A Single-Crystal Neutron Diffraction Study of HIO3 at 295 and 30 K and of DIO3 at 295 K.

Ståhl, Kenny; Szafrański, Marek; Junker, Flemming; Dalbøge, Henrik; Abildgaard, Frits; Led, Jens J.; Christensen, S. Brøgger

doi:10.3891/acta.chem.scand.46-1146

Cited by 18 publications

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“…The fourth I-O distances are 32-35 % longer than the averaged short bonding distance (1.838 Å). The authors claim that these distances are in agreement with bond lengths of previously reported iodate structures [37][38][39][40][41]. Among all these references, the distances corresponding to chemical bonds are in the range 1.72(6)-1.97(6) Å.…”

Section: Introductionsupporting

confidence: 85%

“…The long distances corresponding to interactions are ranging from 2.61-3.30 Å. The only structure which presents an I-O distance as short as 2.486 Å is the structure of iodic acid [41], but the authors of this work classified this distance as an interaction and not as a chemical bond. On the other hand, the authors have considered I-O distances ranging from 2.583(5)-2.644(5) Å (only 5 % longer than 2.481 Å) as "very long contacts" drawn in dashed lined on the crystal structure representation.…”

Section: Introductionmentioning

confidence: 89%

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

Gautier‐Luneau

Suffren

Pilmé

et al. 2010

Zeitschrift anorg allge chemie

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International audienceTwo 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

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Section: Introductionsupporting

confidence: 85%

Section: Introductionmentioning

confidence: 89%

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

Gautier‐Luneau

Suffren

Pilmé

et al. 2010

Zeitschrift anorg allge chemie

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“…These bond lengths and angles are consistent with those of previously reported iodates. [20][21][22][23][24] The IO 5 and IO 3 polyhedra share corners to form the layered structure. In connectivity terms, the layer can be described as a [3(IO2 = 3 O2 = 1 O1 = 2 ) 4 = 3 À (IO3 = 2 ) 2+ ] 2À anion, with charge balance attained by two Cs + cations.…”

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confidence: 99%

The Lone‐Pair Cation I⁵⁺ in a Hexagonal Tungsten Oxide‐Like Framework: Synthesis, Structure, and Second‐Harmonic Generating Properties of Cs₂I₄O₁₁

2004

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Noncentrosymmetric (NCS) oxides exhibit a variety of technologically important properties including ferroelectricity, piezoelectricity, pyroelectricity, and second-order nonlinear optical behavior. [1][2][3] The rational design of new NCS materials, however, remains a challenge, although a number of strategies have been suggested. [4][5][6][7][8][9] We have focused on synthesizing materials containing cations with lone pairs (e.g., Sb 3+ , Se 4+ , Te 4+, etc.) in order to increase the incidence of NCS in any new compound. [10,11] A structural topology that is often observed in NCS is the hexagonal tungsten oxide (HTO) framework. This structure has been reported for a variety of cations, including V 5+ , Mo 6+ , W 6+, and Sb 5+. [12][13][14][15][16][17][18] The framework consists of corner-sharing MO6 = 2 octahedra that are linked to form an array of three-and six-membered rings. [20-24] The IO 5 and IO 3 polyhedra share corners to form the layered structure. In connectivity terms, the layer can be described as a [3(2À anion, with charge balance attained by two Cs + cations. One of the most novel aspects of the structure is the twodimensional IO 5 layer (Figure 1). The HTO-like layer consists of six-membered rings containing corner-sharing IO 5 polyhedra in alternating orientation as one proceeds around the ring. Cs 2 I 4 O 11 is the first example of a lone-pair cation in a HTO-like topology. In the rings themselves, three lone pairs point inward and three outward. Thus, the lone pairs and oxide anions alternate around the ring. The lone pairs have two important structural consequences. First, the local dipole moment on each IO 5 polyhedron is in the direction of the lone pair. If we sum all of the dipole moments with respect to the IO 5 group, the resultant moment is zero. In other words, there is complete cancellation of the dipole moments with respect to the IO 5 polyhedra, that is, the IO 5 layer is pseudocentrosymmetric. This type of pseudocentrosymmetric layer was observed previously in Rb 2 TeW 3 O 12 and Cs 2 TeW 3 O 12 .[17] The cancellation is relevant to the SHG efficiency. Second, the Cs + cations are not coplanar with the IO 5 ring, attributable to the lone pairs. As shown in Figure 2, the Cs + cations sit above and below the rings. The environments of the Cs + cations influence any possible ion-exchange capabilities of the material.[25] The IO 5 layer is capped on one side by an asymmetric three-coordinate I 5+ cation, that is, an IO 3 group (see Figure 3). Alignment of the IO 3 polyhedra in the [001] direction results in an NCS and polar structure. The lone pairs associated with the IO 3 polyhedra also point along the [001]

