Premium
Coordination Chemistry of N , N , N′ , N′ ‐Tetraethylpyridine‐2,6‐dithiocarboxamide ( S ‐dept) – X‐ray Crystal Structures and Magnetic Properties of [Co( S ‐dept)X 2 ] (X = Br, I, and NCS)
Author(s) -
Kapoor Ramesh,
Kataria Ashok,
Venugopalan Paloth,
Kapoor Pratibha,
Hundal Geeta,
Corbella Montserrat
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500318
Subject(s) - chemistry , crystallography , crystal structure , electron paramagnetic resonance , dept , octahedron , square pyramidal molecular geometry , cobalt , molecule , ionic bonding , crystal chemistry , coordination complex , stereochemistry , metal , nuclear magnetic resonance , ion , inorganic chemistry , physics , organic chemistry
Mononuclear cobalt( II ) complexes [Co( S ‐dept)X 2 ] [X = Br ( 1 ), I ( 2 ) and NCS ( 3 )] were synthesized using N , N , N′ , N′ ‐tetraethylpyridine‐2,6‐dithiocarboxamide ( S ‐dept), and characterised by conductivity, spectral and single‐crystal X‐ray diffraction studies. These studies reveal that the compounds consist of discrete monomeric molecules in which the cobalt atoms are five‐coordinate in an environment that is best described as being distorted square‐pyramidal. In dimethylformamide the iodo complex shows significant ionic dissociation (1:1 electrolyte) and its crystal field absorption spectrum is interpretable in terms of an octahedral structure [Co( S ‐dept)(DMF) 2 I] + . The temperature dependence of the magnetic susceptibility data is indicative of a high‐spin compound with an important zero‐field splitting. The best fitwas obtained with | D | = 20.5 cm –1 and g = 2.53 for 1 , | D | = 14.2 cm –1 and g = 2.38 for 2 and | D | = 17.7 cm –1 and g = 2.35 for 3 . The X‐band EPR spectra at low temperature is also characteristic of an S = 3/2 state with important zero‐field splitting. The most important band appears at low fields (ca. 1200 G). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)