Crystal structures, electronic properties and structural pathways of two [Cu(phen)2(OH2)][Y]2 complexes (phen = 1,10-phenanthroline, Y = CF3SO3− or ClO4−)

Abstract

The crystal structures of [Cu(phen) 2 (OH 2 )][CF 3 SO 3 ] 2 1 and [Cu(phen) 2 (OH 2 )][ClO 4 ] 2 2 (phen = 1,10-phenanthroline) have been determined by diffractometer data collection. The CuN 4 O chromophores in both complexes 1 and 2 lie on a crystallographic two-fold axis, with a square pyramidal distorted trigonal bipyramidal stereochemistry, an elongation along the Cu–O direction, Cu–O 2.066(3) and 2.245(4) Å, and an increase in the N(4)–Cu–N(2) α 3 angle to 123.4(1) and 136.0(1)°, respectively. This suggests that the stereochemistry of 1 is best described as near regular trigonal bipyramidal, RTB, and that of 2 as square based pyramidal distorted trigonal bipyramidal, SBPDTB. The structures of 1 and 2 were compared by scatter-plot analysis, with other [Cu(chelate ligand) 2 (OH 2 )][Y] 2 complexes involving two-fold axes of symmetry. This shows that the spread of the data points is not random, is relatively large and suggests the presence of vibronic coupling to account for the distortion from the RTB CuN 4 O chromophore, along the C 2 dominated +A and -A route distortions. A continuous linear structural pathway is suggested, determined by the coupled ν sym str and ν sym bend modes of vibration, involving a progression of 40–50 modes, spanning an angular distortion range of 91–140°, which correlate with electronic and ESR spectral data.