Single crystals of a new organic cyclohexaphosphate (C8H12N)4(Li)2(P6O18)(H2O)6 prepared by an acid/base reaction between cyclohexaphosphoric acid H6P6O18 and 2,6-dimethylaniline, have been successfully grown by slow evaporation technique at room temperature. This compound was characterized using X-ray diffraction (XRD) and FT-IR spectroscopy. The results show that the title compound was phased with a triclinic structure and P-1 space group. The crystal structure was solved by using 5203 independent reflections with a final R value of 0.031. The P6O18 ring is centrosymmetrical. Its main geometrical features are those commonly observed in others cyclohexaphosphates. The atomic arrangement of this compound can be described by an organization in a three-dimensional framework, built up from alternated organic and inorganic species. Adjacent P6O18 rings are linked via corner-sharing by LiO4 tetrahedra, generating anionic [Li2(P6O18)(H2O)]4- layers parallel to (110). Charge balance is achieved by the protonated amine which is trapped in the interlayer space and interacts with the organic framework through strong and medium hydrogen bonding. An extensive network of N[sbnd]H⋯O and O[sbnd]H⋯O hydrogen-bonding interactions link the components into a three-dimensional network and additional stabilization is provided by weak C[sbnd]H⋯O hydrogen bonds. Intermolecular interactions were investigated by Hirshfeld surfaces. The vibrational absorption bands were identified by infrared spectroscopy. The stretching modes of P6O18 ring and band assignments are described.