[TPrA][Mn(dca)3], crystallizes in the previously reported tetragonal structure in the P4̅ 21c space group at room temperature (Fig. ; a = 16.29 Å, c = 17.43 Å; Table ). Here the dca ligand bridges metal centres through nitrogen atoms in a µ1,5 end-to-end fashion. This means that neighboring metal-centered octahedra are cornersharing, and create a pseudo-cubooctahedral cavity in which the tetraalkylammonium cation (TAlA) is located (Fig. ). a The values were taken from our previous report. On the other hand, [TBuA][Mn(dca)3] crystallizes in the orthorhombic space group P21212, a = 16.01 Å, b = 16.01 Å, c = 21.55 Å (Fig. ). This is not a perovskite structure, but instead adopts a distorted triple rutile topology. The Mn coordination sphere contains three crystallographically independent μ1,5 dca anions. Each is joined to five Mn atoms. One is through a doubly bridged dca ligand, which creates an edge sharing MnN6 dimer unit. The further connection of each Mn centre to four additional atoms through single μ1,5 dca ligands then creates a 3D anionic framework. Hexagonal channels contain the TBuA cation.