[NEt4][BiSe2] has been synthesized from the electrochemical reduction of "BiSnSe4", a microcrystalline mixture of Bi2SnSe4, SnSe2, and Se, in an electrolyte solution of NEt4Br in ethylenediamine. [Ge(en)3][enH][SbSe4] has been prepared from the dissolution in ethylenediamine of "GeSbSe4", a microcrystalline mixture of Sb2Se3, GeSe2, and Se. The structures of both compounds have been determined by single-crystal X-ray methods. [NEt4][BiSe2] crystallizes in the rhombohedral space group C3v6-R3c with six formula units in a cell of dimensions a = 19.19(1) Å, α = 118.375(2)°, and V= 2320(2) Å3 (T= 115 K). Final agreement indices for [NEt4][BiSe2] are 0.113 for Rw(Fo2) for all 980 data and 0.054 for R1 for the 787 reflections with o2 ≥ 2σ(Fo2) (65 variables). [Ge(en)3]-[enH][SbSe4] crystallizes in the triclinic space group Ci1-P̄1 with two formula units in a cell of dimensions a = 8.82(2) Å, b = 9.60(2) Å, c = 14.20(3) Å, α = 104.84(7)°, β = 92.66(7)°, γ = 109.44(7)°, and V = 1085.2(4) Å33 (T = 115 K). Final agreement indices for [Ge(en)3][enH][SbSe4] are 0.241 for Rw(Fo2) for all 870 data and 0.101 for R1, for the 393 reflections with Fo2 ≥ 2σ(Fo2) (90 variables). [NEt4][BiSe2] is the first example of a compound that contains a selenobismuthate; its structure features a one-dimensional [BiSe2-]n chain of apex-sharing [BiSe33-] trigonal-pyramidal units. The structure of [Ge(en)3][enH][SbSe4] contains a tetrahedral [SbSe4]3- anion (Sbv) and a [Ge(en)3]2+ cation (GeII) as the Δλλδ conformer (and its enantiomer).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry