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RhSi is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Rh4+ is bonded in a body-centered cubic geometry to eight equivalent Si4- atoms. All Rh–Si bond lengths are 2.58 Å. Si4- is bonded in a body-centered cubic geometry to eight equivalent Rh4+ atoms.
RhSi is alpha-derived structured and crystallizes in the cubic P2_13 space group. The structure is three-dimensional. Rh4+ is bonded in a 7-coordinate geometry to seven equivalent Si4- atoms. There are a spread of Rh–Si bond distances ranging from 2.50–2.55 Å. Si4- is bonded in a 7-coordinate geometry to seven equivalent Rh4+ atoms.
Rh2Si is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Rh sites. In the first Rh site, Rh is bonded to four equivalent Si atoms to form a mixture of distorted edge and corner-sharing RhSi4 tetrahedra. There are a spread of Rh–Si bond distances ranging from 2.42–2.47 Å. In the second Rh site, Rh is bonded in a 3-coordinate geometry to three equivalent Si atoms. There are one shorter (2.49 Å) and two longer (2.50 Å) Rh–Si bond lengths. Si is bonded in a 7-coordinate geometry to seven Rh atoms.
RhSi crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Rh4+ is bonded in a 6-coordinate geometry to six equivalent Si4- atoms. There are a spread of Rh–Si bond distances ranging from 2.43–2.60 Å. Si4- is bonded in a 6-coordinate geometry to six equivalent Rh4+ atoms.
Rh3Si4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Rh sites. In the first Rh site, Rh is bonded in a 6-coordinate geometry to six Si atoms. There are a spread of Rh–Si bond distances ranging from 2.33–2.48 Å. In the second Rh site, Rh is bonded in a 7-coordinate geometry to seven Si atoms. There are a spread of Rh–Si bond distances ranging from 2.33–2.62 Å. In the third Rh site, Rh is bonded in a 7-coordinate geometry to seven Si atoms. There are a spread of Rh–Si bond distances ranging from 2.41–2.62 Å. There are four inequivalent Si sites. In the first Si site, Si is bonded in a 6-coordinate geometry to six Rh atoms. In the second Si site, Si is bonded in a 4-coordinate geometry to four Rh atoms. In the third Si site, Si is bonded in a 6-coordinate geometry to six Rh atoms. In the fourth Si site, Si is bonded to four Rh atoms to form a mixture of distorted corner and edge-sharing SiRh4 tetrahedra.
Rh4Si5 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are four inequivalent Rh3+ sites. In the first Rh3+ site, Rh3+ is bonded to six Si+2.40- atoms to form distorted RhSi6 octahedra that share corners with six equivalent RhSi7 pentagonal bipyramids, corners with six equivalent RhSi6 pentagonal pyramids, edges with six equivalent RhSi6 octahedra, a faceface with one RhSi7 pentagonal bipyramid, and a faceface with one RhSi6 pentagonal pyramid. There are a spread of Rh–Si bond distances ranging from 2.40–2.52 Å. In the second Rh3+ site, Rh3+ is bonded to six Si+2.40- atoms to form distorted RhSi6 pentagonal pyramids that share corners with six equivalent RhSi6 octahedra, corners with four equivalent RhSi7 pentagonal bipyramids, edges with four equivalent RhSi7 pentagonal bipyramids, edges with two equivalent RhSi6 pentagonal pyramids, a faceface with one RhSi6 octahedra, and a faceface with one RhSi7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 46–49°. There are a spread of Rh–Si bond distances ranging from 2.34–2.48 Å. In the third Rh3+ site, Rh3+ is bonded to seven Si+2.40- atoms to form distorted RhSi7 pentagonal bipyramids that share corners with six equivalent RhSi6 octahedra, corners with two equivalent RhSi7 pentagonal bipyramids, edges with five RhSi7 pentagonal bipyramids, edges with four equivalent RhSi6 pentagonal pyramids, and a faceface with one RhSi6 octahedra. The corner-sharing octahedra tilt angles range from 52–59°. There are a spread of Rh–Si bond distances ranging from 2.32–2.68 Å. In the fourth Rh3+ site, Rh3+ is bonded to seven Si+2.40- atoms to form distorted RhSi7 pentagonal bipyramids that share corners with two equivalent RhSi7 pentagonal bipyramids, corners with four equivalent RhSi6 pentagonal pyramids, edges with nine RhSi7 pentagonal bipyramids, and a faceface with one RhSi6 pentagonal pyramid. There are a spread of Rh–Si bond distances ranging from 2.43–2.61 Å. There are five inequivalent Si+2.40- sites. In the first Si+2.40- site, Si+2.40- is bonded to four Rh3+ atoms to form a mixture of distorted corner and edge-sharing SiRh4 tetrahedra. In the second Si+2.40- site, Si+2.40- is bonded in a 6-coordinate geometry to six Rh3+ atoms. In the third Si+2.40- site, Si+2.40- is bonded in a 8-coordinate geometry to six Rh3+ atoms. In the fourth Si+2.40- site, Si+2.40- is bonded in a 6-coordinate geometry to six Rh3+ atoms. In the fifth Si+2.40- site, Si+2.40- is bonded in a 4-coordinate geometry to four Rh3+ atoms.
RhSi is Modderite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Rh4+ is bonded to six equivalent Si4- atoms to form a mixture of distorted edge, face, and corner-sharing RhSi6 octahedra. The corner-sharing octahedra tilt angles range from 41–63°. There are a spread of Rh–Si bond distances ranging from 2.44–2.52 Å. Si4- is bonded in a 6-coordinate geometry to six equivalent Rh4+ atoms.