COMPLEX POLYMERIC CATIONS OF COPPER(I) WITH GRAPHITE-RELATED AND DIAMOND-RELATED LATTICES - CRYSTAL-STRUCTURES OF POLY-TRIS(MU-2,5-DIMETHYLPYRAZINE)DICOPPER(I) HEXAFLUOROPHOSPHATE AND POLY-BIS(MU-2,5-DIMETHYLPYRAZINE)COPPER(I) HEXAFLUOROPHOSPHATE

Yellow crystals of composition [Cu2(2,5-me2pyz)3][PF6]2, 1, and orange-red ones of composition [Cu(2,5-me2-pyz)2] [PF6], 2, were obtained from the reaction Of Cu(ClO4)2-6H2O, KPF6, and 2,5-dimethylpyrazine in ethanol. Single-crystal X-ray diffraction studies on both are reported. Crystals of 1 are monoclinic, a = 7.799(2) angstrom, b = 15.862(1) angstrom, c = 11.225(1) angstrom, beta = 96.11(1)-degrees, Z = 2, and space group P2(1)/n. The structure was solved by the Patterson method and was refined by full-matrix least squares to R = 0.038 and R(w) = 0.044 for 1442 reflections with I > 3sigma(I). The compound is a two-dimensional cationic polymer with a graphite-related lattice. PF6- ions occupy interlayer positions and weakly interact with the copper centers. 2 crystallizes in the tetragonal system, space group P4n2BAR, with a = 13.209(2) angstrom, c = 9.142(2) angstrom, and Z = 4. The structure was solved and refined as for 1 to R = 0.034 and R(w) = 0.033 for 708 reflections with I > 3sigma(I). The compound is a three-dimensional cationic polymer with a diamond-like lattice. PF6- ions are noncoordinating and occupy positions in lattice cavities.