Tc2P3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Tc sites. In the first Tc site, Tc(1) is bonded in a 6-coordinate geometry to one P(2), two equivalent P(1), and three equivalent P(3) atoms. In the second Tc site, Tc(2) is bonded to one P(3), two equivalent P(1), and three equivalent P(2) atoms to form edge-sharing TcP6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Tc(1), two equivalent Tc(2), and one P(1) atom. In the second P site, P(2) is bonded in a 4-coordinate geometry to one Tc(1) and three equivalent Tc(2) atoms. In the third P site, P(3) is bonded in a 5-coordinate geometry to one Tc(2), three equivalent Tc(1), and one P(3) atom.
Tc2P3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Tc sites. In the first Tc site, Tc(1) is bonded in a 6-coordinate geometry to one P(2), two equivalent P(1), and three equivalent P(3) atoms. The Tc(1)-P(2) bond length is 2.28 Å. Both Tc(1)-P(1) bond lengths are 2.39 Å. There are two shorter (2.41 Å) and one longer (2.75 Å) Tc(1)-P(3) bond length. In the second Tc site, Tc(2) is bonded to one P(3), two equivalent P(1), and three equivalent P(2) atoms to form edge-sharing TcP6 octahedra. The Tc(2)-P(3) bond length is 2.42 Å. Both Tc(2)-P(1) bond lengths are 2.41 Å. All Tc(2)-P(2) bond lengths are 2.38 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Tc(1), two equivalent Tc(2), and one P(1) atom. The P(1)-P(1) bond length is 2.23 Å. In the second P site, P(2) is bonded in a 4-coordinate geometry to one Tc(1) and three equivalent Tc(2) atoms. In the third P site, P(3) is bonded in a 5-coordinate geometry to one Tc(2), three equivalent Tc(1), and one P(3) atom. The P(3)-P(3) bond length is 2.39 Å.