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Title: Crystal structure and properties of [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O

Abstract

The structure of a single crystal of tetraammindioxoosmium(VI) sulfate [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O, which is synthesized by the reaction of K{sub 2}[OsO{sub 2}(OH){sub 4}] with (NH{sub 4}){sub 2}SO{sub 4} in an aqueous solution, is investigated using X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system, space group P2{sub 1}/c, a = 13.102(2) A, b = 6.158(3) A, c = 11.866(2) A, {beta} = 98.13(2) deg., and Z = 4. The [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O compound has an island structure. Two crystallographically independent osmium atoms are situated at the centers of symmetry, and their octahedral coordination includes two oxygen atoms and four nitrogen atoms of the ammonia molecules. In both octahedra, the osmyl group is linear. The Os-O distances in the octahedra are identical within the standard deviations [Os(1)-O, 1.762(2) A; Os(2)-O, 1.769(2) A]. The Os-N bond lengths vary from 2.082(3) to 2.101(3) A. The cationic complexes, SO{sub 4} groups, and water molecules are linked via the system of hydrogen bonds. The assignment of the absorption bands in the IR spectrum of the compound synthesized is performed, and its thermal behavior in air is studied.

Authors:
; ;  [1];  [2]
  1. Peoples' Friendship University of Russia (Russian Federation)
  2. Moscow State University, Faculty of Chemistry (Russian Federation)
Publication Date:
OSTI Identifier:
21090952
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystallography Reports; Journal Volume: 52; Journal Issue: 2; Other Information: DOI: 10.1134/S1063774507020095; Copyright (c) 2007 Nauka/Interperiodica; Article Copyright (c) 2007 Pleiades Publishing, Inc; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; AMMONIA; AMMONIUM SULFATES; AQUEOUS SOLUTIONS; INFRARED SPECTRA; MONOCLINIC LATTICES; MONOCRYSTALS; OSMIUM COMPLEXES; OSMIUM COMPOUNDS; POTASSIUM COMPOUNDS; SPACE GROUPS; X-RAY DIFFRACTION

