Bis(diethyldithiocarbamato)pyridinezinc(II) and -copper(II) clathrates M(Edtc)(2)Py center dot nL (L = CH2Cl2 and CHCl3; n=1 and 0.5): Molecular and crystal structures and EPR and high-resolution solid-state (C-13, N-15) NMRspectra

X-ray diffraction analysis, EPR, and high-resolution solid-state (C-13, N-1 5) NMR spectroscopy were used to examine structural organization and spectr al properties of six bis(diethyldithiocarbamato)pyridinezinc(II) and copper (II) solvates with dichloromethane and chloroform, M(Edtc)(2)Py . nL (n = 1 and 0.5). Typical of the clathrate-type structures, the compounds are pene trated by the ordered molecular channels filled with chemically nonbonded c hlorohydrocarbon molecules. At the molecular level, the geometry of coordin ation polyhedra of complexing atoms is intermediate between trigonal bipyra midal and square pyramidal (the contribution of the square-pyramidal compon ent is quantitatively estimated for the zinc clathrate). Accordingly, the g round state of the unpaired electron in the copper(n) compounds is a combin ation of the d(x2-y2) and d(z2) orbitals. It is shown that the nonequivalen ce of the Edtc(-) ligands in zinc(II) clathrates manifests itself both magn etically and structurally. The chlorine atoms of the solvate dichloromethan e molecules, unlike chloroform molecules, are disordered over the two struc tural positions with different multiplicities. The C-13 and N-15 NMR signal s are assigned to the atomic positions in the resolved molecular structures .