Doped semiconductors play a prevalent role in all aspects of modern technology. Because of the trend for smaller and smaller devices, we have investigated N-doping at the sub-nanoscale. For that purpose, we present molecular beam electric and magnetic deflection experiments on SnNP (N = 6-12) and SnNP2 (N = 7-12) clusters combined with quantum chemical calculations and classical beam deflection simulations. The theoretically identified and experimentally confirmed global minima structures resemble the valence-isoelectronic pure tin anions/dianions very closely, while each phosphorus dopant occupies the site of a tin atom. In Stern-Gerlach experiments, the single-doped clusters show a partial atom-like deflection behavior with total electronic angular momentum J = 1/2 whereas the results for the double-doped species suggest singlet states. This is in full agreement with quantum chemical results. The effect of vibrational excitation on magnetic and electric deflection experiments is examined. Our results provide insight into how the electric, magnetic, and structure properties are affected by n-doping at the sub-nanoscale.