Abstract: | 5‐Methylsulfanyl‐1H‐tetrazole, C2H4N4S, crystallizes in dimorphic forms; the α‐form crystallizes at room temperature in the monoclinic crystal system, space group P21/m, and the β‐form crystallizes by sublimation at 423 K in the orthorhombic crystal system, space group Pbcm. In both forms, the molecules occupy crystallographic mirror planes and are connected to one another via N—H⋯N hydrogen bonds, the amino H atoms being disordered. The two forms differ from one another in their packing; there are polar layers in the α‐form and non‐polar layers in the β‐form. |