[Mn2(AsS4)4]8- and [Cd 2(AsS4)2(AsS5)2] 8-: Discrete clusters with high negative charge from alkali metal polythioarsenate fluxes

Ratnasabapathy G. Iyer, Mercouri G Kanatzidis

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Abstract

The reaction of Mn and Cd in alkali metal polythioarsenate fluxes afforded four new compounds featuring molecular anions. K8[Mn 2(AsS4)4] (I) crystallizes in the monoclinic space group P2/n with a = 9.1818(8) Å, b = 8.5867(8) Å, c = 20.3802(19) Å, and β = 95.095(2)°. Rb8[Mn 2(AsS4)4] (II) and Cs8[Mn 2(AsS4)4] (III) both crystallize in the triclinic space group P1̄ with a = 9.079(3) Å, b = 9.197(3) Å, c = 11.219(4) Å, α = 105.958(7)°, β = 103.950-(5)°, and γ = 92.612(6)° for II and a = 9.420(5) Å, b = 9.559(5) Å, c = 11.496(7) Å, α = 105.606(14)°, β = 102.999(12)°, and γ = 92.423(14)° for III. The discrete dimeric [Mn2(AsS4)4]8-clusters in these compounds are composed of two octahedral Mn2+ ions bridged by two [AsS4]3- units and chelated each by a [AsS 4]3- unit. Rb8-[Cd2(AsS 4)2(AsS5)2] (IV) crystallizes in P1̄ with a = 9.122(2) Å, b = 9.285(2) Å, c = 12.400(3) Å, α = 111.700-(6)°, β - 108.744°, and γ = 90.163(5)°. Owing to the greater size of Cd compared to Mn, the Cd centers in this compound are bridged by [AsS5]3- units. The [Cd2(AsS4)4]8- cluster is a minor component cocrystallized in the lattice. These compounds are yellow in color and soluble in water.

Original languageEnglish
Pages (from-to)3656-3662
Number of pages7
JournalInorganic Chemistry
Volume43
Issue number12
DOIs
Publication statusPublished - Jun 14 2004

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Bridged-Ring Compounds
Alkali Metals
alkali metals
Anions
Ions
Fluxes
Color
Water
anions
color
water
ions

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  • Inorganic Chemistry

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[Mn2(AsS4)4]8- and [Cd 2(AsS4)2(AsS5)2] 8- : Discrete clusters with high negative charge from alkali metal polythioarsenate fluxes. / Iyer, Ratnasabapathy G.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 43, No. 12, 14.06.2004, p. 3656-3662.

Research output: Contribution to journalArticle

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title = "[Mn2(AsS4)4]8- and [Cd 2(AsS4)2(AsS5)2] 8-: Discrete clusters with high negative charge from alkali metal polythioarsenate fluxes",
abstract = "The reaction of Mn and Cd in alkali metal polythioarsenate fluxes afforded four new compounds featuring molecular anions. K8[Mn 2(AsS4)4] (I) crystallizes in the monoclinic space group P2/n with a = 9.1818(8) {\AA}, b = 8.5867(8) {\AA}, c = 20.3802(19) {\AA}, and β = 95.095(2)°. Rb8[Mn 2(AsS4)4] (II) and Cs8[Mn 2(AsS4)4] (III) both crystallize in the triclinic space group P1̄ with a = 9.079(3) {\AA}, b = 9.197(3) {\AA}, c = 11.219(4) {\AA}, α = 105.958(7)°, β = 103.950-(5)°, and γ = 92.612(6)° for II and a = 9.420(5) {\AA}, b = 9.559(5) {\AA}, c = 11.496(7) {\AA}, α = 105.606(14)°, β = 102.999(12)°, and γ = 92.423(14)° for III. The discrete dimeric [Mn2(AsS4)4]8-clusters in these compounds are composed of two octahedral Mn2+ ions bridged by two [AsS4]3- units and chelated each by a [AsS 4]3- unit. Rb8-[Cd2(AsS 4)2(AsS5)2] (IV) crystallizes in P1̄ with a = 9.122(2) {\AA}, b = 9.285(2) {\AA}, c = 12.400(3) {\AA}, α = 111.700-(6)°, β - 108.744°, and γ = 90.163(5)°. Owing to the greater size of Cd compared to Mn, the Cd centers in this compound are bridged by [AsS5]3- units. The [Cd2(AsS4)4]8- cluster is a minor component cocrystallized in the lattice. These compounds are yellow in color and soluble in water.",
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N2 - The reaction of Mn and Cd in alkali metal polythioarsenate fluxes afforded four new compounds featuring molecular anions. K8[Mn 2(AsS4)4] (I) crystallizes in the monoclinic space group P2/n with a = 9.1818(8) Å, b = 8.5867(8) Å, c = 20.3802(19) Å, and β = 95.095(2)°. Rb8[Mn 2(AsS4)4] (II) and Cs8[Mn 2(AsS4)4] (III) both crystallize in the triclinic space group P1̄ with a = 9.079(3) Å, b = 9.197(3) Å, c = 11.219(4) Å, α = 105.958(7)°, β = 103.950-(5)°, and γ = 92.612(6)° for II and a = 9.420(5) Å, b = 9.559(5) Å, c = 11.496(7) Å, α = 105.606(14)°, β = 102.999(12)°, and γ = 92.423(14)° for III. The discrete dimeric [Mn2(AsS4)4]8-clusters in these compounds are composed of two octahedral Mn2+ ions bridged by two [AsS4]3- units and chelated each by a [AsS 4]3- unit. Rb8-[Cd2(AsS 4)2(AsS5)2] (IV) crystallizes in P1̄ with a = 9.122(2) Å, b = 9.285(2) Å, c = 12.400(3) Å, α = 111.700-(6)°, β - 108.744°, and γ = 90.163(5)°. Owing to the greater size of Cd compared to Mn, the Cd centers in this compound are bridged by [AsS5]3- units. The [Cd2(AsS4)4]8- cluster is a minor component cocrystallized in the lattice. These compounds are yellow in color and soluble in water.

AB - The reaction of Mn and Cd in alkali metal polythioarsenate fluxes afforded four new compounds featuring molecular anions. K8[Mn 2(AsS4)4] (I) crystallizes in the monoclinic space group P2/n with a = 9.1818(8) Å, b = 8.5867(8) Å, c = 20.3802(19) Å, and β = 95.095(2)°. Rb8[Mn 2(AsS4)4] (II) and Cs8[Mn 2(AsS4)4] (III) both crystallize in the triclinic space group P1̄ with a = 9.079(3) Å, b = 9.197(3) Å, c = 11.219(4) Å, α = 105.958(7)°, β = 103.950-(5)°, and γ = 92.612(6)° for II and a = 9.420(5) Å, b = 9.559(5) Å, c = 11.496(7) Å, α = 105.606(14)°, β = 102.999(12)°, and γ = 92.423(14)° for III. The discrete dimeric [Mn2(AsS4)4]8-clusters in these compounds are composed of two octahedral Mn2+ ions bridged by two [AsS4]3- units and chelated each by a [AsS 4]3- unit. Rb8-[Cd2(AsS 4)2(AsS5)2] (IV) crystallizes in P1̄ with a = 9.122(2) Å, b = 9.285(2) Å, c = 12.400(3) Å, α = 111.700-(6)°, β - 108.744°, and γ = 90.163(5)°. Owing to the greater size of Cd compared to Mn, the Cd centers in this compound are bridged by [AsS5]3- units. The [Cd2(AsS4)4]8- cluster is a minor component cocrystallized in the lattice. These compounds are yellow in color and soluble in water.

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