Using the tripodal ligand N-(carbamoylmethyl)-iminodiacetatic acid (H2ADA), a two dimensional AgI coordination polymer [Ag(HADA)] n (1) and a mononuclear complex [CrIII(ADA)2](H2O)(H3O) (2) have been isolated. Using 2 as a precursor, a novel 3D heterometallic compound $$ \left\{ {\left[ {{\text{Cr}}^{\text{III}} {}_{3}{\text{Na}}_{3} \left( {\text{ADA}} \right)_{6} } \right] \cdot \left( {{\text{H}}_{2} {\text{O}}_{2} } \right)} \right\}_{n} $$ (3) was obtained. In 1 the singly deprotonated HADA− ligand adopts a novel asymmetrical η1,η1,η2,μ4-tetradentate coordination mode while in 3 four different coordination modes of ADA2− are observed. The solid-state fluorescence spectrum of 1 shows a maximum at 615 nm whereas no fluorescence emission band was observed for free H2ADA.