Through the application of synthesis via molten indium flux, we have been able to expand the ternary Sc−Mn−Si system and the quaternary Sc−Mn−Al−Si system. Specifically, we report on five previously unknown chemical compounds, namely β-ScMnSi2, Sc4+xMn4Si7–2x, Sc2Mn4Si5, Sc2Mn3Si4, and Sc4Mn2AlSi4. The compounds with the stoichiometries Sc2Mn4Si5, Sc2Mn3Si4, and Sc4Mn2AlSi4 have previously not been reported. We find that these crystallize in the V6Si5, Hf2Ru3Si4, and Ho4Ni2InGe4 structure types, respectively. For the ternary compounds with the stoichiometries of ScMnSi2 and Sc4+xMn4Si7–2x, we find clearly deviating structural solutions compared to earlier reports. β-ScMnSi2 is found to crystallize in the monoclinic crystal system isostructural to a supercell of the MnTiSi2 structure and clearly deviating from the known orthorhombic α-polymorph. The compound Sc4+xMn4Si7–2x is structurally very similar to Sc4Mn4Si7, but exhibits the P4/nmm space group instead of I4/mmm, and is related to the Zr4Co4Ge7 structure. Disorder between Si and Sc sites leads to the off-stoichiometric composition, for which we found x=0.287(5).