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Solvothermal Synthesis and Crystal Structure of the New Layered Thioantimonate(III) [Ni(C 4 H 13 N 3 ) 2 ] 9 Sb 22 S 42 · 0.5H 2 O: Interconnection of the SbS 3 , SbS 4 , and SbS 5 Primary Building Units Yielding the Very Large Sb 30 S 30 Heteroring
Author(s) -
Stähler Ralph,
Bensch Wolfgang
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200207)628:7<1657::aid-zaac1657>3.0.co;2-c
Subject(s) - triclinic crystal system , chemistry , octahedron , crystallography , crystal structure , diethylenetriamine , stereochemistry , organic chemistry
The novel thioantimonate(III) [Ni(dien) 2 ] 9 Sb 22 S 42 · 0.5H 2 O was synthesised under solvothermal conditions by reacting elemental Ni, Sb and S in an aqueous solution of diethylenetriamine (dien) (80%). The compound crystallises in the triclinic space group P 1¯, a = 8.997(2) Å, b = 15.293(3) Å, c = 34.434(7) Å, α = 85.51(3)°, β = 84.16(3)°, γ = 83.54(3)°, V = 4672.7 (16) Å 3 , Z = 1. The layered ∞ 2 [Sb 22 S 42 18— ] anion in [Ni(dien) 2 ] 9 Sb 22 S 42 · 0.5H 2 O is composed of nine SbS 3 trigonal pyramids, one SbS 4 and one SbS 5 unit. The interconnection of these units by sharing common S atoms yields Sb‐S heterorings of different sizes. Besides the smaller Sb 2 S 2 and Sb 3 S 3 rings a very large Sb 30 S 30 heteroring is observed. The structure directing effect of the [Ni(dien) 2 ] 2+ cations is obvious as they are located above and below the pores of the anion. The nine [Ni(dien) 2 ] 2+ cations exhibit different conformations. All Ni 2+ cations are in an octahedral environment of six N atoms of two dien ligands. The anions and cations are stacked perpendicular to [100] in an alternating fashion.