The structure directing effect of organic cations onto the crystal structures of layered thioantimonates(III): Solvothermal synthesis and crystal structures of five new compounds containing the 2∞[Sb8S13]2− anion

AbstractThe five new thioantimonates(III) (iprH)2[Sb8S13] (I), (1,2-dapH)2[Sb8S13] (II), (1,3-dapH2)[Sb8S13] (III), (dienH2)[Sb8S13]⋅1.5H2O (IV), and (C6H9N2)[Sb8S13]⋅2.5H2O (V) were synthesised under solvothermal conditions (ipr = iso-propylamine; 1,2-dap = 1,2-diaminopropane; 1,3-dap = 1,3-diaminopropane; dien = diethylentriamine; C6H9N2 = 3-(aminoethyl)-pyridine). The structures of compounds I and II are topological very similar and a central motif is a Sb10S10 ring. On both sides of this ring Sb5S5 rings are condensed. These rings are connected via Sb4S4 rings leading to the sequence Sb10S10-Sb5S5-Sb4S4-Sb5S5-Sb10Sb10 in the [010] direction. Further interconnection into the two-dimensional [Sb8S13]2− anion produces a large central Sb18S18 ring with dimensions of 11⋅11 Å in both compounds. The two atoms thick layers are linear and stacked along the a axis generating large channels running along [010]. The layered anion of compound III is constructed by interconnection of the SbS3 and SbS4 units yielding Sb19S19, Sb14S14, Sb13S13, and Sb8S8 rings. The linear layers are two atoms thick and are stacked perpendicular to [001] to form channels running along the same direction. The last two compounds IV and V show a similar network topology. The layered anion is constructed by SbS3 trigonal pyramids and SbS4 units. The layer contains a Sb12S12 rings as the main structural motif. The corrugated layers extending in the (100) plane are two atoms thick and are stacked in a manner that large tunnels run along [100]. The total potential solvent areas are large and range from 20.7% for III to 35% for II.