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The Hydrothermal Synthesis, Crystal Structures and Thermal Stability of the Novel One‐ and Two‐Dimensional Thioantimonate(III) Compounds [Co(tren)]Sb 2 S 4 and [Ni(tren)]Sb 2 S 4
Author(s) -
Stähler Ralph,
Bensch Wolfgang
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200112)2001:12<3073::aid-ejic3073>3.0.co;2-u
Subject(s) - chemistry , crystallography , monoclinic crystal system , orthorhombic crystal system , square pyramid , octahedron , trigonal bipyramidal molecular geometry , ligand (biochemistry) , crystal structure , bipyramid , amine gas treating , transition metal , stereochemistry , biochemistry , receptor , organic chemistry , catalysis
Two novel thioantimonate(III) compounds [Co(C 6 H 18 N 4 )]Sb 2 S 4 ( 1 ) and [Ni(C 6 H 18 N 4 )]Sb 2 S 4 ( 2 ) were synthesised under solvothermal conditions by reacting the transition metal, Sb and S in a 50% solution of tris(2‐aminoethyl)amine (tren). The use of a tetradentate amine yields incompletely shielded transition metal cations which in turn are able to form bonds to the sulfur atoms of thioantimonate(III) anions. Compound 1 crystallises in the orthorhombic space group Pbca , a = 13.886(3) Å, b = 11.452(2) Å, c = 20.549(4) Å, V = 3268(1) Å 3 , Z = 8 and compound 2 crystallises in the monoclinic space group P 2 1 / n , a = 6.906(1) Å, b = 22.822(5) Å, c = 10.347(2) Å, β = 103.17(3)°, V = 1587.9(6) Å 3 , Z = 4. The 2 ∝ [Sb 2 S 4 2− ] anion in compound 1 is formed by an SbS 3 and an SbS 4 unit sharing a common corner. Two SbS 4 units have a common edge to form an Sb 2 S 2 heterocycle. Four such Sb 2 S 2 rings are at the corners of a two‐dimensional square‐like net. Interconnection of the rings by SbS 3 pyramids yields Sb 10 S 10 rings with pores measuring 10·8.4 Å in diameter. The pores are filled by the [Co(tren)] 2+ cations. The [Co] 2+ cation is in a trigonal bipyramidal environment of four N atoms of the tren ligand and one S atom of the SbS 3 pyramid. The one‐dimensional 1 ∝ [Sb 2 S 4 2− ] chain anion in 2 is built by two corner‐sharing SbS 3 units. The [Ni] 2+ cation is in an octahedral environment consisting of four N atoms of the tren ligand and two S atoms of the anion. An NiSb 2 S 3 heteroring in a twist conformation is formed with an unusually large Ni−S(1)−Sb(1) angle of 121.73(3)°. For the [Co] 2+ (d 7 ) cation no significant energy differences can be expected for the trigonal bipyramidal and octahedral coordination, and due to the geometrical requirements of the tetradentate ligand the former environment is preferred. In contrast, for [Ni] 2+ (d 8 ) an octahedral environment is energetically favoured over the trigonal bipyramidal arrangement. Both compounds start to decompose under an Ar atmosphere at about 250 °C. For 1 two not well resolved steps are observed, whereas 2 decomposes in one step. In the X‐ray powder patterns of the grey products Sb 2 S 3 , Co/NiSbS and Co/NiS could be identified.