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

Title: Synthesis and structure of [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O

Abstract

The complex [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O is synthesized by the reaction of K{sub 2}OsBr{sub 6} with thiocarbamide in concentrated HBr and characterized using electronic absorption and IR absorption spectroscopy. Its crystal structure is determined by X-ray diffraction. The crystals are orthorhombic, a = 11.730(2) A, b = 14.052(3) A, c = 16.994(3) A, space group Cmcm, and Z = 4. The [OsBr{sub 6}]{sup 2-} anionic complex has an octahedral structure. The Os-Br distances fall in the range 2.483-2.490 A. The {alpha},{alpha}'-dithiobisformamidinium cation is a product of the oxidation of thiocarbamide. The S-S and C-S distances are 2.016 and 1.784 A, respectively. The H{sub 2}O molecules, Br{sup -}ions, and NH{sub 2} groups of the cation are linked by hydrogen bonds.

Authors:
;  [1];  [2]; ;  [1]
  1. Peoples' Friendship University of Russia (Russian Federation)
  2. Karpov Research Institute of Physical Chemistry (Russian Federation)
Publication Date:
OSTI Identifier:
22050958
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystallography Reports; Journal Volume: 53; Journal Issue: 4; Other Information: Copyright (c) 2008 Pleiades Publishing, Ltd.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ABSORPTION SPECTROSCOPY; BROMINE IONS; CATIONS; CRYSTALS; HYDROBROMIC ACID; ORTHORHOMBIC LATTICES; OSMIUM BORIDES; OSMIUM COMPLEXES; OXIDATION; POTASSIUM COMPOUNDS; SPACE GROUPS; SYNTHESIS; THIOUREAS; X-RAY DIFFRACTION

