A new type of crystalline structure for nonlinear optics whereby octupolar symmetry features are displayed at both molecular and crystalline levels is exemplified by the prototype 2,4,6-triaryloxy-1,3,5-triazine (TPOT) crystal and analyzed in terms of both individual molecular responses and crystal packing features. Polarized harmonic Light scattering permits the full determination of the molecular beta hyperpolarizability tensor and confirms the octupolar trigonal symmetry of the TPOT molecule. An oriented gas model is used to infer therefrom an estimate of the crystalline nonlinear d tensor which is predicted to be of the same order as that of the reference dipolar N-4-nitrophenyl-(L)-prolinol crystal. The concept of optimal packing toward quadratic nonlinear optics, which had been initially introduced in the realm of quasi-one-dimensional structures, is revisited and enlarged to encompass more isotropic uniaxial structures potentially amenable, in the case of octupoles, to larger optimal values than in the one-dimensional case. Moreover, considerations pertaining to phase matching which had been left aside in the earlier one-dimensional optimization framework are now considered and the various type I and type II configurations compared for both one-dimensional and octupolar uniaxial structures. Application perspectives of octupolar structures toward short pulse nonlinear optics are discussed: their structurally built-in polarization independence is outlined as a major asset in contrast with the more traditional one-dimensional structures.