TcP4 is Hausmannite-like structured and crystallizes in the orthorhombic Pbca space group. Tc(1) is bonded to one P(2), one P(3), two equivalent P(1), and two equivalent P(4) atoms to form TcP6 octahedra that share corners with two equivalent Tc(1)P6 octahedra, corners with three equivalent P(1)Tc2P2 tetrahedra, corners with three equivalent P(4)Tc2P2 tetrahedra, corners with four equivalent P(2)TcP3 tetrahedra, corners with four equivalent P(3)TcP3 tetrahedra, and  an edgeedge with one Tc(1)P6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are four inequivalent P sites. In the first P site, P(4) is bonded to two equivalent Tc(1), one P(1), and one P(3) atom to form distorted PTc2P2 tetrahedra that share corners with three equivalent Tc(1)P6 octahedra, corners with two equivalent P(3)TcP3 tetrahedra, corners with four equivalent P(1)Tc2P2 tetrahedra, corners with five equivalent P(2)TcP3 tetrahedra, and  an edgeedge with one P(4)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 64-73°. In the second P site, P(1) is bonded to two equivalent Tc(1), one P(2), and one P(4) atom to form distorted PTc2P2 tetrahedra that share corners with three equivalent Tc(1)P6 octahedra, corners with two equivalent P(1)Tc2P2 tetrahedra, corners with two equivalent P(2)TcP3 tetrahedra, corners with four equivalent P(4)Tc2P2 tetrahedra, and corners with five equivalent P(3)TcP3 tetrahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the third P site, P(2) is bonded to one Tc(1), one P(1), and two equivalent P(3) atoms to form distorted PTcP3 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra,  a cornercorner with one P(3)TcP3 tetrahedra, corners with two equivalent P(1)Tc2P2 tetrahedra, corners with two equivalent P(2)TcP3 tetrahedra, and corners with five equivalent P(4)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. In the fourth P site, P(3) is bonded to one Tc(1), one P(4), and two equivalent P(2) atoms to form distorted PTcP3 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra,  a cornercorner with one P(2)TcP3 tetrahedra, corners with two equivalent P(4)Tc2P2 tetrahedra, corners with two equivalent P(3)TcP3 tetrahedra, and corners with five equivalent P(1)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 48-72°.
TcP4 is Hausmannite-like structured and crystallizes in the orthorhombic Pbca space group. Tc(1) is bonded to one P(2), one P(3), two equivalent P(1), and two equivalent P(4) atoms to form TcP6 octahedra that share corners with two equivalent Tc(1)P6 octahedra, corners with three equivalent P(1)Tc2P2 tetrahedra, corners with three equivalent P(4)Tc2P2 tetrahedra, corners with four equivalent P(2)TcP3 tetrahedra, corners with four equivalent P(3)TcP3 tetrahedra, and  an edgeedge with one Tc(1)P6 octahedra. The corner-sharing octahedral tilt angles are 57°. The Tc(1)-P(2) bond length is 2.39 Å. The Tc(1)-P(3) bond length is 2.36 Å. There is one shorter (2.43 Å) and one longer (2.55 Å) Tc(1)-P(1) bond length. There is one shorter (2.33 Å) and one longer (2.35 Å) Tc(1)-P(4) bond length. There are four inequivalent P sites. In the first P site, P(4) is bonded to two equivalent Tc(1), one P(1), and one P(3) atom to form distorted PTc2P2 tetrahedra that share corners with three equivalent Tc(1)P6 octahedra, corners with two equivalent P(3)TcP3 tetrahedra, corners with four equivalent P(1)Tc2P2 tetrahedra, corners with five equivalent P(2)TcP3 tetrahedra, and  an edgeedge with one P(4)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 64-73°. The P(4)-P(1) bond length is 2.21 Å. The P(4)-P(3) bond length is 2.19 Å. In the second P site, P(1) is bonded to two equivalent Tc(1), one P(2), and one P(4) atom to form distorted PTc2P2 tetrahedra that share corners with three equivalent Tc(1)P6 octahedra, corners with two equivalent P(1)Tc2P2 tetrahedra, corners with two equivalent P(2)TcP3 tetrahedra, corners with four equivalent P(4)Tc2P2 tetrahedra, and corners with five equivalent P(3)TcP3 tetrahedra. The corner-sharing octahedral tilt angles range from 53-60°. The P(1)-P(2) bond length is 2.25 Å. In the third P site, P(2) is bonded to one Tc(1), one P(1), and two equivalent P(3) atoms to form distorted PTcP3 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra,  a cornercorner with one P(3)TcP3 tetrahedra, corners with two equivalent P(1)Tc2P2 tetrahedra, corners with two equivalent P(2)TcP3 tetrahedra, and corners with five equivalent P(4)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. There is one shorter (2.18 Å) and one longer (2.20 Å) P(2)-P(3) bond length. In the fourth P site, P(3) is bonded to one Tc(1), one P(4), and two equivalent P(2) atoms to form distorted PTcP3 tetrahedra that share corners with four equivalent Tc(1)P6 octahedra,  a cornercorner with one P(2)TcP3 tetrahedra, corners with two equivalent P(4)Tc2P2 tetrahedra, corners with two equivalent P(3)TcP3 tetrahedra, and corners with five equivalent P(1)Tc2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 48-72°.