Calcium, strontium, and barium pyrazolate complexes have been synthesized by a variety of methods including transamination, high temperature metal-based reactions and direct metallation by ammonia activation. The resulting structures have brought to light the importance of secondary interactions, such as π- and hydrogen-bonding, in controlling the nuclearity of these complexes. Such control is needed for the design of low-nuclearity, volatile heavy alkaline earth metal complexes for applications in the CVD formation of thin films.