title: Synthesis and characterization of NaNiF3·3H2O: an unusual ordered variant of the ReO3 type.
abstract: A new hydrated sodium nickel fluoride with nominal composition NaNiF3·3H2O was synthesized using an aqueous solution route. Its structure was solved by means of ab initio methods from powder X-ray diffraction and neutron diffraction data. NaNiF3·3H2O crystallizes in the cubic crystal system, space group Pn3̅ with a = 7.91968(4) Å. The framework, derived from the ReO3 structure type, is built from NaX6 and NiX6 (X = O, F) corner-shared octahedra, in which F and O atoms are randomly distributed on a single anion site. The 2a × 2a × 2a superstructure arises from the strict alternate three-dimensional linking of NaX6 and NiX6 octahedra together with the simultaneous tilts of the octahedra from the cube axis (φ = 31.1°), with a significant participation of hydrogen bonding. NaNiF3·3H2O corresponds to a fully cation-ordered variant of the In(OH)3 structure, easily recognizable when formulated as NaNi(XH)6 (X = O, F). It constitutes one of the rare examples for the a(+)a(+)a(+) tilting scheme with 1:1 cation ordering in perovskite-related compounds. The Curie-like magnetic behavior well-reflects the isolated paramagnetic Ni(2+) centers without worth mentioning interactions. While X-ray and neutron diffraction data evidence Na/Ni order in combination with O/F disorder as a main feature of this fluoride, results from Raman and magic-angle spinning NMR spectroscopies support the existence of specific anion arrangements in isolated square windows identified in structural refinements. In particular, formation of water molecules derives from unfavorable FH bond formation.
authors: †Facultad de Farmacia, Departamento de Química y Bioquímica, Universidad CEU San Pablo, Urbanización Montepríncipe, 28668 Boadilla del Monte, Madrid, Spain.
authors: Elena C
authors: EC
authors: Gonzalo
authors: ‡Facultad de Ciencias, Instituto de Ciencia de Materiales de Aragón (Universidad de Zaragoza-CSIC), 50009 Zaragoza, Spain.
authors: María Luisa
authors: ML
authors: Sanjuán
authors: §Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München, D-85747 Garching, Germany.
authors: Markus
authors: M
authors: Hoelzel
authors: †Facultad de Farmacia, Departamento de Química y Bioquímica, Universidad CEU San Pablo, Urbanización Montepríncipe, 28668 Boadilla del Monte, Madrid, Spain.
authors: M Teresa
authors: MT
authors: Azcondo
authors: †Facultad de Farmacia, Departamento de Química y Bioquímica, Universidad CEU San Pablo, Urbanización Montepríncipe, 28668 Boadilla del Monte, Madrid, Spain.
authors: Ulises
authors: U
authors: Amador
authors: ∥Instituto de Ciencia de Materiales de Madrid, CSIC, 28006 Madrid, Spain.
authors: Isabel
authors: I
authors: Sobrados
authors: ∥Instituto de Ciencia de Materiales de Madrid, CSIC, 28006 Madrid, Spain.
authors: Jesús
authors: J
authors: Sanz
authors: †Facultad de Farmacia, Departamento de Química y Bioquímica, Universidad CEU San Pablo, Urbanización Montepríncipe, 28668 Boadilla del Monte, Madrid, Spain.
authors: Flaviano
authors: F
authors: García-Alvarado
authors: †Facultad de Farmacia, Departamento de Química y Bioquímica, Universidad CEU San Pablo, Urbanización Montepríncipe, 28668 Boadilla del Monte, Madrid, Spain.
authors: Alois
authors: A
authors: Kuhn