—O2xii120.13 (6)O2xxi—Co—Csxxiii60.61 (7)
O2iv—Cs—O2xii110.18 (4)O2—Co—Csxxiii158.93 (7)
O1v—Cs—O2xii107.09 (7)O2xxii—Co—Csxxiii63.52 (7)
O1vi—Cs—O2xii132.54 (3)Csxv—Co—Csxxiii99.6
O1vii—Cs—O2xii59.67 (4)Csxvii—Co—Csxxiii131.8
O1viii—Cs—O2xii62.29 (6)Csxviii—Co—Csxxiii99.6
O2ix—Cs—O2xii90.839 (9)Mo—O1—Csxv99.87 (6)
O2x—Cs—O2xii90.839 (9)Mo—O1—Csviii99.87 (6)
O2xi—Cs—O2xii166.10 (7)Csxv—O1—Csviii117.12 (3)
O1—Mo—O2xiii107.78 (8)Mo—O1—Csxvi99.87 (6)
O1—Mo—O2xiv107.78 (8)Csxv—O1—Csxvi117.12 (3)
O2xiii—Mo—O2xiv111.11 (7)Csviii—O1—Csxvi117.12 (3)
O1—Mo—O2107.78 (8)Mo—O2—Co144.02 (12)
O2xiii—Mo—O2111.11 (7)Mo—O2—Csxv101.84 (9)
O2xiv—Mo—O2111.11 (7)Co—O2—Csxv88.30 (7)
O1—Mo—Csviii55.211 (4)Mo—O2—Csxvii117.31 (10)
O2xiii—Mo—Csviii126.13 (7)Co—O2—Csxvii85.48 (7)
O2xiv—Mo—Csviii52.60 (8)Csxv—O2—Csxvii119.35 (6)
O2—Mo—Csviii122.71 (7)
Symmetry codes: (i) z+3/4, y1/4, x1/4; (ii) z+1, x1/2, y+1/2; (iii) z+3/4, y+1/4, x+3/4; (iv) z+1, x+1/2, y; (v) x+1, y1/2, z+1/2; (vi) y+3/4, x+1/4, z+3/4; (vii) y+3/4, x1/4, z1/4; (viii) x+1, y+1/2, z; (ix) y+1/2, z+1/2, x+1; (x) y+1/2, z1/2, x1/2; (xi) y+5/4, x3/4, z+3/4; (xii) y+5/4, x+3/4, z1/4; (xiii) y, z, x; (xiv) z, x, y; (xv) y+1/2, z, x+1; (xvi) z, x+1, y+1/2; (xvii) z+1/2, x1/2, y+1/2; (xviii) y+1/2, z+1/2, x1/2; (xix) x1/2, y+1/2, z+1/2; (xx) x+5/4, z+1/4, y+3/4; (xxi) x+5/4, z+3/4, y1/4; (xxii) x, y+1, z+1/2; (xxiii) z+1/2, x+3/2, y.
(II) 'trirubidium lithium dizinc tetrakis(tetraoxomolybdate)' top
Crystal data top
Rb3LiZn2(MoO4)4Dx = 4.074 Mg m3
Mr = 1033.95Mo Kα radiation, λ = 0.71073 Å
Cubic, I43dCell parameters from 5301 reflections
Hall symbol: I -4bd 2c 3θ = 2.4–34.5°
a = 11.9018 (14) ŵ = 14.37 mm1
V = 1685.9 (3) Å3T = 293 K
Z = 4Fragment, colourless
F(000) = 18800.10 × 0.10 × 0.08 mm
Data collection top
Bruker-Nonius X8 APEX CCD
diffractometer
643 independent reflections
Radiation source: fine-focus sealed X-ray tube617 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ scans, frame data integrationθmax = 35.7°, θmin = 4.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1418
Tmin = 0.264, Tmax = 0.317k = 1019
7827 measured reflectionsl = 1917
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.009P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.011(Δ/σ)max = 0.001
wR(F2) = 0.026Δρmax = 0.31 e Å3
S = 1.07Δρmin = 0.25 e Å3
643 reflectionsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
