Syntheses and structures of solvated tetrasodiumtetrachalcogenostannates [Na4(en)4][SnE4] (en=1,2-diaminoethane;: E = Te, Se), and their reactions toward further ternary of quaternary chalcogenometallates (Mn(en)3]2[Sn2Te6].4H2O or [Na10(H2O)34][Mn4(μ4-Se)(SnSe4)4]

A fusion/extraction technique was applied for the syntheses of en solvated (en = 1,2-diaminoethane) sodium salts of orthochalcogenostannate anions, [Na-4(en)(4])[SnE4] with E = Te (1) or Se (2), possessing homologue composition and similar crystal packing. However, further reactions of I and 2 with Mn(OAC)(2)-4H(2)O yielded different types of Mn/Sn/E compounds: whereas I is converted into an [Mn(en)(3)](2+) salt of dimeric [Sn2Te6](4-) anions (3), the presence of selenium ligands in 2 enables the formation of a ternary anion [Mn-4(mu 4-Se)(SnSe4)(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: 2 (monoclinic space group P2(1)/c): a: 7.5988(15) angstrom, b: 26.496(5) angstrom, c: 13.710(3) angstrom, beta: 92.84(3)degrees, V. 2756.8(9) angstrom(3); 2 (tetragonal space group P4(1)2(1)2): a: 13.0900(19) angstrom, c: 14.548(3) angstrom, V 2492.8(7) angstrom(3); 3 (triclinic space group P1): a: 9.3109(19) angstrom, b: 9.4345(19) angstrom, c: 12.800(3) angstrom alpha: 108.36(3)degrees beta: 98.43(3)degrees gamma: 103.82(3)degrees V. 1005.8(4) angstrom(3); 4 (triclinic space group P1): alpha: 14.903(3)angstrom, b: 15.189(3) angstrom, c: 15.339(3) angstrom, alpha: 90.47(3)degrees, beta: 90.61(3)degrees, gamma: 91.54(3)degrees, V. 3470.9(12) angstrom(3).