Citation Formats

Burvikova, J. N., E-mail: jburvic@rambler.ru, Lin'ko, I. V., Venskovskiy, N. U., and Rybakov, V. B. Crystal structure and properties of [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O. United States: N. p., 2007. Web. doi:10.1134/S1063774507020095.
Burvikova, J. N., E-mail: jburvic@rambler.ru, Lin'ko, I. V., Venskovskiy, N. U., & Rybakov, V. B. Crystal structure and properties of [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O. United States. doi:10.1134/S1063774507020095.
Burvikova, J. N., E-mail: jburvic@rambler.ru, Lin'ko, I. V., Venskovskiy, N. U., and Rybakov, V. B. Thu . "Crystal structure and properties of [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O". United States. doi:10.1134/S1063774507020095.
@article{osti_21090952,
title = {Crystal structure and properties of [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O},
author = {Burvikova, J. N., E-mail: jburvic@rambler.ru and Lin'ko, I. V. and Venskovskiy, N. U. and Rybakov, V. B.},
abstractNote = {The structure of a single crystal of tetraammindioxoosmium(VI) sulfate [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O, which is synthesized by the reaction of K{sub 2}[OsO{sub 2}(OH){sub 4}] with (NH{sub 4}){sub 2}SO{sub 4} in an aqueous solution, is investigated using X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system, space group P2{sub 1}/c, a = 13.102(2) A, b = 6.158(3) A, c = 11.866(2) A, {beta} = 98.13(2) deg., and Z = 4. The [OsO{sub 2}(NH{sub 3}){sub 4}]SO{sub 4} . H{sub 2}O compound has an island structure. Two crystallographically independent osmium atoms are situated at the centers of symmetry, and their octahedral coordination includes two oxygen atoms and four nitrogen atoms of the ammonia molecules. In both octahedra, the osmyl group is linear. The Os-O distances in the octahedra are identical within the standard deviations [Os(1)-O, 1.762(2) A; Os(2)-O, 1.769(2) A]. The Os-N bond lengths vary from 2.082(3) to 2.101(3) A. The cationic complexes, SO{sub 4} groups, and water molecules are linked via the system of hydrogen bonds. The assignment of the absorption bands in the IR spectrum of the compound synthesized is performed, and its thermal behavior in air is studied.},
doi = {10.1134/S1063774507020095},
journal = {Crystallography Reports},
number = 2,
volume = 52,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • Cobalt ethylenediammonium bis(sulfate) tetrahydrate, [NH{sub 3}(CH{sub 2}){sub 2}NH{sub 3}][Co(SO{sub 4}){sub 2}(H{sub 2}O){sub 4}], has been synthesised by slow evaporation at room temperature. It crystallises in the triclinic system, space group P1-bar, with the unit cell parameters: a = 6.8033(2), b 7.0705(2), c = 7.2192(3) A, {alpha} = 74.909(2){sup o}, {beta} = 72.291(2){sup o}, {gamma} = 79.167(2){sup o}, Z = 1 and V = 317.16(2) A{sup 3}. The Co(II) atom is octahedrally coordinated by four water molecules and two sulfate tetrahedra leading to trimeric units [Co(SO{sub 4}){sub 2}(H{sub 2}O){sub 4}]. These units are linked to each other and to the ethylenediammoniummore » cations through OW-H...O and N-H...O hydrogen bonds, respectively. The zero-dimensional structure is described as an alternation between cationic and anionic layers along the crystallographic b-axis. The dehydration of the precursor proceeds through three stages leading to crystalline intermediary hydrate phases and an anhydrous compound. The magnetic measurements show that the title compound is predominantly paramagnetic with weak antiferromagnetic interactions.« less
  • The first microporous solids incorporating two octahedrally coordinated transition elements, the phosphates (TMA)[sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HOP[sub 4])[sub 2]][center dot]11H[sub 2]O (1) and (TMA)[sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]16H[sub 2]O (2) (TMA = (CH[sub 3])[sub 4]N[sup +]), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and water absorption isotherms. Phosphate 1 is prepared in 94% yield from Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (NH[sub 4])[sub 2]HPO[sub 4], (TMA)OH, H[sub 3]PO[sub 4], and H[sub 2]O in a mole ratio of 5:1:1:2:7:16:150 at 200[degrees]C for 64 h, while 2 is synthesizedmore » in 62% yield by the reaction of Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (TMA)OH, H[sub 3]PO[sub 4] and H[sub 2]O in a mole ratio of 5:1:1:8:18:250 at 200[degrees]C for 3 days. Orange crystals of 1 are rhombohedral. Both structures are based on Fe[Mo[sub 6]O[sub 15](H[sub x]PO[sub 4])[sub 2]] units which are connected via their phosphate groups to additional Fe[sup 3+] ions to give three-dimensional frameworks. Both compounds display structures that can be rationalized on the basis of regions of hydrophobic and hydrophilic interactions. The interconnected voids and channels in the ferric molybdenum phosphate frameworks are filled with a mixture of charged-compensating cations and water of solvation. Reversible water absorption isotherms indicate that both compounds are microporous with internal void volumes of about 15 and 25 vol % for 1 and 2, respectively. 23 refs., 10 figs., 3 tabs.« less
