A new polymorph of Ba(AsO 3OH): Synthesis, crystal structure and vibrational spectra

• Published in: Journal of solid state chemistry Vol. 183; no. 12; pp. 2835 - 2844
• Main Authors: DORDEVIC, Tamara, KARANOVIC, Ljiljana
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 01-12-2010; Elsevier
• Subjects: ABSORPTION SPECTROSCOPY; Alkaline earth hydrogen arsenates; ALKALINE EARTH METAL COMPLEXES; ARSENATES; ARSENIC COMPOUNDS; Ba(AsO 3OH); BARIUM COMPLEXES; CHELATING AGENTS; COHERENT SCATTERING; COMPLEXES; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; Exact sciences and technology; Hydrogen bonds; HYDROTHERMAL SYNTHESIS; INFRARED SPECTRA; Infrared spectroscopy; Inorganic compounds; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; LASER SPECTROSCOPY; Lattice dynamics; LAYERS; Materials science; Materials synthesis; materials processing; MATHEMATICS; MONOCLINIC LATTICES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; OXYGEN COMPOUNDS; Phonons and vibrations in crystal lattices; Physics; RAMAN SPECTROSCOPY; SCATTERING; Single crystal structure analysis; SPACE GROUPS; SPECTRA; SPECTROSCOPY; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; SYMMETRY GROUPS; SYNTHESIS; TOPOLOGY; X-RAY DIFFRACTION; Infrared spectroscopy; Hydrothermal synthesis; Hydrogen bonds; Single crystal structure analysis; Ba(AsO 3OH); Alkaline earth hydrogen arsenates; Raman spectroscopy; Barium; Fourier transform spectroscopy; Space groups; XRD; Triclinic lattices; Crystal growth from solutions; OH; Fourier-transformed infrared spectrometry; Crystal structure; Crystal twin; Hydrogen neutral atoms; Crystal defects; Arsenates; Infrared spectra; Monoclinic lattices; Racemates; Monocrystals; Vibrational modes; Orthorhombic lattices; Donor center; Ba(AsO; Polymorphism
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2010.09.027

A new monoclinic polymorph of Ba(AsO
3OH) was synthesized under hydrothermal conditions. It represents a previously unknown structure type. Its crystal structure was determined from a racemic twin using single-crystal X-ray diffraction data collected at 120 and 293
K [space group
P2
1,
a=7.2149(14)/7.2370(2),
b=7.7028(15)/7.7133(2),
c=21.7385(43)/21.8079(5)
Å,
β=95.95(3)/96.073(1)°,
V=1201.6(4)/1210.51(5)
ų,
Z=12]. The crystal structure of
P2
1-Ba(AsO
3OH) has a layered character and is built up of four types of regularly alternating layers parallel to (0
0
1). Every AsO
3OH tetrahedron is chelating to two Ba atoms and bridged by another two Ba atoms. Each OH group acts as hydrogen bond donor toward the oxygen atoms positioned in the same or adjacent layers. Although the H atoms could not be located, no ambiguities are present in the hydrogen-bonding scheme. Single-crystal vibrational spectroscopy (FTIR and Raman) was used to describe the vibrational behavior of the hydrogen bond system; particularly the spectroscopic manifestation of the very short and short hydrogen bonds (2.462(7)–2.575(7)
Å). In order to complement spectroscopic data on protonated orthoarsenates, infrared spectra of triclinic
F1¯-Sr(AsO
3OH) and the orthorhombic variety of
Pbca-Ba(AsO
3OH) were recorded and discussed. Furthermore, structural features of other alkaline earth hydrogen arsenates are discussed.
Mesh type and topological structure of the cation layers seen along [0
0
1];
a-axis vertical,
b-axis horizontal. A trace of the unit cell is drawn for reference.
[Display omitted]