Cs3AgAs4Se8 and CsAgAs2Se4: Selenoarsenates with infinite 1(∞)[AsSe2]- chains in different Ag+ coordination environments

M. Wachhold, M. G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

30 Scopus citations


Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 °C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 °C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1(∞)[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1(∞)[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2(∞)[AgAs4Se8]3- layer with a thickness of about 11.3 Å, The nonbonding Ag···Ag distances are about 4.220 Å, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2(∞)[AgAs2Se4]- {=[Ag2As4Se8]2-} in which the Ag+ atoms are arranged in rows between the 1(∞)[AsSe2]- chains, with alternating Ag···Ag distances of 3.053(3) and 3.488(3) Å. Hereby the 1(∞)[AsSe2]- polyanions show a disorder within the central (-As-Se(b))- chain (b = bridging), while the positions of the terminal Se atoms (Se(t)) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) Å, b = 8.0748(7) Å, c = 22.803(2) Å, β = 116.272(2)°, Z = 8; CsAgAs2Se4 (II), monoclinic, P21/n, a = 10.9211(1) Å, b = 6.5188(2) Å, c = 13.7553(3) Å, β = 108.956(1)°, Z = 4.

Original languageEnglish (US)
Pages (from-to)2337-2343
Number of pages7
JournalInorganic chemistry
Issue number11
StatePublished - May 29 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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