21 parametersExtinction coefficient: 0.00099 (7)
0 restraintsAbsolute structure: Flack (1983), 365 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.004 (6)
Crystal data top
Rb3LiZn2(MoO4)4Z = 4
Mr = 1033.95Mo Kα radiation
Cubic, I43dµ = 14.37 mm1
a = 11.9018 (14) ÅT = 293 K
V = 1685.9 (3) Å30.10 × 0.10 × 0.08 mm
Data collection top
Bruker-Nonius X8 APEX CCD
diffractometer
643 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
617 reflections with I > 2σ(I)
Tmin = 0.264, Tmax = 0.317Rint = 0.023
7827 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0110 restraints
wR(F2) = 0.026Δρmax = 0.31 e Å3
S = 1.07Δρmin = 0.25 e Å3
643 reflectionsAbsolute structure: Flack (1983), 365 Friedel pairs
21 parametersAbsolute structure parameter: 0.004 (6)
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Rb0.87500.00000.25000.03614 (8)
Mo0.392600 (10)0.392600 (10)0.392600 (10)0.01671 (5)
Zn0.62500.50000.25000.01845 (9)0.666667
Li0.62500.50000.25000.01845 (9)0.333333
O10.30910 (10)0.30910 (10)0.30910 (10)0.0284 (4)
O20.52855 (9)0.39715 (11)0.33085 (10)0.0258 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rb0.02241 (16)0.04301 (13)0.04301 (13)0.0000.0000.000
Mo0.01671 (5)0.01671 (5)0.01671 (5)0.00341 (4)0.00341 (4)0.00341 (4)
Zn0.0133 (2)0.02103 (13)0.02103 (13)0.0000.0000.000
Li0.0133 (2)0.02103 (13)0.02103 (13)0.0000.0000.000
O10.0284 (4)0.0284 (4)0.0284 (4)0.0014 (4)0.0014 (4)0.0014 (4)
O20.0214 (5)0.0257 (5)0.0302 (6)0.0001 (4)0.0088 (4)0.0024 (5)
Geometric parameters (Å, º) top
Rb—O2i3.0307 (12)Mo—Rbxvi3.8286 (5)
Rb—O2ii3.0307 (12)Mo—Rbviii3.8286 (5)
Rb—O2iii3.0307 (12)Zn—O2xvii1.9345 (12)
Rb—O2iv3.0307 (12)Zn—O2xviii1.9345 (12)
Rb—O1v3.2339 (19)Zn—O21.9345 (12)
Rb—O1vi3.2339 (19)Zn—O2xix1.9345 (12)
Rb—O1vii3.2339 (19)Zn—Rbxvi3.6442 (4)
Rb—O1viii3.2339 (19)Zn—Rbxx3.6442 (4)
Rb—O2ix3.3270 (13)Zn—Rbxxi3.6442 (4)
Rb—O2x3.3270 (13)Zn—Rbxxii3.6442 (4)
Rb—O2xi3.3270 (13)O1—Rbxvi3.2339 (19)
Rb—O2xii3.3270 (13)O1—Rbviii3.2339 (19)
Mo—O11.721 (2)O1—Rbxv3.2339 (19)
Mo—O2xiii1.7780 (10)O2—Liviii1.9345 (12)
Mo—O2xiv1.7780 (10)O2—Znviii1.9345 (12)
Mo—O21.7780 (10)O2—Rbxvi3.0307 (12)
Mo—Rbxv3.8286 (5)O2—Rbxx3.3270 (13)
O2i—Rb—O2ii130.81 (3)O2x—Rb—O2xii90.360 (3)
O2i—Rb—O2iii72.12 (5)O2xi—Rb—O2xii170.91 (4)
O2ii—Rb—O2iii130.81 (3)O1—Mo—O2xiii107.72 (4)
O2i—Rb—O2iv130.81 (3)O1—Mo—O2xiv107.72 (4)
