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Title: Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]

Abstract

The compounds Ba[H{sub 4}TeO{sub 6}] (I), Ba[H{sub 2}TeO{sub 5}] (II), Ba[Te{sub 2}O{sub 6}(OH){sub 2}] (III) and Ba[TeO{sub 4}] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO{sub 4} and LaSbO{sub 4}. Common feature of the four oxotellurate(VI) structures are [TeO{sub 6}] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains via corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H{sub 4}TeO{sub 6}] → Ba[H{sub 2}TeO{sub 5}] → Ba[TeO{sub 4}]→ Ba[TeO{sub 3}] upon heating to temperatures up to 900 °C. - Graphical abstract:more » The crystal structures of the four oxotellurates(VI) were determined from single crystal data. The thermal decomposition of Ba[H{sub 4}TeO{sub 6}], monitored by temperature-dependent X-ray powder diffraction and simultaneous thermal analysis measurements, involves two condensation reactions according to Ba[H{sub 4}TeO{sub 6}]→Ba[H{sub 2}TeO{sub 5}]+H{sub 2}O(↑)→Ba[TeO{sub 4}]+ H{sub 2}O(↑). Display Omitted.« less

Authors:
 [1];  [1];  [2];  [3]
  1. Institute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna (Austria)
  2. Institute for Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna (Austria)
  3. Institut für Mineralogie und Kristallographie, Fakultät für Geowissenschaften, Geographie und Astronomie, Universität Wien, Althanstr. 14 (UZA 2), A-1090 Vienna (Austria)
Publication Date:
OSTI Identifier:
22584209
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 241; Other Information: Copyright (c) 2016 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; BARIUM; CATIONS; CRYSTAL GROWTH; CRYSTAL STRUCTURE; DIFFUSION; HEATING; HYDROGEN; MONITORS; MONOCRYSTALS; POWDERS; PYROLYSIS; SOLIDS; TEMPERATURE DEPENDENCE; THERMAL ANALYSIS; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at, Stöger, Berthold, Gierl-Mayer, Christian, and Libowitzky, Eugen. Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.06.010.
Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at, Stöger, Berthold, Gierl-Mayer, Christian, & Libowitzky, Eugen. Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]. United States. doi:10.1016/J.JSSC.2016.06.010.
Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at, Stöger, Berthold, Gierl-Mayer, Christian, and Libowitzky, Eugen. Thu . "Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]". United States. doi:10.1016/J.JSSC.2016.06.010.
@article{osti_22584209,
title = {Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]},
author = {Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at and Stöger, Berthold and Gierl-Mayer, Christian and Libowitzky, Eugen},
abstractNote = {The compounds Ba[H{sub 4}TeO{sub 6}] (I), Ba[H{sub 2}TeO{sub 5}] (II), Ba[Te{sub 2}O{sub 6}(OH){sub 2}] (III) and Ba[TeO{sub 4}] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO{sub 4} and LaSbO{sub 4}. Common feature of the four oxotellurate(VI) structures are [TeO{sub 6}] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains via corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H{sub 4}TeO{sub 6}] → Ba[H{sub 2}TeO{sub 5}] → Ba[TeO{sub 4}]→ Ba[TeO{sub 3}] upon heating to temperatures up to 900 °C. - Graphical abstract: The crystal structures of the four oxotellurates(VI) were determined from single crystal data. The thermal decomposition of Ba[H{sub 4}TeO{sub 6}], monitored by temperature-dependent X-ray powder diffraction and simultaneous thermal analysis measurements, involves two condensation reactions according to Ba[H{sub 4}TeO{sub 6}]→Ba[H{sub 2}TeO{sub 5}]+H{sub 2}O(↑)→Ba[TeO{sub 4}]+ H{sub 2}O(↑). Display Omitted.},
doi = {10.1016/J.JSSC.2016.06.010},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 241,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
