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Open AccessArticle

Tris(ethylenediamine) Cobalt(II) and Manganese(II) Nitrates

1
CNRS, Université Bordeaux, Centre de Recherche Paul Pascal, UMR 5031, 33600 Pessac, France
2
CNRS, Université Bordeaux, Bordeaux INP, ICMCB, UMR 5026, 33600 Pessac, France
*
Authors to whom correspondence should be addressed.
Crystals 2020, 10(6), 472; https://doi.org/10.3390/cryst10060472
Received: 6 May 2020 / Revised: 27 May 2020 / Accepted: 28 May 2020 / Published: 3 June 2020
Octahedral tris(ethylenediamine) coordination complexes demonstrate helicoidal chirality, due to the arrangement of the ligands around the metal core. The enantiomers of the nitrate salts [Ni(en)3](NO3)2 and [Zn(en)3](NO3)2 spontaneously resolve to form a mixture of conglomerate crystals, which present a reversible phase transition from space group P6322 to enantiomorphic P6522 or P6122, with the latter depending on the handedness of the enantiomer. We report here the synthesis and characterization of [Mn(en)3](NO3)2 and [Co(en)3](NO3)2, which are isostructural to the Zn(II) and Ni(II) derivatives. The Mn(II) analogue undergoes the same phase transition centered at 150(2) K, as determined by single-crystal X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. The Co(II) derivative does not demonstrate a phase transition down to 2 K, as evidenced by powder X-ray diffraction and heat capacity measurements. The phase transition does not impact the magnetic properties of the Ni(II) and Mn(II) analogues; these high spin compounds display Curie behavior that is consistent with S = 1 and 5/2, respectively, down to 20 K, while the temperature-dependent magnetic moment for the Co(II) compound reveals a significant orbital contribution. View Full-Text
Keywords: chirality; conglomerate crystallization; X-ray crystallography; phase transition; coordination complexes; enantiomorphic space groups chirality; conglomerate crystallization; X-ray crystallography; phase transition; coordination complexes; enantiomorphic space groups
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MDPI and ACS Style

Cortijo, M.; Valentín-Pérez, Á.; Rouzières, M.; Clérac, R.; Rosa, P.; Hillard, E.A. Tris(ethylenediamine) Cobalt(II) and Manganese(II) Nitrates. Crystals 2020, 10, 472.

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