Solid-state cadmium-113 solution NMR, shielding tensor components, and crystal and molecular structures of (bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl] oxide)bis(nitrato-O,O')cadmium(II), and (bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]aminebis(nitrato-O,O')cadmium(II)

Abstract

The /sup 113/Cd NMR spectra have been observed for the title compounds, A and B, respectively, in methanol solution and in the solid state by magic-angle cross-polarization (MAS/CP) techniques. In solution A and B each give a single line at -96.3 and -95.2 ppM (deshielded relative to the 0.1 M Cd(ClO/sub 4/)/sub 2/ in D/sub 2/O standard), respectively, with half-widths at half peak heights of 7.1 and 1.5 ppM, respectively. In the solid state both compounds give a single line at -106 ppM with a half-width at half peak height of 6 and 3 ppM, respectively. Essentially the same species is present both in the solution and in the solid state. The components of the chemical shift tensor were calculated from the spinning side bands for both A and B and were found to be -170, -175, +31 and -169, -170, +12 ppM in a well-defined orientation to the pseudo-fivefold molecular axis. The crystal structures of A and B are made up of discrete molecules separated by ordinary van der Waals distances. The B molecules contain fairly regular pentagonal-bipyramidal Cd/sup 2 +/ with one equatorial and two axial nitrogen donors from the ligand and four equatorial oxygen donors from asymmetricmore » bidentate nitrate groups. The structure of A is made up of two different molecules, A and A', both of which have very distorted pentagonal bipyramidal Cd/sup 2 +/ with two axial nitrogens and one equatorial oxygen from the ligand and four equatorial oxygen atoms from symmetrical bidentate nitrate groups. X-ray data for the crystal structure of the two compounds are presented. 44 references, 5 figures, 3 tables.« less