Interpenetration Phenomena via Anion Template Effects in Fe(II) and Co(II) Coordination Networks with a Bis-(1,2,4-triazole) Ligand
Author:
Jordan Dustin N.1, Straßburg Patrick G.1, Woschko Dennis1, Carrella Luca M.2, Cuignet Laure P.13, Eickmeier Katharina4ORCID, Dronskowski Richard4ORCID, Garcia Yann3ORCID, Rentschler Eva2, Janiak Christoph1ORCID
Affiliation:
1. Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität, D-40204 Düsseldorf, Germany 2. Department of Chemistry, Johannes Gutenberg University Mainz, D-55128 Mainz, Germany 3. Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium 4. Institute of Inorganic Chemistry, RWTH Aachen University, D-52056 Aachen, Germany
Abstract
Seven new coordination networks, [Fe(tbbt)3](BF4)2 (1), [Co(tbbt)3](BF4)2 (2), [Fe(tbbt)3](ClO4)2 (3), [Co(tbbt)3](ClO4)2 (4), [Fe(NCS)2(tbbt)2] (5), [Co(NCS)2(tbbt)2] (6), and [Fe(H2O)2(tbbt)2]Br2·2H2O (7), were synthesized with the linker 1,1’-(trans-2-butene-1,4-diyl)bis-1,2,4-triazole (tbbt) and structurally investigated. The structure of complexes 1–4 is composed of three interpenetrating, symmetry-related 3D networks. Each individual 3D network forms a primitive, nearly cubic lattice (pcu) with BF4– or ClO4– anions present in the interstitial spaces. The structure of compounds 5 and 6 is composed of two-dimensional sql layers, which are parallel to each other in the AB stacking type. These layers are interpenetrated by one-dimensional chains, both having the same formula unit, [M(NCS)2(tbbt)2] (M = Fe, Co). The structure of compound 7 consists of parallel, two-dimensional sql layers in the ABCD stacking type. The interpenetration in 1–6 is not controlled by π–π-interactions between the triazole rings or C=C bonds, as could have been expected, but by (triazole)C-H⋯F4B, C-H⋯O4Cl, and C-H⋯SCN anion hydrogen bonds, which suggests a template effect of the respective non-coordinated or coordinated anion for the interpenetration. In 7, the (triazole)C-H⋯Br anion interactions are supplemented by O-H⋯O and O-H⋯Br hydrogen bonds involving the aqua ligand and crystal water molecules. It is evident that the coordinated and non-coordinated anions play an essential role in the formation of the networks and guide the interpenetration. All iron(II) coordination networks are colorless, off-white to yellow-orange, and have the metal ions in the high-spin state down to 77 K. Compound 5 stays in the high spin state even at temperatures down to 10 K.
Funder
Deutsche Forschungsgemeinschaft Priority Program SPP 1928/2 COORNETs
Subject
Polymers and Plastics,General Chemistry
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