Tina Bunic، نويسنده , , Melita Tramsek، نويسنده , , Evgeny Goreshnik، نويسنده , , Boris Zemva، نويسنده ,
Three new compounds Ca(HF2)2, Ba4F4(HF2)(PF6)3 and Pb2F2(HF2)(PF6) were obtained in the system metal(II) fluoride and anhydrous HF (aHF) acidified with excessive PF5. The obtained polymeric solids are slightly soluble in aHF and they crystallize out of their aHF solutions. Ca(HF2)2 was prepared by simply dissolving CaF2 in a neutral aHF. It represents the second known compound with homoleptic HF environment of the central atom besides Ba(H3F4)2. The compounds Ba4F4(HF2)(PF6)3 and Pb2F2(HF2)(PF6) represent two additional examples of the formation of a polymeric zigzag ladder or ribbon composed of metal cation and fluoride anion (MF+)n besides PbF(AsF6), the first isolated compound with such zigzag ladder. The obtained new compounds were characterized by X-ray single crystal diffraction method and partly by Raman spectroscopy. Ba4F4(HF2)(PF6)3 crystallizes in a triclinic space group P1¯ with a=4.5870(2) Å, b=8.8327(3) Å, c=11.2489(3) Å, α=67.758(9)°, β=84.722(12), γ=78.283(12)°, V=413.00(3) Å3 at 200 K, Z=1 and R=0.0588. Pb2F2(HF2)(PF6) at 200 K: space group P1¯, a=4.5722(19) Å, b=4.763(2) Å, c=8.818(4) Å, α=86.967(10)°, β=76.774(10)°, γ=83.230(12)°, V=185.55(14) Å3, Z=1 and R=0.0937. Pb2F2(HF2)(PF6) at 293 K: space group P1¯, a=4.586(2) Å, b=4.781(3) Å, c=8.831(5) Å, α=87.106(13)°, β=76.830(13)°, γ=83.531(11)°, V=187.27(18) Å3, Z=1 and R=0.072. Ca(HF2)2 crystallizes in an orthorhombic Fddd space group with a=5.5709(6) Å, b=10.1111(9) Å, c=10.5945(10) Å, V=596.77(10) Å3 at 200 K, Z=8 and R=0.028.
Poly-(hydrogen fluorides) , crystal structure , Homoleptic HF environment , Raman spectrum , (MF)n+ ribbon , Hydrogen bonding