Solid-state 2 7 Al NMR spectra have been obtained for a crystalline 1:1 complex of AlCl 3 and OPCl 3 . Aluminum chloride phosphoryl chloride, AlCl 3 . OPCl 3 (1), is unusual in that the Al-O-P bond angle is close to 180 o . From analysis of the 2 7 Al MAS NMR spectra, it was determined that the 2 7 Al nuclear quadrupole coupling constant is 6.0(1) MHz, the asymmetry in the electric field gradient (efg) tensor is 0.15(2), and the isotropic chemical shift, δ i s o ( 2 7 Al), is 88(1) ppm. Solid-state 2 7 Al NMR of a stationary sample reveals a line shape affected by a combination of anisotropic chemical shielding and second-order quadrupolar interactions. Analysis of this spectrum yields a chemical shift anisotropy of 60(1) ppm and orientations of the chemical shift and electric field gradient tensors in the molecular frame. Experimental results are compared with those calculated usingab initioHartree-Fock and density functional theory.