[Rh((C4H3S)COCHCO(C4H3S))(CO)(PPh3)] crystals stack in one dimensional linear chains in the solid state, with slightly slipped π-stacking of the thienyl groups of one molecule and the β-diketonato backbone of a neighbouring molecule. The observed stacking is possible due to the near planar orientation of the two aromatic thienyl groups and the β-diketonato backbone. The experimentally observed stacking and close intermolecular contacts are in agreement with theoretical QTAIM calculated intermolecular bond paths and intermolecular hydrogen bonds between neighbouring molecules. NBO calculations revealed donor – acceptor NBO interactions between the lone pair on rhodium of one molecule and (i) the empty antibonding orbital on C-H of the nearest thienyl group of a neighbouring molecule, as well as with the (ii) the empty antibonding orbital on two carbons of the nearest thienyl group to rhodium on the neighbouring molecule.