Tin(II) methoxide reacts with N,N'-dimethylaminoethanol (dmaeH) to yield Sn(dmae)(2) (1) along with small amounts of the hydrolysis product Sn-6(O)(4)(dmae)(4) (2). The geometrically more regular iso-structural cage Sn-6(O)(4)(OEt)(4) (3) was obtained as the only tractable product isolated from reaction of 2 and Sb(OEt)(3), while 1 reacted with CdX2 (X = acac, I) to afford Sn(dmae)(2)Cd(acac)(2) (4) and Sn(dmae)(2)CdI2 (5). The X-ray structures of 2, 3 and 4 are reported. Decomposition of 4 under aerosol-assisted chemical vapour deposition conditions leads to amorphous tin oxide films with no detectable cadmium (i.e. ca < 2% cadmium), rather than a stoichiometric Sn:Cd oxide. Copyright (c) 2006 John Wiley & Sons, Ltd.