The solvothermal in situ double cycloaddition reaction of 2-cyanopyrimidine, Cu₂O and NaN₃ with aqueous ammonia additive generated a two dimensional copper(I) coordination polymer with 5-pyrimidyl-tetrazolate, 3,5-bispyrimidyl-1,2,4-triazolate and the cyano group as the ligands. This reaction can be tuned to yield two dimensional coordination polymers solely based on tetrazolate or 1,2,4-triazolate ligands.