Crystal growth in aqueous hydrofluoric acid and (HF)x · pyridine solutions: syntheses and crystal structures of [Ni(H2O)6]2+[MF6]2- (M = Ti, Zr, Hf) and Ni3(py)12F6 · 7H2O

Abstract The syntheses and structures of [Ni(H2O)6]2+[MF6]2− (M = Ti,Zr,Hf) and Ni3(py)12F6·7H2O are reported. The former three compounds are isostructural, crystallizing in the trigonal space group R 3 (No. 148) with Z = 3. The lattice parameters are a = 9.489(4), c = 9.764(7) A , with V = 761(1) A3 for Ti; a = 9.727(2), c = 10.051(3) A, with V = 823.6(6) A3 for Zr; and a = 9.724(3), c = 10.028(4)A, with V = 821.2(8)A3 for Hf. The structures consist of discrete [Ni(H2O)6]2+ and [MF6]2− octahedra joined by OH⋯F hydrogen bond Large single crystals were grown in an aqueous hydrofluoric acid solution. Ni3(py)12F6·7H2O crystallizes in the monoclinic space group I2/a (No. 15) with Z = 4. The lattice parameters are a = 16.117(4), b = 8.529(3), c = 46.220(7) A , β = 92.46(2)°, and V = 6348(5) A 3 . The structure consists of discrete Ni(py)4F2 octahedra linked through HOH⋯F and HOH⋯O hydrogen bonding interactions. Single c were grown from a (HF)x·pyridine/pyridine/water solution.

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