TcP3 is Hausmannite-like structured and crystallizes in the orthorhombic Pnma space group. Tc(1) is bonded to one P(2), two equivalent P(3), and three equivalent P(1) atoms to form TcP6 octahedra that share corners with four equivalent Tc(1)P6 octahedra, corners with two equivalent P(1)Tc3P tetrahedra, corners with four equivalent P(3)Tc2P2 tetrahedra, and edges with two equivalent Tc(1)P6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent P sites. In the first P site, P(2) is bonded in a distorted rectangular see-saw-like geometry to one Tc(1), one P(3), and two equivalent P(2) atoms. In the second P site, P(1) is bonded to three equivalent Tc(1) and one P(3) atom to form PTc3P tetrahedra that share corners with two equivalent Tc(1)P6 octahedra, corners with four equivalent P(3)Tc2P2 tetrahedra, corners with six equivalent P(1)Tc3P tetrahedra, and  an edgeedge with one P(3)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles are 64°. In the third P site, P(3) is bonded to two equivalent Tc(1), one P(1), and one P(2) atom to form distorted PTc2P2 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra, corners with two equivalent P(3)Tc2P2 tetrahedra, corners with four equivalent P(1)Tc3P tetrahedra, and  an edgeedge with one P(1)Tc3P tetrahedra. The corner-sharing octahedral tilt angles range from 50-74°.
TcP3 is Hausmannite-like structured and crystallizes in the orthorhombic Pnma space group. Tc(1) is bonded to one P(2), two equivalent P(3), and three equivalent P(1) atoms to form TcP6 octahedra that share corners with four equivalent Tc(1)P6 octahedra, corners with two equivalent P(1)Tc3P tetrahedra, corners with four equivalent P(3)Tc2P2 tetrahedra, and edges with two equivalent Tc(1)P6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Tc(1)-P(2) bond length is 2.36 Å. Both Tc(1)-P(3) bond lengths are 2.35 Å. There is one shorter (2.37 Å) and two longer (2.46 Å) Tc(1)-P(1) bond lengths. There are three inequivalent P sites. In the first P site, P(2) is bonded in a distorted rectangular see-saw-like geometry to one Tc(1), one P(3), and two equivalent P(2) atoms. The P(2)-P(3) bond length is 2.20 Å. Both P(2)-P(2) bond lengths are 2.20 Å. In the second P site, P(1) is bonded to three equivalent Tc(1) and one P(3) atom to form PTc3P tetrahedra that share corners with two equivalent Tc(1)P6 octahedra, corners with four equivalent P(3)Tc2P2 tetrahedra, corners with six equivalent P(1)Tc3P tetrahedra, and  an edgeedge with one P(3)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The P(1)-P(3) bond length is 2.22 Å. In the third P site, P(3) is bonded to two equivalent Tc(1), one P(1), and one P(2) atom to form distorted PTc2P2 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra, corners with two equivalent P(3)Tc2P2 tetrahedra, corners with four equivalent P(1)Tc3P tetrahedra, and  an edgeedge with one P(1)Tc3P tetrahedra. The corner-sharing octahedral tilt angles range from 50-74°.