O2ii—Rb—O2iv72.12 (5)O2xiii—Mo—O2xiv111.17 (4)
O2iii—Rb—O2iv130.81 (3)O1—Mo—O2107.72 (4)
O2i—Rb—O1v167.99 (3)O2xiii—Mo—O2111.17 (4)
O2ii—Rb—O1v53.51 (4)O2xiv—Mo—O2111.17 (4)
O2iii—Rb—O1v96.74 (3)O1—Mo—Rbxv57.080 (3)
O2iv—Rb—O1v59.95 (2)O2xiii—Mo—Rbxv50.64 (4)
O2i—Rb—O1vi59.95 (2)O2xiv—Mo—Rbxv124.31 (4)
O2ii—Rb—O1vi167.99 (3)O2—Mo—Rbxv124.52 (4)
O2iii—Rb—O1vi53.51 (4)O1—Mo—Rbxvi57.080 (3)
O2iv—Rb—O1vi96.74 (3)O2xiii—Mo—Rbxvi124.31 (4)
O1v—Rb—O1vi117.33 (3)O2xiv—Mo—Rbxvi124.52 (4)
O2i—Rb—O1vii53.51 (4)O2—Mo—Rbxvi50.64 (4)
O2ii—Rb—O1vii96.74 (3)Rbxv—Mo—Rbxvi93.266 (4)
O2iii—Rb—O1vii59.95 (2)O1—Mo—Rbviii57.080 (3)
O2iv—Rb—O1vii167.99 (3)O2xiii—Mo—Rbviii124.52 (4)
O1v—Rb—O1vii117.33 (3)O2xiv—Mo—Rbviii50.64 (4)
O1vi—Rb—O1vii94.69 (5)O2—Mo—Rbviii124.31 (4)
O2i—Rb—O1viii96.74 (3)Rbxv—Mo—Rbviii93.266 (4)
O2ii—Rb—O1viii59.95 (2)Rbxvi—Mo—Rbviii93.266 (4)
O2iii—Rb—O1viii167.99 (3)O2xvii—Zn—O2xviii107.20 (8)
O2iv—Rb—O1viii53.51 (4)O2xvii—Zn—O2110.62 (4)
O1v—Rb—O1viii94.69 (5)O2xviii—Zn—O2110.62 (4)
O1vi—Rb—O1viii117.33 (3)O2xvii—Zn—O2xix110.62 (4)
O1vii—Rb—O1viii117.33 (3)O2xviii—Zn—O2xix110.62 (4)
O2i—Rb—O2ix111.99 (2)O2—Zn—O2xix107.20 (8)
O2ii—Rb—O2ix70.98 (2)O2xvii—Zn—Rbxvi155.06 (4)
O2iii—Rb—O2ix59.83 (4)O2xviii—Zn—Rbxvi65.02 (4)
O2iv—Rb—O2ix117.00 (4)O2—Zn—Rbxvi56.23 (3)
O1v—Rb—O2ix57.06 (2)O2xix—Zn—Rbxvi94.09 (3)
O1vi—Rb—O2ix111.79 (4)O2xvii—Zn—Rbxx56.23 (3)
O1vii—Rb—O2ix61.41 (4)O2xviii—Zn—Rbxx94.09 (3)
O1viii—Rb—O2ix130.63 (2)O2—Zn—Rbxx65.02 (4)
O2i—Rb—O2x59.83 (4)O2xix—Zn—Rbxx155.06 (4)
O2ii—Rb—O2x117.00 (4)Rbxvi—Zn—Rbxx99.6
O2iii—Rb—O2x111.99 (2)O2xvii—Zn—Rbxxi65.02 (4)
O2iv—Rb—O2x70.98 (2)O2xviii—Zn—Rbxxi155.06 (4)
O1v—Rb—O2x130.63 (2)O2—Zn—Rbxxi94.09 (3)
O1vi—Rb—O2x61.41 (4)O2xix—Zn—Rbxxi56.23 (3)
O1vii—Rb—O2x111.79 (4)Rbxvi—Zn—Rbxxi131.8
O1viii—Rb—O2x57.06 (2)Rbxx—Zn—Rbxxi99.6
O2ix—Rb—O2x170.91 (4)O2xvii—Zn—Rbxxii94.09 (3)
O2i—Rb—O2xi117.00 (4)O2xviii—Zn—Rbxxii56.23 (3)
O2ii—Rb—O2xi111.99 (3)O2—Zn—Rbxxii155.06 (4)
O2iii—Rb—O2xi70.98 (2)O2xix—Zn—Rbxxii65.02 (4)
O2iv—Rb—O2xi59.83 (4)Rbxvi—Zn—Rbxxii99.6
O1v—Rb—O2xi61.41 (4)Rbxx—Zn—Rbxxii131.8
O1vi—Rb—O2xi57.06 (2)Rbxxi—Zn—Rbxxii99.6
O1vii—Rb—O2xi130.63 (2)Mo—O1—Rbxvi96.38 (4)
O1viii—Rb—O2xi111.79 (4)Mo—O1—Rbviii96.38 (4)
O2ix—Rb—O2xi90.360 (3)Rbxvi—O1—Rbviii118.781 (14)
O2x—Rb—O2xi90.360 (3)Mo—O1—Rbxv96.38 (4)
O2i—Rb—O2xii70.98 (2)Rbxvi—O1—Rbxv118.781 (14)
O2ii—Rb—O2xii59.83 (4)Rbviii—O1—Rbxv118.781 (14)
