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Tc2N is Molybdenite structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two Tc2N sheets oriented in the (0, 0, 1) direction. Tc+1.50+ is bonded in a distorted T-shaped geometry to three equivalent N3- atoms. All Tc–N bond lengths are 2.15 Å. N3- is bonded to six equivalent Tc+1.50+ atoms to form distorted edge-sharing NTc6 pentagonal pyramids.
Tc3N is Molybdenite-like structured and crystallizes in the hexagonal P-6m2 space group. The structure is two-dimensional and consists of one technetium molecule and one Tc2N sheet oriented in the (0, 0, 1) direction. In the Tc2N sheet, Tc1+ is bonded in a distorted T-shaped geometry to three equivalent N3- atoms. All Tc–N bond lengths are 2.14 Å. N3- is bonded to six equivalent Tc1+ atoms to form distorted edge-sharing NTc6 pentagonal pyramids.