Solvothermal Syntheses and Crystal Structures of the Two New Polymeric Compounds [Ce(C 4 N 3 H 13 ) 2 (μ 3 ‐SbS 4 )] n and [La(C 4 N 3 H 13 ) 2 (μ 4 ‐Sb 2 S 5 )(μ 3 ‐SO 4 )] n

The two new one‐dimensional polymeric compounds [Ce(C 4 N 3 H 13 ) 2 (μ 3 ‐SbS 4 )] n ( 1 ) and [La(C 4 N 3 H 13 ) 2 (μ 4 ‐Sb 2 S 5 )(μ 3 ‐SO 4 )] n ( 2 ) were synthesized under solvothermal conditions. In the first compound, the unique Ce 3+ cation is surrounded by six nitrogen atoms of the amine ligands and by three sulfur atoms of the thioantimonate(V) anion. The CeN 6 S 3 polyhedron may be described as a distorted tricapped trigonal prism. The prisms are interconnected by [SbS 4 ] 3– anions, which act in a μ 3 ‐binding mode yielding a chain running along [100]. An extended hydrogen‐bonding network leads to the formation of layers. The second compound features two independent La 3+ cations, one is in a ninefold [La(2)N 6 OS 2 ] and the second is in a tenfold environment [La(1)N 6 O 2 S 2 ]. The unusual features of the structure are a μ 3 ‐bridging SO 4 2– anion and a tetradentate thioantimonate(III) anion [Sb 2 S 5 ] 4– that join the two La 3+ centered polyhedra into a chain being directed along [110]. The oxygen atoms of the sulfate anion and the sulfur atoms of the thioantimonate anion are involved in a complex hydrogen‐bonding network.