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一水合高溴酸锂,温度为296K和173K 。

Lithium perbromate monohydrate at 296 and 173 K.

作者信息

Blackburn A C, Gerkin R E

机构信息

Department of Chemistry, Ohio State University, Columbus 43210.

出版信息

Acta Crystallogr C. 1995 Jan 15;51 Pt 1:3-7. doi: 10.1107/s0108270194008449.

Abstract

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.

摘要

一水合溴酸锂(1-),LiBrO₄·H₂O,其高氯酸盐类似物尚未见报道,发现它与NaBrO₄·H₂O和NaClO₄·H₂O同构。两个不等价的锂离子中的每一个都由六个氧原子配位,从而形成扭曲的八面体,每个八面体有三个不等价的Li-O距离。在室温下,平均Li(1)-O和Li(2)-O距离分别为2.150 Å和2.164 Å。高溴酸根离子呈现出非常接近规则的四面体几何形状,尽管它不受对称约束。在296 K时,观察到的平均Br-O距离为1.610 (4) Å,平均O-Br-O角度为109.5 (6) 度,而在173 K时,相应的值分别为1.613 (4) Å和109.5 (7) 度。高溴酸根离子表现出刚体行为,但锂配位多面体则不然。在296 K时,高溴酸根离子中经刚体校正后的平均Br-O距离为1.624 (3) Å,与报道的NaBrO₄·H₂O的相应值非常吻合。对两个不等价氢原子的精修使得能够对氢键进行详细分析,氢键比在NaBrO₄·H₂O或NaClO₄·H₂O中更为广泛。氢原子的平均观察到的B值[296 K时为2.9 (3) Ų,173 K时为2.8 (3) Ų]足够小,表明氢原子的动态无序(通过NaClO₄·H₂O的磁共振方法确定)在标题盐中不显著。

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