research communications
Garnet-type Na3Te2(FeO4)3
aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/E164-05-01, A-1060 Vienna, Austria
*Correspondence e-mail: matthias.weil@tuwien.ac.at
Na3Te2(FeO4)3 or Na3Te2Fe3O12, trisodium ditellurium(VI) triiron(III) dodecaoxide, was obtained in the form of single-crystals under hydrothermal conditions. Na3Te2(FeO4)3 adopts the garnet structure type in Iad and comprises one Na (multiplicity 24, Wyckoff letter c, 2.22), one Te (16 a, ..), one Fe (24 d, ..) and one O atom (96 h, 1) in the The three-dimensional framework structure is built of [TeO6] octahedra and [FeO4] tetrahedra by vertex-sharing. The larger Na+ cations are situated in the interstices of the framework and are eightfold coordinated in the form of a distorted dodecahedron. Quantitative structural comparisons with isotypic Na3Te2[(Fe0.5Al0.5)O4]3 and Na3Te2(GaO4)3 show a high degree of similarity between the three crystal structures.
Keywords: crystal structure; garnet; oxidotellurate(VI); isotypism; structural similarity.
CCDC reference: 2247314
1. Chemical context
Layered oxidotellurates(VI) comprising an alkali metal (or ammonium) and a transition metal M, such as (NH4)4(VO2)2Te2O8(OH)2·2H2O (Nagarathinam et al., 2022), Li2Ni2TeO6 (Grundish et al., 2019), Na3Ni1.5TeO6 (Grundish et al., 2020) or K2M2TeO6 (M = Ni, Mg, Zn, Co, Cu; Masese et al., 2018) are considered to be promising battery materials. In the quest for new representatives of this group of materials comprising K and FeIII, we obtained a phase under hydrothermal conditions with a supposed composition of K12FeIII6TeVI4O27·3H2O. However, this phase is not layered but crystallizes in a cubic framework structure with positionally disordered crystal water molecules [Z = 4, I3d, a = 14.7307 (12) Å at room temperature; Eder & Weil, 2023], which is closely related to the phase K12+6xFe6Te4–xO27 [x = 0.222 (4), Z = 4, I3d, a = 14.7440 (10) Å at 100 K; Albrecht et al., 2021]. With the intention of synthesizing the possible Na-analogue Na12FeIII6TeVI4O27·3H2O, we obtained garnet-type Na3Te2(FeO4)3 instead, and report here its and quantitative comparisons with related crystal structures.
2. Structural commentary
The garnet X3}[Y2](Z3)φ12 and includes all phases, which crystallize isostructurally with garnet, regardless of the type of elements present at the four atomic sites (Grew et al., 2013). The of garnet comprises a three-dimensional framework built of [Yφ6] octahedra and (Zφ4) tetrahedra in which each octahedron is joined to six others through vertex-sharing tetrahedra. In turn, each tetrahedron shares its vertices with four octahedra, so that the composition of the framework is Y2Z3φ12. Larger X atoms occupy positions in the interstices of the framework and are eightfold coordinated in the form of a distorted dodecahedron (Wells, 1975). In a crystal–chemical sense, the final composition can therefore be expressed as {X3}[8do][Y2][6o](Z3[4t])φ12, or as {X3}[8do][Y2][6o](Z[4t]φ4)3. In the title compound, Na takes the X position (multiplicity 24, Wyckoff letter c, 2.22), Te the Y position (16 a, ..), Fe the Z position (24 d, ..) and O the φ position (96 h, 1). The of Na3Te2(FeO4)3 is displayed in Fig. 1. Bond-valence sums (Brown, 2002) for all atoms were computed with the parameters of Brese & O'Keeffe (1991). The values (in valence units) of 1.19 for Na, 6.00 for Te, 2.98 for Fe and 2.04 for O are in very good agreement with the expected values of 1, 6, 3 and 2, respectively.
