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Updated: Jun 4, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Synthesis, crystal structure and properties of μ-tetra-thio-anti-monato-bis-[(cyclam)zinc(II)] perchlorate
Christian Näther1, Henning Lühmann1, Wolfgang Bensch1
1Institut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, D-24118 Kiel, Germany.
Abstract:
The reaction of Zn(ClO4)2·6H2O with Na3SbS4·9H2O in a water/aceto-nitrile mixture leads to the formation of the title compound, (μ-tetra-thio-anti-monato-κ2 S:S')bis-[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N)zinc(II)] perchlorate 0.8-hydrate, [Zn2(SbS4)(C10H24N4)2]ClO4·0.8H2O or [(Zn-cyclam)2(SbS4)]+[ClO4]-·0.8H2O. The asymmetric unit consists of two crystallographically independent [SbS4]3- anions, two independent perchlorate anions and two independent water mol-ecules as well as four crystallographically independent Zn(cyclam)2+ cations that are located in general positions. Both perchlorate anions and one cyclam ligand are disordered and were refined with a split mode using restraints. The water mol-ecules are partially occupied. Two Zn(cyclam)2+ cations are linked via the [SbS4]3- anions into [Zn2(cyclam)2SbS4]+ cations that are charged-balanced by the [ClO4]- anions. The water mol-ecules of crystallization are hydrogen bonded to the [SbS4]3- anions. The cations, anions and water mol-ecules are linked by N-H⋯O, N-H⋯S and O-H⋯S hydrogen bonds into a three-dimensional network. Powder X-ray diffraction proves that a pure sample had been obtained that was additionally investigated for its spectroscopic properties.
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