Manganese(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionate) complexes with pyridin-4-one (pyon), 3-hydroxypyridin-2-one (hpyon), 1-fluoropyridine (pyF) and methanol were prepared and the solid-state structures were determined by single-crystal X-ray analysis. The coordination of the metal center in all complexes was found to be octahedral. In compounds [Mn(tfpb)2(pyon)2] (1) and [Mn(tfpb)2(hpyon)2] (2) extended hydrogen bonding is present facilitating the formation of a three-dimensional supramolecular structure in 1 and a layered structure in 2 through N-H···O hydrogen bonding enhanced by C-H···O interactions as well as C-F···π interactions. In [Mn(tfpb)2(pyF)2] (3) a layered structure is formed through C-H···O and C-H···F interactions as well as π···π and C-F···π interactions. In [Mn(tfpb)2(MeOH)2] (4) a layered structure is formed through a combination of O-H···O and C-F···π interactions.