SYNTHESIS AND CRYSTAL-STRUCTURE OF THE CO MPLEX-COMPOUNDS NI(PY)(4)F-2-CENTER-DOT-2H(2)O AND CU(PY)(4)F-2-CENTER-DOT-1,33HF-CENTER-DOT-2H(2)O

Single crystals of Ni(py)(4)F-2 . 2H(2)O (1) and Cu(py)(4)F2 . 1.33 HF . 2 H2O (2) have been synthesized by solving the precipitated metal f luoride hydrates in pyridine. Both compounds are sensitive to air. The y crystallize in the monoclinic space group C2/c with lattice paramete rs a = 13.199(2) Angstrom, b = 10.815(2) Angstrom, c = 15.353(2) Angst rom, beta = 108.08(1)degrees for 1 and a = 28.531(6) Angstrom, b = 8.7 67(2) Angstrom, c = 17.572(4) Angstrom, beta = 104.43(3)degrees for 2. Within both structures the metal atoms are coordinated in form of a d istorted square bipyramid. In the case of 1 four pyridine nitrogen ato ms are in the basal plane and two fluorine atoms in the apical positio ns. Hydrogen bonding via water molecules lead to infinite chains of Ni (py)(4)F-2 molecules connected by doubly ridged [F-2(H2O)(2)] ring uni ts. In 2 two different complex moieties exist. In one complex two H2O molecules are in the inner coordination sphere besides the four pyridi ne rings; these molecules are interconnected by two F- ions, which may be partially substituted by HF2--groups forming infinite chains along [010]. In the other, HF2--ions occupy the apical positions of the squ are bipyramid around the copper ion. They are linked to the fluoride i ons of the chains by weak hydrogen bonds of water molecules arranged i n between. Thus, the formula should be better given as [Cu(py)(4)(H2O) (2)][Cu(py)(4)(HF2)(2)]. F-1.66(HF2)(0.33). 2 H2O.