has the general formula {The garnet et al., 2019), using the garnet structure type in Iad and with Si on the Z position as search field revealed about 420 entries, and with atoms other than Si on the Z position about 350 entries. With Te on the Y position, only five phases were found, including the mineral yafsoanite [ideally Ca3Te2(ZnO4)3, Jarosch & Zemann, 1989; Mills et al., 2010], the Li-conducting Nd3(Te2–xSbx)(Li3+xO4)3 (x = 0.05, 0.10) (O'Callaghan et al., 2008), Na3Te2[(Fe0.5Al0.5)O4]3 (Wedel & Sugiyama, 1999) and Na3Te2(GaO4)3 (Frau et al., 2008). The latter two phases comprise Na on the X position and, with respect to the title compound, therefore are the chemically most related compounds. A comparison of relevant bond lengths in the three garnets, together with structural similarity parameters, as revealed by the program compstru (de la Flor et al., 2016) available at the Bilbao Crystallographic Server (Aroyo et al., 2006), is given in Table 1. The cations occupying the Z site apparently influence the two Na—O bond lengths in the crystal structures, although the ionic radii (Shannon, 1976) of Z do not directly correlate with this behaviour. The title compound with Z = Fe (ionic radius 0.49 Å) has the longest Na—O bonds, followed by the mixed-occupied compound with Z = (Fe,Al) (averaged ionic radius 0.44 Å) and the compound with Z = Ga (ionic radius 0.47 Å). On the other hand, the Te—O bond lengths in the three garnet structures are virtually identical.
includes several chemical classes, which is also reflected by the high number of phases that adopt the garnet structure type. A search in the ICSD (version 2022-1; ZagoracAn X-ray powder diffraction pattern of Na3Te2(FeO4)3 has been deposited with the ICDD (PDF 00-048-0300; Gates-Rector & Blanton, 2019) without giving atomic coordinates for the O-atom site or displacement parameters for the atoms. The corresponding unit-cell parameter a = 12.5257 (1) Å determined from room-temperature powder X-ray measurement data is in very good agreement with the one from single-crystal data (Table 2). In the context of investigating the magnetic ordering of FeIII on the Z sites, neutron powder data recorded at room temperature were also reported for Na3Te2(FeO4)3 (Plakhtii et al., 1977).
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3. Synthesis and crystallization
The solid educts Fe(NO3)3·9H2O, TeO2, H6TeO6 and NaOH were weighed in the molar ratios 2:1:2:15 and placed into a Teflon container (inner volume ca 5 ml). The container was filled to about 2/3 of its volume with water, closed with a Teflon lid and embedded into a steel autoclave. The hydrothermal experiment was conducted at 473 K for five days. The solid product was filtered off, washed with water and ethanol and dried in air. It consisted of light-brown microcrystalline material and a few amber-coloured cuboid crystals of Na3Te2(FeO4)3, as well as a very few small yellowish platy crystals of an unknown phase. Preliminary single-crystal measurements of the latter indicated a with hexagonal metrics (a = 5.252, c = 15.724 Å) and obvious which has precluded a structure solution so far. Similar metrics were found for Na2GeTeO6 (Woodward et al., 1998). The powder X-ray diffraction pattern of the bulk revealed Na3Te2(FeO4)3 as a side product and the unknown phase (assuming a close relation with Na2GeTeO6) as the main phase, in an approximate mass ratio of 0.15:0.85.
