skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ab initio structure determination of novel borate NaSrBO{sub 3}

Abstract

A novel orthoborate, NaSrBO{sub 3}, has been successfully synthesized by standard solid-state reaction, and the crystal structure has been determined from powder X-ray diffraction data. It crystallizes in the monoclinic space group P2{sub 1}/c with lattice parameters: a=5.32446(7)A, b=9.2684(1)A, c=6.06683(8)A, {beta}=100.589(1){sup o}. The fundamental building units are isolated BO{sub 3} groups, which are parallelly distributed along two different directions. Because of the anisotropic polarizations of planar BO{sub 3} groups, a considerable birefringence can be expected in it. The Na atoms are six-coordinated with O atoms to form octahedra, and the Sr atoms are nine-coordinated, forming tri-capped trigonal prisms. Those polyhedra connect with each other by bridging-oxygen atoms, forming infinite three-dimensional network, which indicates that the cleaving problem is expected to be overcome during the course of single-crystal growth. The infrared spectrum has been measured, and the result is consistent with the crystallographic study. Moreover, a comparison of the new structure type with the other known orthoborates is presented here.

Authors:
 [1];  [2];  [3];  [4];  [4];  [3]
  1. Key Laboratory of Advanced Technique and Fabrication for Weak-Light Nonlinear Photonics Materials, Ministry of Education, Nankai University, Tianjin 300457 (China) and Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China). E-mail: lwu@nankai.edu.cn
  2. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China). E-mail: xlchen@aphy.iphy.ac.cn
  3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China)
  4. Key Laboratory of Advanced Technique and Fabrication for Weak-Light Nonlinear Photonics Materials, Ministry of Education, Nankai University, Tianjin 300457 (China)
Publication Date:
OSTI Identifier:
20784977
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2006.01.003; PII: S0022-4596(06)00005-3; 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; BIREFRINGENCE; BORATES; CRYSTALLOGRAPHY; INFRARED SPECTRA; LATTICE PARAMETERS; MONOCLINIC LATTICES; MONOCRYSTALS; SODIUM COMPOUNDS; SPACE GROUPS; STRONTIUM COMPOUNDS; X-RAY DIFFRACTION