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“…[45] The I 5 + is linked to three O atoms to form a larger distorted polyhedron, which including three IÀ O bond and and a lone electrons pair, the bond distances of IÀ O bond are range from 1.78(2) to 1.860(17)Å, which are very closed to other reported compounds. [46][47][48][49][50] For silver atoms, Ag (1) Figure 1 ). In each [Sm 2 (IO 3 ) 8 ] unit, the SmO 8 unit are seriously distorted, even though the polarizations of Sm1O 8 and Sm2O 8 are partly cancelled out, their net dipole moment are not completely cancelled, which means there is a resultant dipole moment between these two groups.…”

Section: Introductionmentioning

confidence: 99%

Five New Silver Rare‐Earth Iodates, AgLn(IO₃)₄ (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties

Liu

et al. 2019

ChemistrySelect

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Five new silver rare‐earth iodates AgLn(IO3)4 (Ln= Pr, Sm, Dy, Er and Tm) have been synthesized first time by hydrothermal method, and their structures are confirmed by single crystal X‐ray diffraction. They are isomorphic of previous characterized AgM(IO3)4 (With M= Y, La, Nd, Eu, Gd, Bi) compounds and all crystallized in noncentrosymmetric (NCS) structure. Their structures contain LnO8 polyhedrons, which are interconnected through IO3 groups to form a complex two dimensional (2D) layer. Their powders all show nonlinear optical (NLO) effects which are 2.3 ‐ 4 times stronger than KH2PO4 (KDP) respectively. Energy dispersive X‐ray spectroscopy (EDS), Infrared region (IR) spectra, Ultra‐visible (UV/Vis) spectra and thermogravimetric analysis (TGA) are also performed.

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A Single-Crystal Neutron Diffraction Study of HIO3 at 295 and 30 K and of DIO3 at 295 K.

Cited by 18 publications

References 0 publications

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

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

The Lone‐Pair Cation I⁵⁺ in a Hexagonal Tungsten Oxide‐Like Framework: Synthesis, Structure, and Second‐Harmonic Generating Properties of Cs₂I₄O₁₁

Five New Silver Rare‐Earth Iodates, AgLn(IO₃)₄ (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties

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A Single-Crystal Neutron Diffraction Study of HIO3 at 295 and 30 K and of DIO3 at 295 K.

Cited by 18 publications

References 0 publications

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

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

The Lone‐Pair Cation I5+ in a Hexagonal Tungsten Oxide‐Like Framework: Synthesis, Structure, and Second‐Harmonic Generating Properties of Cs2I4O11

Five New Silver Rare‐Earth Iodates, AgLn(IO3)4 (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties

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

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

The Lone‐Pair Cation I⁵⁺ in a Hexagonal Tungsten Oxide‐Like Framework: Synthesis, Structure, and Second‐Harmonic Generating Properties of Cs₂I₄O₁₁

Five New Silver Rare‐Earth Iodates, AgLn(IO₃)₄ (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties