Special Issue "Crystal Structures of Compounds Containing Ions Selenite"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (20 March 2018)

Special Issue Editor

Guest Editor
Prof. Dr. Claudia Graiff

Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma, 43124 Parma, Italy
Website | E-Mail
Interests: X ray diffraction; coordination complexes; nanostructured functional materials; crystalline nanocellulose

Special Issue Information

Dear Colleagues,

The chemistry of materials containing chalcogen elements, and in particular Se oxyanions in the +4 oxidation state, is of increasing interest to the research community for several reasons: First, it is known that the incorporation of selenite anions can lead to non-centrosymmetric structures and, consequently, to materials displaying remarkable non-linear optical properties, ferroelectricity and piezoelectricity. Moreover, the lone pair on the chalcogen atom could behave as structure-directing agent towards the formation of materials characterized by the presence of hollows or channels in their intimate structures. Moreover, some selenites show highly robust three-dimensional open framework structures, which are retained on the removal of guests or coordinated little molecules. In fact, porous structures, due to the presence of the lone pair on the chalcogen atom, open the utilization of selenite derivatives in the synthesis of Metal Organic Frameworks (MOFs) or Porous Coordination Polymers (PCPs). In addition, when selenite anions act as bridging ligands towards metal atoms, they can hold (keep) close the cationic centers, allowing magnetic exchange between paramagnetic metals. Finally, the weakly coordinative capability of the Se(IV) electron lone pairs could give rise to supramolecular interactions.

For all these reasons a high potential interest on materials containing ion selenites is expected, even though relatively few studies on such compounds have been reported until now. The most important feature is that the full comprehension of the properties of this type of materials cannot be exhaustively understood unless the complete solid state crystal structure is available. In this Special Issue, of which the theme is “Crystal Structures of Compounds Containing Ions Selenite”, we aim to collect a series of examples showing the fundamental role of detailed structural analysis in understanding the interactions in the solid state responsible for the peculiar chemical physical properties of such materials.

Prof. Dr. Claudia Graiff
Guest Editor

Manuscript Submission Information

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Keywords

  • Molecular and crystal structure of materials incorporating selenite anions
  • MOF derived from selenite containing compounds
  • NLO properties of selenite holding materials
  • Supramolecular interactions derived from selenite containing structures
  • Full characterization of new selenite compounds

Published Papers (6 papers)

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Research

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Open AccessArticle Mild Synthesis and Structural Characterization of a Novel Vanadyl Selenite-Hydrogen Selenite Phase, Na[VO(SeO3)(HSeO3)]·1,5H2O
Crystals 2018, 8(5), 215; https://doi.org/10.3390/cryst8050215
Received: 16 March 2018 / Revised: 7 May 2018 / Accepted: 13 May 2018 / Published: 15 May 2018
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Abstract
Single crystals of Na[VO(SeO3)(HSeO3)]·1,5H2O have been prepared by solvent slow evaporation from an equimolar aqueous mixture of sodium selenite and vanadyl sulfate. The overall arrangement consists of VO6 octahedra, [SeO3]2− and [HSeO3
[...] Read more.
Single crystals of Na[VO(SeO3)(HSeO3)]·1,5H2O have been prepared by solvent slow evaporation from an equimolar aqueous mixture of sodium selenite and vanadyl sulfate. The overall arrangement consists of VO6 octahedra, [SeO3]2− and [HSeO3] anions forming a strong backbone with channel-like voids, while sodium cations participate in the framework, ensuring the overall charge balance. The crystal packing of the material features channels with a star-shaped section showing a mean aperture of 6.10 Å with the oxygen atoms of the V=O moieties pointing towards the interior of the cavities. Their dimensions are the narrowest reported until now in vanadium selenite compounds. Disordered sodium cations with occupancy factor of 0.5 are found in the star-shaped section cavities together with disordered water molecules, interacting with each other via hydrogen bonds. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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Open AccessArticle Se–Cl Interactions in Selenite Chlorides: A Theoretical Study
Crystals 2018, 8(5), 193; https://doi.org/10.3390/cryst8050193
Received: 29 March 2018 / Revised: 24 April 2018 / Accepted: 25 April 2018 / Published: 29 April 2018
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Abstract
The Se–Cl interactions in five selenite chlorides (α,β-Zn2(SeO3)Cl2 (sofiite and its polymorph), α,β-Cu5O2(SeO3)2Cl2 (georgbokiite and parageorgbokiite), and KCdCu7O2(SeO3)2Cl9 (burnsite)) have
[...] Read more.
The Se–Cl interactions in five selenite chlorides (α,β-Zn2(SeO3)Cl2 (sofiite and its polymorph), α,β-Cu5O2(SeO3)2Cl2 (georgbokiite and parageorgbokiite), and KCdCu7O2(SeO3)2Cl9 (burnsite)) have been investigated by means of the analysis of their theoretical electron density distributions. The analysis reveals the existence in the structures of two basic types of interactions: intermediate interactions with essential covalent contribution and closed-shell interactions. In Zn2(SeO3)Cl2 polymorphs and burnsite, all metal-oxide and metal-chloride interactions are of the first type, whereas in georgbokiite and parageorgbokiite, the Jahn–Teller distortion results in the elongation of some of the Cu–X bonds and their transition to the closed-shell type. All anion–anion interactions are of the closed-shell type. The energy of the closed-shell Se–Cl interactions can be estimated as 1.4–2.6 kcal.mol−1, which is comparable to weak hydrogen bonds. Despite their weakness, these interactions provide additional stabilization of structural architectures. The Se4+–Cl configurations are localized inside framework channels or cavities, which can be therefore be viewed as regions of weak and soft interactions in the structure. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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Open AccessArticle Sc2[Se2O5]3: The First Rare-Earth Metal Oxoselenate(IV) with Exclusively [Se2O5]2− Anions
Crystals 2018, 8(5), 187; https://doi.org/10.3390/cryst8050187
Received: 23 March 2018 / Revised: 20 April 2018 / Accepted: 20 April 2018 / Published: 26 April 2018
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Abstract
The scandium oxodiselenate(IV) Sc2[Se2O5]3 was synthesized via solid-state reactions between scandium sesquioxide (Sc2O3) and selenium dioxide (SeO2) with thallium(I) chloride (TlCl) as fluxing agent in molar ratios of 1:4:2. Evacuated
[...] Read more.
The scandium oxodiselenate(IV) Sc2[Se2O5]3 was synthesized via solid-state reactions between scandium sesquioxide (Sc2O3) and selenium dioxide (SeO2) with thallium(I) chloride (TlCl) as fluxing agent in molar ratios of 1:4:2. Evacuated fused silica ampoules were used as reactions vessels for annealing the mixtures for five days at 800 °C. The new scandium compound crystallizes in the triclinic space group P 1 ¯ with the lattice parameters a = 663.71(5) pm, b = 1024.32(7) pm, c = 1057.49(8) pm, α = 81.034(2)°, β = 87.468(2)°, γ = 89.237(2)° and Z = 2. There are two distinct Sc3+ positions, which show six-fold coordination by oxygen atoms as [ScO6]9− octahedra (d(Sc–O) = 205–212 pm). Three different [Se2O5]2− anions provide these oxygen atoms with their terminal ligands (Ot). Each of the six selenium(IV) central atoms exhibit a stereochemically active lone pair of electrons, so that all [Se2O5]2− anions consist of two ψ1-tetrahedral [SeO3]2− subunits (d(Se–Ot) = 164–167 pm, d(Se–Ob) = 176–185 pm, ∢(O–Se–O) = 93–104°) sharing one bridging oxygen atom (Ob) with ∢(Se–Ob–Se) = 121–128°. The vibrational modes of the complex anionic [Se2O5]2− entities were characterized via single-crystal Raman spectroscopy. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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Open AccessArticle Role of Bis(triphenylphosphine)iminium Cation [PNP]+ on the Crystal Packing of [PNP]+[HSeO3] Solvate Salt
Crystals 2018, 8(4), 151; https://doi.org/10.3390/cryst8040151
Received: 14 March 2018 / Revised: 23 March 2018 / Accepted: 28 March 2018 / Published: 29 March 2018
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Abstract
Selenate(IV) and hydrogen selenate(IV) salts of bulky cations are very interesting compounds for synthetic and kinetic studies. In this work, bis(triphenylphosphine)iminium ([PNP]+) chloride has been used, which aims to synthesize the corresponding selenate(IV) salt by an exchange reaction in the aqueous
[...] Read more.
Selenate(IV) and hydrogen selenate(IV) salts of bulky cations are very interesting compounds for synthetic and kinetic studies. In this work, bis(triphenylphosphine)iminium ([PNP]+) chloride has been used, which aims to synthesize the corresponding selenate(IV) salt by an exchange reaction in the aqueous solution and subsequent crystallization by solvent evaporation. Unexpectedly, the procedure afforded a solvate form of the [PNP]+[HSeO3] salt (1). In this solid phase, which has a structure that is determined by Single Crystal XRD, the anion tends to maximize the interactions with itself, although it leaves the cationic moiety to have only weak interactions with the anions and the solvent molecules. In turn, the latter builds a network of effective hydrogen bonds. This behavior opposes the general tendency of selenite(IV) and hydrogen selenite(IV) compounds, since these anions are commonly found to have formed effective hydrogen bonds with surrounding chemical species. Moreover, as the exchange reaction is non-quantitative, the exceeding traces of the starting bis(triphenylphosphine)iminium chloride reagent reacted with bis(acetonitrile)dichloropalladium(II) to form the bis(triphenylphosphine)iminium hexachloropalladate (2). In the solid phase, [PNP]+ causes the absence of strong supramolecular interactions, which highlights the peculiar behavior of the cation in the crystal packing of its solid phases. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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Review

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Open AccessReview Selenium-Doped Hydroxyapatite Nanocrystals–Synthesis, Physicochemical Properties and Biological Significance
Crystals 2018, 8(5), 188; https://doi.org/10.3390/cryst8050188
Received: 30 March 2018 / Revised: 23 April 2018 / Accepted: 24 April 2018 / Published: 26 April 2018
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Abstract
Hydroxyapatites (HAs), as materials with a similar structure to bone minerals, play a key role in biomaterials engineering. They have been applied as bone substitute materials and as coatings for metallic implants, which facilitates their osseointegration. One of the beneficial characteristics of HA,
[...] Read more.
Hydroxyapatites (HAs), as materials with a similar structure to bone minerals, play a key role in biomaterials engineering. They have been applied as bone substitute materials and as coatings for metallic implants, which facilitates their osseointegration. One of the beneficial characteristics of HA, when used to create biocompatible materials with improved physicochemical or biological properties, is its capacity for ionic substitution. The aim of the study was to present the current state of knowledge about HAs containing selenate ions IV or VI. The enrichment of HAs with selenium aims to create a material with advantageous effects on bone tissue metabolism, as well as having anticancer and antibacterial activity. The work is devoted to both methods of obtaining Se-HA and an evaluation of its chemical structure and physicochemical properties. In addition, the biological activity of such materials in vitro and in vivo is discussed. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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Open AccessReview Transition Metal Selenite Halides: A Fascinating Family of Magnetic Compounds
Crystals 2018, 8(4), 159; https://doi.org/10.3390/cryst8040159
Received: 12 March 2018 / Revised: 31 March 2018 / Accepted: 2 April 2018 / Published: 4 April 2018
Cited by 1 | PDF Full-text (36223 KB) | HTML Full-text | XML Full-text
Abstract
The problem of searching for low-dimensional magnetic systems has been a topical subject and has attracted attention of the chemistry and physics community for the last decade. In low-dimensional magnetic systems, magnetic ions are distributed anisotopically and form different groups such as dimers,
[...] Read more.
The problem of searching for low-dimensional magnetic systems has been a topical subject and has attracted attention of the chemistry and physics community for the last decade. In low-dimensional magnetic systems, magnetic ions are distributed anisotopically and form different groups such as dimers, chains, ladders, or planes. In 3D frameworks, the distances between magnetic ions are equal in all directions while in low-dimensional systems the distances within groups are different from those between groups. The main approach of searching for desired systems is a priori crystal chemical design expecting the needed distribution of transition metal ions in the resulting structure. One of the main concepts of this structural design is the incorporation of the p-element ions with stereochemically active electron pairs and ions acting as spacers in the composition. Transition metal selenite halides, substances that combine SeO32− groups and halide ions in the structure, seem to be a promising object of investigation. Up to now, there are 33 compounds that are structurally described, magnetically characterized, and empirically tested on different levels. The presented review will summarize structural peculiarities and observed magnetic properties of the known transition metal selenite halides. In addition, the known compounds will be analyzed as possible low-dimensional magnetic systems. Full article
(This article belongs to the Special Issue Crystal Structures of Compounds Containing Ions Selenite)
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