Expanding the Remarkable Structural Diversity of Uranyl Tellurites: \nHydrothermal Preparation and Structures of K[UO&lt;sub&gt;2&lt;/sub&gt;Te&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;(OH)],\nTl&lt;sub&gt;3&lt;/sub&gt;{(UO&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;[Te&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;(OH)](Te&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;6&lt;/sub&gt;)}·2H&lt;sub&gt;2&lt;/sub&gt;O, β-Tl&lt;sub&gt;2&lt;/sub&gt;[UO&lt;sub&gt;2&lt;/sub&gt;(TeO&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;], and\nSr&lt;sub&gt;3&lt;/sub&gt;[UO&lt;sub&gt;2&lt;/sub&gt;(TeO&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;](TeO&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;

Philip M. Almond (2509114); Thomas E. Albrecht-Schmitt (1370601)

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Expanding the Remarkable Structural Diversity of Uranyl Tellurites: \nHydrothermal Preparation and Structures of K[UO2Te2O5(OH)],\nTl3{(UO2)2[Te2O5(OH)](Te2O6)}·2H2O, β-Tl2[UO2(TeO3)2], and\nSr3[UO2(TeO3)2](TeO3)2

Philip M. Almond (2509114)Thomas E. Albrecht-Schmitt (1370601)

Year: 2016 Journal: OPAL (Open@LaTrobe) (La Trobe University) Publisher: La Trobe University

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Abstract

The reactions of UO2(C2H3O2)2·2H2O with K2TeO3·H2O, Na2TeO3 and TlCl, or Na2TeO3 and Sr(OH)2·8H2O under\nmild hydrothermal conditions yield K[UO2Te2O5(OH)] (1), Tl3{(UO2)2[Te2O5(OH)](Te2O6)}·2H2O (2) and β-Tl2[UO2(TeO3)2]\n(3), or Sr3[UO2(TeO3)2](TeO3)2 (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers\nthat are bound by terminal oxo groups and tellurite anions. These UO6 units span between one-dimensional chains\nof corner-sharing, square pyramidal TeO4 polyhedra to create two-dimensional layers. Alternating corner-shared\noxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional\nchains of corner-sharing TeO4 units found in 1 are also present in 2. However, in 2 there are two distinct chains\npresent, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are\nunprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional\n\n\n[UO2(TeO3)2]2-\nchains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ\nbetween 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite\nanions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO32-\nanions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) Å, b = 8.7416(6) Å,\nc = 11.4413(8) Å, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) Å, b = 23.024(2) Å, c = 7.9389(6)\nÅ, Z = 4; 3, monoclinic, space group P21/n, a = 5.4766(4) Å, b = 8.2348(6) Å, c = 20.849(3) Å, β = 92.329(1)°,\nZ = 4; 4, monoclinic, space group C2/c, a = 20.546(1) Å, b = 5.6571(3) Å, c = 13.0979(8) Å, β = 94.416(1)°,\nZ = 4.

Keywords:

Bipyramid Pentagonal bipyramidal molecular geometry Uranyl Group (periodic table) Tetragonal crystal system Square pyramidal molecular geometry Protonation Crystal structure

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Nuclear Materials and Properties

Physical Sciences → Materials Science → Materials Chemistry

Radioactive element chemistry and processing

Physical Sciences → Chemistry → Inorganic Chemistry

Nuclear materials and radiation effects

Physical Sciences → Materials Science → Materials Chemistry

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