Crystal structures of two isotypic lanthanide(III) complexes: tri-aqua-[2,6-di-acetyl-pyridine bis-(benzoyl-hydrazone)]methano-llanthanide(III) trichloride methanol disolvates (LnIII = Tb and Dy).

Chihiro Kachi-Terajima,Norihisa Kimura

doi:10.1107/s2056989018004103

Chihiro Kachi-Terajima, Norihisa Kimura

Open Access

https://doi.org/10.1107/s2056989018004103

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Abstract

The title lanthanide complexes, [Ln(DAPBH2)(CH3OH)(H2O)3]Cl3·2CH3OH [LnIII = Tb and Dy; DAPBH2 = 2,6-di-acetyl-pyridine bis-(benzoyl-hydrazone), C23H21N5O2], are isotypic. The central lanthanide ions are nine-coordinate, being ligated by three N and two O atoms from the penta-dentate DAPBH2 ligand, and four O atoms from the coordinated methanol mol-ecule and three coordinated water mol-ecules. The coordination geometry of the lanthanide ion is a distorted capped square anti-prism. In the crystals, the various components are linked by O-H⋯Cl, N-H⋯Cl and O-H⋯O hydrogen bonds, forming three-dimensional supra-molecular frameworks. Within the frameworks, there are C-H⋯Cl and C-H⋯O hydrogen bonds and offset π-π inter-actions (inter-centroid distance ca 3.81 Å).

Highlights

The title lanthanide complexes, [Ln(DAPBH2)(CH3OH)(H2O)3]Cl3Á2CH3OH [LnIII = Tb and Dy; DAPBH2 = 2,6-diacetylpyridine bis(benzoylhydrazone), C23H21N5O2], are isotypic
The various components are linked by O—HÁ Á ÁCl, N—HÁ Á ÁCl and O—HÁ Á ÁO hydrogen bonds, forming three-dimensional supramolecular frameworks
We report on the TbIII and DyIII complexes with the DAPBH2 ligand containing noncoordinating chloride ions as the coordination–acceptor building units

Summary

Chemical context

Molecule-based magnets based on lanthanide ions have attracted much attention because of their large magnetic moments and magnetic anisotropy. Some lanthanide complexes with 2,6-diacetylpyridine bis(benzoylhydrazone as ligand (DAPBH2) have been reported, viz. The Dy complexes having two DAPBH2 ligands (Batchelor et al, 2014) have demonstrated attractive singlemolecule magnet behaviour, indicating that DAPBH2 ligands are useful for constructing magnetic units. For the use of DAPBH2 complexes as building blocks, coordination active sites are needed. The DAPBH2 ligand is pentadentate, it can make coordination sites in the axial positions of the lanthanide ion. These complexes have coordinated or noncoordinated nitrate ions, which can disturb the coordination of coordination–donor units. We report on the TbIII and DyIII complexes with the DAPBH2 ligand containing noncoordinating chloride ions as the coordination–acceptor building units

Structural commentary

Supramolecular features

Database survey

Synthesis and crystallization

Refinement