The stability of tin compounds in this oxidation state is attributed to the inert pair effect.

[5] The solid state structure is related to that of SnCl2 and PbCl2 and the tin atoms have five near bromine atom neighbours in an approximately trigonal bipyramidal configuration.

SnBr2 is soluble in donor solvents such as acetone, pyridine and dimethylsulfoxide to give pyramidal adducts.

[9] A number of hydrates are known, 2SnBr2·H2O, 3SnBr2·H2O & 6SnBr2·5H2O which in the solid phase have tin coordinated by a distorted trigonal prism of 6 bromine atoms with Br or H2O capping 1 or 2 faces.

With a variety of alkyl bromides oxidative addition can occur to yield the alkyltin tribromide[10] e.g. Tin(II) bromide can act as a Lewis acid forming adducts with donor molecules e.g. trimethylamine where it forms NMe3·SnBr2 and 2NMe3·SnBr2 [11] It can also act as both donor and acceptor in, for example, the complex F3B·SnBr2·NMe3 where it is a donor to boron trifluoride and an acceptor to trimethylamine.