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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Double-salt formation in crystal structures containing [Co(en)3]Cl3.

Megan R Kollitz1, A Graham Lappin1, Allen G Oliver1

  • 1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA.

Acta Crystallographica. Section C, Structural Chemistry
|April 5, 2023
PubMed
Summary

This study determined the crystal structures of three cobalt(III) tris(ethane-1,2-diamine) double salts, revealing similarities to the parent compound and a slight increase in unit-cell volume. The chiral derivative

Keywords:
ammoniumcrystal structuredouble saltethane-1,2-diaminepotassiumsodiumunit-cell volume

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Area of Science:

  • Inorganic Chemistry
  • Crystallography
  • Coordination Chemistry

Background:

  • The parent compound, tris(ethane-1,2-diamine-κ2N,N')cobalt(III) trichloride tetrahydrate ([Co(en)3]Cl3·4H2O), serves as a reference for structural comparison.
  • Double salts involving cobalt(III) complexes with alkali metals and ammonium ions are explored.

Purpose of the Study:

  • To determine the crystal structures of three novel racemic double salts of [Co(en)3]Cl3.
  • To compare the structural features of these double salts with the parent compound.
  • To re-examine the structure of a chiral derivative at cryogenic temperatures.

Main Methods:

  • Single-crystal X-ray diffraction was employed to determine the structures.
  • Crystallographic data were collected and analyzed for four related compounds.
  • Structural comparisons were made based on determined unit-cell parameters and atomic coordinates.

Main Results:

  • Three racemic double salts, [Co(en)3]2[Na(H2O)6]Cl7, [Co(en)3]2[K(H2O)6]Cl7, and (NH4)[Co(en)3]2Cl7·6H2O, were structurally characterized.
  • All four compounds, including the parent [Co(en)3]Cl3·4H2O, crystallize in the trigonal space group P-3c1.
  • The double salts exhibit a modest increase in unit-cell volume compared to the parent compound.
  • The structure of the chiral derivative [Λ-Co(en)3]2[Na(H2O)6]Cl7 was redetermined at 120 K, resolving previously noted disorder.

Conclusions:

  • The study highlights structural similarities among the investigated cobalt(III) double salts and the parent compound.
  • The crystallographic data confirm the trigonal P-3c1 space group for all studied compounds.
  • The findings provide insights into the packing and structural variations in double salts of tris(ethane-1,2-diamine)cobalt(III) complexes.