Supporting information
CCDC reference: 2247314
https://doi.org/10.1107/S2056989023002293/pk2684sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023002293/pk2684Isup2.hkl
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ATOMS for Windows (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Na3Te2Fe3O12 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 683.72 | Cell parameters from 6128 reflections |
Cubic, Ia3d | θ = 4.0–41.1° |
a = 12.5276 (9) Å | µ = 10.39 mm−1 |
V = 1966.1 (4) Å3 | T = 296 K |
Z = 8 | Cube, amber |
F(000) = 2488 | 0.06 × 0.06 × 0.06 mm |
Dx = 4.620 Mg m−3 |
Bruker APEXII CCD diffractometer | 446 reflections with I > 2σ(I) |
ω– and φ–scans | Rint = 0.060 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 41.6°, θmin = 4.0° |
Tmin = 0.677, Tmax = 0.748 | h = −23→23 |
42303 measured reflections | k = −23→23 |
569 independent reflections | l = −23→23 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0169P)2 + 1.9053P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.017 | (Δ/σ)max < 0.001 |
wR(F2) = 0.041 | Δρmax = 1.25 e Å−3 |
S = 1.16 | Δρmin = −0.68 e Å−3 |
569 reflections | Extinction correction: SHELXL-2019/2 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
18 parameters | Extinction coefficient: 0.00158 (6) |
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. |
x | y | z | Uiso*/Ueq | ||
Na1 | 0.250000 | 0.375000 | 0.500000 | 0.01227 (18) | |
Te1 | 0.500000 | 0.500000 | 0.500000 | 0.00480 (5) | |
Fe1 | 0.250000 | 0.625000 | 0.500000 | 0.00637 (7) | |
O1 | 0.35650 (7) | 0.53021 (8) | 0.45633 (8) | 0.00976 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0150 (3) | 0.0068 (4) | 0.0150 (3) | 0.000 | 0.0012 (4) | 0.000 |
Te1 | 0.00480 (5) | 0.00480 (5) | 0.00480 (5) | 0.00038 (3) | 0.00038 (3) | 0.00038 (3) |
Fe1 | 0.00652 (9) | 0.00605 (14) | 0.00652 (9) | 0.000 | 0.000 | 0.000 |
O1 | 0.0068 (4) | 0.0106 (4) | 0.0119 (4) | 0.0023 (3) | −0.0013 (3) | −0.0006 (3) |
Na1—O1i | 2.4208 (10) | Te1—O1viii | 1.9169 (9) |
Na1—O1ii | 2.4208 (10) | Te1—O1ix | 1.9169 (9) |
Na1—O1iii | 2.4208 (10) | Te1—O1x | 1.9169 (9) |
Na1—O1 | 2.4208 (10) | Te1—O1vii | 1.9169 (9) |
Na1—O1iv | 2.6226 (10) | Te1—O1xi | 1.9169 (9) |
Na1—O1v | 2.6226 (10) | Fe1—O1xii | 1.8680 (9) |
Na1—O1vi | 2.6226 (10) | Fe1—O1ii | 1.8680 (9) |
Na1—O1vii | 2.6226 (10) | Fe1—O1xiii | 1.8680 (9) |
Te1—O1 | 1.9169 (9) | Fe1—O1 | 1.8680 (9) |
O1i—Na1—O1ii | 153.42 (4) | O1—Te1—O1viii | 91.50 (4) |
O1i—Na1—O1iii | 73.12 (4) | O1—Te1—O1ix | 88.50 (4) |
O1ii—Na1—O1iii | 113.33 (4) | O1viii—Te1—O1ix | 180.0 |
