Structural Studies on Synthetic A2−x[M2(TeO3)3]·nH2O Phases (A = Na, K, Rb, Cs; M = Mn, Co, Ni, Cu, Zn) with Zemannite-type Structures

Eder, Felix; Marsollier, Alexandre; Weil, Mat­thias

doi:10.21203/rs.3.rs-2222507/v1

Cited by 3 publications

(10 citation statements)

References 20 publications

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“…This suggests that the H 2 O content certainly influences the occurrence of superstructures in zemannite-type phases. We recently observed an influence of the crystal water content on the superstructure formation for several other novel zemannite-type phases (Eder et al 2023) as well, which offers various possibilities for further investigations on the tuning of different zemannite-type (super)structures.…”

Section: Mn IIImentioning

confidence: 96%

“…In the case of K 2 [Zn 2 (TeO 3 ) 3 ]•3H 2 O, it was due to the lack of suitable untwinned crystals, as powder diffraction measurement indicated a monoclinic unit-cell as derived from peak splitting. Following our most recent findings on novel synthetic zemannite-type phases (Eder et al 2023), it was possible to grow crystals of a less hydrated K-Zn-zemannite phase (i.e. K 2 [Zn 2 (TeO 3 ) 3 ]•2H 2 O), which, however, was found to be metrically hexagonal and not monoclinic.…”

Section: Introductionmentioning

confidence: 94%

“…This can be easily understood as Co II , Mn II and Mg II reveal no Jahn-Teller effect compared to the pronounced polyhedral distortions known for Mn III and Cu II . The recently discovered phases Rb 1.5 [(Mn II ,Mn III ) 2 (TeO 3 ) 3 ]•1.25H 2 O and Cs[(Mn II ,Mn III ) (TeO 3 ) 3 ]•H 2 O (Eder et al 2023) also exhibit such a fourfold superstructure, with the channels widening up in the direction of the A cations due to the lower crystal water content and the higher off-center displacement of the larger Rb + and Cs + cations. Together with the presence of Jahn-Teller-active Mn within the framework, the larger A cations inside the channels lead to increased distortions of the channels with differences in the corresponding M•••M distances (as drawn in yellow in Fig.…”

Section: Distribution Of Extra-framework K + Ions and H 2 O Moleculesmentioning

confidence: 99%

“…During our current research on novel zemannite-type oxidotellurate(IV) phases, we found two further zemannite-type phases exhibiting a twofold superstructure with similar metrics, viz. K 2 [Cu 2 (TeO 3 ) 3 ]•2H 2 O and K 2 [Co 2 (TeO 3 ) 3 ]•2.5H 2 O (Eder et al 2023). The latter also exhibits an incommensurate modulation along the reciprocal direction parallel to the channel axis.…”

Section: Mn IIImentioning

confidence: 99%

“…x (TeO 3 ) 3 ]•3H 2 O (0.55 ≤ x ≤ 1.25), were synthesized by Missen et al (2019a). Most recently, several novel representatives of zemannite-type phases, partially with formation of superstructures and/or symmetry reductions, were described by Eder et al (2023).…”

Section: Introductionmentioning

confidence: 99%

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K[(CuII,MnII,MnIII)2(TeO3)3]∙2H2O, the first zemannite-type structure based on a Jahn-Teller-distorted framework

2023

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Synthetic single crystals of K[(CuII,MnII,MnIII)2(TeO3)3]·2H2O were obtained from an overconcentrated alkaline aqueous solution in the system K2O-MnO-CuO-TeO2 under hydrothermal conditions at T ≤ 220 °C. Subeuhedral single crystals have been investigated by means of single-crystal X-ray diffraction. The crystal structure of this new zemannite-type representative adopts a monoclinic twofold superstructure. The doubling of the unit-cell volume is accompanied by a hexagonal-to-monoclinic symmetry reduction, resulting in threefold twinning with individual crystal domains following the space group symmetry P21. Refinements of site-occupation factors and the evaluation of bond valences suggest a distribution of di- and trivalent cations at the octahedrally coordinated M sites with a ratio (CuII + MnII):MnIII approximating 1:1. Based on arguments about the cation sizes and the individual bond valence sums, a distribution of CuII1–xMnIIIx and MnIIx MnIII1–x at each two of the four M sites can be assumed with x between ~ 0.14 and ~ 0.50. The K+ cations and H2O molecules inside the channels are located off the central channel axis. In contrast to most other known zemannite-type phases, the extra-framework atoms show full occupancies and are not disordered. The distribution of the channel contents supports the anisotropic deformation of the surrounding framework, which follows the local symmetry reduction as required for the Jahn-Teller distortion of the octahedrally coordinated M sites within the framework. The arrangement of the deformed channels can be understood as the origin of the existing superstructure.

