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Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

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Abstract

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd2(AsO4)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P21/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) Å3 (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO4(OH) and CdO4(OH)2 polyhedra, linked via corner-sharing to AsO4 tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd2(AsO4)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.

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Acknowledgments

Financial support of the Austrian Science Foundation (FWF) (Grant T300-N19) to the first author is gratefully acknowledged. Part of this work was done while the second author was financially supported by the FWF (Grant P17623-N10). We thank Prof. Dr. Manfred Wildner for the editorial handling.

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  1. Institute of Mineralogy and Crystallography, University of Vienna, Althanstr. 14, A-1090, Vienna, Austria

    Tamara Ðorđević & Uwe Kolitsch

  2. Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Burgring 7, A-1010, Wien, Austria

    Uwe Kolitsch

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  1. Tamara Ðorđević
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Correspondence to Tamara Ðorđević.

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Editorial handling: M. Wildner

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Ðorđević, T., Kolitsch, U. Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH). Miner Petrol 107, 243–251 (2013). https://doi.org/10.1007/s00710-012-0235-5

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