O1i—Na1—O1 | 113.33 (4) | O1—Te1—O1x | 91.50 (4) |
O1ii—Na1—O1 | 73.12 (4) | O1viii—Te1—O1x | 88.50 (4) |
O1iii—Na1—O1 | 153.42 (4) | O1ix—Te1—O1x | 91.50 (4) |
O1i—Na1—O1iv | 125.56 (2) | O1—Te1—O1vii | 88.50 (4) |
O1ii—Na1—O1iv | 77.63 (3) | O1viii—Te1—O1vii | 91.50 (4) |
O1iii—Na1—O1iv | 63.92 (4) | O1ix—Te1—O1vii | 88.50 (4) |
O1—Na1—O1iv | 94.14 (3) | O1x—Te1—O1vii | 180.0 |
O1i—Na1—O1v | 94.14 (3) | O1—Te1—O1xi | 180.0 |
O1ii—Na1—O1v | 63.92 (4) | O1viii—Te1—O1xi | 88.50 (4) |
O1iii—Na1—O1v | 77.63 (3) | O1ix—Te1—O1xi | 91.50 (4) |
O1—Na1—O1v | 125.56 (2) | O1x—Te1—O1xi | 88.50 (4) |
O1iv—Na1—O1v | 106.99 (4) | O1vii—Te1—O1xi | 91.50 (4) |
O1i—Na1—O1vi | 63.92 (4) | O1xii—Fe1—O1ii | 113.83 (3) |
O1ii—Na1—O1vi | 94.14 (3) | O1xii—Fe1—O1xiii | 101.06 (6) |
O1iii—Na1—O1vi | 125.56 (2) | O1ii—Fe1—O1xiii | 113.83 (3) |
O1—Na1—O1vi | 77.63 (3) | O1xii—Fe1—O1 | 113.83 (3) |
O1iv—Na1—O1vi | 169.86 (4) | O1ii—Fe1—O1 | 101.06 (6) |
O1v—Na1—O1vi | 73.94 (4) | O1xiii—Fe1—O1 | 113.83 (3) |
O1i—Na1—O1vii | 77.63 (3) | Fe1—O1—Te1 | 135.38 (5) |
O1ii—Na1—O1vii | 125.56 (2) | Fe1—O1—Na1 | 92.91 (4) |
O1iii—Na1—O1vii | 94.14 (3) | Te1—O1—Na1 | 107.08 (4) |
O1—Na1—O1vii | 63.92 (4) | Fe1—O1—Na1ix | 116.33 (4) |
O1iv—Na1—O1vii | 73.94 (4) | Te1—O1—Na1ix | 99.78 (4) |
O1v—Na1—O1vii | 169.86 (4) | Na1—O1—Na1ix | 98.95 (3) |
O1vi—Na1—O1vii | 106.99 (4) |
Symmetry codes: (i) −z+3/4, −y+3/4, −x+3/4; (ii) −x+1/2, y, −z+1; (iii) z−1/4, −y+3/4, x+1/4; (iv) y−1/4, −x+3/4, z+1/4; (v) −z+1/2, x, −y+1; (vi) −y+3/4, −x+3/4, −z+3/4; (vii) z, x, y; (viii) −y+1, −z+1, −x+1; (ix) y, z, x; (x) −z+1, −x+1, −y+1; (xi) −x+1, −y+1, −z+1; (xii) −z+3/4, −y+5/4, x+1/4; (xiii) z−1/4, −y+5/4, −x+3/4. |
Na3Te2(FeO4)3 | Na3Te2[(Al,Fe)O4]3 | Na3Te2(GaO4)3 | |
Na1—O1 (4×) | 2.4208 (10) | 2.396 (3) | 2.3907 (17) |
Na1—O1 (4×) | 2.6226 (10) | 2.597 (3) | 2.5609 (17) |
Te1—O1 (6×) | 1.9169 (9) | 1.914 (2) | 1.9124 (17) |
M1—O1 (4×) | 1.8680 (9) | 1.829 (2) | 1.8405 (16) |
Degree of lattice distortion, S | 0.0064 | 0.0079 | |
Atomic displacement of O1a) / Å | 0.0205 | 0.0322 | |
Measure of similarity, Δ | 0.001 | 0.002 |
a) The three other atomic sites do not show a displacement due to their site symmetries |
Acknowledgements
We thank Ruben do Carmo for assistance during preparative studies. The X-ray centre of TU Wien is acknowledged for providing access to the single-crystal and powder X-ray diffractometers.
Funding information
The authors acknowledge TU Wien Bibliothek for financial support through its Open Access Funding Programme.
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