Fluorite structure

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In solid state chemistry, the fluorite structure refers to a common motif for compounds with the formula MX2. [1] [2] The X ions occupy the eight tetrahedral interstitial sites whereas M ions occupy the regular sites of a face-centered cubic (FCC) structure. Many compounds, notably the common mineral fluorite (CaF2), adopt this structure.

Contents

Many compounds with formula M2X have an antifluorite structure. In these the locations of the anions and cations are reversed relative to fluorite (an anti-structure); the anions occupy the FCC regular sites whereas the cations occupy the tetrahedral interstitial sites. For example, magnesium silicide, Mg2Si, has a lattice parameter of 6.338 Å with magnesium cations occupying the tetrahedral interstitial sites, in which each silicide anion is surrounded by eight magnesium cations and each magnesium cation is surrounded by four silicide anions in a tetrahedral fashion. [3]

Lattice constants for fluorite and antifluorite materials at 300 K [3]
MaterialLattice constant (Å)Crystal structure
BaF26.196Fluorite (FCC)
β-PbF25.94Fluorite (FCC)
PuO25.399Fluorite (FCC)
SrF25.7996Fluorite (FCC)
UO2 5.47065Fluorite (FCC)
CaF25.463Fluorite (FCC)
ZrO2 5.14Fluorite (FCC)
K2O6.449Antifluorite (FCC)
K2S7.406Antifluorite (FCC)
Li2O4.61Antifluorite (FCC)
Na2O5.55Antifluorite (FCC)
Na2S6.54Antifluorite (FCC)
Rb2O6.74Antifluorite (FCC)
Mg2Si6.338Antifluorite (FCC)

Calcium fluoride Example

Crystallography is a powerful tool to investigate the structures of crystalline materials. It is important to understand the crystal structure of materials to form structure-property relationships. These relationships can help predict the behavior of crystalline materials, as well as introduce the ability to tune their properties. Calcium fluoride is a classic example of a crystal with a fluorite structure. Crystallographic information can be collected via x-ray diffraction, providing information on the locations of electron density within a crystal structure. Using modern software such as Olex2, [4] one can solve a crystal structure from crystallographic output files.

Views of calcium fluoride crystal structure

In calcium fluoride, the calcium cations are surrounded by fluorine anions that occupy the tetrahedral sites, with an 8:4 coordination number, fluorine to calcium. This ratio is consistent with the stoichiometry of the compound, where the ratio of fluorine to calcium is 2:1. This relationship can be visualized as a cubic array of anions surrounding the calcium cations.

Extended fluorite structure

Beyond the until cell, the extended crystal structure of fluorite continues packing in a face-centered cubic (fcc) packing structure (also known as cubic close-packed or ccp). [5] This pattern of spherical packing follows an ABC pattern, where each successive layer of spheres settles on top of the adjacent hole of the lattice. In contrast, hexagonal close-packed (hcp), are successively layered with an ABAB pattern. These two types of packing are the most closely packed forms of spherical packing. [6]

See also

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<span class="mw-page-title-main">Magnesium fluoride</span> Chemical compound of magnesium and fluorine

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<span class="mw-page-title-main">Magnesium silicide</span> Chemical compound

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In materials science, an interstitial defect is a type of point crystallographic defect where an atom of the same or of a different type, occupies an interstitial site in the crystal structure. When the atom is of the same type as those already present they are known as a self-interstitial defect. Alternatively, small atoms in some crystals may occupy interstitial sites, such as hydrogen in palladium. Interstitials can be produced by bombarding a crystal with elementary particles having energy above the displacement threshold for that crystal, but they may also exist in small concentrations in thermodynamic equilibrium. The presence of interstitial defects can modify the physical and chemical properties of a material.

<span class="mw-page-title-main">Bismuth trifluoride</span> Chemical compound

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<span class="mw-page-title-main">Tin(IV) fluoride</span> Chemical compound

Tin(IV) fluoride is a chemical compound of tin and fluorine with the chemical formula SnF4 and is a white solid with a melting point above 700 °C.

Ammonium fluorosilicate (also known as ammonium hexafluorosilicate, ammonium fluosilicate or ammonium silicofluoride) has the formula (NH4)2SiF6. It is a toxic chemical, like all salts of fluorosilicic acid. It is made of white crystals, which have at least three polymorphs and appears in nature as rare minerals cryptohalite or bararite.

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The spinels are any of a class of minerals of general formulation AB
2
X
4
which crystallise in the cubic (isometric) crystal system, with the X anions arranged in a cubic close-packed lattice and the cations A and B occupying some or all of the octahedral and tetrahedral sites in the lattice. Although the charges of A and B in the prototypical spinel structure are +2 and +3, respectively, other combinations incorporating divalent, trivalent, or tetravalent cations, including magnesium, zinc, iron, manganese, aluminium, chromium, titanium, and silicon, are also possible. The anion is normally oxygen; when other chalcogenides constitute the anion sublattice the structure is referred to as a thiospinel.

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<span class="mw-page-title-main">Interstitial site</span> Empty space between atoms in a crystal lattice

In crystallography, interstitial sites, holes or voids are the empty space that exists between the packing of atoms (spheres) in the crystal structure.

<span class="mw-page-title-main">Platinum tetrafluoride</span> Chemical compound

Platinum tetrafluoride is the inorganic compound with the chemical formula PtF
4
. In the solid state, the compound features platinum(IV) in octahedral coordination geometry.

<span class="mw-page-title-main">Anti-structure</span>

In crystallography, an anti-structure is obtained from a salt structure by exchanging anion and cation positions.

<span class="mw-page-title-main">Ytterbium(II) fluoride</span> Chemical compound

Ytterbium(II) fluoride is a binary inorganic compound of ytterbium and fluorine with the chemical formula YbF2.

References

  1. Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN   0-12-352651-5
  2. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. 1 2 3 4 Rizescu, Costel; Rizescu, Mihaela (2018). Structure of Crystalline Solids, Imperfections and Defects in Crystals (First ed.). Parker, TX: Shutter Waves. ISBN   978-1-947641-17-4 . Retrieved 29 January 2020.
  4. "OlexSys". OlexSys.
  5. Shriver; et al. (January 2014). Inorganic Chemistry (Sixth ed.). Oxford University Press. ISBN   978-1-4292-9906-0.
  6. Redwing, Ronald. "Face Centered Cubic Structure (FCC)". The Pennsylvania State University.