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American Mineralogist; September 1999; v. 84; no. 9; p. 1456-1460
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Wyartite; crystallographic evidence for the first pentavalent-uranium mineral

Peter C. Burns, and Robert J. Finch

University of Notre Dame, Department of Civil Engineering and Geological Sciences, Notre Dame, IN, United States
Argonne National Laboratory, United States

Determination of the structure of wyartite provides the first evidence for a pentavalent-U mineral. The structure of wyartite, CaU (super 5+) (UO 2 ) 2 (CO 3 )O 4 (OH)(H 2 O) 7 , Z = 4, orthorhombic, a = 11.2706(8), b = 7.1055(5), c = 20.807(1) Aa, V = 1666.3(3) Aa 3 , space group P2 1 2 1 2 1 , was solved by direct methods and refined to an agreement index (R) of 4.9% for 2309 unique reflections collected using MoKalpha X-radiation and a CCD-based detector. The structure contains three unique U positions; two contain U (super 6+) and involve uranyl ions with typical pentagonal-bipyramidal coordination. Seven anions coordinate the other U position, but there is no uranyl ion present. The polyhedral geometry, the bond-valence sum incident at this U site, and electroneutrality requirements, all indicate that this site contains U (super 5+) The Uphi 7 (phi : O, OH, H 2 O) polyhedra share edges and corners to form a unique sheet in which a CO 3 group shares an edge with the U (super 5+) phi 7 polyhedron. The structure contains one Ca site coordinated by seven anions. The Ca atom and its associated H 2 O groups occupy interlayer sites, along with two H 2 O groups that are held in the structure by H bonds only. The Caphi 7 polyhedron is linked to one adjacent sheet by sharing an edge with the CO 3 group and an O atom with a U (super 6+) phi 7 polyhedron. Structural units are linked together through hydrogen bonds only.

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