Synthesis and Characterization of Iron Bispyridine Bisdicyanamide, Fe[C5H5N]2[N(CN)2]2

Laura Henrich; Peter C. Müller; Jan Hempelmann; Markus Mann; Jan van Leusen; Simon Steinberg; Richard Dronskowski

doi:10.3390/molecules28134886

Molecules (Jun 2023)

Synthesis and Characterization of Iron Bispyridine Bisdicyanamide, Fe[C5H5N]2[N(CN)2]2

Laura Henrich,
Peter C. Müller,
Jan Hempelmann,
Markus Mann,
Jan van Leusen,
Simon Steinberg,
Richard Dronskowski

Affiliations

Laura Henrich: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Peter C. Müller: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Jan Hempelmann: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Markus Mann: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Jan van Leusen: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Simon Steinberg: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Richard Dronskowski: Chair of Solid State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany

DOI: https://doi.org/10.3390/molecules28134886
Journal volume & issue: Vol. 28, no. 13
p. 4886

Abstract

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Fe[C5H5N]2[N(CN)2]2 (1) was synthesized from a reaction of stoichiometric amounts of NaN(CN)2 and FeCl2·4H2O in a methanol/pyridine solution. Single-crystal and powder diffraction show that 1 crystallizes in the monoclinic space group I2/m (no. 12), different from Mn[C5H5N]2[N(CN)2]2 (P21/c, no. 14) due to tilted pyridine rings, with a = 7.453(7) Å, b = 13.167(13) Å, c = 8.522(6) Å, β = 114.98(6)° and Z = 2. ATR-IR, AAS, and CHN measurements confirm the presence of dicyanamide and pyridine. Thermogravimetric analysis shows that π-stacking interactions of the pyridine rings play an important role in structural stabilization. Based on DFT-optimized structures, a chemical bonding analysis was performed using a local-orbital framework by projection from a plane-wave basis. The resulting bond orders and atomic charges are in good agreement with the expectations based on the structure analysis. SQUID magnetic susceptibility measurements show a high-spin state FeII compound with predominantly antiferromagnetic exchange interactions at lower temperatures.

Published in Molecules

ISSN: 1420-3049 (Online)
Publisher: MDPI AG
Country of publisher: Switzerland
LCC subjects: Science: Chemistry: Organic chemistry
Website: http://www.mdpi.com/journal/molecules

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