Research output: Contribution to journal › Article › peer-review
Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4 : Different filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure. / Solodovnikov, Sergey F.; Solodovnikova, Zoya A.; Zolotova, Evgeniya S. et al.
In: Acta Crystallographica Section C: Structural Chemistry, Vol. 73, No. 11, 01.11.2017, p. 946-952.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4
T2 - Different filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure
AU - Solodovnikov, Sergey F.
AU - Solodovnikova, Zoya A.
AU - Zolotova, Evgeniya S.
AU - Kadyrova, Yulia M.
AU - Savina, Aleksandra A.
AU - Stefanovich, Sergey Yu
AU - Khaikina, Elena G.
PY - 2017/11/1
Y1 - 2017/11/1
N2 - Two new compounds, namely cubic tricaesium lithium dizinc tetrakis(tetraoxotungstate), Cs3LiZn2(WO4)4, and tetragonal trirubidium dilithium gallium tetrakis(tetraoxomolybdate), Rb3Li2Ga(MoO4)4, belong to the structural family of Cs6Zn5(MoO4)8 (space group I3d, Z = 4), with a partially incomplete (Zn5/6□1/6) position. In Cs3LiZn2(WO4)4, this position is fully statistically occupied by (Zn2/3Li1/3), and in Rb3Li2Ga(MoO4)4, the 2Li + Ga atoms are completely ordered in two distinct sites of the space group I2d (Z = 4). In the same way, the crystallographically equivalent A+ cations (A = Cs, Rb) in Cs6Zn5(MoO4)8, Cs3LiZn2(WO4)4 and isostructural A3LiZn2(MoO4)4 and Cs3LiCo2(MoO4)4 are divided into two sites in Rb3Li2Ga(MoO4)4, as in other isostructural A3Li2R(MoO4)4 compounds (AR = TlAl, RbAl, CsAl, CsGa, CsFe). In the title structures, the WO4 and (Zn,Li)O4 or LiO4, GaO4 and MoO4 tetrahedra share corners to form open three-dimensional frameworks with the caesium or rubidium ions occupying cuboctahedral cavities. The tetrahedral frameworks are related to that of mayenite 12CaO·7Al2O3 and isotypic compounds. Comparison of isostructural Cs3MZn2(MoO4)4 (M = Li, Na, Ag) and Cs6Zn5(MoO4)8 shows a decrease of the cubic lattice parameter and an increase in thermal stability with the filling of the vacancies by Li+ in the Zn position of the Cs6Zn5(MoO4)8 structure, while filling of the cation vacancies by larger Na+ or Ag+ ions plays a destabilizing role. The series A3Li2R(MoO4)4 shows second harmonic generation effects compatible with that of β′-Gd2(MoO4)3 and may be considered as nonlinear optical materials with a modest nonlinearity.Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4 represent two distinct series of filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure with three-dimensional tetrahedral frameworks related to that of mayenite 12CaO·7Al2O3. The series of tetragonal A3Li2R(MoO4)4 compounds exhibits second harmonic generation effects compatible with that of β′-Gd2(MoO4)3.
AB - Two new compounds, namely cubic tricaesium lithium dizinc tetrakis(tetraoxotungstate), Cs3LiZn2(WO4)4, and tetragonal trirubidium dilithium gallium tetrakis(tetraoxomolybdate), Rb3Li2Ga(MoO4)4, belong to the structural family of Cs6Zn5(MoO4)8 (space group I3d, Z = 4), with a partially incomplete (Zn5/6□1/6) position. In Cs3LiZn2(WO4)4, this position is fully statistically occupied by (Zn2/3Li1/3), and in Rb3Li2Ga(MoO4)4, the 2Li + Ga atoms are completely ordered in two distinct sites of the space group I2d (Z = 4). In the same way, the crystallographically equivalent A+ cations (A = Cs, Rb) in Cs6Zn5(MoO4)8, Cs3LiZn2(WO4)4 and isostructural A3LiZn2(MoO4)4 and Cs3LiCo2(MoO4)4 are divided into two sites in Rb3Li2Ga(MoO4)4, as in other isostructural A3Li2R(MoO4)4 compounds (AR = TlAl, RbAl, CsAl, CsGa, CsFe). In the title structures, the WO4 and (Zn,Li)O4 or LiO4, GaO4 and MoO4 tetrahedra share corners to form open three-dimensional frameworks with the caesium or rubidium ions occupying cuboctahedral cavities. The tetrahedral frameworks are related to that of mayenite 12CaO·7Al2O3 and isotypic compounds. Comparison of isostructural Cs3MZn2(MoO4)4 (M = Li, Na, Ag) and Cs6Zn5(MoO4)8 shows a decrease of the cubic lattice parameter and an increase in thermal stability with the filling of the vacancies by Li+ in the Zn position of the Cs6Zn5(MoO4)8 structure, while filling of the cation vacancies by larger Na+ or Ag+ ions plays a destabilizing role. The series A3Li2R(MoO4)4 shows second harmonic generation effects compatible with that of β′-Gd2(MoO4)3 and may be considered as nonlinear optical materials with a modest nonlinearity.Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4 represent two distinct series of filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure with three-dimensional tetrahedral frameworks related to that of mayenite 12CaO·7Al2O3. The series of tetragonal A3Li2R(MoO4)4 compounds exhibits second harmonic generation effects compatible with that of β′-Gd2(MoO4)3.
KW - crystal chemistry
KW - crystal structure
KW - filling vacancies
KW - second harmonic generation
KW - structural family
KW - tetrahedral framework
KW - thermal stability
KW - triple molybdate
KW - triple tungstate
KW - LASER CRYSTALS
KW - OXIDE
KW - MOLYBDATES
KW - CRYSTAL-STRUCTURE
KW - CA12AL14O33
KW - ELEMENTS
KW - TUNGSTATES
KW - GROWTH
KW - LITHIUM
UR - http://www.scopus.com/inward/record.url?scp=85032918491&partnerID=8YFLogxK
U2 - 10.1107/S205322961701378X
DO - 10.1107/S205322961701378X
M3 - Article
C2 - 29111524
AN - SCOPUS:85032918491
VL - 73
SP - 946
EP - 952
JO - Acta Crystallographica Section C: Structural Chemistry
JF - Acta Crystallographica Section C: Structural Chemistry
SN - 2053-2296
IS - 11
ER -
ID: 9721540