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The complex of 2,4,6-triethyl-1,3,5-tris[(4-methyl-1H-indazol-1-yl)methyl]benzene with ammonium hexafluorophosphate, C39H42N6·NH4+·PF6−, crystallizes in the monoclinic space group P21 with two molecules of the receptor, two NH4+ and two PF6− ions in the asymmetric unit. In each of the complexes the ammonium ion resides in the cavity of the receptor molecule and is fixed in its position by three N—H...N bonds, while the remaining hydrogen atom of the cation acts as a bifurcated binding site for N—H...F bonding to the counter-anion. The crystal is composed of one-dimensional supramolecular aggregates extending along the a-axis direction.