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The self-assembly and self-organization of water molecules are relevant in many fields of research. When water spontaneously reacts with 2,2,6,6-tetramethylpiperidine (TMP) to form colourless and crystalline discrete needles, only in the exact ratio of 2:1, it is important to understand the phenomenon. Single-crystal X-ray and neutron diffraction data have unveiled that TMP self-assembles around columns of water molecules, and as such, the resulting adduct may be described as a series of molecular water pipes.