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Title: Hygroscopic La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O: Insight into the evolution of borate fundamental building blocks

Borates have exceptionally diverse fundamental building blocks (FBBs), but factors controlling the formation of borate FBBs are poorly understood. The title compound La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O crystallizes in the space group P2{sub 1}/n with a=6.5396(12) Å, b=15.550(3) Å, c=10.6719(19) Å, β=90.44(1)° and Z=4 at 173(2) K. Its structure has been refined from single-crystal X-ray diffraction data to R{sub 1}=0.049 (for 2465) and wR{sub 2}=0.173 (for 2459 I>2σ(I)). This structure analysis and first-principles calculations show that the change of the FBB from 3Δ2□ in the title compound to 2Δ3□ in La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by a rotation of the NO{sub 3} group. FTIR, Rietveld and thermal analysis results show that the hygroscopic title compound is partially changed to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O, with the conversion of [BO{sub 3}] to [BO{sub 3}(H{sub 2}O)] by water absorption. - Graphical abstract: The change of fundamental building blocks from La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by a rotation of the NO{sub 3} group . Display Omitted - Highlights: • Synthesis of a new hydrous lanthanum polyborate nitrate. • Single-crystal XRD structure with the 3Δ2⎕ FBB and an oriented NO{sub 3}more » group. • DFT calculations locate the H positions in three lanthanide polyborate nitrates. • Rietveld, FTIR and DFT results show hygroscopicity changes the FBBs.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1]
  1. Fujian Provincial Key Laboratory of Advanced Materials, Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, Fujian Province (China)
  2. Department of Geological Sciences, University of Saskatchewan, 114 Science Place, SK, S7N 5E2 (Canada)
Publication Date:
OSTI Identifier:
22274109
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 206; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; BORATES; FOURIER TRANSFORMATION; HYGROSCOPICITY; INFRARED SPECTRA; LANTHANUM; MOLECULAR DYNAMICS METHOD; MONOCLINIC LATTICES; MONOCRYSTALS; NITRATES; NITROGEN OXIDES; ROTATION; SPACE GROUPS; THERMAL ANALYSIS; X RADIATION; X-RAY DIFFRACTION