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@ARTICLE{Murphy:902463,
author = {Murphy, Gabriel L. and Kegler, Philip and Langer, Eike M.
and Alekseev, Evgeny V.},
title = {{T}he {R}ole of {A}cidity in the {S}ynthesis of {N}ovel
{U}ranyl {S}elenate and {S}elenite {C}ompounds and {T}heir
{S}tructures},
journal = {Crystals},
volume = {11},
number = {8},
issn = {2073-4352},
address = {Basel},
publisher = {MDPI},
reportid = {FZJ-2021-04282},
pages = {965 -},
year = {2021},
abstract = {Herein, the novel uranyl selenate and selenite compounds
Rb2[(UO2)2(SeO4)3], Rb2[(UO2)3(SeO3)2O2],
Rb2[UO2(SeO4)2(H2O)]·2H2O, and (UO2)2(HSeO3)2(H2SeO3)2Se2O5
have been synthesized using either slow evaporation or
hydrothermal methods under acidic conditions and their
structures were refined using single crystal X-ray
diffraction. Rb2[(UO2)2(SeO4)3] synthesized hydrothermally
adopts a layered 2D tetragonal structure in space group
P42/ncm with a = 9.8312(4) Å, c = 15.4924(9) Å, and V =
1497.38(15) Å, where it consists of UO7 polyhedra
coordinated via SeO4 units to create units UO2(SeO4)58−
moieties which interlink to create layers in which Rb+
cations reside in the interspace. Rb2[(UO2)3(SeO3)2O2]
synthesized hydrothermally adopts a layered 2D triclinic
structure in space group P1¯ with a = 7.0116(6) Å, b =
7.0646(6) Å, c = 8.1793(7) Å, α = 103.318(7)°, β =
105.968(7)°, γ = 100.642(7)° and V = 365.48(6) Å3, where
it consists of edge sharing UO7, UO8 and SeO3 polyhedra that
form [(UO2)3(SeO3)2O2] layers in which Rb+ cations are found
in the interlayer space. Rb2[UO2(SeO4)2(H2O)]·2H2O
synthesized hydrothermally adopts a chain 1D orthorhombic
structure in space group Pmn21 with a = 13.041(3) Å, b =
8.579(2) Å, c = 11.583(2) Å, and V = 1295.9(5) Å3,
consisting of UO7 polyhedra that corner share with one H2O
and four SeO42− ligands, creating infinite chains.
(UO2)2(HSeO3)2(H2SeO3)2Se2O5 synthesized under slow
evaporation conditions adopts a 0D orthorhombic structure in
space group Cmc21 with a = 28.4752(12) Å, b = 6.3410(3) Å,
c = 10.8575(6) Å, and V = 1960.45(16) Å3, consisting of
discrete rings of [(UO2)2(HSeO3)2(H2SeO3)2Se2O5]2.
(UO2)2(HSeO3)2(H2SeO3)2Se2O5 is apparently only the second
example of a uranyl diselenite compound to be reported. A
combination of single crystal X-ray diffraction and bond
valance sums calculations are used to characterise all
samples obtained in this investigation. The structures
uncovered in this investigation are discussed together with
the broader family of uranyl selenates and selenites,
particularly in the context of the role acidity plays during
synthesis in coercing specific structure, functional group,
and topology formations},
cin = {IEK-6},
ddc = {540},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {1411 - Nuclear Waste Disposal (POF4-141)},
pid = {G:(DE-HGF)POF4-1411},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000689925500001},
doi = {10.3390/cryst11080965},
url = {https://juser.fz-juelich.de/record/902463},
}