Citation Formats

Wu, L., Chen, X.L., Zhang, Y., Kong, Y.F., Xu, J.J., and Xu, Y.P.. Ab initio structure determination of novel borate NaSrBO{sub 3}. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2006.01.003.
Wu, L., Chen, X.L., Zhang, Y., Kong, Y.F., Xu, J.J., & Xu, Y.P.. Ab initio structure determination of novel borate NaSrBO{sub 3}. United States. doi:10.1016/j.jssc.2006.01.003.
Wu, L., Chen, X.L., Zhang, Y., Kong, Y.F., Xu, J.J., and Xu, Y.P.. Sat . "Ab initio structure determination of novel borate NaSrBO{sub 3}". United States. doi:10.1016/j.jssc.2006.01.003.
@article{osti_20784977,
title = {Ab initio structure determination of novel borate NaSrBO{sub 3}},
author = {Wu, L. and Chen, X.L. and Zhang, Y. and Kong, Y.F. and Xu, J.J. and Xu, Y.P.},
abstractNote = {A novel orthoborate, NaSrBO{sub 3}, has been successfully synthesized by standard solid-state reaction, and the crystal structure has been determined from powder X-ray diffraction data. It crystallizes in the monoclinic space group P2{sub 1}/c with lattice parameters: a=5.32446(7)A, b=9.2684(1)A, c=6.06683(8)A, {beta}=100.589(1){sup o}. The fundamental building units are isolated BO{sub 3} groups, which are parallelly distributed along two different directions. Because of the anisotropic polarizations of planar BO{sub 3} groups, a considerable birefringence can be expected in it. The Na atoms are six-coordinated with O atoms to form octahedra, and the Sr atoms are nine-coordinated, forming tri-capped trigonal prisms. Those polyhedra connect with each other by bridging-oxygen atoms, forming infinite three-dimensional network, which indicates that the cleaving problem is expected to be overcome during the course of single-crystal growth. The infrared spectrum has been measured, and the result is consistent with the crystallographic study. Moreover, a comparison of the new structure type with the other known orthoborates is presented here.},
doi = {10.1016/j.jssc.2006.01.003},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 179,
place = {United States},
year = {Sat Apr 15 00:00:00 EDT 2006},
month = {Sat Apr 15 00:00:00 EDT 2006}
}
  • A new mixed valence molybdate, La{sub 7}Mo{sub 7}O{sub 30}, first prepared by high energy ball milling, has been successfully synthesized by controlled hydrogen reduction of La{sub 2}Mo{sub 2}O{sub 9}. Its original crystal structure was determined from X-ray and neutron powder diffraction (space group R{sub 3}; a = b = 17.0051(2) {angstrom}, c = 6.8607(1) {angstrom}; Z = 3; reliability factors: R{sub p} = 0.081, R{sub wp} = 0.091, {chi}{sup 2} = 3.1, R{sub Bragg} = 0.049, R{sub F} = 0.033). It consists in the hexagonal stacking of individual cylinders of perovskite-type arrangement. These cylinders are built up from perovskite cagesmore » sharing corners in trans-position along their diagonal axis. Two different mixed-valence molybdenum sites coexist, with more (Mo{sup +5.75}) or less (Mo{sup +4.5}) distorted octahedral environments. Lanthanum atoms are located within the perovskite cages and around them, very close to their regular positions in the perovskite structure. Lanthanum and molybdenum atoms thus form two rows of almost perfect cubes, shifted from each other by c/2. An electron microscopy study revealed the defect-free cationic and octahedral arrangements in the (a,b) plane.« less
  • Bi{sub 2}O{sub 3}-MoO{sub 3} system shows a large panoply of phases depending on Bi/Mo ratio, among them, the low temperature phases of the homologous series Bi{sub 2(n+2)}Mo{sub n}O{sub 6(n+1)} with n=3, 4, 5 and 6. They exhibit, alike most of the phases of this system, strong fluorite sub-network. Nevertheless, a multitechnique approach has been followed in order to solve the crystal structure of the n=3 member, i.e. Bi{sub 10}Mo{sub 3}O{sub 24}. From ab initio indexing X-ray powder pattern cell parameters were derived. It belongs to the monoclinic system, space group C2, with cell parameters: a=23.7282(2) A, b=5.64906(6) A, c=8.68173(9) A,more » beta=95.8668(7){sup o} with Z=2. The matrix relating this cell with the fluorite one is 4 0 1/0 1 0/-1/2 0 3/2 and a cationic localization was derived. HRTEM allowed the cationic Bi and Mo order to be modified and specified, as well as to build up a full structural ab initio model on the basis of crystal chemistry considerations. Simultaneous Rietveld refinement of multipattern X-ray and