An　organo-bismuth　benzoate　with　phen　as　auxiliary　ligand,　[Bi(Phen)(C5H5COO)(C6H4COO)]　(1)　(phen　=　1,10-phenanthroline)　has　been　hydrothermally　synthesized　from　bismuth　nitrate,　2-mercaptonbenzoic　acid　with　phen　as　auxiliary　ligand　and　characterized　by　single-crystal　X-ray　diffraction,　elemental　analyses,　PXRD,　IR　spectra,　TG　analyses,　temperature-depended　2D-IR　COS　(two-dimensional　infrared　correlation　spectroscopy).　Interestingly,　benzoate　anions　in　1　came　from　the　desulfuration　reaction　of　2-mercaptonbenzoic　acid　under　hydrothermal　condition.　Compound　1　is　a　discrete　organo-bismuth　compound　with　benzoate　and　phen　ligands.　The　offset　face-to-face　pi-pi　stacking　interactions　and　C-H　center　dot　center　dot　center　dot　O　hydrogen　bonds　link　the　isolate　complex　into　a　3D　supramolecular　network.　The　temperature-depended　2D-IR　COS　indicates　that　the　stretching　vibrations　of　C=C/C=N　of　aromatic　rings　and　C=O　bonds　are　sensitive　to　the　temperature　change.　(C)　2016　Elsevier　B.V.　All　rights　reserved.