Abstract: | Weak Sn…I Interactions in the Crystal Structures of the Iodostannates SnI4]2– and SnI3]– Iodostannate complexes can be crystallized from SnI2 solutions in polar organic solvents by precipitation with large counterions. Thereby isolated anions as well as one, two or three‐dimensional polymeric anionic substructures are established, in which SnI3– and SnI42– groups are linked by weak Sn…I interactions. Examples are the iodostannates Me3N–(CH2)2–NMe3]SnI4] ( 1 ), (Ph4P)2Sn2I6] ( 2 ), Me3N–(CH2)2–NMe3]Sn2I6] ( 3 ), Fe(dmf)6]SnI3]2 ( 4 ) and (Pr4N)SnI3] ( 5 ), which have been characterized by single crystal X‐ray diffraction. Me3N–(CH2)2–NMe3]SnI4] ( 1 ): a = 671.6(2), b = 1373.3(4), c = 2046.6(9) pm, V = 1887.7(11) · 106 pm3, space group Pbcm;(Ph4P)2Sn2I6] ( 2 ): a = 1168.05(6), b = 717.06(4), c = 3093.40(10) pm, β = 101.202(4)°, V = 2541.6(2) · 106 pm3, space group P21/n;Me3N–(CH2)2–NMe3]Sn2I6] ( 3 ): a = 695.58(4), b = 1748.30(8), c = 987.12(5) pm, β = 92.789(6)°, V = 1199.00(11) · 106 pm3, space group P21/c;Fe(dmf)6]SnI3]2 ( 4 ): a = 884.99(8), b = 1019.04(8), c = 1218.20(8) pm, α = 92.715(7), β = 105.826(7), γ = 98.241(7), V = 1041.7(1) · 106 pm3, space group P1;(Pr4N)SnI3] ( 5 ): a = 912.6(2), b = 1205.1(2), c = 1885.4(3) pm, V = 2073.5(7) · 106 pm3, space group P212121. |