neutron powder diffraction data taking advantage of the neutron scattering length for O location have been performed. The goodness of the model was ascertained by low reliability factors, weighted R{sub b}=4.97% and R{sub f}=3.21%. This complex Bi{sub 10}Mo{sub 3}O{sub 24} structure, with 5Bi, 2Mo and 13O in different crystallographic positions of the asymmetric unit, shows good agreement between observed and calculated patterns within the data resolution. Moreover, the determination of this structure sets the basis for the crystallographic characterization of the complete family Bi{sub 2(n+2)}Mo{sub n}O{sub 6(n+1)}, whose guidelines are also evidenced in this paper. - Graphical abstract: This work reports on the ab initio determination of Bi{sub 10}Mo{sub 3}O{sub 24} structure, as well as its refinement by using the Rietveld method, from the combination of X-ray and neutron diffraction powder data. It belongs to the monoclinic system, space group C2, with cell parameters: a=23.7282(2) A, b=5.64906(6) A, c=8.68173(9) A, beta=95.8668(7){sup o} with Z=2.« less
  • The crystal structures of Ln{sub 3}(BO{sub 3}){sub 2}F{sub 3} (Ln = Sm, Eu, and Gd) are determined ab initio from X-ray powder data. The unit cell is monoclinic, space group C2/c, Z = 4, with a = 12.534(1) {angstrom}, b = 6.237(1) {angstrom}, c = 8.360(1) {angstrom}, {beta} = 97.404(6){degree}, V = 648.1(2) {angstrom}{sup 3} for Gd{sub 3}(BO{sub 3}){sub 2}F{sub 3}. The Rietveld refinement reliability converged to R{sub p} = 0.121, R{sub wp} = 0.147, R{sub exp} = 0.050, {chi}{sup 2} = 8.75. The structure presents a 3D network of Archimedian monocapped antiprisms Gd(1)O{sub 4}F{sub 5} and Gd(2)O{sub 7}F{sub 2}.more » These polyhedra form trimeric entities Gd{sub 3}O{sub 12}F{sub 9}, which build infinite layers parallel to the (010) plane.« less
  • The fluoride (H{sub 3}O)Yb{sub 3}F{sub 10}, H{sub 2}O (SG:Fd3m, a=15.326(1) {angstrom}, Z=16) was synthesized in the form of powder by a {open_quotes}chimie douce{close_quotes} route. The compound {delta}-KYb{sub 3}F{sub 10}, H{sub 2}O (SG: Fd3m, a = 15.339(1) {angstrom}, Z=16), a new member of the KYb{sub 3}F{sub 10} family, was obtained by an acid-base neutralization. The structural description is based upon the stacking of [Yb{sub 6}F{sub 32}]{sup 14-}{open_quotes}octahedral units of antiprism,{close_quotes} called UOA{sub [8]}, where the three-dimensional [Yb{sub 6}F{sub 20}]{sup 2-} network is simply a diamond type stacking of UOA{sub [8]} connected by vertices. The counterions are located in the middle ofmore » the chair hexagons. The zeolithic character of the water molecules is related to their mobility through the tunnels of this diamond structure. The simplifying description of this phase as a diamond type structure built up from UOA{sub [8]} (A{sub 2}[Yb{sub 6}F{sub 20}], 2H{sub 2}O, A=H{sub 3}O{sup +}, Z=8) is the basis of the reexamination of the structural description of numerous complex structures built up of antiprisms.« less
  • A novel non-centrosymmetric borate, BiCd{sub 3}(AlO){sub 3}(BO{sub 3}){sub 4}, has been prepared by solid state reaction methods below 750 {sup o}C. Single-crystal XRD analysis showed that it crystallizes in the hexagonal group P6{sub 3} with a=10.3919(15) A, c=5.7215(11) A, Z=2. In its structure, AlO{sub 6} octahedra share edges to form 1D {sup 1}{sub {infinity}}[AlO{sub 4}]{sup 5-} chains that are bridged by BO{sub 3} groups through sharing O atoms to form the 3D {sup 3}{sub {infinity}}[AlBO{sub 4}]{sup 2-} framework. The 3D framework affords two kinds of channels that are occupied by Bi{sup 3+}/Cd{sup 2+} atoms only or by Bi{sup 3+}/Cd{sup 2+}more » atoms together with BO{sub 3} groups. The IR spectrum further confirmed the presence of BO{sub 3} groups. Second-harmonic-generation measurements displayed a response of about 0.5xKDP (KH{sub 2}PO{sub 4}). UV-vis diffuse reflectance spectrum showed a band gap of about 3.19 eV. Solid-state fluorescence spectrum exhibited the maximum emission peak at around 390.6 nm. Band structure calculations indicated that it is an indirect semiconductor. -- Graphical abstract: BiCd{sub 3}(AlO){sub 3}(BO{sub 3}){sub 4} has a 3D network formed by stitching 1D chains of edge-sharing AlO{sub 6} octahedra via BO{sub 3} groups. There are channels occupied by Bi{sup 3+}/Cd{sup 2+} only or by Bi{sup 3+}/Cd{sup 2+} with BO{sub 3} groups. Display Omitted« less