The investigation of H-1-H-1 spin-diffusion build-up curves using a rate matrix analysis approach shows that high-resolution magic angle spinning NMR of protons, applied to powdered organic compounds, provides a method to probe crystalline arrangements. The comparison between experimental H-1 data and simulation is shown to depend strongly on the parameters of the crystal structure, for example on the unit cell parameters or the orientation of the molecule in the unit cell, and those parameters are experimentally determined for a model organic compound.