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Ionic Crystal Structures02:42

Ionic Crystal Structures

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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Structural Polytypism in B-Site-Deficient Azetidinium-Based Pnictogen Halide Hexagonal Perovskites.

Hang Liu1, Rebecca Rae2, James Dalzell3

  • 1EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, U.K.

Inorganic Chemistry
|June 27, 2025
PubMed
Summary
This summary is machine-generated.

Azetidinium-based halide perovskites (Az₃B₂X₉) exhibit diverse structures (2D layered or 0D dimer) based on B-site vacancy ordering. These findings reveal structural flexibility in these novel hybrid materials.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Crystallography

Background:

  • B-site deficient perovskite analogues offer unique structural possibilities.
  • Azetidinium (Az⁺) cations introduce organic-inorganic hybrid characteristics.
  • Understanding vacancy ordering is key to controlling material properties.

Purpose of the Study:

  • To systematically investigate Azetidinium-based antimony and bismuth halide perovskite analogues (Az₃B₂X₉).
  • To elucidate the impact of B-site vacancy ordering on crystal structure.
  • To explore the resulting structural diversity and phase transitions.

Main Methods:

  • Synthesis and characterization of Az₃B₂X₉ compounds (B = Sb, Bi; X = Cl, Br, I).
  • Variable-temperature single-crystal and powder X-ray diffraction (XRD).
  • Differential Scanning Calorimetry (DSC), Differential Thermal Analysis (DTA), and dielectric spectroscopy.

Main Results:

  • All Az₃B₂X₉ compounds adopt hexagonal close-packed perovskite structures (6H stacking).
  • Az₃Sb₂Cl₉ and Az₃Sb₂Br₉ form 2D layered polar structures due to vacancy ordering in face-sharing octahedra.
  • Az₃Sb₂I₉, Az₃Bi₂Br₉, and Az₃Bi₂I₉ form 0D dimer structures from vacancies in corner-sharing octahedra.
  • Low-temperature phase transitions were observed in Az₃Sb₂Cl₉ and Az₃Sb₂Br₉, linked to octahedral distortions and Az⁺ cation disorder.

Conclusions:

  • Vacancy ordering in B-site deficient perovskites dictates the formation of distinct structural motifs (2D layered vs. 0D dimer).
  • Azetidinium-based halide perovskites demonstrate significant structural flexibility.
  • This study provides insights into the structure-property relationships of novel hybrid perovskite materials.