Reinterpretation of Three Crystal Structures of Alkali Oxoiodate(V) - Description of the [I3O8]- Anion and the Infinite 2D [I3O8-]∞ Anion - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie Année : 2010

Reinterpretation of Three Crystal Structures of Alkali Oxoiodate(V) - Description of the [I3O8]- Anion and the Infinite 2D [I3O8-]∞ Anion

Yan Suffren
Julien Pilmé

Résumé

Two Cs2(IO3)(I3O8) polymorph phases and the Rb2(I3O8)- (IO3)(HIO3)2(H2O) compound were prepared by hydrothermal syntheses and characterised by X-ray single crystal diffraction. α-Cs2(IO3)- (I3O8) crystallises in the hexagonal space group P63 (a = 7.366(1) Å; c = 13.883(1) Å; V = 652.3(1) Å3; Z' = 2) whereas β-Cs2(IO3)(I3O8) crystallises in monoclinic space group P21/n (a = 12.733(1) Å; b = 7.437(1) Å; c = 14.359(2) Å; β = 106.98(1)°; V = 1300.4(2) Å3; Z = 4) and Rb2(I3O8)(IO3)(HIO3)2(H2O) in triclinic space group P1¯ (a = 7.043(1) Å, b = 7.496(1) Å, c = 18.203(3) Å; α = 79.70(2)°; β = 85.04(2)°; γ = 70.66 (1)°; V = 891.8(2) Å3; Z = 2). β-Cs2(IO3)(I3O8) and Rb2(I3O8)(IO3)(HIO3)2(H2O) reveal the presence of [I3O8]- anion. These compounds have already been characterised as β-Cs2I4O11 and Rb2I6O15(OH)2*(H2O) for which the descriptions do not reflect the chemical structure. The previous descriptions are based on different choices for the I-O bonding character. In Rb2(I3O8)(IO3)(HIO3)2(H2O), the shortest I***O interaction (2.316(5) Å) observed between a [IO3 -] anion and HIO3 is in the same range of I-O bond length (2.201(4) Å) in the [I3O8]- anion. Bond valence calculations clearly show three classes of I-O interactions. Finally, DFT calculations coupled to the Electron Localisation Function analysis were performed to describe chemical schemes of these bonds, which justified our chemical description of the structures. The non-centrosymmetric α-Cs2(IO3)(I3O8) compound, revealed the presence of the infinite two-dimensional [I3O8 -]∞, which was obtained by condensation of iodate anions.

Dates et versions

hal-00908537 , version 1 (24-11-2013)

Identifiants

Citer

Isabelle Gautier-Luneau, Yan Suffren, Julien Pilmé, Hélène Jamet. Reinterpretation of Three Crystal Structures of Alkali Oxoiodate(V) - Description of the [I3O8]- Anion and the Infinite 2D [I3O8-]∞ Anion. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, 2010, 636, pp.1368-1379. ⟨10.1002/zaac.200900508⟩. ⟨hal-00908537⟩
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