The reaction of 4-cyanopyridine with NaN3 in the presence of H2O and a Lewis acid (CdCl2) affords a novel 3D pillared-layered fluorescent and phosphorescent coordination polymer Cd-3(OH)(2)Cl-2(4-PTZ)(2) (4-PTZ = 5-(4-pyridyl)tetrazolate) (1) while the direct reaction of CdCl2 with H-PTZ gives the simpler species Cd(4-PTZ)(2)(H2O)(2). The solid-state structure and nature of 1 provide an indication of the type of materials that may be formed as intermediates in the Sharpless-Demko reaction for the generation of 5-substituted 1H-tetrazoles.