Abstract
A series of six new single crystals of fully stoichiometric As3+-bearing Mo-oxides and partially W-substituted Mo-oxides with formula AsmO(Mo1−xWxO3)p (m = 1, 2; p = 5, 7, 9, 10 and 11 and 0 ≤ x ≤ 0.6) was successfully grown using vapor-phase transport in vacuo. The crystal structures were determined using single-crystal X-ray diffraction data. All these compounds exhibit acentric orthorhombic symmetry with Z = 2, and belong to the so-called (n)-ITB (intergrowth tungsten bronzes) family, with n = 2, 3, 4 and 5. The six (n)-ITB phases have the following formulae: (2)-AsMo5O16 (Pm 2a), (2)-As2Mo10O31 (Pma 2), (3)-AsMo7O22 (Pmn 21), (3)-As(Mo5.53W1.47)O22 (Pmn 21), (4)-As(Mo4.33W4.67)O28 (Pm 2a) and (5)-As(W6.63Mo4.37)O34 (Pmn 21). Their structures consist of vertex-sharing MO6 octahedral units (with M either Mo or Mo/W) connected so as to form three-dimensional frameworks. Such frameworks consist of perovskite tungsten bronzes (PTB) type slabs, from 2- to 5-octahedra wide, intergrown with single hexagonal tungsten bronzes (HTB) type slabs, stacked up to form pseudo-hexagonal tunnels along the a-axis. As3+ and additional oxygen atoms are located in off-center positions inside the tunnels, forming As–O bonds with peculiar arrangements. In particular, we obtained the first examples of structures where, besides the usual AsO3E distorted pyramidal geometry, As3+ adopts AsO4E coordination with a seesaw configuration.
Acknowledgements
The authors acknowledge Thierry Roisnel for the X-ray single-crystal diffraction measurements at CDIFX, Centre de DIFfractométrie des rayons X, University of Rennes1, Rennes (France) and CRIST, Centro di Studi per la Cristallografia Strutturale, University of Firenze, Firenze (Italy). Dr. Vittorio Morandi, CNR-IMM, Consiglio Nazionale delle Ricerche-Istituto per la Microelecttronica e Microsistemi, Bologna (Italy), is gratefully acknowledged for his kind contribution with Scanning Electron Microscopy.
The work of M. Goudjil was financially supported by the Algerian Ministry of Higher Education and Scientific Research (MESRS) as part of the National Exceptional Program (PNE) (Grant number: 306/PNE: 2016/17) and by the Italian Ministry of Foreign Affairs and International Cooperation (MAECI Grant 2018/19).
The CCDC deposition numbers
Compound (A) – CSD n: 1914483
Compound (B) – CSD n: 1914491
Compound (C) – CSD n: 1914466
Compound (D) – CSD n: 1914524
Compound (E) – CSD n: 1914528
Compound (F) – CSD n: 1914537
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Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2019-0018).
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