A. Preisinger et al., HYDROGEN-BONDING IN POTASSIUM FLUORIDE DIHYDRATE - A CRYSTALLOGRAPHIC, SPECTROSCOPIC, AND THEORETICAL-STUDY, Inorganic chemistry, 33(21), 1994, pp. 4774-4780
Crystal structure data of orthorhombic KF.2H(2)O are reported that wer
e obtained from neutron diffraction refinements at 295 K (Pmc2(1); Z =
2; a = 4.082(2) Angstrom, b = 5.182(2) Angstrom, c = 8.825(5) Angstro
m; R = 0.020) and from X-ray diffraction refinements at 298 and 120 K
(R = 0.018 and 0.009, respectively). Each of the two independent water
molecules is coordinated by two potassium ions and forms two O-H...F
hydrogen bonds (neutron values: O-H = 0.966-0.971 Angstrom, H...F = 1.
752-1.796 Angstrom, and O...F = 2.719-2.753 Angstrom). Vibrational spe
ctra of partially deuterated samples yielded three rather similar unco
upled <(nu)over bar>(OD) frequencies (2462, 2478, and 2491 cm(-1) at 7
5 K) in agreement with the three crystallographically different, but g
eometrically similar O-H...F hydrogen bonds. Energy band calculations
have been performed using the LAPW method. Total and partial densities
of states show that the water-potassium interactions are almost exclu
sively electrostatic, while the hydrogen bond interactions with the fl
uorine anions have additional covalent contributions or at least polar
ization effects of about 20%.