[TPnA][Mn(dca)3] crystallizes in the Pnna space group, a = 13.22 Å, b = 11.63 Å, c = 20.31 Å (Fig. ), and adopt a LiSbO3 structure. Here, each octahedral Mn coordination environment contains three crystallographically independent nitrile groups. These octahedra share edges with two neighbouring Mn coordination spheres through double μ1,5 dca ligands, which creates a zigzag chain motif. They also share edges with two additional Mn octahedra through single μ1,5 dca ligands, which link these chains together. The cell parameters obtained were then used in a Pawley refinement of powder X-ray diffraction data collected on bulk samples (Fig. and), to confirm phase purity of in each case. Altogether, these compounds, in addition with the previously reported [TPrA][M(dca)3] series (Table ) provide an opportunity to relate chemical composition to changes in physical properties.