Author:
Gregório Thaiane,Giese Siddhartha O. K.,Nunes Giovana G.,Soares Jaísa F.,Hughes David L.
Abstract
Two new mononuclear cationic complexes in which the TbIIIion is bis-chelated by the tripodal alcohol 1,1,1-tris(hydroxymethyl)propane (H3LEt, C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and molecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris(hydroxymethyl)propane]terbium(III) nitrate dimethoxyethane hemisolvate, [Tb(NO3)2(H3LEt)2]NO3·0.5C4H10O2,1, in which the lanthanide ion is 10-coordinate and adopts ans-bicapped square-antiprismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-molecule of dimethoxyethane (completed by a crystallographic twofold rotation axis) is also present. In product aquanitratobis[1,1,1-tris(hydroxymethyl)propane]terbium(III) dinitrate, [Tb(NO3)(H3LEt)2(H2O)](NO3)2,2, one bidentate nitrate ion and one water molecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water molecule was found in either of the crystal structures and, only in the case of1, dimethoxyethane acts as a crystallizing solvent. In both molecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex2, the methyl group of one of the H3LEtligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and intermolecular, are found in the crystal structures due to the number of different donor and acceptor groups present.
Publisher
International Union of Crystallography (IUCr)
Subject
Condensed Matter Physics,General Materials Science,General Chemistry
Reference36 articles.
1. Tuning Anisotropy Barriers in a Family of Tetrairon(III) Single-Molecule Magnets with an S = 5 Ground State
2. Benelli, C. & Gatteschi, D. (2015). In Introduction to Molecular Magnetism: From Transition Metals to Lanthanides. Weinheim, Germany: Wiley-VCH.
3. Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
4. Bruker (2014). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
5. Bruker (2015). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.