Trimeric Units [Ag3X8]5– with Face‐sharing Polyhedra in the Series Tl2AgX3 (X = Cl, Br, I): Synthesis, Crystal Structure, and Vibrational Spectra

Trimeric Units [Ag3X8]5– with Face‐sharing Polyhedra in the Series Tl2AgX3 (X = Cl, Br, I):... The ternary compounds Tl2AgX3 (X = Cl, Br, I) were obtained as colorless single crystals by reaction of the binary halides AgX and TlX (X = Cl, Br, I) together with concentrated HX solutions under hydrothermal conditions. Silica glass ampoules were filled to 50 % with these solutions and heated for several days up to 250 °C. The reaction was carried out in steel autoclaves to prevent bursting. All the compounds are isostructural and crystallize trigonally with the already known Tl2AgI3 type (R3, Z = 9), but Tl2AgCl3 [a = 9.5075(6), c = 18.585(2) Å, R1 = 0.035, wR2 = 0.062] and Tl2AgBr3 [a = 9.8758(6), c = 19.1532(14) Å, R1 = 0.046, wR2 = 0.085] were characterized for the first time. The crystal structure consists of unique [Ag3X8]5– units, which are formed by a central [AgX6]5– octahedron with two face‐sharing [AgX4]4– tetrahedra in trans position. The Ag+···Ag+ distance is nearly independent from the anion size and amounts to 3.13–3.16 Å. The distance results just from repulsive interactions. Vibrational spectra were recorded for the complete series. DTA measurements confirm the peritectic formation of both compounds with X = Cl and Br. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Zaac-Journal of Inorganic and General Chemistry Wiley

Trimeric Units [Ag3X8]5– with Face‐sharing Polyhedra in the Series Tl2AgX3 (X = Cl, Br, I): Synthesis, Crystal Structure, and Vibrational Spectra

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0044-2313
eISSN
1521-3749
D.O.I.
10.1002/zaac.201700358
Publisher site
See Article on Publisher Site

Abstract

The ternary compounds Tl2AgX3 (X = Cl, Br, I) were obtained as colorless single crystals by reaction of the binary halides AgX and TlX (X = Cl, Br, I) together with concentrated HX solutions under hydrothermal conditions. Silica glass ampoules were filled to 50 % with these solutions and heated for several days up to 250 °C. The reaction was carried out in steel autoclaves to prevent bursting. All the compounds are isostructural and crystallize trigonally with the already known Tl2AgI3 type (R3, Z = 9), but Tl2AgCl3 [a = 9.5075(6), c = 18.585(2) Å, R1 = 0.035, wR2 = 0.062] and Tl2AgBr3 [a = 9.8758(6), c = 19.1532(14) Å, R1 = 0.046, wR2 = 0.085] were characterized for the first time. The crystal structure consists of unique [Ag3X8]5– units, which are formed by a central [AgX6]5– octahedron with two face‐sharing [AgX4]4– tetrahedra in trans position. The Ag+···Ag+ distance is nearly independent from the anion size and amounts to 3.13–3.16 Å. The distance results just from repulsive interactions. Vibrational spectra were recorded for the complete series. DTA measurements confirm the peritectic formation of both compounds with X = Cl and Br.

Journal

Zaac-Journal of Inorganic and General ChemistryWiley

Published: Jan 15, 2018

Keywords: ; ; ; ;

References

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