Diversity of fundamental building blocks [M(IO3)6] in iodate families and new trigonal polymorph of Cs2HIn(IO3)6

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Crystals of new structural high-symmetry modification of Cs2HIn(IO3)6, which crystallyzes in sp. gr. R3 with parameters of unit cell a = 11.8999(4), c = 11.6513(5) Å were obtained in hydrothermal conditions. Crystal chemical comparison with triclinic modification the investigated earlier was carried out. Both structures are composed of isolated blocks [In(IO3)6]3–. The new modification belongs to the family of trigonal iodates isostructural to K2Ge(IO3)6 compound. Local symmetry of separated blocks [M(IO3)6] (M = Ge, Ti, Sn, Ga, In and other metals) are analyzed. Structural systematic of iodate families is suggested on the base of comparative crystal chemical analysis. The influence of cation composition and synthesis conditions on symmetry and topology of crystal structures as well as local symmetry of blocks on physical properties of compounds are discussed.

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作者简介

O. Reutova

Lomonosov Moscow State University

Email: elbel@geol.msu.ru

Geological Faculty, Department of Crystallography and Crystal Chemistry

俄罗斯联邦, Moscow

E. Belokoneva

Lomonosov Moscow State University

编辑信件的主要联系方式.
Email: elbel@geol.msu.ru

Geological Faculty, Department of Crystallography and Crystal Chemistry

俄罗斯联邦, Moscow

A. Volkov

Skolkovo Institute of Science and Technology

Email: elbel@geol.msu.ru
俄罗斯联邦, Moscow

О. Dimitrova

Lomonosov Moscow State University

Email: elbel@geol.msu.ru

Geological Faculty, Department of Crystallography and Crystal Chemistry

俄罗斯联邦, Moscow

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2. Fig. 1. Projection of the structure: lateral Cs2HIn(IO3)6 (a); trigonal Cs2HIn(IO3)6 along the ternary axis (b); triclinic Cs2HIn(IO3)6 along the ternary axis of the pseudorhombohedral cell (c).

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3. Fig. 2. Centrosymmetric blocks [M(IO3)6] with point symmetry with different configurations in the structures of iodates of the family: АnM(IO3)6 (A = Na, K, Rb, Cs, Ag, Tl+, H3O+, Ba, Sn2+; M = Ge, Ti, Pt, Sn, Zr, Mo4+, Ga, In) (a); AM(IO3)6 (A = Ba, Sr; M = Ti, Sn) (b); SrTi(IO3)6 2H2O (c); M(IO3)3 (M = In, Sc, Tl) (d); M(IO3)3 (M = In, Sc, Tl) – connection of blocks into a layer (e).

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4. Fig. 3. Acentric blocks [M(IO3)6] (M = Ge, Ti) with point symmetry 3 in the structures of aqueous iodates BaGe(IO3)6 H2O (a), BaTi(IO3)6 0.5H2O (b).

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5. Рис. 4. Блоки [Ta(IO3)6] и [Sc(IO3)6] с точечной псевдосимметрией 3 в структурах Cs3Ta(IO3)8 (а) и KSc(IO3)3Cl (б) соответственно, боковые проекции структур Cs3Ta(IO3)8 (в) и KSc(IO3)3Cl (г).

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6. Fig. 5. Block [Nb(IO3)6] with point symmetry 1 in the pseudotrigonal structure (H3O)HCs2Nb(IO3) (a); projection of the structure (H3O)HCs2Nb(IO3)9 onto the ac plane (b).

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7. Fig. 6. Configuration of the acentric [M(IO3)6] block (M = Li, Ti, Sn, Pt, Al, Cr, Fe3+, Ga, In, Mg, Mn2+, Zn, Cd, Co, Ni, Cu2+) with point symmetry 3 in the structures of hexagonal (space group P63) and pseudohexagonal (space group P21) iodates (a); rods of [Li(IO3)6] blocks in the framework of α-LiIO3 (b); rods of [M(IO3)6] blocks in the structures of the A2M(IO3)6 family (A = Li, Na, H3O+; M = Ti, Sn, Pt) (c); a framework of [M(IO3)6] blocks in the structures of the M(IO3)3 (M = Al, Cr, Fe3+, In, Ga) and M(IO3)2 (M = Mg, Zn, Co, Ni, Cu2+, Mn2+) families (d); a framework of [M(IO3)6] and [Li(IO3)6] blocks in the structures of the LiM(IO3)3 family (M = Mg, Zn, Cd) (e); a framework of alternating [Zn(IO3)6] and [Li(IO3)6] blocks in the structure of LiZn(IO3)3 (space group P21) (e).

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8. Fig. 7. [M(IO3)6] blocks with pseudosymmetry 2/m in the structures of α-K3In(IO3)6 and A3M(IO3) families (A = Na, K, Rb, Ag, Tl+; M = In, Tl, Fe3+, Mn3+) (a); 2/m in K3Sc(IO3)6 (b); m in Rb3Sc(IO3)6 (c).

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9. Fig. 8. The [In(IO3)6] block with symmetry 1 in the structure of NaIn(IO3)4 (a); 1 in AgIn(IO3)4 (b); projection of a chain of [In(IO3)6] blocks in the structures of NaIn(IO3)4 (c) and AgIn(IO3)4 (d).

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10. Fig. 9. Acentric block [M(IO3)6] with symmetry 1 in the structures of the AgM(IO3)4 family (M = Ga, Mn3+) (a); a chain of blocks in the structures of AgGa(IO3)4 (b) and AgMn(IO3)4 (c).

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11. Fig. 10. Centrosymmetric blocks [M(IO3)6] (M = Sn, In) with symmetry 1 (a); their connection into chains in the structures of Sn(IO3)4 and LiIn(IO3)4 (b).

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12. Fig. 11. Dimers [Mn2(IO3)10] (a); their connection into a framework in the structure of AgMn(IO3)3 (b).

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13. Fig. 12. Projection onto the ac plane of the Cs5[Sc2(IO3)9](IO3)2 structure with a framework of [Sc(IO3)6] blocks (a); individual [Sc(IO3)6] blocks with point symmetry 1 and 1 in the Cs5[Sc2(IO3)9](IO3)2 structure (b).

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