Single crystals of TPAPyBP and TPAPyBPN were obtained by slow evaporation of a saturated toluene solution at room temperature. The structure and packing mode of both molecules in the solid state are shown in Figure and the crystallographic data are shown in Table . The phenylene bridge is near coplanar with the adjacent ring of the acceptor in both compounds, except in one independent molecule of TPAPyBP, where it is more noticeably out of plane (TPAPyBP: 2.79 (Figure ) and 31.03° (Figure ), TPAPyBPN: 4.36° (Figure )). TPAPyBP packs as arrays of co-planar compounds along the b-axis, the donor groups of alternate molecules oriented to opposite sides to avoid steric clash. These arrays are held together by slipped p-p stacking interactions, with adjacent molecules 3.24 and 3.49 Å apart, centroid•••centroid distances of 3.522(2) to 3.753(2) Å (Figures and). In addition to these, CH•••π interactions occur both to help further link adjacent molecules within the stacks (H•••centroid distances of 2.78 Å), and also to link adjacent stacks together (two independent H•••centroid distances of 2.92 Å).