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Concomitant dimorphism in poly[di-μ-azido-(5,5'-dimethyl-2,2'-bipyridine)iron(II)].

Zouaoui Setifi1, Sylvain Bernès2, David K Geiger3

  • 1Département de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria.

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Summary

This study details a novel iron-based metal-organic polymer with unique azide bridging. Computational analysis reveals the monoclinic polymorph is more stable than the triclinic form.

Keywords:
DFTazide bridgeconcomitant crystallizationconcomitant polymorphscrystal structureinorganic polymer

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Crystallography

Background:

  • Metal-organic polymers offer tunable properties through diverse ligand and metal combinations.
  • Azide ligands are versatile linkers in coordination chemistry, enabling various bridging modes.
  • Polymorphism in coordination compounds can lead to distinct physical and chemical properties.

Purpose of the Study:

  • To synthesize and characterize a novel iron(II) metal-organic polymer with double azide bridges.
  • To investigate the structural differences between two polymorphs of the synthesized compound.
  • To determine the relative stability of the observed polymorphs using computational methods.

Main Methods:

  • Single-crystal X-ray diffraction to elucidate molecular and crystal structures.
  • Density functional theory (DFT) calculations to assess the energetic stability of polymorphs.
  • Analysis of Hirshfeld surfaces and fingerprint plots for structural comparison.

Main Results:

  • A one-dimensional metal-organic polymer, [Fe(N3)2(C12H12N2)]n, was synthesized, featuring alternating end-on and end-to-end azide bridges.
  • Two polymorphs (triclinic P-1 and monoclinic P21/c) were identified, differing primarily in the conformation of the Fe(μ-1,3-N3)2Fe metallacycle.
  • DFT calculations indicated the monoclinic polymorph is more energetically stable than the triclinic form by approximately 30.5 kJ/mol.

Conclusions:

  • The study successfully synthesized and characterized a novel iron-azide metal-organic polymer.
  • Structural analysis revealed subtle conformational differences between polymorphs, impacting crystal packing minimally.
  • Computational results provide insight into the thermodynamic preference for the monoclinic polymorph.