title: Structure of magnesium selenate enneahydrate, MgSeO4·9H2O, from 5 to 250 K using neutron time-of-flight Laue diffraction.
abstract: The complete structure of MgSeO4·9H2O has been refined from neutron single-crystal diffraction data obtained at 5, 100, 175 and 250 K. It is monoclinic, space group P2₁/c, Z = 4, with unit-cell parameters a = 7.222 (2), b = 10.484 (3), c = 17.327 (4) Å, β = 109.57 (2)°, and V = 1236.1 (6) Å(3) [ρ(calc) = 1770 (1) kg m(-3)] at 5 K. The structure consists of isolated [Mg(H2O)6](2+) octahedra, [SeO4](2-) tetrahedra and three interstitial lattice water molecules, all on sites of symmetry 1. The positions of the H atoms agree well with those inferred on the basis of geometrical considerations in the prior X-ray powder diffraction structure determination: no evidence of orientational disorder of the water molecules is apparent in the temperature range studied. Six of the nine water molecules are hydrogen bonded to one another to form a unique centrosymmetric dodecamer, (H2O)12. Raman spectra have been acquired in the range 170-4000 cm(-1) at 259 and 78 K; ab initio calculations, using density functional theory, have been carried out in order to aid in the analysis of the Raman spectrum as well as providing additional insights into the geometry and thermodynamics of the hydrogen bonds. Complementary information concerning the thermal expansion, crystal morphology and the solubility are also presented.
authors.affiliation: Department of Earth Sciences, University College London, Gower Street, London WC1E 6BT, England.
authors.forename: A Dominic
authors.initials: AD
authors.lastname: Fortes
authors.affiliation: Department of Earth and Planetary Sciences, Birkbeck, University of London, Malet Street, London WC1E 7HX, England.
authors.forename: Dario
authors.initials: D
authors.lastname: Alfè
authors.affiliation: Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Campus de Cantoblanco, 28049 Madrid, Spain.
authors.forename: Eduardo R
authors.initials: ER
authors.lastname: Hernández
authors.affiliation: ISIS Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX, England.
authors.forename: Matthias J
authors.initials: MJ
authors.lastname: Gutmann
keywords: dodecamer; magnesium selenate enneahydrate; neutron diffraction