Abstract: | ![]() The molecular structure of the title compound, [SnBr2(C9H12N)(C9H13N)][SnBr4(C9H12N)], consists of a dibromobis[2‐(dimethylaminomethyl)phenyl][2‐dimethylammoniomethyl)phenyl]tin(IV) cation and a tetrabromo[2‐(dimethylaminomethyl)phenyl]tin(IV) anion. As a result of strong intramolecular N→Sn interactions, distorted trigonal–bipyramidal and octahedral coordination geometries are established for the metal centres of the diorganotin(IV) and monoorganotin(IV) fragments, respectively. The cation and anion are linked together by two Br⋯H contacts, while three additional similar contacts result in a dimeric fragment which repeats in a two‐dimensional supramolecular arrangement. |