Isolation of β-Ag3AsSe3, (Me3NH)[Ag3As2Se5], K5Ag2As3Se9, and KAg3As2S5: Novel solid state silver thio- and selenoarsenates from solvento-thermal synthesis

Mercouri G Kanatzidis, Jun Hong Chou

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

Three new solid state silver selenoarsenates and one thioarsenate prepared from hydro- and methanothermal synthesis are described. β-Ag3AsSe3 (I) and (Me3NH)[Ag3As2Se5] (II) were synthesized hydrothermally at 110°C from a mixture of AgBF4/3K3AsSe3 and AgBF4/3K3AsSe3/6Me3NHCl, while K5[Ag2As3Se9] (III) and K[Ag3As2S5] (IV) were synthesized methanothermally at 110°C from a mixture of AgBF4/3K3AsS3 and AgBF4/3K3AsSe3, respectively. β-Ag3AsSe3(I) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 8.111(1) Å, b = 11.344(2) Å, c = 20.728(3) Å, Z = 8, V = 1907(1) Å3. This compound is a new allotrope of α-Ag3AsSe3 and has a complex three-dimensional structure composed of distorted trigonal planar and tetrahedral Ag+ ions and [AsSe3]3- units. (Me3NH)[Ag3As2Se5] (II) crystallizes in the triclinic space group P - 1 (No. 2) with a = 10.119(2) Å, b = 18.010(4) Å, c = 14.932(3) Å, α = 110.20 (1)°, β = 103.98(2)°, γ = 99 99(1)°, Z = 2, V = 729.3(8) Å3. The [Ag3As2Se5]n-n anion in (II) has a complex two-dimensional layered structure with tetrahedral Ag+ ions and [As2Se5]4- units. K5[Ag2As3Se9] (III) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 12.599(2) Å, b = 12.607(4) Å, c = 14.067(3) Å, Z = 8, V = 2234(1) Å3. The [Ag2As3Se9]5n-n anion in (III) has a two-dimensional layered structure with tetrahedral Ag+ ions and two different kinds of selenoarsenate units, [AsSe4]3- and [As2Se5]4-. K[Ag3As2S5] (IV) also crystallizes in the orthorhombic space group Pnma (No. 62) with a = 19.210(2) Å, b = 16.867(2) Å, c = 6.3491(7) Å, Z = 8, V = 2057.2(7) Å3. The [Ag3As2S5]n-n anion in (IV) possesses a complicated two-dimensional structure with tetrahedral Ag+ ions and two kinds of thioarsenate ligands, [AsS3]3- and [As3S7]5-. The thermal stability and optical absorption properties of these compounds are reported.

Original languageEnglish
Pages (from-to)186-201
Number of pages16
JournalJournal of Solid State Chemistry
Volume127
Issue number2
DOIs
Publication statusPublished - Dec 1996

Fingerprint

Silver
isolation
silver
Ions
solid state
Anions
Negative ions
synthesis
anions
ions
Light absorption
optical absorption
Thermodynamic stability
thermal stability
Ligands
ligands
Hot Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

