Lithium tetraoxobromate(1-) monohydrate, LiBrO4.-H2O, whose perchlorate analog has not yet been described, is found to be isomorphic with NaBrO4.H2O and NaClO4.H2O. Each of the two inequivalent Li ions is coordinated by six O atoms, thus forming distorted octahedra, each of which has three inequivalent Li-O distances. At room temperature, the average Li(1)-O and Li(2)-O distances are 2.150 and 2.164 A, respectively. The perbromate ion displays very nearly regular tetrahedral geometry, although it is not subject to symmetry constraints. At 296 K the average observed Br-O distance is 1.610 (4) A and the average O-Br-O angle is 109.5 (6) degrees, while at 173 K the corresponding values are 1.613 (4) A and 109.5 (7) degrees. The perbromate ion shows rigid-body behavior but the lithium coordination polyhedra do not. At 296 K, the average rigid-body corrected Br-O distance in the perbromate ion is 1.624 (3) A, in excellent agreement with the corresponding value reported for NaBrO4.H2O. Refinement of the two inequivalent H atoms allowed detailed analysis of the hydrogen bonding, which is more extensive than in NaBrO4.H2O or in NaClO4.H2O. The average observed B values for the H atoms [2.9 (3) A2 at 296 K and 2.8 (3) A2 at 173 K] are sufficiently small to suggest that dynamic disordering of the H atoms (determined by magnetic resonance methods for NaClO4.H2O) is not significant in the title salt.
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http://dx.doi.org/10.1107/s0108270194008449 | DOI Listing |
Inorg Chem
September 2011
Southern Nevada Water Authority, Applied Research & Development Center, P.O. Box 99954, Las Vegas, Nevada 89193, USA.
Historically, the synthesis of perbromate ion through conventional oxidation routes has proven elusive. Herein, we report perbromate ion formation through the reaction of hypobromite and bromate ions in an alkaline sodium hypobromite solution. Formation was established via LC-MS/MS analysis of the bromate and perbromate ions in the reaction solutions over a 13-day period.
View Article and Find Full Text PDFInorg Chem
September 2007
Département de Chimie, Université de Montréal, C. P. 6128, Succursale Centre-ville, Montréal, Québec, Canada H3C 3J7.
The reaction of NiBr2 with the bidentate ligand diphenyl(dipyrazolyl)methane (dpdpm) gives the pentacoordinated complexes [(dpdpm)Ni(mu-Br)Br]2 (1), [(dpdpm)NiBr2(H2O)] (2a), and [(dpdpm)NiBr(H2O)2]Br (2b), or the octahedral complexes [(dpdpm)NiBr(H2O)2(CH3CN)]Br (3), [(dpdpm)2NiBr2] (4), and [(dpdpm)2NiBr(H2O)]Br (5). All of these complexes are paramagnetic, both in the solid state and in solution, and have been characterized by spectroscopic (IR, NMR, and UV-vis-NIR) and X-ray diffraction studies. The unoccupied coordination site in the pentacoordinated compounds allows long-range interactions, in the solid state, between the Ni center and a Ph substituent of the dpdpm ligand.
View Article and Find Full Text PDFActa Crystallogr C
January 1995
Department of Chemistry, Ohio State University, Columbus 43210.
Lithium tetraoxobromate(1-) monohydrate, LiBrO4.-H2O, whose perchlorate analog has not yet been described, is found to be isomorphic with NaBrO4.H2O and NaClO4.
View Article and Find Full Text PDFActa Crystallogr C
August 1993
Department of Chemistry, Ohio State University, Columbus 43210.
The structure of the title compound consists of columns of Ca ions surrounded by four columns of perbromate ions and four columns of water molecules alternating in pairs. The CaO8 complex was found to be dimensionally similar to corresponding complexes in other simple tetrahydrated calcium salts. The eight coordinating O atoms form a polyhedron which departs only slightly from a (distorted) square antiprism.
View Article and Find Full Text PDFActa Crystallogr C
March 1992
Department of Chemistry, Ohio State University, Columbus 43210.
NaBrO4.H2O, Mr = 184.90, monoclinic, C2/c, a = 15.
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