B. Wagner et al., GEOMETRY AND ELECTRONIC-STRUCTURE OF CUCL64- POLYHEDRA DOPED INTO (3-CHLOROANILINIUM)(8)[CDCL6]CL-4 - AN EPR AND STRUCTURAL INVESTIGATION, Inorganic chemistry, 35(13), 1996, pp. 3967-3974
The EPR single-crystal and powder spectra of mixed crystals of (3-chlo
roanilinium)(8)(Cd1-xCuxCl6)C-4 are measured as a function of temperat
ure and x and analyzed with respect to the geometry and bonding proper
ties of the CuCl6 polyhedra. These undergo strong distortions due to v
ibronic Jahn-Teller coupling, with the resulting tetragonal elongation
being superimposed by a considerable orthorhombic symmetry component
induced by a host site strain acting as a compression along the crysta
llographic a axis. This strain becomes apparent in the cadmium compoun
d (x = 0), whose crystal structure is also reported [a = 8.701(2) Angs
trom, b = 13.975(2) Angstrom, c = 14.173(2) Angstrom, alpha = 81.62(1)
degrees, beta = 72.92(1)degrees, gamma = 77.57(1)degrees, triclinic P1
, Z = 1]. A calculation of the ground state potential surface and its
vibronic structure nicely reproduces the g values, Cu-Cl spacings, and
ligand field data. At high copper concentrations (including x = 1), t
he CuCl6 polyhedra are coupled elastically, with the long axes of neig
hboring polyhedra having perpendicular orientations. antiferrodistorti
ve type, however. Above about 55 K, the angular Jahn-Teller distortion
component becomes dynamically averaged within the time scale of the E
PR experiment, leading to local tetragonally compressed CuCl6 octahedr
a.