Crystal Growth, Structural Characterization, Cation–Cation Interaction Classification, and Optical Properties of Uranium(VI) Containing Oxychlorides, A₄U₅O₁₆Cl₂ (A = K, Rb), Cs₅U₇O₂₂Cl₃, and AUO₃Cl (A = Rb, Cs)

Author(s)

Cory Michael Read, University of South Carolina - Columbia
Jeongho Yeon, University of South Carolina - Columbia
Mark D. Smith, University of South Carolina - ColumbiaFollow
Hans-Conrad zur Loye, University of South Carolina - ColumbiaFollow

Document Type

Article

Subject Area(s)

Chemistry

Abstract

Single crystals of five new alkali metal uranium oxychlorides, K₄U₅O₁₆Cl₂, Rb₄U₅O₁₆Cl₂, Cs₅U₇O₂₂Cl₃, RbUO₃Cl, and CsUO₃Cl, have been grown from molten chloride fluxes and structurally characterized by single crystal X-ray diffraction. All of the materials are monoclinic. The first three crystallize in the space group P21/n and exhibit a 2D layered structure with a novel layer topology, consisting of UO₆, UO₇, and UO₄Cl₂ polyhedra and cation–cation interactions (CCIs) within the plane of the uranyl sheet. A general cation–cation classification scheme is presented. RbUO₃Cl and CsUO₃Cl crystallize in the space group P21/m and exhibit 1D zipper-like chains of UO₅Cl₂ polyhedra. The lattice parameters of the new oxychlorides are: K₄U₅O₁₆Cl₂, a = 9.9574(4) Å, b = 6.9766(3) Å, c= 14.3920(6) Å, and β = 105.7690(10)°; Rb₄U₅O₁₆Cl₂, a = 10.2164(4) Å, b = 7.0160(3) Å, c= 14.4930(5) Å, and β = 103.8290(10)°; Cs₅U₇O₂₂Cl₃, a = 10.6214(5) Å, b = 18.1071(8) Å, c= 16.0857(7) Å, and β = 102.9850(10)°; RbUO₃Cl, a = 7.3602(6) Å, b = 4.1127(3) Å, c = 8.5556(7) Å, and β = 104.602(2)°; CsUO₃Cl, a = 7.7768(4) Å, b = 4.1245(2) Å, c = 8.7701(5) Å, and β = 105.4680(10)°. The materials were further characterized by UV-vis reflectance spectroscopy and fluorescence spectroscopy.

Digital Object Identifier (DOI)

https://doi.org/10.1039/C4CE00281D

Publication Info

Published in CrystEngComm, Volume 16, Issue 31, 2014, pages 7259-7267.

© CrystEngComm 2014, Royal Society of Chemistry.

APA Citation

Read, C., Yeon, J., Smith, M., & zur Loye, H.-C. (2014). Crystal Growth, Structural Characterization, Cation–Cation Interaction Classification, and Optical Properties of Uranium(VI) Containing Oxychlorides, A₄U₅O₁₆Cl₂ (A = K, Rb), Cs₅U₇O₂₂Cl₃, and AUO₃Cl (A = Rb, Cs). CrystEngComm, 16(31), 7259–7267. https://doi.org/10.1039/C4CE00281D

Rights

© CrystEngComm 2014, Royal Society of Chemistry.