Citation Formats

Rudnitskaya, O. V., E-mail: orudnitskaya@rambler.ru, Kultyshkina, E. K., Stash, A. I., Glukhova, A. A., and Venskovskii, N. U.. Synthesis and structure of [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O. United States: N. p., 2008. Web. doi:10.1134/S1063774508040093.
Rudnitskaya, O. V., E-mail: orudnitskaya@rambler.ru, Kultyshkina, E. K., Stash, A. I., Glukhova, A. A., & Venskovskii, N. U.. Synthesis and structure of [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O. United States. doi:10.1134/S1063774508040093.
Rudnitskaya, O. V., E-mail: orudnitskaya@rambler.ru, Kultyshkina, E. K., Stash, A. I., Glukhova, A. A., and Venskovskii, N. U.. 2008. "Synthesis and structure of [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O". United States. doi:10.1134/S1063774508040093.
@article{osti_22050958,
title = {Synthesis and structure of [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O},
author = {Rudnitskaya, O. V., E-mail: orudnitskaya@rambler.ru and Kultyshkina, E. K. and Stash, A. I. and Glukhova, A. A. and Venskovskii, N. U.},
abstractNote = {The complex [(NH{sub 2}){sub 2}CSSC(NH{sub 2}){sub 2}]{sub 2}[OsBr{sub 6}]Br{sub 2} . 3H{sub 2}O is synthesized by the reaction of K{sub 2}OsBr{sub 6} with thiocarbamide in concentrated HBr and characterized using electronic absorption and IR absorption spectroscopy. Its crystal structure is determined by X-ray diffraction. The crystals are orthorhombic, a = 11.730(2) A, b = 14.052(3) A, c = 16.994(3) A, space group Cmcm, and Z = 4. The [OsBr{sub 6}]{sup 2-} anionic complex has an octahedral structure. The Os-Br distances fall in the range 2.483-2.490 A. The {alpha},{alpha}'-dithiobisformamidinium cation is a product of the oxidation of thiocarbamide. The S-S and C-S distances are 2.016 and 1.784 A, respectively. The H{sub 2}O molecules, Br{sup -}ions, and NH{sub 2} groups of the cation are linked by hydrogen bonds.},
doi = {10.1134/S1063774508040093},
journal = {Crystallography Reports},
number = 4,
volume = 53,
place = {United States},
year = 2008,
month = 7
}
  • Three new hydrated scandium selenites have been hydrothermally synthesized as single crystals and structurally and physically characterized. Sc2(SeO3)3.H2O crystallizes as a new structure type containing novel ScO7 pentagonal bipyramidal and ScO6+1 capped octahedral coordination polyhedra. Sc2(SeO3)3.3H2O contains typical ScO6 octahedra and is isostructural with its M2(SeO3)3.3H2O (M=Al, Cr, Fe, Ga) congeners. CsSc3(SeO3)4(HSeO3)2.2H2O contains near-regular ScO6 octahedra and has essentially the same structure as its indium-containing analogue. All three phases contain the expected pyramidal [SeO3]2- selenite groups. Crystal data: Sc2(SeO3)3.3H2O, Mr=524.85, trigonal, R3c (No. 161), a=9.6481(5)A, c=20.7832(12)A, V=1675.45(16)A3, Z=6, R(F)=0.018, wR(F2)=0.036; Sc2(SeO3)3.H2O, Mr=488.82, orthorhombic, P212121 (No. 19), a=6.5913(6)A, b=11.1596(11)A, c=12.1368(11)A, V=892.74(14)A3,more » Z=4, R(F)=0.051, wR(F2)=0.086; CsSc3(SeO3)4(HSeO3)2.2H2O, Mr=1067.60, orthorhombic, Pnma (No. 62), a=16.670(3)A, b=13.167(3)A, c=9.575(2)A, V=2101.6(7)A3, Z=4, R(F)=0.035, wR(F2)=0.070.« less
  • Anhydrous osmium tetrabromide was initially produced in a tube at bromine vapor pressure 6 to 10 atm. Tube temperatures were 500 to 550 deg C at the hot end and 150 to 200 deg C at the cool. Br: O/sub 3/ ratios were 3.93 to 3.96. Further experiments produced a purer product at 20 atm with 530 to 580 deg C at one end and 150 to 200 deg C at the other end of the tube. The anhydrous OsBr/sub 4/ is nonhygroscopic and insoluble in water, dilute hydrochloric acid, and concentrated HCl, HBr, HNO/sub 3/, and H/sub 2/SO/sub 4/.more » At 350 to 400 deg C OsBr/sub 4/ decomposes into tribromide and bromine. (R.V.J.)« less
  • OsBr/sub 3/ appears as a dark-gray, non-hygroscopic, water -insoluble powder with a density of d/sup 20//sub 4/ = 6.32. OsBr/sub 3/ dissociates into metal and bromide in vacuum at 340 deg C. (R.V.J.)
  • The solid-state reactions occurring during the moderation of recoiling /sup 38/Cl, produced by the (n,..gamma..) reaction, have been studied in K/sub 2/OsCl/sub 6/-K/sub 2/OsBr/sub 6/ mixed crystals. The main products are Os/sup 38/ClCl/sub 5//sup 2 -/, Os/sup 38/ClBr/sub 5//sup 2 -/, and /sup 38/Cl/sup -/, but even the more intimately mixed species Os/sup 38/ClCl/sub n/Br/sub 5-n//sup 2 -/ (n = 1, ..., 4) are obtained in significant amounts. The most important reaction found is the replacement process (billiard-ball process). In some cases the recoil atom interacts with more than one ligand and intermediate ligand vacancy (denoted by square) species Os/supmore » 38/ClCl/sub n/square/sub 5-n//sup 2 -/ and Os/sup 38/ClBr/sub n/square/sub 5-n//sup 2 -/ (n = O, ..., 4) are formed. The vacancies are assumed to be filled by mobile halides from the lattice. From the products Os/sup 38/ClCl/sub n/Br/sub 5-n//sup 2 -/ (n = O, ..., 5) and /sup 38/Cl/sup -/ and their yield dependence on the mixed crystal composition the following results were obtained with the help of the program PRIMULA: interstitials 11%, primary retention 5%, replacement 62%, replacement plus one additional vacancy 14%, replacement plus two or more additional vacancies 7%. These results together with some experiments with K/sub 2/ReCl/sub 6/-K/sub 2/ReBr/sub 6/ targets are in accordance with all other so far known /sup 36/Cl and /sup 82/Br recoil reactions in K/sub 2/M'Cl/sub 6/-K/sub 2/M''Br/sub 6/ mixed crystals. They do not confirm the reported ligand vacancy transfer mechanism (kinetic theory) elaborated for /sup 38/Cl recoil atoms.« less