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Flux syntheses and single-crystal structures of CsNa₁₀ M ₄(AsO₄)₉ (M = Zr, Hf).

ABSTRACT: The isostructural compounds caesium deca-sodium tetra-zirconium nona-arsenate, CsNa₁₀Zr₄(AsO₄)₉, and caesium deca-sodium tetra-hafnium nona-arsenate, CsNa₁₀Hf₄(AsO₄)₉, arose as unexpected single-crystal products from the reactions of Na₂CO₃, MO₂ (M = Zr, Hf) and As₂O₅ in a eutectic flux of NaCl and CsCl. They consist of MO₆ octa-hedra and AsO₄ tetra-hedra sharing vertices to generate three-dimensional polyhedral networks encapsulating the caesium and sodium ions. The MO₆ groups share all their vertices with adjacent As atoms but the As atoms have one or two 'terminal' O atoms not bonded to Zr or Hf. The Cs⁺ ion adopts a squashed octa-hedral geometry and the coordination polyhedra of the partially occupied sodium ions are variously trigonal bipyramidal, tetra-hedral, square pyramidal and trigonal pyramidal. Site symmetries: Cs ; M 3; As 1 and 2; O 1; Na 1, 2 and 3. The M = Zr crystal was refined as an obverse/reverse rhombohedral twin.

SUBMITTER: Harrison WTA

PROVIDER: S-EPMC9260365 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Publications

Flux syntheses and single-crystal structures of CsNa10 M 4(AsO4)9 (M = Zr, Hf).

Harrison William T A WTA

Acta crystallographica. Section E, Crystallographic communications 20220621 Pt 7

The isostructural compounds caesium deca-sodium tetra-zirconium nona-arsenate, CsNa10Zr4(AsO4)9, and caesium deca-sodium tetra-hafnium nona-arsenate, CsNa10Hf4(AsO4)9, arose as unexpected single-crystal products from the reactions of Na2CO3, MO2 (M = Zr, Hf) and As2O5 in a eutectic flux of NaCl and CsCl. They consist of MO6 octa-h ...[more]

PMID: 35855358

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Project description:By treating gaseous, liquid, or solid fluorides with UV-photolyzed O2/F2 mixtures and by treating solid oxides with UV-photolyzed F2 (or O2/F2 mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O2MIIIF4 (M = B, Fe, Co, Ag), O2MIVF5 (M = Ti, Sn, Pb), (O2)2MIVF6 (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O2MIV2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV2F11 (M = Pt), O2MVIF7 (M = Se), (O2)2MVIF8 (M = Mo, W), and O2MVIIF8 (M = I). The approach has been successful in the case of previously known O2BF4, O2MF6 (M = As, Sb, Au; Pt), O2GeF5, and (O2)2(Ti7F30). Novel compounds O2GeF5·HF, α-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of β-O2Sn2F9 (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF6 (M = Ge, Sn) units. The anion in the crystal structure of O2GeF5·HF is comprised of infinite ([GeF5]-)∞ chains of GeF6 octahedra that share common vertices. The HF molecules and O2+ cations are located between the chains. The crystal structure of α-O2SnF9 (1-D) is constructed from [O2]+ cations and polymeric ([Sn2F9]-)∞ anions which appear as two parallel infinite chains comprised of SnF6 units, where each SnF6 unit of one chain is connected to a SnF6 unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O2][Sn2F9]·0.9HF reveals that it is comprised of two-dimensional ([Sn2F9]-)∞ grids with [O2]+ cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn2F9]-)∞ layer contains both six- and seven-coordinated Sn(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O2]+ salt, O2[Hg(HF)]4[SbF6]9, was prepared. In its crystal structure, the Hg atoms bridge to SbF6 units to form a 3-D framework. The O2+ cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O2+ fluorine salts (i.e., O2TiCl5 and O2MCl6 (M = Nb, Sb)) failed.

Dataset Information

Flux syntheses and single-crystal structures of CsNa₁₀ M ₄(AsO₄)₉ (M = Zr, Hf).

Publications

Flux syntheses and single-crystal structures of CsNa<sub>10</sub> <i>M</i> <sub>4</sub>(AsO<sub>4</sub>)<sub>9</sub> (<i>M</i> = Zr, Hf).

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