title: High-pressure studies of three polymorphs of a palladium(II) oxathioether macrocyclic complex.
abstract: The three reported phases of the mononuclear macrocyclic Pd(II) complex [PdCl2([9]aneS2O)] [(1); [9]aneS2O = 1-oxa-4,7-dithiacyclononane] were each studied up to pressures exceeding 9 GPa using high-pressure single-crystal X-ray diffraction. The α- and γ-phases both exhibit smooth compression of the unit-cell parameters with third-order Birch-Murnaghan bulk moduli of 14.4 (8) and 7.6 (6) GPa, respectively. Between 6.81 and 6.87 GPa β-[PdCl2([9]aneS2O)] was found to undergo a reversible transition to a phase denoted as β' and characterized by a tripling of the unit-cell volume. Across the phase transition, rearrangement of the conformation of the bound macrocycle at two of the resulting three unique sites gives rise to an extensively disordered structure.
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England.
authors.forename: Jeremiah P
authors.initials: JP
authors.lastname: Tidey
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England.
authors.forename: Henry L S
authors.initials: HL
authors.lastname: Wong
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England.
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003460:Crystallization; D018360:Crystallography, X-Ray; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry*; D044367:Phase Transition; D011312:Pressure; D013440:Sulfides / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D047028:Macrocyclic Compounds; D013440:Sulfides; D010165:Palladium; C008756:palladium chloride
keywords: coordination chemistry; disorder; high pressure; phase transition; polymorphism