Influence of the Counterions on the Structures of Ternary Zn/Sn/Se Anions: Synthesis and Properties of [Rb 10 (H 2 O) 14.5 ][Zn 4 ( μ 4 ‐Se) 2 (SnSe 4 ) 4 ] and [Ba 5 (H 2 O) 32 ][Zn 5 Sn( μ 3 ‐Se) 4 (SnSe 4 ) 4 ]

Reactions of rubidium or barium salts of the ortho ‐selenostannate anion, [Rb 4 (H 2 O) 4 ][SnSe 4 ] ( 1 ) or [Ba 2 (H 2 O) 5 ][SnSe 4 ] ( 2 ) with Zn(OAc) 2 or ZnCl 2 in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb 10 (H 2 O) 14.5 ][Zn 4 ( μ 4 ‐Se) 2 (SnSe 4 ) 4 ] ( 3 ) and [Ba 5 (H 2 O) 32 ][Zn 5 Sn( μ 3 ‐Se) 4 (SnSe 4 ) 4 ] ( 4 ). 1 – 4 have been determined by means of single crystal X‐ray diffraction: 1 : triclinic space group $P{\bar 1}$ lattice dimensions at 203 K: a = 8.2582(17) Å, b = 10.634(2) Å, c = 10.922(2) Å, α = 110.16(3)°, β = 91.74(3)°, γ = 97.86(3)°, V = 888.8(3) Å 3 ; R 1 [ I > 2 σ ( I )] = 0.0669; wR 2 = 0.1619; 2 : orthorhombic space group Pnma ; lattice dimensions at 203 K: a = 17.828(4) Å, b = 11.101(2) Å, c = 6.7784(14) Å, V = 1341.5(5) Å 3 ; R 1 [ I > 2 σ ( I )] = 0.0561; wR 2 = 0.1523; 3 : triclinic space group $P{\bar 1}$ ; lattice dimension at 203 K: a = 17.431(4) Å, b = 17.459(4) Å, c = 22.730(5) Å, α = 105.82(3)°, β = 99.17(3)°, γ = 90.06(3)°, V = 6563.1(2) Å 3 ; R 1 [ I > 2 σ ( I )] = 0.0822; wR 2 = 0.1782; 4 : monoclinic space group P 2 1 / c ; lattice dimensions at 203 K: a = 25.231(5) Å, b = 24.776(5) Å, c = 25.396(5) Å, β = 106.59(3)°, V = 15215.0(5) Å 3 ; R 1 [ I > 2 σ ( I )] = 0.0767; wR 2 = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb + (aq) stabilizes a P1‐type Zn/Sn/Se supertetrahedron in 3 like K + , the Ba 2+ (aq) ions better fit to an anionic T3‐type Zn/Sn/Se cluster arrangement as do Na + ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.