O2iii—Rb—O2xii117.00 (4)Mo—O2—Zn139.90 (8)
O2iv—Rb—O2xii111.99 (2)Mo—O2—Rbxvi102.39 (5)
O1v—Rb—O2xii111.79 (4)Zn—O2—Rbxvi91.72 (4)
O1vi—Rb—O2xii130.63 (2)Mo—O2—Rbxx117.93 (5)
O1vii—Rb—O2xii57.06 (2)Zn—O2—Rbxx83.17 (4)
O1viii—Rb—O2xii61.41 (4)Rbxvi—O2—Rbxx122.16 (4)
O2ix—Rb—O2xii90.360 (3)
Symmetry codes: (i) z+3/4, y1/4, x1/4; (ii) z+1, x1/2, y+1/2; (iii) z+3/4, y+1/4, x+3/4; (iv) z+1, x+1/2, y; (v) x+1, y1/2, z+1/2; (vi) y+3/4, x+1/4, z+3/4; (vii) y+3/4, x1/4, z1/4; (viii) x+1, y+1/2, z; (ix) y+1/2, z1/2, x1/2; (x) y+1/2, z+1/2, x+1; (xi) y+5/4, x3/4, z+3/4; (xii) y+5/4, x+3/4, z1/4; (xiii) y, z, x; (xiv) z, x, y; (xv) z, x+1, y+1/2; (xvi) y+1/2, z, x+1; (xvii) x+5/4, z+1/4, y+3/4; (xviii) x+5/4, z+3/4, y1/4; (xix) x, y+1, z+1/2; (xx) z+1/2, x1/2, y+1/2; (xxi) y+1/2, z+1/2, x1/2; (xxii) z+1/2, x+3/2, y.

Experimental details

(I)(II)
Crystal data
Chemical formulaCs3LiCo2(MoO4)4Rb3LiZn2(MoO4)4
Mr1163.341033.95
Crystal system, space groupCubic, I43dCubic, I43d
Temperature (K)293293
a (Å)12.2239 (2) 11.9018 (14)
V3)1826.54 (5)1685.9 (3)
Z44
Radiation typeMo KαMo Kα
µ (mm1)10.4014.37
Crystal size (mm)0.11 × 0.10 × 0.010.10 × 0.10 × 0.08
Data collection
DiffractometerBruker-Nonius X8 APEX CCD
diffractometer
Bruker-Nonius X8 APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Multi-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.394, 0.9030.264, 0.317
No. of measured, independent and
observed [I > 2σ(I)] reflections
8959, 705, 615 7827, 643, 617
Rint0.0380.023
(sin θ/λ)max1)0.8240.821
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.038, 0.99 0.011, 0.026, 1.07
No. of reflections705643
No. of parameters2021
Δρmax, Δρmin (e Å3)0.54, 0.610.31, 0.25
Absolute structureFlack (1983), 303 Friedel pairsFlack (1983), 365 Friedel pairs
Absolute structure parameter0.002 (17)0.004 (6)

Computer programs: SMART or APEX2? (Bruker, 2004), SMART or APEX2?, SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), BS (Ozawa & Kang, 2004), SHELXL97.

Selected interatomic distances (Å) for (I) and (II) top
AM = CsCoAM = RbZn
M—O1i3.350 (2)3.2339 (19)
M—O2ii3.262 (2)3.0307 (12)
M—O2iii3.361 (2)3.3270 (13)
R,Li—O2i1.9338 (19)1.9345 (12)
Mo—O11.719 (4)1.721 (2)
Mo—O21.7715 (18)1.7780 (10)
Symmetry codes: (i) -x+1, y-1/2, -z+1/2; (ii) z+3/4, y-1/4, x-1/4; (iii) y+1/2, z-1/2, x-1/2.
 

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