  • Crystals of three new ternary pnictides—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} have been prepared by reactions of the respective elements in molten Al or Pb fluxes. Single-crystal X-ray diffraction studies reveal that the three phases are isotypic, crystallizing in the orthorhombic Ba{sub 7}Ga{sub 4}Sb{sub 9}-type structure (space group Pmmn, Pearson symbol oP40, Z=2), for which only the prototype is known. The structure is based on TrPn{sub 4} tetrahedra (Tr=Al, Ga; Pn=P, As, Sb), connected in an intricate scheme into 1D-ribbons. Long interchain Pn–Pn bonds (d{sub P–P}>3.0 Å; d{sub As–As}>3.1 Å; d{sub Sb–Sb}>3.3 Å)more » account for the realization of 2D-layers, separated by Ba{sup 2+} cations. Applying the classic valance rules to rationalize the bonding apparently fails, and Ba{sub 7}Ga{sub 4}Sb{sub 9} has long been known as a metallic Zintl phase. Earlier theoretical calculations, both empirical and ab-initio, suggest that the possible metallic properties originate from filled anti-bonding Pn–Pn states, and the special roles of the “cations” in this crystal structure. To experimentally probe this hypothesis, we sought to synthesize the ordered quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga). Single-crystal X-ray diffraction work confirms Ba{sub 6.145(3)}Ca{sub 0.855}Al{sub 4}Sb{sub 9} and Ba{sub 6.235(3)}Ca{sub 0.765}Ga{sub 4}Sb{sub 9}, with Ca atoms preferably substituting Ba on one of the three available sites. The nuances of the five crystal structures are discussed, and the chemical bonding in Ba{sub 7}Ga{sub 4}As{sub 9} is interrogated by tight-binding linear muffin-tin orbital calculations. - Graphical abstract: The new Zintl phases—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9}, and their quaternary variants Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga)—crystallize in the Ba{sub 7}Ga{sub 4}Sb{sub 9} structure type. The structures are based on TrPn{sub 4} tetrahedra (a perspective of the crystal structure is shown, as viewed along the c axis). - Highlights: • Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} are new compounds in the respective phase diagrams. • The quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga) show nearly ordered Ba/Ca distribution. • Very weak Pn–Pn bonds and pairing distortion are observed for Ba{sub 7}Ga{sub 4}Pn{sub 9} (Pn=P, As).« less
  • Reaction of oxo-bis(tetrachlorocatecholate) Tc(V) complex ((n-C{sub 4}H{sub 9}){sub 4}N)(TcO(C{sub 6}Cl{sub 4}O{sub 2}){sub 2}) (1) with n, N-diphenylhydrazine in Ch{sub 2}Cl{sub 2} yields the binuclear paramagnetic Tc(V)/Tc(VI) mixed-valence complex ((n-C{sub 4}H{sub 9}){sub 4}N)(Tc{sub 2}(NNPh{sub 2}){sub 2}(C{sub 6}Cl{sub 4}O{sub 2}){sub 4}){times}CH{sub 2}Cl{sub 2}{times}2CH{sub 3}OH (2). The structure of the molecular anion of 2 consists of two distorted octahedral Tc centers bridged by two hydrazido (2{minus}) groups bonding s in the {eta}{sup 1} mode, an unusual bonding motif for this ligand, having previously described only for cyclopentadienyl-metal species. Complex 2 is also a unique example of a Tc(V)/Tc(VI) mixed-valence species; the Tc-Tc distancemore » of 2.612 (2) {angstrom} is consistent with direct metal-metal interaction. Crystal data for 1 and 2. 46 refs., 2 figs., 5 tabs.« less
