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<p>The title novel iron cage complex was obtained using the direct template condensation of the three dichloroglyoximate ligand synthons with methylboronic acid as a Lewis-acidic cross-linking agent on the iron(II) ion as a matrix. This coordination-driven reaction proceeded under the vigorous reaction conditions. Charge density distribution in two solvent-free crystal polymorphs grown from a benzene – <i>iso</i>-octane mixture was experimentally studied using the precise single-crystal XRD experiment. The asymmetric unit of the polymorph <i>P</i> (space group <i>P2</i><sub><i>1</i></sub><i>/c</i>, <i>a</i> = 8.4499(1), <i>b</i> = 24.2386(4), <i>c</i> = 9.7489(2)Å, <i>β</i> = 108.667(1)°) contains one independent macrobicyclic iron(II)-centered molecule. This molecule in the polymorph <i>C</i> (space group <i>C2/c</i>, <i>a</i> = 15.159(2), <i>b</i> = 8.0971(11), <i>c</i> = 15.366(3)Å, <i>β</i> = 93.850(8)°) lies on the crystallographic axis C<sub>2</sub>; only half of such molecule is symmetrically independent. The polymorph <i>P</i> is isostructural to the earlier-studied cobalt(II)-centered derivative of the same encapsulating ligand. QTAIM analysis of a charge density distribution and the k-Φ analysis of the non-covalent interactions for all these three cage metallocomplexes were performed. Peculiarities of an electron population of <i>3d</i>-orbitals in them and an effect of the trigonal prismatic – trigonal antiprismatic distortion of their <i>MN</i><sub><i>6</i></sub>-coordination polyhedra were analyzed. Differences in their molecular conformations and electrostatic potential distributions, as well as in the intermolecular interactions in their crystals, were observed and explained.</p>

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Charge density view on two polymorphs of novel methylboron-capped iron(II) hexachloroclathrochelate and their cobalt(II)-centered analogue

  • 期刊论文

  • 发表日期：

    2026年7月13日

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  • Anna V. Vologzhanina,
  • Alexander S. Belov,
  • Yan Z. Voloshin

摘要

The title novel iron cage complex was obtained using the direct template condensation of the three dichloroglyoximate ligand synthons with methylboronic acid as a Lewis-acidic cross-linking agent on the iron(II) ion as a matrix. This coordination-driven reaction proceeded under the vigorous reaction conditions. Charge density distribution in two solvent-free crystal polymorphs grown from a benzene – iso-octane mixture was experimentally studied using the precise single-crystal XRD experiment. The asymmetric unit of the polymorph P (space group P21/c, a = 8.4499(1), b = 24.2386(4), c = 9.7489(2)Å, β = 108.667(1)°) contains one independent macrobicyclic iron(II)-centered molecule. This molecule in the polymorph C (space group C2/c, a = 15.159(2), b = 8.0971(11), c = 15.366(3)Å, β = 93.850(8)°) lies on the crystallographic axis C2; only half of such molecule is symmetrically independent. The polymorph P is isostructural to the earlier-studied cobalt(II)-centered derivative of the same encapsulating ligand. QTAIM analysis of a charge density distribution and the k-Φ analysis of the non-covalent interactions for all these three cage metallocomplexes were performed. Peculiarities of an electron population of 3d-orbitals in them and an effect of the trigonal prismatic – trigonal antiprismatic distortion of their MN6-coordination polyhedra were analyzed. Differences in their molecular conformations and electrostatic potential distributions, as well as in the intermolecular interactions in their crystals, were observed and explained.