@article{274b8f7466d949f98d267185f65f0eb3,
title = "Isolation of β-Ag3AsSe3, (Me3NH)[Ag3As2Se5], K5Ag2As3Se9, and KAg3As2S5: Novel solid state silver thio- and selenoarsenates from solvento-thermal synthesis",
abstract = "Three new solid state silver selenoarsenates and one thioarsenate prepared from hydro- and methanothermal synthesis are described. β-Ag3AsSe3 (I) and (Me3NH)[Ag3As2Se5] (II) were synthesized hydrothermally at 110°C from a mixture of AgBF4/3K3AsSe3 and AgBF4/3K3AsSe3/6Me3NHCl, while K5[Ag2As3Se9] (III) and K[Ag3As2S5] (IV) were synthesized methanothermally at 110°C from a mixture of AgBF4/3K3AsS3 and AgBF4/3K3AsSe3, respectively. β-Ag3AsSe3(I) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 8.111(1) {\AA}, b = 11.344(2) {\AA}, c = 20.728(3) {\AA}, Z = 8, V = 1907(1) {\AA}3. This compound is a new allotrope of α-Ag3AsSe3 and has a complex three-dimensional structure composed of distorted trigonal planar and tetrahedral Ag+ ions and [AsSe3]3- units. (Me3NH)[Ag3As2Se5] (II) crystallizes in the triclinic space group P - 1 (No. 2) with a = 10.119(2) {\AA}, b = 18.010(4) {\AA}, c = 14.932(3) {\AA}, α = 110.20 (1)°, β = 103.98(2)°, γ = 99 99(1)°, Z = 2, V = 729.3(8) {\AA}3. The [Ag3As2Se5]n-n anion in (II) has a complex two-dimensional layered structure with tetrahedral Ag+ ions and [As2Se5]4- units. K5[Ag2As3Se9] (III) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 12.599(2) {\AA}, b = 12.607(4) {\AA}, c = 14.067(3) {\AA}, Z = 8, V = 2234(1) {\AA}3. The [Ag2As3Se9]5n-n anion in (III) has a two-dimensional layered structure with tetrahedral Ag+ ions and two different kinds of selenoarsenate units, [AsSe4]3- and [As2Se5]4-. K[Ag3As2S5] (IV) also crystallizes in the orthorhombic space group Pnma (No. 62) with a = 19.210(2) {\AA}, b = 16.867(2) {\AA}, c = 6.3491(7) {\AA}, Z = 8, V = 2057.2(7) {\AA}3. The [Ag3As2S5]n-n anion in (IV) possesses a complicated two-dimensional structure with tetrahedral Ag+ ions and two kinds of thioarsenate ligands, [AsS3]3- and [As3S7]5-. The thermal stability and optical absorption properties of these compounds are reported.",
author = "Kanatzidis, {Mercouri G} and Chou, {Jun Hong}",
year = "1996",
month = "12",
doi = "10.1006/jssc.1996.0375",
language = "English",
volume = "127",
pages = "186--201",
journal = "Journal of Solid State Chemistry",
issn = "0022-4596",
publisher = "Academic Press Inc.",
number = "2",

}

TY - JOUR

T1 - Isolation of β-Ag3AsSe3, (Me3NH)[Ag3As2Se5], K5Ag2As3Se9, and KAg3As2S5

T2 - Novel solid state silver thio- and selenoarsenates from solvento-thermal synthesis

AU - Kanatzidis, Mercouri G

AU - Chou, Jun Hong

PY - 1996/12

Y1 - 1996/12

N2 - Three new solid state silver selenoarsenates and one thioarsenate prepared from hydro- and methanothermal synthesis are described. β-Ag3AsSe3 (I) and (Me3NH)[Ag3As2Se5] (II) were synthesized hydrothermally at 110°C from a mixture of AgBF4/3K3AsSe3 and AgBF4/3K3AsSe3/6Me3NHCl, while K5[Ag2As3Se9] (III) and K[Ag3As2S5] (IV) were synthesized methanothermally at 110°C from a mixture of AgBF4/3K3AsS3 and AgBF4/3K3AsSe3, respectively. β-Ag3AsSe3(I) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 8.111(1) Å, b = 11.344(2) Å, c = 20.728(3) Å, Z = 8, V = 1907(1) Å3. This compound is a new allotrope of α-Ag3AsSe3 and has a complex three-dimensional structure composed of distorted trigonal planar and tetrahedral Ag+ ions and [AsSe3]3- units. (Me3NH)[Ag3As2Se5] (II) crystallizes in the triclinic space group P - 1 (No. 2) with a = 10.119(2) Å, b = 18.010(4) Å, c = 14.932(3) Å, α = 110.20 (1)°, β = 103.98(2)°, γ = 99 99(1)°, Z = 2, V = 729.3(8) Å3. The [Ag3As2Se5]n-n anion in (II) has a complex two-dimensional layered structure with tetrahedral Ag+ ions and [As2Se5]4- units. K5[Ag2As3Se9] (III) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 12.599(2) Å, b = 12.607(4) Å, c = 14.067(3) Å, Z = 8, V = 2234(1) Å3. The [Ag2As3Se9]5n-n anion in (III) has a two-dimensional layered structure with tetrahedral Ag+ ions and two different kinds of selenoarsenate units, [AsSe4]3- and [As2Se5]4-. K[Ag3As2S5] (IV) also crystallizes in the orthorhombic space group Pnma (No. 62) with a = 19.210(2) Å, b = 16.867(2) Å, c = 6.3491(7) Å, Z = 8, V = 2057.2(7) Å3. The [Ag3As2S5]n-n anion in (IV) possesses a complicated two-dimensional structure with tetrahedral Ag+ ions and two kinds of thioarsenate ligands, [AsS3]3- and [As3S7]5-. The thermal stability and optical absorption properties of these compounds are reported.

