Linear tricobalt compounds with Di(2-pyridyl)amide (dpa) ligands: Temperature dependence of the structural and magnetic properties of symmetrical andunsymmetrical forms of Co-3(dpa)(4)Cl-2 in the solid state
R. Clerac et al., Linear tricobalt compounds with Di(2-pyridyl)amide (dpa) ligands: Temperature dependence of the structural and magnetic properties of symmetrical andunsymmetrical forms of Co-3(dpa)(4)Cl-2 in the solid state, J AM CHEM S, 122(26), 2000, pp. 6226-6236
The linear trinuclear compound Co-3(dpa)(4)Cl-2 (1; dpa = di(2-pyridyl)amid
e anion) crystallizes from CH2Cl2 solution in two forms simultaneously, nam
ely, an orthorhombic form 1 . CH2Cl2 and a tetragonal form 1 . 2CH(2)Cl(2).
The three linearly arranged cobalt atoms in 1 are supported by four dpa li
gands in a spiral configuration. The chain of cobalt atoms is symmetrical i
n 1 . CH2Cl2, but unsymmetrical in 1 . 2CH(2)Cl(2). Both crystal structures
have been studied at various temperatures. A reversible second-order phase
transition (165 K) from orhorhombic (Pnn2) to monoclinic (Pn) symmetry for
the crystal of 1 . CH2Cl2 has been documented by X-ray studies at 296, 168
, and 109 K as well as a neutron diffraction study at 20 K. The linear tric
obalt unit in 1 . CH2Cl2 becomes slightly unsymmetrical at low temperature
although the two Co-Co bonds remain statistically equivalent (Co-Co approxi
mate to 2.32 Angstrom) throughout the experimental temperature range. No ph
ase transition was observed for the tetragonal form 1 . 2CH(2)Cl(2) at low
temperature, but the Co-Co distances in 1 changed from 2.299(1) and 2.471(1
) Angstrom at 298 K to 2.3035(7) and 2.3847(8) Angstrom at 20 K. Magnetic s
usceptibility measurements indicate that the two compounds are in an S = 1/
2 ground state at low temperature and exhibit gradual spin-crossover at hig
her temperature.