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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.
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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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Do halogen bonds dictate the packing preferences in solid solutions?

Titas Pramanik1, Mysore S Pavan, Tayur N Guru Row

  • 1Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India. ssctng@sscu.iisc.ernet.in.

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Summary

Two isomeric benzoic acids form novel solid solutions, demonstrating how halogen bonding dictates crystal structure and packing. This finding offers new insights into supramolecular assembly and crystal engineering.

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Area of Science:

  • Crystallography
  • Supramolecular Chemistry
  • Chemical Physics

Background:

  • Isomeric halogenated benzoic acids exhibit distinct crystal structures.
  • Halogen bonding and hydrogen bonding play crucial roles in stabilizing crystal lattices.
  • Understanding intermolecular interactions is key to controlling solid-state properties.

Purpose of the Study:

  • To investigate the crystal structures and intermolecular interactions of 4-bromo-2-chlorobenzoic acid and 2-bromo-4-chlorobenzoic acid.
  • To explore the formation and characteristics of solid solutions between these isomers.
  • To elucidate the role of halogen bonding in dictating crystal packing and supramolecular assembly.

Main Methods:

  • Single crystal X-ray diffraction
  • Charge density analysis
  • Powder X-ray diffraction (PXRD)
  • Differential scanning calorimetry (DSC)
  • Cocrystallization

Main Results:

  • The two isomers crystallize in different space groups with distinct hydrogen-bonded dimer and halogen-bonded motifs.
  • Charge density analysis quantifies halogen bond strengths and reveals packing variations.
  • Novel solid solutions with varied ratios were successfully formed, a first-time observation.
  • The triangular halogen-bonded motif in 4-bromo-2-chlorobenzoic acid governs solid solution packing.

Conclusions:

  • Halogen bonding hierarchy influences supramolecular assembly and solid solution formation.
  • The study establishes a precedent for creating solid solutions from distinct crystalline forms.
  • Findings provide a foundation for rational design of crystalline materials based on halogen bonding.