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Issue 47, 2011
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Molecular geometries of H2S⋯ICF3 and H2O⋯ICF3 characterised by broadband rotational spectroscopy

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Abstract

The rotational spectra of three isotopologues of H2S⋯ICF3 and four isotopologues of H2O⋯ICF3 are measured from 7–18 GHz by chirped-pulse Fourier transform microwave spectroscopy. The rotational constant, B0, centrifugal distortion constants, DJ and DJK, and nuclear quadrupole coupling constant of 127I, χaa(I), are precisely determined for H2S⋯ICF3 and H2O⋯ICF3 by fitting observed transitions to the Hamiltonians appropriate to symmetric tops. The measured rotational constants allow determination of the molecular geometries. The C2 axis of H2O/H2S intersects the C3 axis of the CF3I sub-unit at the oxygen atom. The lengths of halogen bonds identified between iodine and sulphur, r(S⋯I), and iodine and oxygen, r(O⋯I), are determined to be 3.5589(2) Å and 3.0517(18) Å respectively. The angle, ϕ, between the local C2 axis of the H2S/H2O sub-unit and the C3 axis of CF3I is found to be 93.7(2)° in H2S⋯ICF3 and 34.4(20)° in H2O⋯ICF3. The observed symmetric top spectra imply nearly free internal rotation of the C2 axis of the hydrogen sulphide/water unit about the C3 axis of CF3I in each of these complexes. Additional transitions of H216O⋯ICF3, D216O⋯ICF3 and H218O⋯ICF3 can be assigned only using asymmetric top Hamiltonians, suggesting that the effective rigid-rotor fits employed do not completely represent the internal dynamics of H2O⋯ICF3.

Graphical abstract: Molecular geometries of H2S⋯ICF3 and H2O⋯ICF3 characterised by broadband rotational spectroscopy

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Publication details

The article was received on 18 Jul 2011, accepted on 27 Sep 2011 and first published on 24 Oct 2011


Article type: Paper
DOI: 10.1039/C1CP22339A
Citation: Phys. Chem. Chem. Phys., 2011,13, 21093-21101

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    Molecular geometries of H2S⋯ICF3 and H2O⋯ICF3 characterised by broadband rotational spectroscopy

    S. L. Stephens, N. R. Walker and A. C. Legon, Phys. Chem. Chem. Phys., 2011, 13, 21093
    DOI: 10.1039/C1CP22339A

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