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1 Bulletin of the Polish Academy of Sciences. Chemistry

1 2002

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Single-crystal neutron study on cobalt iodate tetrahydrate, a compound with H...|I(V)O3- hydrogen bonds?

Nagel R., Kümmerle E., Lutz H. D.

Bulletin of the Polish Academy of Sciences. Chemistry

2002

Vol. 50, No. 1

51-66

The crystal structure of cobalt iodate tetrahydrate Co(IO(3)(2)-4H(2)O (space group P21/c, Z=2, a=836.8(5) pm, b=656.2(3) pm, c=850.2(5) pm, and Beta=100.12°, final Rl = 0.0349 (I>i mniejszości 2 sigma(I) for 1031 unique reflections) was redetermined by single-crystal neutron diffraction studies. The structure is built up by layers parallel (100) connected by interionic O(3)I(-..'OIO(-)(2) bonds. Unequivocal interpretation of the four differently strong OH(...) OIO(-3) hydrogen bonds of the two crystallographic different hydrate H(2)O molecules of the isostructural series M(IO3)(2)-4H(2)O (M = Mg, Co, Ni) on the basis of the observed hydrogen-bond distances and assignment to the uncoupled OD stretching modes of matrix isolated HDO molecules is only possible if weak hydrogen bonds to the iodine lone-pairs of adjacent IO-(3) ions are additionally considered. The potential strength of H(...)I(V)O-(3) hydrogen bonds with respect to H(...) I distances and H(...)IO(-)(3) angles is discussed. A bond-valence concept for estimating the strength of H(...I)I(V)O(-)(3) hydrogen bonds is given.