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Title: Low-temperature flux syntheses and characterizations of two 1-D anhydrous borophosphates: Na{sub 3}B{sub 6}PO{sub 13} and Na{sub 3}BP{sub 2}O{sub 8}

Abstract

Two new anhydrous sodium borophosphates with one-dimensional structure, Na{sub 3}B{sub 6}PO{sub 13}(1) and Na{sub 3}BP{sub 2}O{sub 8}(2), were synthesized by low-temperature molten salts techniques using boric acid and sodium dihydrogen phosphate as flux, respectively. The crystal structures were solved by means of single-crystal X-ray diffraction (1, orthorhombic, Pnma (no. 62), a=9.3727(4)A, b=16.2307(7)A, c=6.7232(3)A, Z=4; 2 , monoclinic, C2/c (no. 15), a=12.567(4)A, b=10.290(3)A, c=10.210(3)A, {beta}=92.492(5){sup o}, Z=8). Compound 1 is characterized by an infinite chain of {sub {approx}}{sup 1}{l_brace}[B{sub 6}PO{sub 13}]{r_brace}{sup 3-} containing eight-membered rings in which all vertexes of borate groups contribute to interconnection. Compound 2 reveals an infinite straight chain {sub {approx}}{sup 1}{l_brace}[BP{sub 2}O{sub 8}]{r_brace}{sup 3-} built of vertex-sharing four-membered rings, and chains in neighboring layers arranged along different orientations. The relations between structures and the synthetic conditions with only traced water are discussed.

Authors:
 [1];  [2];  [1];  [1];  [3]
  1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China)
  2. (China)
  3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China), E-mail: jtzhao@mail.sic.ac.cn
Publication Date:
OSTI Identifier:
21015642
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.09.034; PII: S0022-4596(06)00518-4; Copyright (c) 2006 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; BORATES; BORIC ACID; BOROPHOSPHATE GLASS; FLUX SYNTHESIS; MONOCLINIC LATTICES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; SODIUM PHOSPHATES; X-RAY DIFFRACTION