  • Single crystals of (NH{sub 3}(CH{sub 2}){sub 3}NH{sub 3})(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5} (1), C(NH{sub 2}){sub 3}(UO{sub 2})(OH)(MoO{sub 4}) (2), (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2} (3) and (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O (4) have been synthesized hydrothermally by using UO{sub 2}(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O, (NH{sub 4}){sub 2}Mo{sub 2}O{sub 7}, HF{sub (aq)}, H{sub 2}O, and the respective organic template. The materials have layered structures with anionic uranium molybdate sheets separated by cationic organic templates. Compound 1 has an unprecedented uranium molybdate topology, whereas 2 is structurally related to johannite, Cu[(UO{sub 2}){sub 2}(SO{sub 4}){sub 2}(OH){sub 2}](H{submore » 2}O){sub 8}, and 3 and f4 have layer topologies similar to zippiete, K{sub 2}[UO{sub 2}(MoO{sub 4}){sub 2}]. Thermogravimetric measurements indicate all that four materials, after template loss, form a crystalline mixture of UO{sub 2}MoO{sub 4} and MoO{sub 3}. Crystal data: (NH{sub 3}(CH{sub 2}){sub 3}(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5}, orthorhombic, space group Pbnm (No. 62), with a = 10.465(1) {angstrom}, b = 16.395(1) {angstrom}, c = 20.241(1) {angstrom}, and Z = 4; C(NH{sub 2}){sub 3}(UO{sub 2})(OH)MoO{sub 4}), monoclinic, space group P2{sub 1}/c (No. 14), with a = 15.411(1) {angstrom}, b = 7.086(1) {angstrom}, c = 18.108(1) {angstrom}, {beta} = 113.125(2){degree}, and Z = 4; (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}, triclinic, space group P{bar 1} (No. 2), with a = 7.096(1) {angstrom}, b = 8.388(1) {angstrom}, c = 11.634(1) {angstrom}, {alpha} = 97.008(3){degree}, {beta} = 96.454(2){degree}, {gamma} = 110.456(3){degree}, and Z = 2; (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O, orthorhombic, space group Pbca (No. 61), with a = 12.697(1) {angstrom}, b = 13.247(1) {angstrom}, c = 17.793(1) {angstrom}, and Z = 8.« less
  • Using tris(2-ethylamino)amine (tren) as a template, three new fluorides are obtained by solvothermal synthesis: [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}NH].[Zr{sub 3}F{sub 16}(H{sub 2}O)] (I), [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}N]{sub 2}.[ZrF{sub 6}].[Zr{sub 2}F{sub 12}] (II) and [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}N].[TaF{sub 7}].F (III). The structure determinations are performed by single crystal technique. The structure of I consists of infinite spiral-like [Zr{sub 3}F{sub 16}(H{sub 2}O)]{sup 4-} chains connected by tetraprotonated [trenH{sub 4}]{sup 4+} cations which possess a plane configuration. In II, isolated [ZrF{sub 6}] octahedra or [Zr{sub 2}F{sub 12}] dimers are linked to organic cations by a tridimensional hydrogen bond network. In III,more » [TaF{sub 7}]{sup 2-} monocapped trigonal prisms and 'isolated' fluoride ions are connected by hydrogen bonds to template moieties. In II and III, every organic moiety is triprotonated [trenH{sub 3}]{sup 3+} with a 'spider' configuration. In the tantalum phase, the hydrogen bond network leads to the formation of a layered structure.« less
  • The bifunctional (sulfonylmethyl)phosphonates (i-C{sub 3}H{sub 7}O){sub 2}P(O)CH{sub 2}S(I){sub 2}C{sub 6}H{sub 11}, (i-C{sub 3}H{sub 7}O){sub 2}P(O)CH{sub 2}S(O){sub 2}(p-CH{sub 3}C{sub 6}H{sub 4}), and (C{sub 6}H{sub 5}){sub 2}P(O)CH{sub 2}S(O){sub 2}N(CH{sub 3}){sub 2} and (sulfinylmethyl)phosphonate (i-C{sub 3}H{sub 7}O){sub 2}P(O)CH{sub 2}S(O)(p-CH{sub 3}C{sub 6}H{sub 4}) have been synthesized. The ligands have been characterized by spectroscopic methods, and selected coordination chemistry with UO{sub 2}(NO{sub 3}){sub 2}, La(NO{sub 3}){sub 3}, and Gd(NO{sub 3}){sub 3} has been evaluated. The structures of two complexes, UO{sub 2}(NO{sub 3}){sub 2}((i-C{sub 3}H{sub 7}O){sub 2}P(O)CH{sub 2}S(O){sub 2}C{sub 6}H{sub 11}){sub 2} (2) and Gd(NO{sub 3}){sub 3}((i-C{sub 3}H{sub 7}O){sub 2}P(O)CH{sub 2}S(O)(p-CH{sub 3}C{sub 6}H{sub 4})){center dot}H{sub 2}Omore » (8), have been determined by single-crystal x-ray diffraction techniques at 23{degree}C, and the crystal parameters are reported. The molecular structures of the two complexes are also reported. 25 refs., 2 figs., 4 tabs.« less