Abstract: | The syntheses and single crystal X‐ray structure determinations are reported for [Li(thf)4][SnCl5(thf)] ( 1 ) and {[Li(Et2O)2]2‐(μ‐Cl2)2‐SnIVCl2} ( 2 ). Compound 1 is ionic with a tetrahedral coordinated lithium cation and distorted octahedral tin (IV) atom in the anion, while compound ( 2 ) is a centrosymmetric heteronuclear double salt of LiCl and SnCl4. [Li(thf)4][SnCl5(thf)] is monoclinic, P21/n, a = 11.204(1), b = 15.599(1), c = 17.720(2) Å; β = 96.734(2)°, Z = 4, R 0.0418; {[Li(Et2O)2]2‐(μ‐Cl2)2‐SnIVCl2} is monoclinic, P21/n, a = 10.848(2), b = 12.764(2), c = 11.748(2) Å; β = 90.388(3)°, Z = 4, R = 0.0851. |