The title compound, C25H25N9O9·C16H36N+·H2PO4
− (I) or (C25H25N9O9)·(n-Bu4N+)·(H2PO4
−) (systematic name: 3-(4-nitrophenyl)-1,1-bis{2-[3-(4-nitrophenyl)ureido]ethyl}urea tetrabutylammonium dihydrogen phosphate), comprises a tris-urea receptor (R), a dihydrogen phosphate anion and a tetra-n-butylammonium cation. It crystallizes with two independent formula units in the asymmetric unit. The conformations of the two tris-urea receptors are stabilized by N—H...O and C—H...O intramolecular hydrogen bonds. Each dihydrogen phosphate anion has two O—H...O intermolecular hydrogen-bonding interactions with the other dihydrogen phosphate anion. Inversion-related di-anion units are linked by further O—H...O hydrogen bonds, forming a chain propagating along the a-axis direction. Each dihydrogen phosphate anion makes a total of four N—H...O(H2PO4
−) hydrogen bonds with two ureido subunits from two different tris-urea receptors, hence each tris-urea receptor provides the two ureido subunits for the encapsulation of the H2PO4
− hydrogen-bonded chain. There are numerous intermolecular C—H...O hydrogen bonds present involving both receptor molecules and the tetra-n-butylammonium cations, so forming a supramolecular three-dimensional structure. One of the butyl groups and one of the nitro groups are disordered over two positions of equal occupancy.