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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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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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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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To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
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Crystal structures of two dimeric nickel di-phenyl-acetate com-plexes.

A A Nikiforov1,2, D O Blinou1, E N Dubrov1

  • 1St Petersburg State Institute of Technology, Moskovsky pr. 26, 190013 St Petersburg, Russian Federation.

Acta Crystallographica. Section E, Crystallographic Communications
|November 12, 2019
PubMed
Summary

The crystal structures of two nickel(II) compounds reveal that bulky dip-henyl-acetate ligands do not hinder the formation of aqua-bridged dimeric cores. These complexes exhibit stabilization through various hydrogen bonds and aromatic interactions.

Keywords:
Hirshfeld surface analysisNiII dimercarboxyl­ate com­plexcrystal structurehydrogen bondsπ-stacking

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Area of Science:

  • Coordination Chemistry
  • Crystal Engineering
  • Supramolecular Chemistry

Background:

  • Nickel(II) complexes with carboxylate ligands are of interest due to their diverse structural motifs and potential applications.
  • The role of sterically demanding ligands in dictating the assembly of metal-organic frameworks and coordination polymers is an active area of research.
  • Understanding non-covalent interactions is crucial for designing predictable crystal structures.

Purpose of the Study:

  • To elucidate the crystal structures of two novel nickel(II) compounds featuring dip-henyl-acetate ligands.
  • To investigate the influence of sterically bulky dip-henyl-acetate and chelating 2,2'-bi-pyridine ligands on the formation of aqua-bridged dimeric nickel(II) cores.
  • To identify and analyze the stabilizing intra- and inter-molecular interactions within the crystal lattices.

Main Methods:

  • Single-crystal X-ray diffraction was employed to determine the three-dimensional structures of the title compounds.
  • Analysis of hydrogen bonding (including O-H···O, N-H···O, C-H···O), C-H···π, and π-π stacking interactions was performed.
  • The coordination environment around the nickel(II) centers and the bridging modes of the ligands were examined.

Main Results:

  • The crystal structures of two nickel(II) complexes, [Ni2(dip-henyl-acetato)4(pyridine)4(H2O)] (1) and [Ni2(dip-henyl-acetato)4(2,2'-bi-pyridine)2(H2O)]·2.5CH3CN·dip-henyl-acetic acid (2), were successfully determined.
  • Both compounds feature a μ-aqua-bridged dimeric nickel(II) core, demonstrating the robustness of this motif.
  • The dip-henyl-acetate ligand, despite its steric bulk, effectively coordinates to the nickel centers, and various non-covalent interactions stabilize the overall crystal packing.

Conclusions:

  • The formation of the aqua-bridged dimeric nickel(II) core is achievable even with sterically hindered dip-henyl-acetate ligands.
  • The presence of pyridine and 2,2'-bi-pyridine ligands, along with dip-henyl-acetate, leads to complex supramolecular assemblies stabilized by hydrogen bonding and π-π interactions.
  • These findings contribute to the understanding of structural diversity in nickel(II) coordination compounds and the role of ligand design in crystal engineering.