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Section: Mn IIImentioning

confidence: 96%

Section: Introductionmentioning

confidence: 94%

Section: Distribution Of Extra-framework K + Ions and H 2 O Moleculesmentioning

confidence: 99%

Section: Mn IIImentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

K[(CuII,MnII,MnIII)2(TeO3)3]∙2H2O, the first zemannite-type structure based on a Jahn-Teller-distorted framework

2023

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Crystal chemistry of zemannite-type structures: IV. Wortupaite, the first new tellurium oxysalt mineral described from an Australian locality

Missen,

Mills,

Brugger

et al. 2023

MinMag

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Wortupaite (IMA2022–107) is a new hydrated magnesium nickel tellurite mineral with a zemannite-like structure, described from the Wortupa gold mine, South Australia, Australia. Wortupaite forms needles up to 25 μm in length, generally clustered and sometimes in blocky masses of shorter (10‒15 μm) crystals. Wortupaite is found growing on melonite, from which the component nickel and tellurium are derived, and is associated with calcite. The strongest powder diffraction lines are [dobsÅ(Iobs)(hkl)]: 8.059 (93) (100), 4.034 (92) (200), 2.832 (43) (211 and 121), 2.769 (100) (202) and 1.920 (45) (213 and 123). The empirical formula of wortupaite as determined by electron probe microanalysis is (Mg0.57Ni0.39Mn0.04)Σ1(Ni2+1.87Fe3+0.13)Σ2(Te4+O3)3⋅3H2O, simplified to the ideal formula of MgNi2+2(Te4+O3)3⋅3H2O with H2O content calculated from the crystal structure. The average crystal structure of wortupaite was determined by single-crystal X-ray diffraction with synchrotron radiation (R1 = 0.0558 for 100 independent reflections). Wortupaite is hexagonal, crystallising in the space group P63/m, with a = 9.2215(13) Å, c = 7.5150(15) Å, V = 553.43(19) Å3 and Z = 2. Wortupaite has a microporous structure, with the negatively charged zemannite-like framework formed by Te4+O3 trigonal pyramids and Ni2+O6 octahedra. For charge balance, Mg2+ and Ni2+ dominant sites are assumed to be located on central sites in the channels, coordinated by 6 H2O groups. An OW site was refined around the Mg2+ dominant site, but OW position(s) were not locatable around the Ni2+ dominant site. A discussion of the different models for crystallographic arrangement of channel species is provided, taking into account possible Fourier truncation effects. Unlike the other four minerals with zemannite-like structures which have a near 50% split of divalent and trivalent framework cations, wortupaite is the first natural phase to have only divalent cations in the framework sites.

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The Cobalt(II) Oxidotellurate(IV) Hydroxides Co2(TeO3)(OH)2 and Co15(TeO3)14(OH)2

et al. 2023

Self Cite

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Previously unknown Co2(TeO3)(OH)2 and Co15(TeO3)14(OH)2 were obtained under mild hydrothermal reaction conditions (210 °C, autogenous pressure) from alkaline solutions. Their crystal structures were determined from single-crystal X-ray diffraction data. Co2(TeO3)(OH)2 (Z = 2, P1¯, a = 5.8898(5), b = 5.9508(5), c = 6.8168(5) Å, α = 101.539(2), β = 100.036(2), γ = 104.347(2)°, 2120 independent reflections, 79 parameters, R[F2 > 2σ(F2)] = 0.017) crystallizes in a unique structure comprised of undulating 2∝[Co2(OH)6/3O3/3O2/2O1/1]4− layers. Adjacent layers are linked by TeIV atoms along the [001] stacking direction. Co2(TeO3)(OH)2 is stable up to 450 °C and decomposes under the release of water into Co6Te5O16 and CoO. Magnetic measurements of Co2(TeO3)(OH)2 showed antiferromagnetic ordering at ≈ 70 K. The crystal structure of Co15(TeO3)14(OH)2 (Z = 3, R3¯, a = 11.6453(2), c = 27.3540(5) Å, 3476 independent reflections, 112 parameters, R[F2 > 2σ(F2)] = 0.026) is isotypic with Co15(TeO3)14F2. A quantitative structural comparison revealed that the main structural difference between the two phases is connected with the replacement of F by OH, whereas the remaining part of the three-periodic network defined by [CoO6], [CoO5(OH)], [CoO5] and [TeO3] polyhedra is nearly unaffected. Consequently, the magnetic properties of the two phases are similar, namely being antiferromagnetic at low temperatures.

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Structural Studies on Synthetic A2−x[M2(TeO3)3]·nH2O Phases (A = Na, K, Rb, Cs; M = Mn, Co, Ni, Cu, Zn) with Zemannite-type Structures

Cited by 3 publications

References 20 publications

K[(CuII,MnII,MnIII)2(TeO3)3]∙2H2O, the first zemannite-type structure based on a Jahn-Teller-distorted framework

K[(CuII,MnII,MnIII)2(TeO3)3]∙2H2O, the first zemannite-type structure based on a Jahn-Teller-distorted framework

Crystal chemistry of zemannite-type structures: IV. Wortupaite, the first new tellurium oxysalt mineral described from an Australian locality

The Cobalt(II) Oxidotellurate(IV) Hydroxides Co2(TeO3)(OH)2 and Co15(TeO3)14(OH)2

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