| Abstract: | Reactions of K4SnSe4], Na4GeS4] or Ba2GeSe4] with different 1,2‐diaminoethane (= en) coordinated complexes of CrCl3 (Cr(en)2Cl2]Cl or Cr(en)3]Cl3) in MeOH or aqueous solution yielded three novel compounds that contain complexes of Cr3+ with ortho‐chalcogenotetrelate anions E′E4]4? (E′ = Ge, Sn; E = S; Se): the crystal structures of K6(MeOH)9]Sn2Se6]Cr(en)2(SnSe4)]2 ( 1 ), Na(H2O)4]Cr(en)3]2GeS3OH]2Cr(en)2(GeS4)] ( 2 ), and Ba(H2O)10]{Cr(en)}2(GeSe4)2] ( 4 ) have been determined by means of single crystal X‐ray diffraction ( 1 : triclinic space group ; lattice dimensions at 203 K: a = 1175.7(2), b = 1315.3(3), c = 1326.7(3) pm, α = 61.99(3)°, β = 64.05(3)°, γ = 83.57(3)°, V = 1617.4(6)·106 pm3; R1 I > 2σ(I)] = 0.0788; wR2 = 0.1306; 2 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2445.3(5), b = 1442.5(3), c = 1579.3(3) pm, β = 94.61(3)°, V = 5552.9(19)·106 pm3; R1 I > 2σ(I)] = 0.0801; wR2 = 0.2046; 4 : triclinic space group ; lattice dimension at 203 K: a = 1198.4(2), b = 1236.8(3), c = 1297.5(3) pm, α = 65.69(3)°, β = 63.35(3)°, γ = 81.21(3)°, V = 1565.2(5)·106 pm3; R1 I > 2σ(I)] = 0.0732; wR2 = 0.1855). 1 and 2 show the yet unprecedented complexation of transition metal ions by non‐bridging, single chalcogenotetrelate ligands to produce dinuclear, heterobimetallic complexes. Compound 2 contains the first structurally characterized complex with an ortho‐thiogermanate ligand. The formation of these compounds, and of a by‐product of 2 , Cr(en)3]GeS3OH]·6H2O ( 3 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2396.8(5), b = 1463.4(3), c = 1740.1(4) pm, β = 132.99(3)°, V = 4463.8(15)·106 pm3; R1 I > 2σ(I)] = 0.0462; wR2 = 0.1058), provides some insight in fundamental differences between the reaction behavior of SnE4]4? anions one the one hand and GeE4]4? anions on the other hand. The crucial role of the counterion charge becomes evident when comparing the structure motifs of the ternary anions in 1 and 2 with that observed in the Ba2+ compound 4 . |
