Photothermographic (PTG) imaging materials have become an indispensable application of silver technology that capitalizes on the capability of silver to undergo reduction to form a black and white image. Metallic silver, the light absorbing component of these imaging materials, has a unique morphology that provides good optical density and image tone. Understanding the silver chemistry portion of the metallic image formation process is important toward improving the photographic response of these materials. We have continued our investigation of various aspects of the silver coordination chemistry and report the solid state structures of several new silver complexes, utilizing ligands present in the PTG formulation, as well as model structures. Depending on the complexing agent and silver counterion, various silver complexes can be isolated and characterized. This report illustrates the silver-ligand interactions of silver compounds based on ortho-dicarboxylic acids, as well as the role ligand functionality could play in the imaging reactions based on these compounds.