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 (infinity)~2[Sb_8Si_(13)]~(2-) anion

摘要

The five new thioantimonates(III) (iprH)_2[Sb_8S_(13)] (I), (l,2-dapH)_2[Sb_8S_(13)] (II), (l,3-dapH2)[Sb8Si3] (III), (dienH_2)CSb_8S_(13)] centre dot 1.5H_2O (IV), and (C_6H_9N_2)[Sb_8S_(13)] centre dot 2.5H_2O (V) were synthesised under solvothennal conditions (ipr = iso-propylamine; l,2-dap = 1,2-diaminopropane; 1,3-dap = 1,3-diaminopropanedien = diethylentriamine; C_6H_9N_2 = 3-(ammoethyl)-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_5S_5 rings are condensed. These rings are connected via Sb4S4 rings leading to the sequence Sb_(10)S_(10)-Sb_5S_5-Sb_4S_4-Sb_5S_5-Sb_(10)Sb_(10) in the [010] direction. Further interconnection into the two dimensional [Sb_8S_(13)]~(2-) anion produces a large central Sb_(18)S_(18) ring with dimensions of 11 centre dot 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_8S_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 percent for III to 35 percent for II.