Syntheses and structures of the infinite chain compounds Cs4Ti3Se13, Rb4Ti3S14, Cs4Ti3S14, Rb4Hf3S14, Rb4Zr3Se14, Cs4Zr3Se14, and Cs4Hf3Se14

F. Q. Huang, J. A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticle

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The alkali metal/group 4 metal/polychalcogenides Cs4Ti3Se13, Rb4Ti3S14, Cs4Ti3S14, Rb4Hf3S14, Rb4Zr3Se14, Cs4Zr3Se14, and Cs4Hf3Se14 have been synthesized by means of the reactive flux method at 823 or 873 K. Cs4Ti3Se13 crystallizes in a new structure type in space group C22-P21 with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) Å, b = 32.468(2) Å, c = 14.6747(8) Å, β = 100.008(1)°. Cs4Ti3Se13 is composed of four independent one-dimensional 1[Ti3Se134-] chains separated by Cs+ cations. These chains adopt hexagonal closest packing along the [100] direction. The 1[Ti3Se134-] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs4-Ti3Se13. The compounds Rb4Ti3S14, Cs4Ti3S14, Rb4Hf3S14, Rb4Zr3Se14, Cs4Zr3Se14, and Cs4Hf3Se14 crystallize in the K4Ti3S14 structure type with four formula units in space group C2h6-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) Å, b = 8.1169(5) Å, c = 13.1992(8) Å, β = 112.835(1)° for Rb4Ti3S14; a = 21.329(3) Å, b = 8.415(1) Å, c = 13.678(2) Å, β = 113.801(2)° for Cs4Ti3S14; a = 21.643(2) Å, b = 8.1848(8) Å, c = 13.331(1) Å, β = 111.762(2)° for Rb4Hf3S14; a = 22.605(7) Å, b = 8.552(3) Å, c = 13.880(4) Å, β = 110.919(9)° for Rb4Zr3Se14; a = 22.826(5) Å, b = 8.841(2) Å, c = 14.278(3) Å, β = 111.456(4)° for Cs4Zr3Se14; and a = 22.758(5) Å, b = 8.844(2) Å, c = 14.276(3) Å, β = 111.88(3)° for Cs4Hf3Se14. These A4M3Q14 compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed 1[M3Q144-] chains that run in the [101] direction and are separated by A+ cations. Each 1[M3Q144-] chain is built from a [M3Q14] unit that consists of two MQ7 pentagonal bipyramids or one distorted MQ8 bicapped octahedron bonded together by edge- or face-sharing. Each [M3Q14] unit contains six Q22- dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) Å for S-S and 2.367(1)-2.391(2) Å for Se-Se. The A4M3Q14 compounds can be formulated as (A+)4(M4+)3 (Q22-)6(Q2-)2.

Original languageEnglish (US)
Pages (from-to)2346-2351
Number of pages6
JournalInorganic chemistry
Issue number10
StatePublished - May 7 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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