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

The five new thioantimonates(III) ( i prH) 2 [Sb 8 S 13 ] ( I ), (1,2-dapH) 2 [Sb 8 S 13 ] ( II ), (1,3-dapH 2 )[Sb 8 S 13 ] ( III ), (dienH 2 )[Sb 8 S 13 ]⋅1.5H 2 O ( IV ), and (C 6 H 9 N 2 )[Sb 8 S 13 ]⋅2.5H 2 O ( V ) were synthesised under solvothermal conditions ( i pr = iso-propylamine; 1,2-dap = 1,2-diaminopropane; 1,3-dap = 1,3-diaminopropane; dien = diethylentriamine; C 6 H 9 N 2 = 3-(aminoethyl)-pyridine). The structures of compounds I and II are topological very similar and a central motif is a Sb 10 S 10 ring. On both sides of this ring Sb 5 S 5 rings are condensed. These rings are connected via Sb 4 S 4 rings leading to the sequence Sb 10 S 10 –Sb 5 S 5 –Sb 4 S 4 –Sb 5 S 5 –Sb 10 Sb 10 in the [010] direction. Further interconnection into the two-dimensional [Sb 8 S 13 ] 2− anion produces a large central Sb 18 S 18 ring with dimensions of 11⋅11 A 11 ⋅ 11 A 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 SbS 3 and SbS 4 units yielding Sb 19 S 19 , Sb 14 S 14 , Sb 13 S 13 , and Sb 8 S 8 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 SbS 3 trigonal pyramids and SbS 4 units. The layer contains a Sb 12 S 12 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 .