Syntheses and Structures of Solvated Tetrasodiumtetrachalcogenostannates [Na 4 ( en ) 4 ][SnE 4 ] ( en = 1,2‐diaminoethane; E = Te, Se), and their Reactions Toward Further Ternary or Quaternary Chalcogenometallates [Mn( en ) 3 ] 2 [Sn 2 Te 6 ]·4H 2 O or [Na 10 (H 2 O) 34 ][Mn 4 ( μ 4 ‐Se)(SnSe 4 ) 4 ]

A fusion/extraction technique was applied for the syntheses of en solvated ( en = 1,2‐diaminoethane) sodium salts of ortho ‐chalcogenostannate anions, [Na 4 ( en ) 4 ][SnE 4 ] with E = Te ( 1 ) or Se ( 2 ), possessing homologue composition and similar crystal packing. However, further reactions of 1 and 2 with Mn(OAc) 2 ·4H 2 O yielded different types of Mn/Sn/E compounds: whereas 1 is converted into an [Mn( en ) 3 ] 2+ salt of dimeric [Sn 2 Te 6 ] 4− anions ( 3 ), the presence of selenium ligands in 2 enables the formation of a ternary anion [Mn 4 ( μ 4 ‐Se)(SnSe 4 ) 4 ] 10− in 4 , which is the first Na + salt of this P1‐type anionic cluster. The reactions show both the influence of en ligands on the reaction behavior of ortho‐ chalcogenostannate anions and enhance the knowledge of the complex influences onto molecular structures of supertetrahedral cluster anions. Compounds 1 – 4 were structurally determined by means of single crystal X‐ray diffractometry; lattice dimensions at 203 K: 1 (monoclinic space group P2 1 /c): a : 7.5988(15) Å, b : 26.496(5) Å, c : 13.710(3) Å, β : 92.84(3)°, V : 2756.8(9) Å 3 ; 2 (tetragonal space group P 4 1 2 1 2): a : 13.0900(19) Å, c : 14.548(3) Å, V : 2492.8(7) Å 3 ; 3 (triclinic space group $P{\bar 1}$ ): a : 9.3109(19) Å, b : 9.4345(19) Å, c : 12.800(3) Å α: 108.36(3)° β : 98.43(3)° γ : 103.82(3)° V : 1005.8(4) Å 3 ; 4 (triclinic space group P 1): a : 14.903(3) Å, b : 15.189(3) Å, c : 15.339(3) Å, α: 90.47(3)°, β : 90.61(3)°, γ : 91.54(3)°, V : 3470.9(12) Å 3 .