X-ray crystallographic analysis of 1-3 was carried out to investigate the coordination geometry and molecular packing of each coordination compound. Single crystals of complex 1 were obtained from slow evaporation of THF while for complex 2 the crystals were obtained solely from the solvothermal synthesis. The crystals for complex 3 were obtained through various methods, including solvothermal synthesis, vapor diffusion of ethanol to DMF and slow evaporation of THF solution of the complex. All complexes crystallized in a bi-octahedron coordination geometry with each molecular unit consisting of two Bi(III) centers each coordinated to a thiophene substituted phenanthroline ligand (L) along with chlorine, bromine and iodine as the ancillary ligands in 1, 2, and 3 respectively (Figure ). Each bismuth atom in a molecule coordinates with one organic ligand and four units of halogens while two bismuth units in a molecule are bridged by two units of halogens (Cl, Br, I).