The effects of protonated heterocyclic cations on the structural and magnetic properties of tetrachlorocuprate(ii) anions; X-ray, magnetochemical and EPR studiesElectronic supplementary information (ESI) available. CCDC 1455402 (2) and 1530155 (3). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8nj03155j

The crystal and molecular structures and magnetic properties of two new complexes (HMepy) 2 [CuCl 4 ]·2H 2 O, 2 , and (H 2 Me 2 ppz)[CuCl 4 ], 3 , formed by tetrachlorocuprate( ii ) anions and organic heterocyclic cations, bis(3-amino-2-chloro-5-methylpyridinium) (HMepy) and trans -2,5-dimethylpiper...

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Main Authors Kersen, Ülo, Wojtczak, Andrzej, Bienko, Alina, Jezierska, Julia
Format Journal Article
Published 24.09.2018
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Summary:The crystal and molecular structures and magnetic properties of two new complexes (HMepy) 2 [CuCl 4 ]·2H 2 O, 2 , and (H 2 Me 2 ppz)[CuCl 4 ], 3 , formed by tetrachlorocuprate( ii ) anions and organic heterocyclic cations, bis(3-amino-2-chloro-5-methylpyridinium) (HMepy) and trans -2,5-dimethylpiperazinium (H 2 Me 2 ppz), respectively, have been determined by the analysis of their X-ray diffraction data, magnetic susceptibility behaviour and EPR spectral parameters. These characteristics differentiate the [CuCl 4 ] 2− anions in 2 and 3 as well as that previously reported in (H 2 bipip)[CuCl 4 ]·H 2 O, 1 , (bipip = 4,4′-bipiperidine) (Tuikka et al. , CrystEngComm , 2013, 15 , 6177; Wikaira et al. , J. Coord. Chem. , 2016, 69 (1), 57). The present study reveals a significant effect of the organic cations on the geometry and magnetic properties of the [CuCl 4 ] 2− anions caused evidently by the changes in the crystal packing structure. A characteristic relationship was observed between the average cis -angles around the Cu( ii ) ions in [CuCl 4 ] 2− for 1-3 , affected by the Cu( ii ) coordination geometry, and g -tensor components derived from the EPR spectra, a measure of interaction of copper( ii ) unpaired electrons in the [CuCl 4 ] 2− anions with an external magnetic field. The magneto-structural correlations revealed weak antiferromagnetic exchange interactions between the [CuCl 4 ] 2− anions transmitted by different pathways. The crystal and molecular structures and magnetic properties of two new complexes (HMepy) 2 [CuCl 4 ]·2H 2 O, 2 , and (H 2 Me 2 ppz)[CuCl 4 ], 3 , formed by tetrachlorocuprate( ii ) anions and organic heterocyclic cations, have been determined by the analysis of their X-ray diffraction data, magnetic susceptibility behaviour and EPR spectral parameters.
Bibliography:Electronic supplementary information (ESI) available. CCDC
For ESI and crystallographic data in CIF or other electronic format see DOI
10.1039/c8nj03155j
1455402
2
3
and
1530155
(
ISSN:1144-0546
1369-9261
DOI:10.1039/c8nj03155j