The addition of Nb and Sn to Zr2AlC is investigated, targeting the synthesis of a Zr-rich bulk MAX phase free of ZrC. The 211 phase formation in the two quaternary Zr-Nb-Al-C and Zr-Al-Sn-C systems is evaluated. Solubility over the entire compositional range in (Zr, Nb)2AlC and Zr2(Al, Sn)C is observed. In terms of effectiveness, the addition of Sn is preferred over the addition of Nb, as the former is selectively incorporated into the 211 structure. A combinatorial approach results in the formation of phase-pure (Zr0.8, Nb0.2)2(Al0.5, Sn0.5)C. The effect of the added solutes on the microstructure and crystallographic parameters is investigated. The addition of Nb and Sn reduces the distortion parameter of the trigonal prism compared to pure Zr2AlC. Therefore, an attempt is made to establish a more general stability criterion for the M2AC structure based on the steric relationship between the atoms in the M6A trigonal prism. Inspired by the Hume-Rothery rules, it is suggested that comparable atomic radii of the M- and A-atoms provide a good starting point to obtain a stable 211 MAX phase.