The coordination polymer Ag[N(CH2CH2)3N]2[CH3COO]·5H2O has been obtained by co-grinding in the solid state and in the air of a stoichiometric amount of silver acetate and of [N(CH2CH2)3N]. Single crystals suitable for X-ray diffraction have been obtained from a water–methanol solution and used to compare calculated and experimental X-ray powder diffractograms. When ZnCl2 is used instead of AgCH3COO in the equimolar reaction with [N(CH2CH2)3N], the solution and solid-state treatments afford different products. Single crystals of the Zn-based coordination polymer Zn[N(CH2CH2)3N]Cl2 have been obtained by layering a solution of ZnCl2 in methanol over a solution of [N(CH2CH2)3N] in CH2Cl2. The product of the co-grinding, identified only on the basis of X-ray powder diffraction, converts, on prolonged grinding, into the crystalline material obtained from the reaction in solution, namely anhydrous Zn[N(CH2CH2)3N]Cl2.
    
         
            
                     
                    
                        
                            
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