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Synthesis, X‐ray Crystal Structure and Magnetism of [NiCl 2 {(bis(2‐benzimidazolyl)propane}] 2 · (C 2 H 5 OH) 2 – A Second Example of a Ferromagnetically Coupled Five‐Coordinated High‐Spin Dichloro‐Bridged Nickel(II) Dimer
Author(s) -
van Albada Gerard A.,
Kolnaar Jeroen J. A.,
Smeets Wilberth J. J.,
Spek Anthony L.,
Reedijk Jan
Publication year - 1998
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/(sici)1099-0682(199809)1998:9<1337::aid-ejic1337>3.0.co;2-s
Subject(s) - chemistry , crystallography , antiferromagnetism , crystal structure , nickel , ligand (biochemistry) , ferromagnetism , dimer , magnetism , ion , magnetic susceptibility , stereochemistry , biochemistry , physics , receptor , organic chemistry , condensed matter physics , quantum mechanics
The ligand bis(2‐benzimidazolyl)propane coordinates to Ni II with chloride as an anion, thereby forming a dinuclear compound with the formula: [NiCl 2 (tbz) 2 ] 2 (C 2 H 6 O) 2 . This compound crystallizes in the space group P 2 1 / c . Each five‐coordinated Ni II ion has a distorted trigonal bipyramidal environment which consist of two asymmetrically bridging Cl anions with distances of 2.3556(17) and 2.4275(16) Å, a terminal Cl anion with a distance of 2.3496(17) Å and two nitrogen atoms of the ligand with distances of 2.022(4) and 2.000(4) Å. The Ni–Ni distance is 3.5891(12) Å, while the Ni–Cl–Ni angle is 97.23(6)°. The magnetic properties of the compound, as studied in the range 5–280 K, have been fitted with a zero‐field splitting parameter D (–14.3 cm −1 ) and a ferromagnetic exchange between the Ni ions in the dinuclear unit ( J = +2.5 cm −1 ). The title compound appears to be the second example for a five‐coordinated ferromagnetic dinuclear Ni II compound of this type, and its magnetic properties appear to correlate with the ligand structure. With the availability of an increasing number of examples of such species it appears that antiferromagnetic exchange is found for all cases with the chromophore N 2 ClNiCl 2 NiClN 2 where the MN 2 ring is 5‐membered. In the case, where this ring is six‐membered, the exchange is ferromagnetic.