AB - Three new solid state silver selenoarsenates and one thioarsenate prepared from hydro- and methanothermal synthesis are described. β-Ag3AsSe3 (I) and (Me3NH)[Ag3As2Se5] (II) were synthesized hydrothermally at 110°C from a mixture of AgBF4/3K3AsSe3 and AgBF4/3K3AsSe3/6Me3NHCl, while K5[Ag2As3Se9] (III) and K[Ag3As2S5] (IV) were synthesized methanothermally at 110°C from a mixture of AgBF4/3K3AsS3 and AgBF4/3K3AsSe3, respectively. β-Ag3AsSe3(I) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 8.111(1) Å, b = 11.344(2) Å, c = 20.728(3) Å, Z = 8, V = 1907(1) Å3. This compound is a new allotrope of α-Ag3AsSe3 and has a complex three-dimensional structure composed of distorted trigonal planar and tetrahedral Ag+ ions and [AsSe3]3- units. (Me3NH)[Ag3As2Se5] (II) crystallizes in the triclinic space group P - 1 (No. 2) with a = 10.119(2) Å, b = 18.010(4) Å, c = 14.932(3) Å, α = 110.20 (1)°, β = 103.98(2)°, γ = 99 99(1)°, Z = 2, V = 729.3(8) Å3. The [Ag3As2Se5]n-n anion in (II) has a complex two-dimensional layered structure with tetrahedral Ag+ ions and [As2Se5]4- units. K5[Ag2As3Se9] (III) crystallizes in the orthorhombic space group Pnma (No. 62) with a = 12.599(2) Å, b = 12.607(4) Å, c = 14.067(3) Å, Z = 8, V = 2234(1) Å3. The [Ag2As3Se9]5n-n anion in (III) has a two-dimensional layered structure with tetrahedral Ag+ ions and two different kinds of selenoarsenate units, [AsSe4]3- and [As2Se5]4-. K[Ag3As2S5] (IV) also crystallizes in the orthorhombic space group Pnma (No. 62) with a = 19.210(2) Å, b = 16.867(2) Å, c = 6.3491(7) Å, Z = 8, V = 2057.2(7) Å3. The [Ag3As2S5]n-n anion in (IV) possesses a complicated two-dimensional structure with tetrahedral Ag+ ions and two kinds of thioarsenate ligands, [AsS3]3- and [As3S7]5-. The thermal stability and optical absorption properties of these compounds are reported.

UR - http://www.scopus.com/inward/record.url?scp=0001076324&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001076324&partnerID=8YFLogxK

U2 - 10.1006/jssc.1996.0375

DO - 10.1006/jssc.1996.0375

M3 - Article

AN - SCOPUS:0001076324

VL - 127

SP - 186

EP - 201

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

IS - 2

ER -