title: Effect of inclining strain on the crystal lattice along an extended series of lanthanide hydroxysulfates Ln(OH)SO4 (Ln = Pr-Yb, except Pm).
abstract: A series of trivalent lanthanide hydroxysulfates, Ln(OH)SO(4), (Ln = Pr through Yb, except radioactive Pm) has been synthesized via hydrothermal methods from Ln(2)(SO(4))(3)·8H(2)O by reaction with aqueous NaOH at 170 °C in Teflon lined Parr steel autoclaves, and were characterized by single crystal X-ray diffraction and FT-IR spectroscopy. Two types of arrangements were found in the solid state. The lighter (Ln = Pr-Nd, Sm-Gd) and heavier lanthanide(III) hydroxysulfates (Tb-Yb) are each isostructural. Both structure types exhibit the monoclinic space group P2(1)/n, but the unit cell content is doubled with two crystallographically distinct LnO(8) polyhedra for the heavier lanthanide compounds. The lighter complexes maintain the coordination number 9, forming a three-dimensional extended lattice. The heavier counterparts exhibit the coordination number 8, and arrange as infinite columns of two crystallographically different LnO(8) polyhedra, while extending along the "c" axis. These columns of LnO(8) polyhedra are surrounded and separated by six columns of sulfate ions, also elongating in the "c" direction. The rigid sulfate entities seem to obstruct the closing in of the lighter LnO(9) polyhedra, and show an inclining degree of torsion into the "ac" layers. The crystal lattice of the lighter 4f complexes can sufficiently withstand the tension buildup, caused by the decreasing Ln(3+) radius, up to Gd(OH)SO(4). The energy profile of this structural arrangement then seems to exceed levels at which this structure type is favorable. The lattice arrangement of the heavier Ln-analogues seems to offer a lower energy profile. This appears to be the preferred arrangement for the heavier lanthanide hydroxysulfates, whose crystal lattice exhibits more flexibility, as the coordination sphere of these analogues is less crowded. The IR absorbance frequencies of the hydroxide ligands correlate as a function of the Ln(3+) ionic radius. This corresponds well with the X-ray single crystal analysis data.
authors.affiliation: Department of Chemistry, University of Louisiana at Monroe, Monroe, Louisiana 71209, USA. zehnder@ulm.edu
authors.forename: Ralph A
authors.initials: RA
authors.lastname: Zehnder
authors.forename: Christopher S
authors.initials: CS
authors.lastname: Wilson
authors.forename: Hunter T
authors.initials: HT
authors.lastname: Christy
authors.forename: Kenneth S
authors.initials: KS
authors.lastname: Harris
authors.forename: Varun
authors.initials: V
authors.lastname: Chauhan
authors.forename: Victor
authors.initials: V
authors.lastname: Schutz
authors.forename: Matthew
authors.initials: M
authors.lastname: Sullivan
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.forename: Frank R
authors.initials: FR
authors.lastname: Fronczek
authors.forename: Jacob A
authors.initials: JA
authors.lastname: Myers
authors.forename: Kyle
authors.initials: K
authors.lastname: Dammann
authors.forename: James
authors.initials: J
authors.lastname: Duck
authors.forename: Peter M
authors.initials: PM
authors.lastname: Smith
authors.forename: Antony
authors.initials: A
authors.lastname: Okuma
authors.forename: Kristin
authors.initials: K
authors.lastname: Johnson
authors.forename: Robert
authors.initials: R
authors.lastname: Sovesky
authors.forename: Cameron
authors.initials: C
authors.lastname: Stroudt
authors.forename: Robert A
authors.initials: RA
authors.lastname: Renn
mesh_terms: D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D017550:Spectroscopy, Fourier Transform Infrared; D013431:Sulfates / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D028581:Lanthanoid Series Elements; D013431:Sulfates