RhSi3P3 is Hausmannite-derived structured and crystallizes in the triclinic P1 space group. Rh(1) is bonded to one Si(1), one Si(2), one Si(3), one P(1), one P(2), and one P(3) atom to form RhSi3P3 octahedra that share corners with three equivalent Si(1)Si2PRh tetrahedra, corners with three equivalent Si(2)SiP2Rh tetrahedra, corners with three equivalent Si(3)SiP2Rh tetrahedra, corners with three equivalent P(1)Si2PRh tetrahedra, corners with three equivalent P(3)Si2PRh tetrahedra, and corners with three equivalent P(2)SiP2Rh tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted SiSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent P(1)Si2PRh tetrahedra, and corners with four equivalent P(3)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. In the second Si site, Si(2) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted SiSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(3)SiP2Rh tetrahedra, and corners with four equivalent P(2)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. In the third Si site, Si(3) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted SiSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(2)SiP2Rh tetrahedra, and corners with four equivalent P(2)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 53-72°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted PSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent Si(1)Si2PRh tetrahedra, and corners with four equivalent P(3)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 51-71°. In the second P site, P(2) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted PSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(2)SiP2Rh tetrahedra, and corners with four equivalent Si(3)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 53-69°. In the third P site, P(3) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted PSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent Si(1)Si2PRh tetrahedra, and corners with four equivalent P(1)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 52-70°.
RhSi3P3 is Hausmannite-derived structured and crystallizes in the triclinic P1 space group. Rh(1) is bonded to one Si(1), one Si(2), one Si(3), one P(1), one P(2), and one P(3) atom to form RhSi3P3 octahedra that share corners with three equivalent Si(1)Si2PRh tetrahedra, corners with three equivalent Si(2)SiP2Rh tetrahedra, corners with three equivalent Si(3)SiP2Rh tetrahedra, corners with three equivalent P(1)Si2PRh tetrahedra, corners with three equivalent P(3)Si2PRh tetrahedra, and corners with three equivalent P(2)SiP2Rh tetrahedra. The Rh(1)-Si(1) bond length is 2.45 Å. The Rh(1)-Si(2) bond length is 2.43 Å. The Rh(1)-Si(3) bond length is 2.36 Å. The Rh(1)-P(1) bond length is 2.38 Å. The Rh(1)-P(2) bond length is 2.38 Å. The Rh(1)-P(3) bond length is 2.43 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted SiSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent P(1)Si2PRh tetrahedra, and corners with four equivalent P(3)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. The Si(1)-Si(2) bond length is 2.34 Å. The Si(1)-Si(3) bond length is 2.34 Å. The Si(1)-P(2) bond length is 2.28 Å. In the second Si site, Si(2) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted SiSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(3)SiP2Rh tetrahedra, and corners with four equivalent P(2)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 50-73°. The Si(2)-P(1) bond length is 2.31 Å. The Si(2)-P(3) bond length is 2.27 Å. In the third Si site, Si(3) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted SiSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(2)SiP2Rh tetrahedra, and corners with four equivalent P(2)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 53-72°. The Si(3)-P(1) bond length is 2.27 Å. The Si(3)-P(3) bond length is 2.25 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted PSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent Si(1)Si2PRh tetrahedra, and corners with four equivalent P(3)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 51-71°. The P(1)-P(2) bond length is 2.22 Å. In the second P site, P(2) is bonded to one Rh(1), one Si(1), one P(1), and one P(3) atom to form distorted PSiP2Rh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(1)Si2PRh tetrahedra,  a cornercorner with one P(1)Si2PRh tetrahedra,  a cornercorner with one P(3)Si2PRh tetrahedra, corners with four equivalent Si(2)SiP2Rh tetrahedra, and corners with four equivalent Si(3)SiP2Rh tetrahedra. The corner-sharing octahedral tilt angles range from 53-69°. The P(2)-P(3) bond length is 2.20 Å. In the third P site, P(3) is bonded to one Rh(1), one Si(2), one Si(3), and one P(2) atom to form distorted PSi2PRh tetrahedra that share corners with three equivalent Rh(1)Si3P3 octahedra,  a cornercorner with one Si(2)SiP2Rh tetrahedra,  a cornercorner with one Si(3)SiP2Rh tetrahedra,  a cornercorner with one P(2)SiP2Rh tetrahedra, corners with four equivalent Si(1)Si2PRh tetrahedra, and corners with four equivalent P(1)Si2PRh tetrahedra. The corner-sharing octahedral tilt angles range from 52-70°.