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8: Ionic and Covalent Solids - Structures

  • Page ID
    183345
  • Learning Objectives

    • Describe many crystal structures in terms of close-packed frameworks with systematic filling of octahedral and tetrahedral holes.
    • Represent crystal structures by drawing them in sections.
    • Rationalize, using chemical principles, why certain crystal structures are stable for certain compounds but not for others, as well as why certain structural and bonding motifs are preferred for certain compounds relative to others.
    • Predict which crystal structures are most favorable for a given composition based on ionicity and periodic trends.
    • Explain structure-dependent properties such as ferroelectricity and magnetic ordering based on crystal structures.
    • Understand intercalation reactions in layered and open framework solids.
    • Predict the preferred formation of normal or inverse spinels using arguments from transition metal chemistry (e.g. crystal field stabilization energies).

    Inorganic solids often have simple crystal structures, and some of these structures are adopted by large families of ionic or covalent compounds. Examples of the most common structures include NaCl, CsCl, NiAs, zincblende, wurtzite, fluorite, perovskite, rutile, and spinel. We will develop these structures systematically from the close packed and non-close packed lattices shown below. Some layered structures, such as CdCl2 and CdI2, can be thought of as relatives of simple ionic lattices with some atoms "missing."

    • 8.0: Prelude to Ionic and Covalent Solids - Structures
    • 8.1: Close-packing and Interstitial Sites
      Many common inorganic crystals have structures that are related to cubic close packed (face-centered cubic) or hexagonal close packed sphere packings. These packing lattices contain two types of sites or "holes" that the interstitial atoms fill, and the coordination geometry of these sites is either tetrahedral or octahedral. An interstitial atom filling a tetrahedral hole is coordinated to four packing atoms, and an atom filling an octahedral hole is coordinated to six packing atoms.
    • 8.2: Structures Related to NaCl and NiAs
      There are a number of compounds that have structures similar to that of NaCl, but have a lower symmetry (usually imposed by the geometry of the anion) than NaCl itself.
    • 8.3: Tetrahedral Structures
      In ccp and hcp lattices, there are two tetrahedral holes per packing atom. A stoichiometry of either M2X or MX2 gives a structure that fills all tetrahedral sites, while an MX structure fills only half of the sites.
    • 8.4: Layered Structures and Intercalation Reactions
      Layered structures are characterized by strong (and typically covalent) bonding between atoms in two dimensions and weaker bonding in the third. A broad range of compounds and allotropes of some pure elements (B, C, P, As) exist in layered forms. Structurally, the simplest of these structures (for example binary metal halides and sulfides) can be described as having some fraction of the octahedral and/or tetrahedral sites are filled in the fcc and hcp lattices.
    • 8.5: Bonding in TiS₂, MoS₂, and Pyrite Structures
      Many layered dichalcogenides, such as TiS₂ and ZrS₂, have the CdI₂ structure. In these compounds, as we have noted above, the metal ions are octahedrally coordinated by S. Interestingly, the structures of MoS₂ and WS₂, while they are also layered, are different. In these cases, the metal is surrounded by a trigonal prism of sulfur atoms. NbS₂, TaS₂, MoSe₂, MoTe₂, and WSe₂ also have the trigonal prismatic molybdenite structure, which is shown below alongside a platy crystal of MoS₂.
    • 8.6: Spinel, Perovskite, and Rutile Structures
      There are three more structures, which are derived from close-packed lattices, that are particularly important because of the material properties of their compounds. These are the spinel structure, on which ferrites and other magnetic oxides are based, theperovskite structure, which is adopted by ferroelectric and superconducting oxides, and the rutile structure, which is a common binary 6:3 structure adopted by oxides and fluorides.
    • 8.7: Discussion Questions
    • 8.8: Problems
    • 8.9: References