Citation Formats

Xiong Dingbang, Graduate School of Chinese Academy of Science, Beijing, Chen Haohong, Yang Xinxin, and Zhao Jingtai. Low-temperature flux syntheses and characterizations of two 1-D anhydrous borophosphates: Na{sub 3}B{sub 6}PO{sub 13} and Na{sub 3}BP{sub 2}O{sub 8}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.09.034.
Xiong Dingbang, Graduate School of Chinese Academy of Science, Beijing, Chen Haohong, Yang Xinxin, & Zhao Jingtai. Low-temperature flux syntheses and characterizations of two 1-D anhydrous borophosphates: Na{sub 3}B{sub 6}PO{sub 13} and Na{sub 3}BP{sub 2}O{sub 8}. United States. doi:10.1016/j.jssc.2006.09.034.
Xiong Dingbang, Graduate School of Chinese Academy of Science, Beijing, Chen Haohong, Yang Xinxin, and Zhao Jingtai. Mon . "Low-temperature flux syntheses and characterizations of two 1-D anhydrous borophosphates: Na{sub 3}B{sub 6}PO{sub 13} and Na{sub 3}BP{sub 2}O{sub 8}". United States. doi:10.1016/j.jssc.2006.09.034.
@article{osti_21015642,
title = {Low-temperature flux syntheses and characterizations of two 1-D anhydrous borophosphates: Na{sub 3}B{sub 6}PO{sub 13} and Na{sub 3}BP{sub 2}O{sub 8}},
author = {Xiong Dingbang and Graduate School of Chinese Academy of Science, Beijing and Chen Haohong and Yang Xinxin and Zhao Jingtai},
abstractNote = {Two new anhydrous sodium borophosphates with one-dimensional structure, Na{sub 3}B{sub 6}PO{sub 13}(1) and Na{sub 3}BP{sub 2}O{sub 8}(2), were synthesized by low-temperature molten salts techniques using boric acid and sodium dihydrogen phosphate as flux, respectively. The crystal structures were solved by means of single-crystal X-ray diffraction (1, orthorhombic, Pnma (no. 62), a=9.3727(4)A, b=16.2307(7)A, c=6.7232(3)A, Z=4; 2 , monoclinic, C2/c (no. 15), a=12.567(4)A, b=10.290(3)A, c=10.210(3)A, {beta}=92.492(5){sup o}, Z=8). Compound 1 is characterized by an infinite chain of {sub {approx}}{sup 1}{l_brace}[B{sub 6}PO{sub 13}]{r_brace}{sup 3-} containing eight-membered rings in which all vertexes of borate groups contribute to interconnection. Compound 2 reveals an infinite straight chain {sub {approx}}{sup 1}{l_brace}[BP{sub 2}O{sub 8}]{r_brace}{sup 3-} built of vertex-sharing four-membered rings, and chains in neighboring layers arranged along different orientations. The relations between structures and the synthetic conditions with only traced water are discussed.},
doi = {10.1016/j.jssc.2006.09.034},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • Two members of M{sup III}{sub 2}BP{sub 3}O{sub 12} borophosphates, namely Fe{sub 2}BP{sub 3}O{sub 12} and In{sub 2}BP{sub 3}O{sub 12}, were synthesized by the solid-state method and characterized by the X-ray single crystal diffraction, the powder diffraction and the electron microscopy. They both crystallize in the hexagonal system, space group P6(3)/m (no. 176) and feature 3D architectures, build up of the M{sub 2}O{sub 9} units and B(PO{sub 4}){sub 3} groups via sharing the corners; however, they are not isomorphic for the different crystallographically distinct atomic positions. Optical property measurements of both compounds and magnetic susceptibility measurements of Fe{sub 2}BP{sub 3}O{sub 12}more » also have been performed. Moreover, in order to gain further insights into the relationship between physical properties and band structure of the M{sup III}{sub 2}BP{sub 3}O{sub 12} borophosphates, theoretical calculations based on density functional theory (DFT) were performed using the total-energy code CASTEP. - Graphical abstract: Two anhydrous metal borophosphates of M{sup III}{sub 2}BP{sub 3}O{sub 12} (M=Fe, In) have been prepared and characterized. They both crystallize in the hexagonal system, space group P6(3)/m (no. 176) and feature 3D architectures build up of the M{sub 2}O{sub 9} units and B(PO{sub 4}){sub 3} groups via sharing the corners, but they are not isomorphic for the different crystallographically distinct atomic positions.« less
  • Carboxylic acid (HORc)-modified Ti(OR){sub 4} products were used to study the effect that similarly ligated species with substantially varied structures have on the final densification of the resultant ceramic (in this case TiO{sub 2}). The 1:1 stoichiometric products isolated from the reactions of [Ti({mu}-ONep)(ONep){sub 3}]{sub 2} (1, ONep = OCH{sub 2}CMe{sub 3}) and a variety of sterically hindered carboxylic acids [HORc: HOFc (HO{sub 2}CH), HOAc (HO{sub 2}CCH{sub 3}), HOPc (HO{sub 2}CCHMe{sub 2}), HOBc (HO{sub 2}CCMe{sub 3}), or HONc (HO{sub 2}CCH{sub 2}CMe{sub 3})] were identified by single-crystal X-ray diffraction and solid-state {sup 13}C MAS NMR spectroscopy at Ti{sub 3}({mu}{sub 3}-O)(OFc){sub 2}(ONep){submore » 8} (2), Ti{sub 3}({mu}{sub 3}-O)(OAc){sub 2}(ONep){sub 8} (3), Ti{sub 6}({mu}{sub 3}-O){sub 6}(OPc){sub 6}(ONep){sub 6} (4), Ti{sub 2}({mu}-OBc){sub 2}(ONep){sub 6} (5), and Ti{sub 3}({mu}{sub 3}-O)(ONc){sub 2}(ONep){sub 8} (6). Compounds 2, 3, and 6 adopt a triangular arrangement of Ti atoms linked by a {mu}{sub 3}-oxide moiety with ORc and ONep ligands supporting the basic framework. Compound 4 adopts a distorted, hexagon-prism geometry of two offset [Ti-O-]{sub 3} rings with each six-coordinated metal possessing a terminal ONep and two monodentate OPc ligands. The unique, nonesterified product 5 is dimeric with two {mu}-ONep, two unidentate bridging OBc, and two terminal ONep ligands. The solution behaviors of 2--6 were investigated by NMR experiments and were found to retain the solid-state structure in solution with a great deal of ligand rearrangement. Films of TiO{sub 2} were made from redissolved crystals of 2--6. The highest density TiO{sub 2} thin films were derived from the partially hydrolyzed, trinuclear, low-carbon-containing ONep complexes 2 and 3, as determined from ellipsometric data.« less
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • This paper describes the syntheses of three transition metal diphosphonate compounds: Na{sub 4}Zn{l_brace}NH{sub 3}CH(PO{sub 3}){sub 2}{r_brace}{sub 2}.4H{sub 2}O (1), Ni{l_brace}NH{sub 3}CH(PO{sub 3}H){sub 2}{r_brace}{sub 2}.xH{sub 2}O (2) and NaNi{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (3). Compound 1 contains chains of [Zn{l_brace}NH{sub 3}CH(PO{sub 3}){sub 2}{r_brace}{sub 2}]{sub n}{sup 4n-} made up of corner-sharing ZnO{sub 6} octahedra and CPO{sub 3} tetrahedra, which are further connected by tetramers of edge-sharing NaO{sub 6} octahedra, forming a three-dimensional open-framework structure. Compound 2 shows a square-grid layer structure where the NiO{sub 6} octahedra are corner shared with CPO{sub 3} tetrahedra. The adjacent layers aremore » linked by strong inter-layer hydrogen bonds, resulting in a three-dimensional open-network structure with channels where the lattice water molecules reside. The structure of compound 3 is analogous to that of NaCo{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2}.xH{sub 2}O in which layers of Ni{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2} are connected by NaO{sub 6} linkages into an open-framework structure. The magnetic studies show that weak antiferromagnetic interactions are mediated between the nickel ions in compounds 2 and 3. Crystal data for 1: triclinic, space group P-1, a=5.551(2)A, b=6.166(2)A, c=12.424(4)A, {alpha}=92.422(6){sup o}, {beta}=92.687(7){sup o}, {gamma}=93.926(6){sup o}, V=423.3(2)A{sup 3}, Z=2. For 2: triclinic, space group P-1, a=9.043(1)A, b=9.180(1)A, c=9.271(1)A, {alpha}=89.693(3){sup o}, {beta}=70.202(3){sup o}, {gamma}=89.530(3){sup o}, V=724.1(2)A{sup 3}, Z=2.« less
  • The new compounds NaBi{sub 6}O{sub 9}X (X = Br, I) were synthesized. Attempts to synthesize the analogous RbBi{sub 6}O{sub 9}X (X = Br, I) compounds yielded mixed systems with about 10% of the Rb atoms replaced by Na and K atoms. Another mixed system, Na{sub 0.77(3)}K{sub 0.23(3)}Bi{sub 6}O{sub 9}I, was obtained incidentally. The corresponding ABi{sub 6}O{sub 9}X compounds with X = Cl or A = Cs could not be obtained. The influence of A and X on the size of the ABi{sub 6}O{sub 9}X unit cell is discussed.