MSb2O6 compounds (M = Mg, Co, Ni, Cu, Zn) are known in the tetragonal trirutile forms, slightly distorted monoclinically with M = Cu due to the Jahn-Teller effect. In this study, using a low-temperature exchange reaction between ilmenite-type NaSbO3 and molten MSO4-KCl (or MgCl2-KCl) mixtures, these five compositions were prepared for the first time as trigonal layered rosiaite (PbSb2O6)-type phases. Upon heating, they irreversibly transform to the known phases via amorphous intermediates, in contrast to previously studied isostructural MnSb2O6, where the stable phase is structurally related to the metastable phase. The same method was found to be applicable for preparing stable rosiaite-type CdSb2O6. The formula volumes of the new phases show an excellent correlation with the ionic radii (except for M = Cu, for which a Jahn-Teller distortion is suspected) and are 2-3% larger than those for the known forms although all coordination numbers are the same. The crystal structure of CoSb2O6 was refined via the Rietveld method: P3[combining macron]1m, a = 5.1318(3) Å, and c = 4.5520(3) Å. Compounds with M = Co and Ni antiferromagnetically order at 11 and 15 K, respectively, whereas the copper compound does not show long-range magnetic order down to 1.5 K. A comparison between the magnetic behavior of the metastable and stable polymorphs was carried out. FeSb2O6 could not be prepared because of the 2Fe2+ + Sb5+ = 2Fe3+ + Sb3+ redox reaction. This electron transfer produces an additional 5s2 shell for Sb and results in a volume increase. A comparison of the formula volume for the stable mixture FeSbO4 + 0.5Sb2O4 with that extrapolated for FeSb2O6 predicted that the trirutile-type FeSb2O6 can be stabilized at high pressures.