  • In the system BaF{sub 2}/BF{sub 3}/PF{sub 5}/anhydrous hydrogen fluoride (aHF) a compound Ba(BF{sub 4})(PF{sub 6}) was isolated and characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF{sub 4})(PF{sub 6}) crystallizes in a hexagonal P6-bar2m space group with a=10.2251(4) A, c=6.1535(4) A, V=557.17(5) A{sup 3} at 200 K, and Z=3. Both crystallographically independent Ba atoms possess coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF{sub 4}{sup -} and PF{sub 6}{sup -} anions. In the analogous system with AsF{sub 5} instead of PF{sub 5} the compound Ba(BF{sub 4})(AsF{sub 6}) was isolated and characterized.more » It crystallizes in an orthorhombic Pnma space group with a=10.415(2) A, b=6.325(3) A, c=11.8297(17) A, V=779.3(4) A{sup 3} at 200 K, and Z=4. The coordination around Ba atom is in the shape of slightly distorted tri-capped trigonal prism which includes five F atoms from AsF{sub 6}{sup -} and four F atoms from BF{sub 4}{sup -} anions. When the system BaF{sub 2}/BF{sub 3}/AsF{sub 5}/aHF is made basic with an extra addition of BaF{sub 2}, the compound Ba{sub 2}(BF{sub 4}){sub 2}(AsF{sub 6})(H{sub 3}F{sub 4}) was obtained. It crystallizes in a hexagonal P6{sub 3}/mmc space group with a=6.8709(9) A, c=17.327(8) A, V=708.4(4) A{sup 3} at 200 K, and Z=2. The barium environment in the shape of tetra-capped distorted trigonal prism involves 10 F atoms from four BF{sub 4}{sup -}, three AsF{sub 6}{sup -} and three H{sub 3}F{sub 4}{sup -} anions. All F atoms, except the central atom in H{sub 3}F{sub 4} moiety, act as mu{sub 2}-bridges yielding a complex 3-D structural network. - Graphical abstract: The first three compounds, containing simultaneously tetrahedral BF{sub 4}{sup -} and octahedral AF{sub 6}{sup -} (A=P, As) anions have been synthesized and characterized by Raman spectroscopy and X-ray single crystal diffraction. In the system BaF{sub 2}/BF{sub 3}/PF{sub 5}/anhydrous hydrogen fluoride (aHF) the compound Ba(BF{sub 4})(PF{sub 6}) was isolated. In the analogous system with AsF{sub 5} instead of PF{sub 5} the compound Ba(BF{sub 4})(AsF{sub 6}) was obtained. When the system BaF{sub 2}/BF{sub 3}/AsF{sub 5}/aHF is made basic with an extra addition of BaF{sub 2}, the compound Ba{sub 2}(BF{sub 4}){sub 2}(AsF{sub 6})(H{sub 3}F{sub 4}) was prepared.« less
  • The hydrothermal syntheses, X-ray single-crystal structures, and some properties of Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} and Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O are described. Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} contains a three-dimensional network of VO{sub 6} and (H)SeO{sub 3} polyhedra, linked via V-O-Se bonds. The Ba cation is 10-coordinate, the VO{sub 6} group contains a short vanadyl V{double_bond}O bond typical of V{sup IV}, and the (H)SeO{sub 3} groups are pyramidal. Magnetic susceptibility data are consistent with V{sup IV} and show paramagnetic behavior from 4 to 300 K. Crystal data for Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2}:M{submore » r} = 781.06, monoclinic, space group P2{sub 1}/c (No. 14), a = 9.680(3) {angstrom}, b = 7.024(2) {angstrom}, c = 9.882(4) {angstrom}, {beta} = 116.42(3){degrees}, V = 601.75 {angstrom}{sup 3}, Z = 2, R = 3.89%, R{sub w} = 3.64% [1637 observed reflections with I > 3{sigma}(I)]. Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O contains a complex network of VO{sub 6} and PO{sub 4}/HPO{sub 4} groups, which form two different types of one-dimensional chains: one chain contains fairly regular V{sup IV}O{sub 6} and (H)PO{sub 4} groups; the other is built up from distorted V{sup IV}O{sub 6} octahedra and (hydrogen) phosphate groups. 10- and 13-coordinate Ba{sup 2+} cations complete the structure, which shows antiferromagnetic ordering of the V{sup IV} centers at {approximately}20 K. Crystal data for Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O: M{sub r} = 2800.05, monoclinic, space group C2/m (No. 12), a = 31.685(11) {angstrom}, b = 5.208(2) {angstrom}, c = 7.784(3) {angstrom}, {beta} = 90.59(3){degrees}, V = 1284.5(7) {angstrom}{sup 3}, Z = 1, R = 4.03%, and R{sub w} = 5.28% [1892 observed reflections with I > 3{sigma}(I)].« less